Interpretation of Mass Spectra-4Ed

INURPRETAfION
OE'MASS SREC:YRA
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~.1
INTERPRETATION OF
MASS SPECTRA
FOUR TH E D ITI O N
Fred W. McLafferty
..-".
_~.
Frantilek Turetek
Uni"""ily Scirn "" 8 00b

~~D Gate Fi, -e Road
Sau.ol;,o, CA 94%5
Fax:
( 41 5 )3 3 2. ~ W 3
Producti<m m.n'i<r: I ", ,,,, l oif~ ~

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Koprodu<t i"" or "a n. I" I" " ,ora "y p,rl " I' Ihi' ""r\< ocyond ,h ., jlC, nlllt od
~y So>;li "" 1117." I n ~ " I' II,. IQ76 lln,!,'<l Shtlc. CD P l, i~ h' Act ,.i,h"u' tbo
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Prin ted in [be L:" j,O<1 Sr.' " <It ,h"'n<:8

10 9 " 7 6 I ~
Preface
10 the Fourth Edition
Molecular ma" "f!" Clmm~ry o:m hnu e' to , Jo nw an ' '' f'''ncnti. 1gm ..,th. "'ilb a
.u ~ta u tlal l'<"poTf icu of it, appl<Cati" u, ' I' ll feq u inn ~ lhe idcnlirJCol'"'' 01
unkn",. n mass ' f'<'.1 ' ~ . T I>e fin' !iti on ." Ih', bo ok ..". publi......J more th n
2.\ }~~ n ~ go. whell m'.... in.uuulcnL, could "",aWf< oll il ~ fe..' unh " wn rna..
'f"'I.1ta per b"ur T he Pref:au; 1o the I~ H IJ Tbird L.ili" on e' tirna:d worid wi'k:
imtrumenl .~ 81 flCarl}' 1,1))) ,' ,,"" .pe.:tro melo", ~t ~""t, the p"' '''nl . ale i<
"""" , ,,I lirn., \h.lf. wilh m,,' o than a ....PCn n, . jot m" n,dllclu, c"''' The'" ;",1"'
aT<: ~l "" far more riflei"nt, lhe ~ ""' t m"jorily f>eing computerized sa,enro nu' <>gTap h,ima" . l'C"llOmeIC' IUC/M SJ ,).tcm, thal ...,n tum ......1 up to
lOt) unl M ",'n ma>! ~p' el ra in a In-minute GC/MS ,,'n. ...lt ho ugh . ulomMed
e" m pul",.m,nclm,,, f'1"",..edUl'e ~ nf , """ 'f''lta are "0" _umeient ly f.!t to b :q '
up " ' lh thi' oUlp" t tChapl<t 1OJ, the.., a ro: '"~ oIl I}' " n . id 1<,.not " rt'l' laccmout
tor. ,lie " ~led ;nw'Vf<ter. .... ~ collfj' muLion oI th,,, the CO"",, ~ ;"'.n b~' Ihe
auth" l'> "" ~ l " ter p re t a.l i " n 01 M ~ .. Spectra lOT T e~ d," ", <:>t Intnl",' " tion
Cou, ,' at .he 1'ilI! Conl"t"C ""'" of ' he Allle",,, n Sociely f"t )vi" ", ~P"'''''''I
met.) a lLr" etod JO a Uc'1\dees.
Ib e MOSt lmpoltant addItion to lhi, bool , in Ih" opi ni,m of lhe " ."ior
"uthor . u. iI' coa uth" r. F ranl TUJ'eCel, .. ho is Ilm'" at the IIni"" " ity (II
W" , h il\,i;l<:m a _ . n ,,""' Oei. l. Profe.,,,,, hM had ~ d, ot l,,~ u i , h c d rost a, w. ""'e<f.
...uh well m 'CI a bundro:d p uhticalionl in m" ,,>, aU-a_ "S mo" , pcetJ"''''lr )
CTili",,] to 10;' bocl. He loa' made ~..piall)' imlX'l tJn[ "" ntribulion, 10 Ibe
med ...' ''<otll in (,h " pt ~n 7~ "_ ro:p,."",,\ing more lh ~ n o"" -third of the 1><",.
Our e' le,I>' '''' ,evi,; on. ~ " .. haJ lhc o~ ;ect i " c " I wr ,. l ~ l' n~ ;Oll d;_...~ " t i o n
mec h ~ n " t'" o n a m ~ cb broaJ,:. "",It. .... ith <mplw .i<on b." ic a lLribtM1 such a,
ioml J ' ;On c"Ol ~'es, pJOton a!flniLic.... aDd h< ,n d -d i"oc i .'~ .n eI.., r~"" . We ba ""
. 1" . allemplecl [ (> .t",,,
tbe'" " "-",h. nlSrr,, ~re apphc:ml~ to the unim,>k
~lL l~ r di....x:iolll O'" or i o,, ~ r
d by an y i"n;zaj ,on method , ; "" l uJi n~ t h~
~'; li n~ v....., y .~ new m,: lhod, for ot>I. ' ning nla"" 'lJ"'Clra of 1. ' ll" Jncle<.uk '
,,,,,nt,
C,
."
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ou ~ "
woo..
Il<; maillin<t "~ ch~,, # d. how",c., i' ,1>0 COll" icl;on W ' lh. n",,1 ;n1I"'M.tnl
how to in ~'I'UI unknown tn. OJ spn 1. a ;, ~ClU~ UI , ,, pru<,ic.
part of
inteTl' fd ing Mol>' ; pcc"a. A~ ' h" b< x, k ha ' el l,orle, ll h. '!mk o!
n,OI'o than
25)~ J OU. h" " HJ au .... pl (0, ,,11.'. one or 1.." Ullkll OW,,' (" . ~~r) ho'" or
loc:tuOT or ", If-'l ud ) . TI}" ""'io",ly \<' ." l>e the Ul1 k ~ "",,,, b::fore <hocl.in, the
I nr u" in C I1 . p~, 11. ,n ile down nc. 1 10 the ' l'Cctr al da ta your c~kub 'M
1<:;0'"""
f".
""'n"''' l,,1",lmpo:;l'ion
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' lruefur'.... ~nd ,.<m utated m..:r,a
" ,, " " "" tha t ' " '' ""11 b Ltel' w m l',,,e lh . ", t~ til<: bouk", 'e.\'''"i n~ in
<: bro"
11 T ry f loc", .1Cp; also on " .. ~ n""' Il' Iw m your 0"'" Ie",a, ch You .h""ld find
th" \ pullin, l ~ g. l h cr lhe p;..ees (If the MS jill"a" 1'" "le i' l im, II ""n~j lll y h'"
\>u.." f d Ol 'or u,
Pm,,,,,,, In til.
1"'0 ed ill(>l>' 1>... had qu" la.;" .... from the rM1JI<>US
11)01'" ' pcc\m m.lf" l "1. 0 T,. -T Ll n ~ As .u g gc , ( e <1 l> ~ Do. Roy W . K i,, ~ a r>d
Kain Sa K...~,l. W,lhJll1 Sha k""l"""'" MI, ,, <1e,,"'''''' cilali' >11 , >. ying in Hamiel
"Wilne.. ' h,. arm)'. of , uch rna.. ;md eh.r ~ ". r.:,,,"p. t.. . " t IC1{'IIt.... It.. n"""
co -. LOti,..,.. re>'J. io n, in Chapl' l ~ " 'ilh hi. "'0'''' in O"iul"'m" "(;"1 y<.>u ho me ,
p,,,,.;,,,,,
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Contents
Pr.t."" to ltle F_
1h Edilion
. du>owl ~ .
I j~
Gl olI...Yend Abb.eyi . Uonl
Intr04\lctlo n
Ii
'v
1.~
"'P P""OU1oC<I' oI,"e _~ , .....

F"'''' ' hCl n 01 tf><! M.... Spect,u m 4
'-1 "
, ~ .'. 01 Ion .
r
Ion All
n"" M~ Mu .., m_ ' 1
S . m,' ~ Int ' e>d uctl on S t. ",.
11
1.6
' .7
\.1i
""
' .S
1-9
St. M a,d Inl. 'prel ' ''Cln P'OO@d Uf'

~ e 'A " "' _
15
1.1
I .~
I'
14
""lyOi' ' Z
: 01. ' $ trun.,. Infoo.... oon
:l I Elem.nlal Co m position
2.1
2,2
2.4
2.5
13
11
Sta b- . l.o!cI>e. Clus,fi" ICl n "'coo,aing tCl Na'", ,1 " O</flda" .

" A " 2" ~", e" ts Ooyg", Silioor> . S,llu ' . Cb lo' '' e r<l
Bro ,."....
2. ~
IZ
20
" A +" lo, on,.ot . C., bc><, " nd N" ' " gon 23
.... '. EIe "'...."' l'ydlov" . fl uo ' ;.... .... _ " '.... . no:! 10'h _
fli"91 pi" " 00" " 9 8<l _
V
25
Z~
2,6
E,erci ..",
2.1
2.8
C O" I"'"'IO(" ... .. A1I ~ _ a ... _

.....
Oed.J C,,,,, Element,1CompO." ion . :r.J
J , Tile MolecUlar Ion

3 .1
3.2
3.3
~ 4
3.5
,~
om
35
11""""."'''''10 '0< (h. _
Ioe", ,..-I"" J6
Ot!I' f lec t, .,., "' '''' 3ti
Th. NI I'""e n f><J le 37
R g l. ~ _ Imoo .... noe 01 P10Ih
3Il
L O~ ic . 1 Ne" t,.l l o, . . .
:9
J Ji
M"""",II"" "~_ '"1C" \fVSU' SI.>en,,,,
3.7
Ty po<;;o l
M_~
Sf>OCl. .
.,
.,
Viii
4 , a.&ic Mech .niwns 01 Io n Fragmentat ion
81
41
LJ.'''OIeeu'a r loti D"""",po. ;(,ono
a2
Ba. ,c Fac t"'" lha t Influ. "". 11m Aoondo ",,~ 52
52
OI""eli"" lo" ,a lion '" A""" a l or Cha rg. Si..,. 501

Re a cti"" CI. " ihe.,on" ~
4~
Sigma _
o;sooc ial i"" I ~ ) twtl
4.6
~ oo<l;~.al -So l. 'M i' lion ("-D<l" "V"1 57
4.7 C na , ~ SUQ Inll'Ol ion (IndUCI"'e C'eava go, i) 54
4 8 Clecompo, ilion. 01 Crdic SI" . tMe. 58
49
R. d , C ~ I _ S i t e
R<oa" . nG_nlS 72
4 10 ChM gO_$ ilC OIear' ''''Il''!''' 8nts 7B
4, t 1 S u m ~r. '" TYP"" of R. OtCl ion ~"" ...... " 8-3
5 I POSlulililion 01 Molecular StTud u res

5. 1
5.2
5.3
~ .4
5~
55
o.. "" ra l Appe "". ol th. SpeWLJm II';

Low 1oA~" " Ion SOOr.... 91
6m.H.....""a' l o... . 97
a..ra""', i" 't Ion. ~
Poo1ulat '"," poss il>le 5h\1 du..... t OO
""'''g n''' OOI of the ""'" PrDb<lble S" UClY..e 101
6 , A Ullllillry Te c hniques
6 .1
6.2
(; 3
64
6. ~
ee
61
6 .S
IS
103
Soft lonizaho o Me\hod . 103

Ion':ali "" of La rge .....1"""'... 105
b a cI Mass Io.! ou u , e _ rtts fHign "' ~ ' a l u l io n )
T ' '''' ~m M.". 5p00ct,o me lry (MSiU SI 109
Co roltl<...... Tecnniq" . .. 11 ~
Th ~ St.;" l ... hnique
11~
c""..i... ro.o ri vat i Y~ " " .
Genera l ~ ~ 18"""'"'' 114
109
7 , Theory 01 Uni~u l e.r Ion Dec omposillon,

7.'
z. a
13
F"",9'o' De po;iliM a M Rille F.-.cn"" " 11~

TherMOdYna mic _8 , IV",,"c E" ~ c " 117
Ou""" -e q u i t i b ri ,,mTh _ ~
ns
14
T~
O<! , ivat, on <II 1'( 8 Fu flC1 ,on.
'e
7.7
7.8
120
C" l c " la ~ ..... ol ~ I E I
FunOIl"" . US
The rmo<n.m o<a l lle la ti"" 0/1,'" and Pot.nl,a l Ene rll)' S u' ''COS
, a... ~,," 1 3 ~
G .n cr . l ll~ f ~ ' . "' n
134
8 I ()@lailed Mechanisl'Itt a nd Ion Fragmentation

e. 1
6~
8.3
115
u.. "' '''eeu'a , "", D. c omwsilio....

138
Sto , ic fa OIO'. IS'
Prod,,", $l . bility
1:15
135
127
"
8.4
8.S
RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e.

Re llCl''''' C '~ t i c.\ i "". 185
86
8'llmt-Bo 'l<1 Di,"oc iali on ( ~ l
e7
&8
ll . o i< .I S,'~
B9
[)e{:_ ~ . ' ti O ""
C ~ " ' ~ . S ' l'e
e. 10
6.1 1
8.12
,eo)
.ti!I
Initi.tioo (~ -e l uv.go ) 111

Imt,a tio<! (I".....eli. . 0..... ' ''9'' . i)
aI Cyclic S"uo;t~r ..
liyd rOOl'" R"'''...gements 111 1
Othe r R.....' . _ _ m. 213
GeM ' .. ' PeI...... ..",.. ~ 1
113
\ 7~
9 / M. .s Spectr a 01 C om m on Compound Cle nes

g,
~2
9.3
9.4
9.5
9.6
9.7
~8
';1'1
Hy<lroca, boo . 226

",,,,o001. 240
"' '''o ~ yde . e n<l M1O,...
eel."
22!i
2016
25 1
ACid., ~.- , eno l A<' ''''' U

1'.1... ,. 2tJO
2!>ll
Th'D1e . "" "'W'de '
~ _IO
265
Am,,,,,,, 210
An",l.. .74
Nit,; I. a nd Nitro Compoo"".
9"
.'I' ivh aticH.li<lfl.
g'2
OIhe rTYP".<>ICofflPO_
1/6
~1tI
200
10 I Computer klenlltW;"t lon 01 Unknown M . .. Spectra

10 '
16 ~
100a
The O."'bftSe DI Aa'.renee ~I Mass SpoocIfe 2601

l: Tfle P, ob.bi lity llaoed .... 1Ching 8 y. tom 2M
l ", oW ~ " . ' i o n : The SeIH
h>1orp,eli, e a nd F1olr i.vel
S""te m 2e7
10.4
,",pplic otlO n 01 P1l ~ ;III d STI llS
Fl<>",,,
283
"""'''\I
10,5 Go"" ' o l "'. ~~
290
2\1 1
11 I Solut io ns to U"'nownI;
203
Il ll>liOO"''''''' 311
' _ nella 339
NLJ<I' d oc "'_
_
'""", pi, "~u"<la<>ees 339
N. "" . I " llo.Jnd .",:<,. '" Combin . tio ,," '"
8 mmi.... SilieOn. and Sulfur J40
h b" " 3 loni,.""" Ene 'll Ya nd Pm'"" ""'lilly V. ,.... 343
T80I. " 4 11I061>0 " '" Ion Atlund. nces ,," , ComJ'o."'d Type 346
T8OIe " S Com rnM No"" ol F' ra y ..enllo 34&
l a_ " 6 Com mM F, a ~ . ", I"... 351
Tat>le A 7 Co mmoo E1e.........1(:(>m_ " ioo . of M o lecu l. r
Ta ble A. 1
Table A..2
CIllo"""',
Ie ,,"
~del
361
35!i
"
8.4
8.S
RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e.

Re llCl''''' C '~ t i c.\ i "". 185
86
8'llmt-Bo 'l<1 Di,"oc iali on ( ~ l
e7
&8
ll . o i< .I S,'~
B9
[)e{:_ ~ . ' ti O ""
C ~ " ' ~ . S ' l'e
e. 10
6.1 1
8.12
,eo)
.ti!I
Initi.tioo (~ -e l uv.go ) 111

Imt,a tio<! (I".....eli. . 0..... ' ''9'' . i)
aI Cyclic S"uo;t~r ..
liyd rOOl'" R"'''...gements 111 1
Othe r R.....' . _ _ m. 213
GeM ' .. ' PeI...... ..",.. ~ 1
113
\ 7~
9 / M. .s Spectr a 01 C om m on Compound Cle nes

g,
~2
9.3
9.4
9.5
9.6
9.7
~8
';1'1
Hy<lroca, boo . 226

",,,,o001. 240
"' '''o ~ yde . e n<l M1O,...
eel."
22!i
2016
25 1
ACid., ~.- , eno l A<' ''''' U

1'.1... ,. 2tJO
2!>ll
Th'D1e . "" "'W'de '
~ _IO
265
Am''''''' 210
An",l.. .74
Nit,; I. a nd Nitro Compoo"".
9"
.'I' ivh aticH.li<lfl.
g'2
OIhe rTYP".<>ICofflPO_
1/6
~1tI
200
10 I Computer klenlltW;"t lon 01 Unknown M . .. Spectra

10 '
16 ~
100a
The O."'bftSe DI Aa'.renee ~I Mass SpoocIfe 2601

l: Tfle P, ob.bi lity llaoed .... 1Ching 8 y. tom 2M
l ", oW ~ " . ' i o n : The SeIH
h>1orp,eli, e a nd F1olr i.vel
S""te m 2e7
10.4
,",pplic otlO n 01 P1l ~ ;III d STI llS
Fl<>",,,
283
"""'''\I
10,5 Go"" ' o l "'. ~~
290
2\1 1
11 I Solut io ns to U"'nownI;
203
Il ll>liOO"''''''' 311
' _ nella 339
NLJ<;I' d oc "'_
_
'""", pi, "~u"<la<>ees 339
N. "" . I " llo.Jnd .",:<,. '" Combin . tio ,," '"
8 mmi.... SilieOn. and Sulfur J40
h b" " 3 loni,.""" Ene 'll Ya nd Pm'"" ""'lilly V. ,.... 343
T80I. " 4 111061>0 " '., Ion Atlund. nces ,," , ComJ'o."'d Type 346
T8OIe " S Com rnM No"" ol F' ra y ..enllo 34&
l a_ " 6 Com mM F, a ~ . ", I"... 351
Tat>le A 7 Co mmoo E1e.........1(:(>m_ " ioo . of M o lecu l. r
Ta ble A. 1
Table A..2
CIllo"""',
Ie ,,"
~del
361
35!i
Glossary a nd Abbf e'li3 tioo.
Il.Jic'.d cal ion. uJokl.:, :I"'.. k'n lro., <' u m pll'. <:H. '
.....". ((ull a.-" "" I
T """..f<,;t o. "" d<drQn J'IIir.
~( r. , h h < k 'U
T to,,,fer {'( "nlli. el... tt<><'
[ l
KoI . li, ,,
,, 1w~d; ,,1<'
ul t1w
'O ~
W;(nlh the bt ;><hll
K t c, Y :dcaYago "r ~ bOO1d""lln ~t"".a dJ "celll

lo lI>:; "\Q~l ""Olll1g Ihe od d tl K ffQn(but "' ,. th~
lx>nd!o the lalle, a to m,.
ama . II
Atom ic m,,, unJl, dolto n
AF
IIppear allOO energy; formerly oppearo,>: poo l. m ial.

M un"i :>lopic clome" t (h yMo~.n il , 1>0 oonl J<lered
to be '" " A" elem.. eu
".\ I I" clement
Elemem with a ll i,otope Wh OR muS j, I am" ~ bQ , e

tha t of the mQ,t a buoo." l ;"" [01"', hul ",hi ch;> n,,\
all "A
+ 2"
eb"" nl.
[ Iemem "' ilh " " i"'lOpe who"" m. ... i. 2 ..rna

lh" ' "f the mml a hundanl ;" )I,,f'<:
(,"'j peak
(A
I) pe a k
Pc." who"" m ai n clctne nlal l"o rm ul;,;'

o nl} th e
" huTI ,lanl j", I"JlC"
ffi""
.1><,,"
~,)ft1P<,.c.t
<It
Th e JlCuk on e rna" uni l a"' '''. 'he 1\ !"""k
ha >e pea k
Peak rep,,;;eot jng Ihe mo st .bund811t jon jn lhe

. pec!r llm
M agnelic r..ld str ength: magneti c analy<er
e ll
Colli'io nal activa tio n. colli, iol1 . 1excit. tio n
CAD
Colli, io na lly aCliva,,,,1di",,,i,, li" n; .1.0 <:II),

"olli, ion ind uocd di" "",ial, C'n ,
CI
Chemi"" l i<mizalwn,
_....-...........
c~ dization.
"
Rea"l; on in ", hich .. cyeli...... p, <><luc, killtc' lh' ion
'"
n~u {ral)
i'lorr" ,"<l.
D IA --BI
Dissociation .......... g~ nf lhe ., ,-- B bo nd.
d :ol"'n
" n ~I"mic 1lL1SS un it I" C ~ 12 J al to" . ;
l .Ni
d ~~ ~ 1",
i"n
DLdc, olrt ,,'"
III "I.')
S p'....I ~ cl i<m.
O>, cU g~ n cT a l j o n of wn' lrum ~ ..~ ",dc n", d pha ' r
" u nplc.
K~J C l i oll
in .. hid . cycl u..IJM 10 fo rm a "",",' ho..<1 J'
a " . , bo' l (or "" he1) ,,'om ,,,,ul t. in tbe "'" " I a.....,h~.,.
gwur a l"'d>t<l 10 l h~l " " ,hon alom
An ion ' " ill> ":r a , alod rad ical " 00
~h. ,1lC
..1...
R n ion in ,,hich cyd Jzation 10 r"m, J ,, ~ ..' bond

be1
n lwo I'~r\ . "r ." io" re" dll in ll>." k" . of lhe
~,l u al
g rQllp CCDnc.;linl.l ' he."., l>arlS ,
eIllical " "'J~)' tOf . he ,,,,,..I i,,,, M +- --> 0 ' ,~ I" ,

..-li.auOfl en. Jn . 1': ,
c~ ll c d
f~. ( M -
_ O' )
I"ft ill1e.-nal . ... r~y rC4 ui, cU '" thJ t hJ lf of M " ~ .n .

..,ill ,10"'''11' '''''' 10 ~'i cld f)' h,.;,,~ leaYJII~ , "" ion
SOUle<
fA
F.k cln m
ff" ~"",,.,, ~I e< "o n
l"n in ,,'lIiclllhe
"<:1,,,,-",, , he ll~ ;,>n.
EI
~ I ,..; u
EfF10
r""'T1m ",uLLc.d
cV
Uool"1I\ ,olt _ % ..(8 1 ~ J ;", . ~ _ 23.06 k""li mo l
'"
FD. n
F" 'I " I " ", h",nl>ardn.. nT.
rrvs
F"uri."T- lJ~ " l!o,m
OCi MS
,\
" l h, id M S/MS
' l1Io t LL tilizinj( two l~'"" , ,,j" n"'" ' p"ctronw"''" , , ,,cll
'" J "" ble-focu "", "Td <j";"h,,po l. instrument.
l e ll
Ion . yd<m"n InOD"n,,,.
II'
I "" i' J tlon e"".~y, rormerly i"ni zal ion ['OIen ' ;. l
"
~rr.n ill-
",,'e,-,hell oloel"'''' l'~ r" Ur "" ,ra\;
Fi "l ~
..n i,,,,j,,atio n,
citJ!l<>n ,n "'l"'n ie>
<Io." I'uoo. ioniL.tion.
MS.
ga~ ch , o m " t"~r,, ph
iotcrfaa<l ' o a m ~ ... ' re, lrOntcte, .
"'
....,.-
n'
] nducliv'e initi", ion of a Tcad ion thro ugh electr on

",ilhduwa l by lhe e h a r ~e ,M ,
inL
Relat ;v. intemil)' or a peal,
or
the ,ame oominal

compo,m ons,
n",,, bul or diffe,enl clemenlal
Peal who,e elemental composition contains an

i,, 'lope no l o[ lhc hig hc' l nal ural abunda",,"
I'hc funclion de'crihing lru, change ill Ill' rate
eonstan!. Ie, with eh""ge in lhe internal energy, F., or
lhe preeutw r ion [Ot a panic"lat ion-deco'lJpo,ition
rcaclion.
LC ,MS
... li4Uid chro rnal og ra ph interfaced 10 a rna"

' pcot, omoloc
La",,]' desorption [Ot ionization of non-volatile
",mple,
I'hc ma" of the ion in dalto", divided by ilS charge

lusuaUy unity), a Thom,on: mie ha, al,o been used
li n ion d ecomposin ~ between lhe jon source and
deteclor of the mass spectrometer,
M ' , mok cular ion
Tb<,; iuni ,,,,,! molcoulc, "'doe moleoula, ion" i, I ho peak

represent ing the ioni zed molecule thai cOllta;ns only
the i, otope, of grea le' l nalUral abundance.
(M - 11+
The ion formed by lhe los> of one rna" unit from
M'
.\le
MelhyL CH "
.\IW
Protonated mok culc" (M + H )
.\1I ' pectra
Ma" speclra formed by mcta., I;iblc ion di, ,, ,,,-iat ion,
tmn u, millima" un it'
0.001 alo mlc ma" unil; a millidallo n,
'"
.\Ia..,
MSi MS, M S"
~ t l'Ometr)'.
.\fS do~ in tandem .,ith mult iple (n) rna" analy', cr<;
"'p:uatod ion< Im m one analF",r arc
,lj' '''lC;ai<xl or rc~cd to form lie"" ion, rna"
>epara led by the next ana lyzer,
m ~"
Non ho ml; n~ ct""(r<>n<.

A pea l whooe elemental wmpo,ition hI' only
i""topo , of highest " ' lural . bu" da" "".
N en In Ii...1i000-r.ionizatio".
xviII
OF' ,,,,,ld-,,Io"I"'11
>00
I"n in which an outer-sh"1l electron is llnpaired; a

radical ion,
Pascal (l Pa _ 0.0075 lorr; I atm _ 1.013 x 10' Pal.
Proton affinily.
P""u"or, p'lrcnl
The decomposing ion in any l"action.
Product id'l\lghlcr)
The ion formed by dissociation of a p,"cnrsor ion.
'"0
!'{I;J
'0
Plasma de'''rrtion ioni/alion, such a, thaI ulilizing
'''CL
Oua,!rupnle analyzer
Q
1',
rhe dislrihulion funclion ,Io,enbing Ih" prob"bilit),

ror parlicular value, ofinlem"1 energy of an ion.
rearrangemenl
A reaclion in which lhe m"koul"r conncoli,'ily of the

atom, in either the ionic or neutral product i' not the
same as thai in the precursor ion.
r I <Ib
Number of rings plus doubl" bonds.
rI'.rJ,re,rH
Remrangement, involving cyclization, displac"ment,

. Iimination, and hydrogen transfer. re,pe,li"e1y
RDA
RCiro-Did,-Alder reaclion,
rolati;-e ahundance
The abundance 01 "" ion relalive to tbat of the most

"bundanl ion in tho sp"ctrum (or, if '0 staled, reiali 1'0
ro L~.J
sigma-el"ctron
ionizallO!\ reactlOl\
A simpl" cleavage r.aclion vi,uali""d as taking place

throlLgh i[\ilial ionization al the sigma bond clea\'ed
in the reaction.
0,
rolal ahunuance of all ion< in the , peclrum,

rotal ahundance of all ion< in the 'pc<:lrum
40 and alx,..".
"I"",,,
An ion-decomposilion reaction which in\'ol\'es

cleavage of only a ,ingle bond
"M
Selected ion monitoring,
srvs
Secondary ion ma" sp.ctrom"11'y.
Thorn,on
An miz uni!.
Volts: speciflc use, accelerating I,ollage.
The number of charges on an ion ("e' was formerly
"'"d for thi' definilion).
1
Introduction
1.1 App
r.nee 01 .. . m." specttllnl
(.....n;n' ho", to identify ~ ";mrk onol<CII lc [wnt i/O ~ ," lr "" ;'ll n jZll l1 o n I ~ l)
" ,ass 'pee\'um ilInUe!. ca>icr lhan fw m othe r t~ of . ""CUI . The ,na,'. ' r.,u~, ,,!low, II", ""... nf ,It. m.)/tr ul, I", J /Io<....usn ,,! pi"C~ 1 ./r"'" i1. 11,,,, ,Ill:
" homi, t doe. 10'" ha,'. to l. " m . nyt bing "'''' - 1'''' appro"ch \1 siml1.u 10 an
Mit!> ",,,' ;c trno in " ~ a"' t_ TTy on. ,,0<1 "'"
_ ....... 1.'
""' ~
..
In 1"" b.ar-~rap" ' m m of a l pectr um t"" in that lor Un kn " ",'''' 1.1 ~ the ~",,"i .. a
IndiClllC'l Lh< nLaM laclu" lIy " / : . the ratio of " "., 10 the
01 charJ'.~ o n
II... JUT" cmplolcd). and tbt o rdi "~tc lndicaln the "-... ti.... Intensity_ If yo u
need a him. "_ mber that lhe l " 'm ic w.i~h t, ,II hr<!rogcn an,l " , ygen
I
" lid I~ re, poc tj ' ~ I ~ , ( :lJottl yonr an ,we..- lt"" so!uliom In the unkn"
a~
b~""n ill Ch. pt,;r 1
"""'ber
1 I ' ..."...110.
No", Ir)' another ,imple 'pectrum, Unknown 1.2. Your stnletUfe wiD be correel jf the molecule and it, picce, have rna,,", co"nl'onding '" th"," of Ihe
,pectrum. (\1" ke a ,eri"us attempt to ,oh-e each llllknown before looking al lhe
,,,luLion. rhi, is a vilal pan of the book-, in,lruciion.)
Unknown 1.2
100-
t.
Unknown U contain< ~aTf><lll_ hydrogen. and oxygen atoms. ObviollSly

the possibilities for a,ranging thc,c in a molecule of mokouliiT weight 32 are
limiled. Compa,e any makeul",-structure possibilities with the major peak< or
(he 'peclrum.
Unknown 1.3
Th. tabular d"la lor Unknown, 1.1. 1.2, and l.3 include additional lowabundance peak> lhal run Ix: ;mportanl ("lnL" is Lhe peak inlen,;ty rdali"e [()
the most intense peak as 100). The mass speell'ome!., has a dynamic range
mud, greater lhan the lloree ordeT< "I magnilude ,h",m; lhal i" ion ahundances
' .1 _ ,.... 0< ......
or O, I~~ can l-.. mca'un.'I! "'rrodlleil>l.y, Fo. th.: m.... ' pectr al data "f (l>c
unknov..m in ,hi,
a re pr oclu ~jb i' i l.l' "r l~~ ffl Qliw or 1-0.2 ~ b ",l u l.e,
whi<:hc"". ;. ' M ~,.m.r. will be
WIth m od ' I n ''', Irli monl'' ' ucll ff prod ucihili.y l~ <>eblt \'abk wil h fd .. l.i ,~ ll W1~D . ample
and fur measu",m" n ,
limes.
"'.>k,
""Ono ... , ,1
miL
,",
,
"" ' "00 o
" "
<0 ,
i
Ii"'"
,i",
linO..... 1.Z
~
,
"
""
"""
"
.."
..""
' 00
"
U.k.._H
~
"""
,H
"te
"
,.
"
"
"
"
"'
"
-o
aa
"
""
""
"
""
"
<0
T!>< .., buL" ,,",I,, "I' lJnkno,"ns 1.1 to L3 abo .,]\0 ," sm a U p<ab " I
r1U ~
aIJ<JH , h~ , """ ponding to the: 'n"k..... I ~r ,.. i~ht. T ho, c aT"lO d ue h' rhe' ...._
....."" " I 1...,~bu o,l ant iwt" p"" tht .:.aroot>- 12 f" und ill nato ", rom! be ac" " ""
p9t1J<<l by t _t 'X, c ~f"" , n- l J, Thrse iso,,'fI'<: ",,~ b a.. p ~rt,,"hr l y i"'J>'1'l"lam for
d.d uc ing the " I ~fntfltal compo:;;li"" " r the mo l,cllle ami ii, r ;""'t'> dis played in
the m a" ' rc<'lf um (O apt er 2). FI<.'Tl\c " I ~ 1 compo,,;tiQO,...... al<to be dete<m ineJ
fro IT' tho c u d mus of l he p<",k (Chapter 6 ~ b ul Ihe n",-'C,, ,," '1' high _rooolulio "
," ' t, umeo ralioo i. k.", commonly' ''''aiJ.. blc. T he spect ra in Ihi, "'>o~ "'-lU l>e
unil nla... resc lunon {~ ..... i,~ " bK' o.ring t~c lad that i, otopic ma.~
,"0"""...lh
d iffer from iOI , gor "al ue, [T al.>lf A.I, ~,u m i n ~ carbon "" 1 2 .()()()fO)~
The m. a,urcd spect ra o! (Ill;,.. romJ1<lm>d. cont,,;nc'd add jtiooal J".- ..h (nUl
show nJ d"" to lhe "b"c k ~o .. nJ ~ in 110< instr ume nt. Thi$ ! rion (rom com pounJ s
lhal a re delolbin~ fm m (he ...,lIs of tho in'trn nlMt o r ;ore IcaLing in f",m
variou, ,~uTU."', To a void ctm fu, ,,m , ~ u c h a "ba, k gm und Sp"C1fllm " i, " sp a Ul
ru n tx: r~ " 1I>e U l1>p1e " a,luaHy in t ro:>d uocJ. into l he i.... IUmCnl. Suc h a 'peo
(rum is rJ><>.. n _ I )nLoo wu 1.4, Can )'nll .denlil)- any of l he co mpo n, nt, '
"
__
Uok'lO". 1.4
", '"
_._-
..
001
,,,
"" "oe
"" Mr .e
" "
" '""
" "
.
"
s:
00
"e.c
,,,,,,
_
0.10
O ne "I the compo nent, in il, p ure , la lC

Can you iden tify it'
~ i,e ,
00
' be 'p"c lrum ofl nknown 1.5
Un' " ". ,.

ml<
"re
,""
."
,.
I" L
"a.s
"
U
,e
'00"
"
0-
00
u
_
00
1 ! i, ~n aClu,tI m~ " ,pcClrun, of the "l artian atmo, phe", (after

or co a nd CO, ) from the US- ",'...SA Viling mission,
F i~ ~ r~
tL"",,,,'~ 1
TIl<: inlctprrtalion of rna.. spectra i. baS! 011 the ,-hemi'lr}' "I ga>ro u. ion >;
!~ c.1n no'" be t,,,mcd by wi,lc ""-Tictj' of met hod. ~nd CJD be m "",,anal y",d ~n J dc'''''ted "' ilb ~ ...-id< ,'ar~t y of i"'!lllmolltat;on. Of nc, >:." . ily t ni'
boot ~i,'C< a limned d",cu . , ;un
\ hc""" m mplete det ail' a", .v~ila bl . in tho
~,.,.I1<nt boo.. li"' cd at th..."d of this ch apter, CDmpil..tion. of rcbcn"'" to
t he m.......I""' U..."""l')' llleranlf " a", . 1", a~. ;Jable frQrn CMm ~'ai .~ b "r",-~, and
,."" Mas" S!"'cu...... try Bwltl'lill of l h~ Roy al So"'ct)' of Cbmlinry.'.
<*
,
....
,,-' ..
_AT~ ""~'
...
... ~ 0,. , . ""' .. "" ~ " T
" <>.II<"""
'"'
"""...-r--rr-
"
"
"
'" "' ","." ,

"'........
1 19 ,,'
c."
'"
...
-, 500 ag
"
,'"
100 ag
,"'
"
,~-
~I," ,. U . G .. , h' '''''-'l<'i''''' '" 10 " \~ l~ " i llOO,UOO "",kc", I.., of

"",..n"",crt. phth. l."", dotO<l illl' .....-, 112 M - ' io n r",m
chem ic.1 ioa " .,iou
IM , Lllk fl~
'00
" ~il "<,,, ,< , 1992 ~
''''Ilo'';''''
m. "y <"'e m;"" l nollcti" n, ~"'" f". ,m. I ~ ,i . _ I he b ~,ic pu rpo.., of!h. rna"
>f'<u" ""C~{'f i.> lu oon n lh~ ....mple int~ mea..... bk pr OO ll<:lI l b.1! arc indicat""11 <of the on g".ol m~l . T ~ plOO,,,,1> k>< mcd ~r~ _I><, ra Lhco- un u.... al:
I'a><;<,.... l" " ;\;' c i{On" .,1".... m. -..e<; .00 re1a tj~ ab unda,,= . re displa )'ed in
the mus . pe<'t rll'D. ~..~.Il'e
,,;to I>i"" ~;I'~er "e""d i, ;ly file ~(.;x,tront:gll..
Ii..., "" , "",~ I<; . Wi!",'" I . 2~ lIo we. c, . lllcir rt otmenlations ( Budllk....io:z 1981,
Il<,..'ic: 19 /1'}, Hild 19M1 a re nO( ulC'd mu,h for "'ructur.: d etornllllllti Oll,. OO '"
"-e will 001 dlSCUSl. them. T M Iy!'"" uf io niut;Qf1 u1li<.'<l fall m1.<' t ..~, ~rIlJ
" .;~
io,"
1I ,,,,,"",d"o
..-..., ..
. IX
'
, _ . U . M"" -' pc<1rom<; lcr iun "'"Cc<.
cla,""" ~ H , m l- ; 'm; / ~\; " n . " L~h a. with 70 -. V . 1. Cl eo"" P<()(!<u-,,,, a , uh-< l;o.tIlW
pf(Jpnr lion cl lhe ionized mole cule, will1 ' \leh high internal ""e , g;"" tha I t he)'
l, ,,gmeut before lea v;n,l lhc ion ,,,uf"", lh. rna, ,,,,. of the.. rragrnont ion. " rc lhe
ha,ie , ub, lm c!urc ;nf" IlM, ion uled iu im erp rct ,,\i,ln. "sor," i" ni....w n, Oft 1M
other hand, minimize, lu, h j1llthn rr"""",M~linfl: thi . i, particularly us.rut lOf
example, for
ch'iT ~ "t c d , ;n l' m i ~ I U",S
Iec/con ;on;:atio. ( FI) , h ." 1 ~ ", w ~ . rd ~ iOUllatwn method Wig..,c 1 3 ~ lhe

"reagent " pr,,<lucin ~ tloc ,"nk p..od~'" is I bc.am of <"Il"'l"'Lic (aW roJIin ..'ely 10
oYj electrons.
are Ml:>oik d "IT'" in in ;"c~ nde=nl IiIiIm cn i. a nd ' T. .. I
t h rou gh the io n c haml\c r tQ an a" ode ("elecllo n \l4 P"')rm ' OC ""pooile ,"doe. The
,IITam <or ""I". ri,M <au' ple mok"les~' .. "''''''''''' of a Pl"o~ima!ely 10 ' I'a
( 10- ' torrl ellt"rin ~ (he "",n;" inter/lcl ..,it h . he be;,m of d e.1.m m to form a
...-id ~, of rrod""'-'. ;ndudinJl posih'e ' Vn" Th""" ~, e pu;.h<d out of !he , oure<;
by .. n:lati wl)' sm.dI ....Jld .... ~ j ", - d ' 3... -ouf') potenlla l. and lhen are acreler~tod in '" the .... ~'HOnItl}.. ir.device. Tho; em.;,;,,,,,) of l.: l i. 0.. 1)' _ 1,/10' ; !he bulk
.... . be ... mple molea~ .. ;" e rem,,~"'<.l edlll i" ""ul1y by YJenu m pump, on the
;"" -;.ouroe hoo";n,, Will> f.I " no ,-~ n al, o m trodu ce , ample, or larj<:l-"- mol.cnl.,
n ,.,..,
im olt<ular ..... i8h1'
~ l ~) ~ ,rn ~
11>0 p;lMJd t-btarn tt<hllM.j ... (abo callt<!
- ~M G I (- ~
~I
imoi:tllitHl. By incr~~loi nl' 1M p, ~"' ur~ in , be iDnizauOJl cLim b.. 10

- lOll I'"~ (0.15 lm . l. ""'" ""n en<D'e lhal ~ "" m pk m"""-"lJk ...,n UlJ<k'i<> h UBd redf. of roHi"ons bofor~ if
EIocIron bomb.lld.... " l 01 me l ha... 0' 011><.
1."""''' ~I ""h " " .."" U"" in a d " d Irrn'~1cd pUm Plnll .~11') ' ou
1'. 0d uces 8 11 a bundance of ft..... ~ l~ ions ....eh 8S C H , . I h= will ", ~ ,1 wil h
added ...mpk m ok<1~ .. th' Ollllh a vallely 01 ~>J~ , eo<:/"",-" ..,.... a ~
~ '>Oft, y ",l d i o ~ Sl a bl ~ prOOIl<1 ion ...."lTo,enling Ilnofu.""';~ l ed ;.;"rnplc m o l.,.
col"". W ith Ih.. ehem irnl iOJlI2J.t'o n lei: ,.,. M '''''''II aIld F i~ld 1%6:. Hamoon
of ""''''''III"" ""n ht- ",I""livelv ilmi...,.) ...il h """,.;oc "'...
1983). d ilkrenl
";1I'c. and ... It''n v ~ reatttD1 roos. H el ~roal om -<:OD1 aillJ n~ m olt<u"" ouch u
am i...... and <1 h..... n.nally go. e ahn",,,", nl MH '
" 1IJ. a'oo hl d r~
often ,Jrid 1\1 - 1)- i. - Bolh l ype;. ofirm, a ,., lI",flll for m d "", li n ~ 11>0 molecular ",. lj!hl. btcau.. tMy a~ oft.n pr=nl in 1bo CI ' pecI,a or rompou nds
" h<,.... U '<J"'ClTa ,ho", no m " locllhu i"..... MO'O t i<m ir..I;.... ""'hnM.j ...... lm " " '-""
molocul.. imolecu la, " e,gbt s ."... n > I ~; """ SecliDn (d)...uch as Fa.. Alon.
"' .... b:lIIl>..., nt 1t"i\R; """ IkIrbcr t1 ,,[ 1'P1l 1. ca n hi: m ade , ~l a l "",l ! -ooft- 10
, Jrid stlIblr j ",,~ m,>l<cuLo.r 'fI."'"
.""'pes.
"""CC'
I,,,,,,,
i"".,
I .J lilian _
lysis of Ions
I he ion bea m fw m l he .... UTCC <:an hi: ""I"'r:an:d a<alTJinjj 10 the .... . p<:<1ivc
ma.... laduaUy '" 'I, l be ran<> of tbe roas; 10 l he n um ber of ch.1'g<'S. ror which
i.
i,,,,.
the term WT h, om"",, ~1"" n.oo) of Ihe

by ~ , ~rict , of l' -" " M.j l&e'O , "" J. ~ net
ic ddlot.1 io n, q uadru pole tilt, io u l nlf', time-of-fllf-ht, a nd cycl ot ron ..,..,na...,.
a rc the """"nd ing lu:hnM.j 1lC" m """ ... .... ""ml, """" in ",,,,,"""";al rna '" ""'"'"
1ro me ters. E,reI k-" t detailed d i." 'II'oS"''''' ' " IIt= me th<>d, a~ ha ~ahle in the
geoen l
"*= .
Wq,tIrlk .....,..,. The ilin ilie-focutill&(f"""'<llI& ro, d il'CCliDn l rna.. 'roa rome~,
ill F ireu,," U ""'"' a lorw: f\Oten li.a1 di lfe~ ( I to 10 k \'l be tween l be io n
accclc ro<t;on d ,,,..tr, odc's (F il,!ure 1 . 3 ~ Sma ll ""lenl'a l. ""plied I" tt>c ~ rqJ<; ll er"
and ftitl n _ foc",,~ electm.k< are adj'h ted I" ma. , im i.oe the ion CU<Tm1 out or lhe
"""fOC " , il , IiI. T h ;, , Iii a c\!. a , Ihe enl' anO<' focal l'O'nl of the ;o n -<Jp Ji<:l; ' Y'I""m
nf tI,c nut" an :>lY"-"T. all" ,,';" g a ..ti .<.~ n g hl:am ' M enlt"Tin !'. in " , 'M I ll<: ", me
ma,,-to-d>a' ttt rali" ,mil) I" be focu soJ on the . naly.." ""it . Iit.
11Ie mag nctio: f>eld lOt:l . ~ . tho: ro.", analy'..,r. "Tbe "'il nIne in Tho m",ns
nf Ihe wns which rn n pa" th (o ,, ~h the n ;t . Iil depend. QA I h ~ , ad ,,,, (r . ......l
' Mtoc i" n "",Ih in tlte n..gne tic lield. (be field stre llf.(h ( U, ~atl .. ~ and the in"
acceJenling 1" >lenliJl.I I l-'; "li t,) a . de fined b~ the fa nd " mcm ,,1 ""'n "" .... (Beynon
"",,
"
_-_.
...
"
".
"
.....' a u . S.ingk- I"" , ,, n' ~ _ fi\1lgnotL''<eto , m. ..

'I"'C', om <l<'J.
( 1.1)
-I hi. ~~" "" derived on th. b.1Si, that the io", of elementary "hafy " (a. ,(i, l;n_
sl ,i, hed from : . lh. numb" of ,M arg e, <>n Ihe ion) ha l-o a ll bun gi,, " II><: .,' me
l ;JlI:I;< <n,:' gy " r _ ; m,? (hLLI diffe' e<ll ,'e1 ocit~', d in accel" ati oll, aDd that l~
f",~ u en ed by th. magn et, Be". mu ,t be oqual l" Ihe <;cnlrifug. I I",,,, . m,,' ,/'
~ (lIe Ih al ~ n io n of,",.': _ 1(1) wn u k! TC4 uirc I x l()- ' , (0 "'~" 'lb<: ' on
a"~"' r" lm ~I ",m 1I 1). \' ",pe lle" ~ mm Ji'lance). and I x 10-' , [0 tra. el I III
all., "",, ~ml jo n by 5 l: \',
~ ,>t the rn. .. analy, i, of , uch ions, the pressure j . maiotaioe<l at _ 1(1 p "
(1.5 X 10- -' [Off ), or 10- atm, " me,on free palh ("ie) or _70 " L
""'=
",un jilt 111<4 ion rrllP. W olfgang r aul .hared the 1'I~'1 N" hd
in Phy , ; ~ , ti " hi, conccplkln of tfoi" nMel i"'tr unlellt' liotl, For the qua
u,up" le (!'is" r. I.S~ ions from l lIe roure. dli ft .. ~tll\< bet'.,,,,,n the fmu ",d <\1 alS sep'tr " llo n j , "~ll~vo(l b)' ~ ",,,,, bin:tlilln of radi tl. f""l.""""Y ( RI') a md
(} . ~J'~r u~
!' flle
' .j
. . .,-1_-
II." .......'.......
Tur....." _ '
."'_ 0'..,.
'"
,u
;"(\
,,.=-n~=FF==:r=-'
""
,,,.......,.,,.i
~ I 'I - [1--{~'
~_ , ~ I.~~.
, ,-~=----~
~""~~,
_~iL~
j_~
"'" f"","'..... .'.............
'I '
m .. "9
","""", . _
,--
"::;~"." \
Cs" ;ang. "
C:-I'". ;"", ''"I'
-.. U
ul, 1'l'J1
m .~~ ~J'Kl "')Ol "''' ,
,"...."'" '..... ..... m
(Mepri",od ..-;tn ro,n, i..ioo from C""h or
f ""'J- .~ ..... 69(11, 211-,. oory r i ~h ' ' ''''1 by ,0< Aln " i<an Chcn,icol Socie' y.
di. .....-<."Un crJl (DC) J>cld. wilh 0l'l""ile p"l ~ril ie . un the p.i" of oppo, i" & rod "
Palh osciJIali<>J" cau.. <1 by til< cll<l ni!in ~ RF tield tell<1 '0 cau,", thc ti~ h ter
I" . Iri kc ,he I">,<il;"< 1"').,,; and th. heavier 10 m ike tho n.gati\'e p"ir,
r.lte' JnIt out all jon. hilt l hm" of t ho d.,irw rna", Da w,,,~ (19 76, 1 9~ 6) h. ,
COffipatfll this t" k "" pi n ~ h. ll fm m fa~i ~g ont or a , addl. b}' inv.Ming th
.addle al ,he aJ'l".>prial< r~ q lL. n CY . Til. ion trap (Figure 1.6) i, b",ieally the
throe-1itme"";" n.1 analnjl, of the qu adrupole ICook, N at. 1'I<)(), 19911, An adu fllnlle of Ih""" " Ye, "",,,nclie in'!r lLmonb i. thaI the fields requi red to f,,,,u,
II ""nk ulil. m,,,, <:.In be ch.njl,ed vel)' rapidly 10-" '1, which i, e,peeially
,.Iu;.blc lot com pulcr-eontm lk d mea,uremen " , ueh a, ",elected ion moniI,>, ;,,! "' !>.,., X<l;"n 1.5)
i"".
.
;j, '
Ii
.,
r"
o
o
o
,,
,
L __
,,.
.-
"ro-
r:'
'!
!.
,
I
t .: _
-==
.. ~--LJ11
'-- t
1!
"'
,
s" ,, o'
..
:I:
1.' ..",...
-Jo~od,,"""
.,oto",.
J<i!urie, trull,'furm/i,m C)'dutrun ,e.,u",,"e" (f"1'/ICR). Ion' exeiled at I"" ki_

netic enorgie, perpendiclliarly to " magnetic field will follow circular cydotron
",hil< (M ~T<h~1I ~n(1 Verdun I~~() FiEturc I,7i. A p~cke\ of ion, of the ,~me mi;
value will induce a sine-wave ClJrrent in parallel plate, just out,id, and on
oppo,it<; ,ide, "f tile ion orbil; the ,ine-wove freqlloncy i, determined only by
lhe mi, ,'alu~ and the maEtneli~ l'ield 'lrmglh. and the amplitude h)' the numlJcr
of eharges in the ion packet. Orbiting iOll paclet, of many miz ,'alues produce
many frcquencic,. with Ihe Fourier tran,lo,m of the",e overlapping ,ign"l, yielding the ma" 'p'Clrum of miI and ,nten,ity ,alue.. FTilCR ad,anlage. include
,imult~ncou" nnn_dcslmcli"e mea,uremmt, of a hroad ",nEte of mio value"
unllsually high rewl"ing power (>10" at mi. 100), and capabilities for ionmolecule rca"ti"", and tandem n",,, ,pc<;trometry (MS').
1.4 lon-abund..nce measurement
The po,ili I'e iom 'lriling lhe colleclor produce a flow of neutralizing electron>
proportional to the 'on abundance. and thi, curren! "an h<; mea,ured accuralely
and with great ,en,itivily h)" modern ekctronic leehniqu",_ Amplification of lhe
ion ,ignal by an electron multiplier can mal. possible the deleclion of a sin"le
ion arriving;n Ihe collector. AlthouEth t.he effi"ienc)' nr ionizati"n ~nd l",n,mi,_
,ion in the ma" 'peclrometer may yield only one ion al the collector for _10'
sample molecules introduced, usoful spoetra can be obtained from subnanogram
,ample,. and ,pecific deleclion of .\uhpic"lJ"am {< lOng} _,ampb i, po"iblc
(Figure 1.2)_ Thus the method can be used;n a variety of research and analyti"al
problems for which mo,t of the u,ual "tru"tur~l to"l, do nol h,,,'c ,uITiL;'-"Tll
",n,ili"ily_
Changing tho magnetic or elenric fields thm effect separation cause, ion,
of difl"eITnl m.. . z ""Iues 10reach the eolled"'_ On_line eompuler 'y,tom, prod uce
sel' of mass and abundauce values directly b~' moa,uring tho field and ion
"unenl corre,ponding to each po"k. Thc," 'l"lem, e~n 1"'-"emd complete ma"
'peclra ",,,eral lime, per =o1\d, which I, e,pec;ally v'aluable for GC/MS (see
below), However, the sean rate alleci. Ihe accuracy of ion-abundance mea""ement which is imporlam for deducing elemeotal compo,ition> from isotope
ratio", e~eek the perform,,,,,,,, of your imtrumem wit.~ known ,~mplc, t" h" ,ure
you have not sacrificed lhi, accuracy unnecessarily_
1.5 Sample-Inlroductlon systems
For conventional EI and CT, the sample must be vaporized '0 thm the molecule, will b" ,ep"r~t"d from each other h<;r",c ioni,,,ti,,n_ Dired int.roduclion
inlo lhe Ion ,ouree i, pref"red for the 'lUdy of compounds of low volatility;
samples are inserted with a prob . through a vacuum lock inlo the ion source,
,,----
"
. 'he, e ohey 2rc "apot" .,d by lKaling, Wit h Ihll ' y' tem, " n. caL ~ n \ll i n 'P"C"
It.. o( no np"la, m"l ocule, Di molecular ...'. j~ht ~ 1(0) in llJ.llogmm I moun,S.
W~rniH" " i. " ..~ ~""~ I.<J Use "'" lu~ch "" nplc in the di re<:-lIll",d " Cli""
Sl " rnt: ope cr;....al lhal is
I~,g. e" ., ugh \" ..., ' hould be ,umClcnl. T he
hC~l ;n~ T~te ' hould a lso be conTrolled C.1rd ully lQ """ id "Ol"lili, jng Tho ""mplf
100 rapidl y, "Iore vc>l; ile ... mples ca l' I>c itltro;l...-td thWUf.h a fC
~1"
l<.~n_ A !a' 1l" ., """" " f """pic I ~ 0.1 "'tJ '5 1'ap<,,,zed m to An cv~,u~'ed. lJcal.d
"""n"iT. from ",h ' h lite ".-lm p ;~ now. thro ugh J ,mall orilk " (ruolo"ula r leakl
, ~ ' o the i o~ . o nTOI' n l . ne"l y N n<l . o l ri le , 11>i, m a k e!"Xlnl "'''''iUrt'mlOlll$
ftlo e. {cp<oo ,,<;i bk. .. hid . .. hdptul f". q U ~Dli la b~ ~n~ ~~ of "'. ll>C<.>mro""'"
Sf......... as .. elf 3' 10f malchm K"[ unkn,, wn and ""krcncc _peeln ,
'Ille rna.. ' peel",m. l. r C~n SilO be d il ~ C lly coar kd (0 l g~ . , \romawgrap/'l
(a Ci l,..l ~ , see Scc1lon 65) "" Ih<t t~ d u\CJ OOlapuneuI' I " dl uctJy to> lhe " on
fOUr= .. he", ~ hei. \'.m1J'kfe _('Ira a ' c "blam' d -u n lho Oy." 8~- .d~ct< d jon
m" ~J1 <mY'~ ~ r.", ~" u ' ln 8 Iwo or 1t,,"~ !",.,h " ~ lle n li all}'. b<>lh h;J!,h _r.." ,ificily
aud high sr n.oli" ity of d.tect ~m "'"'I n "" :>chi.<,c.J for co mr<>uD<hl cho..eu in
. " ' -:<f\oe (Fi~ .. ~ 1.21. Melbo<l. for inl~"J'flcifll to .>1her ",,,,,,rm in! do' -,en. , uch
~. rho high_pcrlon naocc- li,,"i ~ chcomal0gca pr. ( 1.t:("1:S~ hd>O aho be. n 'k_
't!,h<;d (. ... !)u:lion 6.5).
J""
,.""ir
r ile an..,lylica: ~ 1.'l"" "f't<'(rm Jl<lCf w;t. i Jll rod~-d ~om",,-.. ~-ia 111 in IWI. I'm
1"0 ,I""an... it> ",a;o a ppli<alic.. .. ~. quall' ila,h;e an" ly",' ol lia H hydr oc;o.rlxm
mi' h " es and "; m i l ~ , , a mpk ,. ,,[l.en with a CCl.:rci<:: ~ of -':: , ~~ ab. olll\e Soch
"n , I}",", drl'f'nd dite ctl~ on li",, ~ ! ' ''I''''l lO''tion of the 'f"'<'(ra <>f l ilt com",..
nen'.. ,n the .. me W;t~ lhat lb....'. Jaw 1I'''-nn, >J"-" lropbol,Y""lric m"ture
~ n ~ IYJj .. 1-.... Jo,. -rr~"""" "lJ">olil ium fot el1nm in,a z. lion cau", eac h m ,X!a ' c
cOlllpnIlent ttl com rib .,,",, illd.pen,lcn lly to the m. u ul<>d ' pet;t,"m <)(
-ample.0 lh..,t the s.t->odm m '. aoo" J~,..,... ""n toe r:l'h1o:d b) a ""r ltS 01 ..... ~'l~nc
om ~ 'l"'riolU "";ng d.~ t "
n:""...."" ,~ .. or the fKIr~ cOIl'I'"nenh, fha' ,
j f Y" " COil iJ,,,,,jf)' coer"", I;' " oc c" tn pcmenl of an .,n~nowD mi'l ll", ' pc<:tru m,
yOll caDlhe n . ub tr act out lhe ,of' I...",
tIll ' onmpolKnl ,"'>ptcllv.m
'Iril'Piu8"~ uJ " ' telllpl h>;ut..-p"'l lho raid u.J "P"'1Jam. NO\<, howe""" t ba!
'l'f:'CIr ~1 , upt."po, ilion wllt J1' ~ 'le<::oI""aril}' ~ !i""ar fN Cl anj Olher ,!'C"tTa
ob\~'n"d al p'e ur .s l1 igl1 . no ugl1 fol'
i<>nmalecul< r ea.cli<>n. , To>,b )', most MS "" ,'!,,~ ~"" I1"is " hl l"" oorrboru:d ,n.l JU<1\""tl li,m ~b ""
G Ci M:. ,K~ ,a ... ~ ~ n d ~ I ~ M : I1vr " f>N 198": C ~ ! k> w ,,0<1 Roso 1 ~~9 ) ,
t"'
f,,,...
'f"lCI"'''' ".
""" "'1ft"",
1.1 MOlecal ar . Iruetur. Ink>r..... llon
1b< main purp<'l~ " f ll" . bc><>k i. 10 ' how hew mol ule, ~ a r, be , tructUI;,J!y
characleri , cu from Ihc ,n.,,,,,, of their i"" iU<! ff ~n l .. n,~ El "'. ... 5pteUam
... ..."'
,,[ an
__ . _..
"
a .' ~r. ~
.'.1u<...
rompouml mn , ~i n , _ 2" bit' of duta. the rna.. and abundance

""",,11m! from .fe<tron lx> mb;ltdmc nl "r
"' o~~. Tbc:", <la la d,-
t""
I'"
mol= I<" muelurc; ~hc intorprota tion P"""""' Uti"",,,... lo conv' J1

l ho ;,potlr.l in/m m:<liu" into m o l .n, ln " ru~ UfC p" ,d iL'1",n, WlllCh are ao , om
flk:tr ~".J l'\'tial>lc ", possible.
Tho 7O-eV "!ectron cnc rgiL.. used U. \Ii'Uaoovc ' he _ 10 3.V r~qu; l'Ild ror
til< i" ni, ,,~ i"n of molo<ule<. The ... mplc p"'....~l'\' in 1M ionizalion c.....m hcr i,
KepI low ' "0U~ Ib"".. 10 ' PaJ 1"'1 _ oud al)' colli, ion, "f the iu os \011 11
mol" ul" or ck.u "" n. * ill l>< ""gli~ l ~le , Th.. ,niti.1 r",~ l t or Ill, . !trOll IIllcT"
a<lion with lh. molecule ;,. " mIlau on or lh. moJulur km It)' ci<ction of anolher
. l'<tron, I'" tt 1.. ,,,,,, lm, c'$ aliI or lh. molecul" . i"n .kc:<>nll""" furrbn '0 ) 'cld
lh<: (rag",.,,! ion;. 01 11><: ,~1 mm _ For . <amp!<. Ih. pr in,~ ","l l"'ab in th.
spodr..rn of m, lh.n,,' (IJ" k no wn 1,3) Of< probahf} j" , mc'<l by , "" unimoJecu\".
pr"",,,,,,,,, in !'.qualion, l.2;
""n<l <>n
c>i, 0t< _ . - _
" ",0"-
CH ,o H~ (""~
3<) ,
_ CH .oH'I ""~ " )
_ a. ,'
CH,Ot<' _ 1;><0"
1m'" "1
I""~ 191
l.
,. H
OH
" 2)
H_
11", JiH will ~ u"~I I,, inJ i<a lC a rad ical, >0 t h ~' ' he t)ml,,,l '<igniJi. . a raJ Lcal
iolI. SJICL-icoo wn lU tTl ill ~ such au unp aired c1""" ... n u ' I....mod - od d -.le ~r< , n"
(O "~ simiL1Il).
all tOa wilh only pai red el:tnl ns If a n -ne r>- c ke ~ ", n" (ll(!) ion.
N<>Ie ;n F<luati"n, 1. 2 thal only on. um Clll he f" ' m<d in lhe unimol. ro !OlI
JccomJp',, il1 01\ of an iOI1. 00 thai a nuli",,1pmd "':l (1"" 11 ml Of ionic) mu, ( ""
lorm, d from an OF ' i..... II , ho uld be , .. m pba";m d Ih l onl y un,,,,,JutJ.,..
",acl;on< 11," i,npotlanl III El fl a"", nt "t~ ,m ; lhc 'a m ~l . pre,"",,,, in the i....
IOal'C. i, mad, 10...' ."ou, h '" a ,,~J ..ac, ions bolW" " ionl an,I mol<:cw...
Wit.:" on< is inl" rj>l'\'l;ng 11>0; H rna" spectrum, i<!< ntlf....li" n " r Ih. molecular ~ "I 1M " 1<Stu""......." ,h" nw !<clLlar w, ighl al1 d ,1flen litonon"'nta l , ompo ,;
lion of lhe mnl "",uk 1f!>O M i, pre, onT. ",1ft i"nwuj on ( ~ I' on 6.1) ""an oftell
, upply 11115 i d" ,m ~ l; on_ T h. cl rrngllKD' k.n. inJicu,c If", ~ s of ",hiol1 the
mo"-""ulc i. el..-npo",d, and lh, illlc"f f'l" el<:t aU""'p'. to cltdu<e h" .. lhe.. pi",,.
iii 'o~he, in the original " w lerular ' IN " " , e.. ~pc"" ltaim uct ur~ OOlt ellllio""
"""" no ..' heen puh li,hed for a ..,ok ~a ""1 y '" co>rnpkx mol<cule, _
1.8 Sto"....rd lnloo 'p' . ... _

III \1>c
g~m<:
<"",,,i(}'
Ihe
"'...edur.
.01 - 1" c"f11y 'lu" lion' th, mo>,1 e/fl'; 'cnl "I'1"l"" h u.u.illy 11 to>
rUIl bc:twoen maj or "'leg",i" e,g.. - Is ' '''' person male',
Mo l<cu"'r .. ruct ~re cJw; id"li" n i, , imllar : - !>lind al"ys~ ClIo b,,,l b<: rninlmi-e d
uo~ n O"' n
..
,,- -
il ""!'l ain t yp'" of d~l~ in the ' I"'ctr um arc "sod hd",. oth en, A'
3ppro"ch, informa'ion ll ac<jui~ . f1icictltly In the following ,,,dor,
J i:<""f~1
(al "'<>I..,~l " "'~ fh,. ""m,,.,101 com",,,, " i"n, ,;n ~' ~lu,-dO'u".~bon d'l;
(h) Sllb' tr \&<lu re, ;
(<;l C<>nntn,y;tic""
"r iU b.!nK1~r ~
a,.i",'
(d ) P,,,tulated p<>MIbk m"'..".. lu. "'''''p'' rlnlcacll m uet,...,

all ..vaij
a!>le <4L. Relor(I'ltt H m. " 'f'<et ra of 22O,o:xl dil'r= lll com!""" ,," "'~
collecte<! in McLIllf. rly .1ld Stauffer 1992,
To.> Jearn I"..... I"" '. "~'Y ct i"fo,m"' "," ,h,, '" a>~ ;I:I bk- ; n ,.... rna... ,.,....,.
.h(>U ld loiJO'o' lh. cm lLO<' " r !hil "'~) k .' I .p b) 'llep in inte,protiQlI
' pectrum This "Slandard IDICT'p retat ion Procedu,," i. ,", forLh
i"sid<;
M e:' em'" in t l>c r"'tIl (If a d "",kW I" be U9W ",'her. yo " an:: inter_
lwelm!' an IInk""" 'D. This i. ~ wcnc"fa L ..... pfi 6cd """",,"eh app!ic" hIo 10 th"
"i '-era gc" l.! l mas> 'rcclnlm, Wilh e~ pe ri<; nc e lhe Ii,,, <en ral ,tel" wlil b< fa' l
' nd larg_Iy " "I" m' tic, While you lin: ~a,nin lj. howen " ~" c h ' tep , hould \'C
d" ne i.. rhi<. ''fJer, a nd you, f'O"lul.:lllO"" a~"""""" aud "",,,,1...;0... '''''''
ea~h .1<-1 ' ,~o<,ld "" re.;" ,o,kd ",,*,~hly Oil "'"
If. m,," lholl OJlt
"planat ion _rrean p"""ible 10' apanic" l" r ' l'-'l:lr al !e,nute, be " " " h' no t.
i""wbililic""
l rUIn.
~() U
~n un k n ow~
'b"
'peel",m.
an
Otlor, _ ph "" "'lfHttiNo. II '. import.lnl III i"corp " alt aD :>ll><r /l,."JI"l>k
, In"l ural informalion l.e"" m;'a!, ' pc"I,al, 'ampl" hi>!ory) in!" 11K> i nt~ rp r el a .
Ii,,,, ..here,e, ~ ppropti ~te When " ...~m pk i ubmitled b~ anot "" r rese"cn
..orker e" tht 1lU/"" pe<: tro," cLcr b l>o",w ry t:>r an "'., ,,,,, ,t i' ",,,,<hioll hIlI'
ollc" m"'" p<' hnenl inf.. m, ~UOll i. n", lran""iu cd, O M "r Ih' SII<>nl"'" re.l
, on. to ha ,'c the re, car ch. , interpret the m. " 'p. ~tra "f hi. or her o.-n , am.
pic. ;, Ihe impo ,rT . ,1Ct of Ihi, infCHm.' ion. for "" hich that I".-t "',, will h.... the
I,,-,..dn t aoc m<>st 1h.'''''Ulth uoo..~t"l>d ;nt T his. ;. ~I>O .:0... of el\e main
'".,.,, ' ;h .. lOr , b. r n-r . rn' " ,,, "r Ih. hn,'k: Ina.. SJX'.1., o m 'l r ~ >h:,uld mOl be j"",
fOI rna" , pe<;tm met, i' h.
".<4'"
Oi><" i"'",
SI'"'Htt. T he jnr~rp""3I iom pr....clur.. rot 1" :5 book ..'Ill ......
rl" unknown E l , pecuum '" !Ie eha' "r ~ p"l<; "'>rI1J'O u~ J. ll f ~""ra l com p" und,
are pre..ent i' lht la mpk, the I" uh j,, ~ , peel' ,lm will ,e p!li",nl a lillu r ' " per1",,;,(00 of ' hr co m!,,,,,,,n r 'f'<" era,l b en ...-ith ' '''>d <ample purJ )'. CIl'e ml" t he
,al~ n ' u a.u. d ,ho"m,,1'" , ....Iyt... do;]nl"'.iI ,.,." d"";nll ,:"", .J"etioo" " no ",_
a!o". pr ab "-:tn n ~so a"'" from " backlruund" d uo 10 1.,,1::0, p:' Yio\l' .....mple.
(""mem"'i'~ or chr~ma l"gc"rhic cotumn bleeJ. A backgroulld s))C, lrUln lak,,"1l
ju" bri~l c " . afre,' I h ~ .am p!< run >llOuld he ",bTIJ..1.cJ from ' l>c ""n' pk <peeIm m; " " "'e... . , .... re Ihal Ihe p~.>4' Ih.. .. mpte can ~lTec t b~ d.:so,ptilm
ral, "f the bac kglountl ma"ri,\. t )n ~ ' l ,,-"a~ lime, mll<l be minimiled. rho
, p<-"Cf rum , hnuk! he ""ann.d trum mil 1~ , or <t I. ",r m/z 26. to> well aha the
,..
__.
"
" ' p<Cled molecular ...ei ~h l 01 t~ ' ampl e, ~nd """.. fUrl hor if uonb~ \c g ""und
peak, ' till arc (....nd. (Dala fOT the Il""tra in thi> h...... "" U ~ene",lIy . IMI al ""i!
12, , in", l he'" i , li,.," u",ful infor ma t;"" beIo-..' that , .I ~ e ;n rna." , ,..,...1 ra
of of~.nio; m ol""" Ies.l 1f " . of, io n""''''''l l hni4ue i' ~, .i1" b1 ... u'" il 10 obMlll
a n i"",,,,,nd. nt mea 'lll c"",nl of tbe rnot.:.:ular we igh t.
11 II illlpe", ti,'c lh l tilt n" ,,"uJoo m,/; ,'n lu o, h" C<'H'. ...... I < ll. ~ mas, unJl'~
C'omm"~ h~ck~round pea k... ' \J'Ch as lh o ,,", ,,f oir (UnkDOl'!n 14), can "I"" a.
,m ental .rand,lI d,. [f [ lot.,." i:l. Qny do uhl, add. on iOlCmal rna" "andMd. " ..." , a,
per fluofD. lkan.... C.F::"." . " d I.k OCCODi~ "",m"
The reprodue-;!>ility 01 ))Oak.ink.....ty ..... ' urom en.. Ih" uk! al.., "" checked,
A mult>-(1,,'B, contpound .....::II I" C ,(1. " w ide. ~ ""n... .......1 u ~nd" rd , sin""
il> i.Olo pie abun "a n,~ are a",;",al.l:l)' l'fedietabk: (Ch " rlet 2~
))0""
M~lrif'IJ ..I' Mrt eJ .... . MOlt

in " .1\IlSS $pectr urn I J>rear, c<m" :,, ienllJ , . 1
inl egra l rn"'" num hi>n (fo r rMc exact rna .. dill'e..""""'" , ee ""eli" ,, f> J). H_ eye.,.,
mult;pl) char,w io n' call arrear at f. ~< [i o " al rna" ,, ; 1m t '4.,mpk, in Vn. "","" l.3 Ih, n: i, a pe. k at Itt! ' 1 ~5 01 o,r~ i ~l.l: n ";[ )'. rcp,ncntOn! tr.. do ubly
d "n gc,1 i""" of rna" 31 (1jOC Cha pler 61.
..-N,,,,,,,,.
1,8 G_ r..1
Wil h IHttIlz in~ " i, io n, Sir J J. Tloom" ,n , 19 13) wr Ole: 'T""no an fn;l.n)' problem,
in chtm" lry whieh coa l<! .., ""I..d mu ch I><:l te r bJ th i' lh;,n by a n y ,~ h"r
me tho d~ There is now" b ' $e . u ~ fa'eina\in$ blernlUJc Ihat ;. hi ~bl j' n:c<lfU_
monded to
mo ", bfOlldll' intefC.lcd r<>a<le.
t'"
HtJtJIo . , o"ynofl lW'-' lIeyn"u et <rJ I%it.; Beyno n and IIrento n 1':ht.2; lIir ma nn
1% 2; Bo.>w"" In ?, 1984; I\ULi u na h 1987; I\udzikiewia '" Qt 1% 7; n" rhn~"mc
I Yll~ 1'ilI5; Chapman t ~6; C" mli,n' in "I " I, 19'10; n ",i, and Fr eam m 1 ~1;
l>a....,n 197(,; Dd "n @h 197 5: Dtocklo. o n h l'r 01. 1'I>t6; r~ CC h. tli [9R5; G ""-ell
1 1I ~ 6; Oro., 1971l; H a nlm i n ~ and F" m,. 1911; Hill 11l72; Ho"", eI aL 19&1;
Kara ,,' " nd Clom""l 1 ~ ~ ~, Ki'e< 1% ~ I eh"""n ~ nd Dursey I n h; le'WD 191 H;
\I " c" ,, 11 1<)11; " b rch 19 ~Q ; M a"'hall [91lQ "!o:C Io, ke) ( 9\lO; "!cO..,....d l 1963;
McEwen ~f>d La " en 1990; \kLalTe")' 1% ." 19n M el ~ (f.,l\ y hnd S," uITe.,.
198'l, 19'11; \ol cLMlmy " nd \<~ l al am g h a" an 1982; \l i,j,lIct1ilch / 979i Milt" rd
[1178: Milu" 197 I: r orter 198 5; R,"'" and J ahn, w n" 1 9~1; Selbl 1970; Spilel ler
1%6; Sud ler and W~ ...,n l \>-)(j; Wall" 1972; Wallet ,' lid De n ner 1911O; W. I"'"
' ~H5; Wh ite 19~(\, Wri, hl and Woo d I Y ~li: Vino n 1'-'117; lare tstii [97t1.
JOI.-q!> oMJ , tri. I,. tJ"~a njc -"to" Spn:,,,,",,,,,,y, Wiley IChlCloes\cT, I n ,l a l1 d ~
In"''''OIU>tull J our",,1or ,\.1 W .\'f " """,rry ~'lSfJ, FI"", it' (Am' ter_
"
. . .- . 0....
(~"" ~
lh."""tC<l1 ,\ 1"" SJN,,:' romelry (r~rm erl)' w-J;rn l ,,"" L~ri"'mn"'ta l

Wiley (Chich" t , J- n!llan<l l JII..." SprCl'Om""J' Rn, j~,.,." ,
WiI",l""'''' Y"'I:~ R"pIJ C""'mu"'..." "... . '"~ M<lff SPft' I",m, "y , Wiley (Chi
~ht 'l~ ' , Engl and l; J"ur ",,1 'if 1M A"""u-"" S' ~"" ) PN" M,,'" Sp"," r ", ,,,,',~) ,
EI..,'ie [ ('\cw y ", ~); M u S"""""<et>P.... I I", MS.l Spectro",oPl ~"-~ )' of
Japan (Tokyo); MaS! Sl'ff,n,,,,..,,) l!ulI.ri~, R ~ l"~ ~ ,,"i c \}' or C hemistry IC ",,
b, idge, Ellglu" ,U: Rud ingame el ai, 19W I'W2. "lIio"nial Re, iews of M.", SI"'Ctlo rnc lr~'. "; n ,1""1..,,,,, 1 ChtltllS/, )"; S pecial",", l'Ui M l<',oJ R ~/I"mJr : \ 1"", Spe<;Uo""""I, R" yal SocieTy , of (' ",-.."",\,y \Camb [i d~e. Fn gl.. ro<l ~ Vor" 1- 10; e ll",. i,:,,1
,0/1'>/"'<'11 ~~: M m" SI'I"t,,'mrtr y. ChL'ffi ; c~1 "ho.-rac~ Se, v;c.: if .\,lum bm,
O HI.
Uo;to re OOlllm uing lo C hApter ~ tr y tlnk ........o> 1,1> 10 1.9. "Kain ignOTing
I'" ' 11'011 ",a" adjacent to ~,, ~ "n ~.... Wi ll u nt ~ }'Oll ar e n;;o lly ""uck- bolore
Ibcnins h ' Chapter 11 for hd p
.\f=
St>nl """'r".I' ~
unknown ...
mi'
.,
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icc
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U_
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ee
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2
Elemental Composition
'I'
A firSl kel' rO=tt of iol" , ma,;on ro, id.." lif}';ng a u unkno wn OC'l"l",und ..
molecul. r ron""I. , Ih. " " mtx:. of o. , h of j l> con<l'! " "ol e!ement.. T he TOC,h<J<J
nf d>.>lCe lin l ~ ; ' j , UI U;' UV rna.. "I'<C'I . o met ry_Il' mo, t """" "f,~ l~~h nLq lle fm
this usc cu ct ma" mel ~ u "",.. l wil h " high-, oso l". ;,.., m nss ' J'oI'lro m<:Lcr:
m.",un:lll~llf of the maM of p<ak wilh _" IT"'; en t "",""taC)' de fines it~ ok"""'lal
~ o m po 5 il i on " " e<j un,,,.:lIltl' (So"ti" n 6.)). H" weve " .,en with in, lr wne nlali""
of ul1 il-ma.. "",I... i".. the p,o"".."" of
of known 1>lI\ w-aJ abunda nce
m . ~<:o possible a ",oful aoo ;lI"O'" as ,mo m.lo u, m ","in~ {he nn kno ..',", of
( 1uple, 1, Even If }Oll "".. high-n; .,,1.,(jon info. ....tion on clemen tal u mtp<>S\
liom .,a~.ble to Y"~' it i, ;ml""rt ~m 10 nndeuran J thoro"gh.~ Ihe "'"' of
i" ' '''r k abuodam.~. whkh ;, ba";,, " . a n tinde"l "ndi,,~ of rna" $ptClra and of
eq>erim.", ,, lh m "" 13.i'l<'linjt wil h 'lable ;,,' 101""" F IP.Uv. l he eleme nta l . om
p"""1;,rn 11 also important inf" , n"" tio" f,," the Ir_~' ",,~h <lI l he 1"." ' pe<:Ir um: '0 ),ou , h<, uId an em po [0 iden tifl tllt f1elhl;QIS m~k' oll up each peal. of Ihe
m... '1"-"1.1C, mn ...!>e,e,'or p""ihle.
i"""r<'
i\ I.'he",~,'ll;' P"" " ' Illinic com l'" und .... ill I've a ""(IU ~ or m'" ;l""1 '~ heca~ ...
lhe eIen"...,. ,h. I con'!",''''' il are not ;"'lopically p ure, Roc. ll l h,: ca.. of ,he
cl.: me,.. ne o n. " 'hich Sir J. l . T hom$o" t l~ 1-') sho wed p ., nol """ I""'..k at it.
" ... nital . ~"mic w<ight .,f 20.~ hut 1" 0 pta.. . 1 m.~ 2tHl aDd 22.0, ;n
loLo ~i .. ~bul\d" )":c,, " r 10 : 1. Of ~he co mm on dl'menu e""" utllered in ,organic
~ om p oun<h ( . ho"o m h hok 2.1, inside lhoe fro m 'Y"l~ ,nM y ha ve mOle 1....0
OM ;" ' h,,,e of appn;~iahle nntulU1a,...,ndan"'. Tk is" to pic .\>lU>ll8n<lCS of .Hller
"
c"menlo aTe ' ho", n in "I able A.I (it1 lhe Af'l'Cndi , ): howe,'O[. thi. bool< OO"Cr>
Ihc 1JL~" ,[>Cella onll' of co mpound! c(>nl" ; ll i n~ 11'1< "k,,,n" Ie""... " "f T~"" :U _
"" 0" . 2, 1
"'iz
"
'tz"'
' 00 ,
' 00
"' ""
00 ,
"
~.
m.
The etIca or ;'>OfollC< on a rna.. 'J'C'-~ r ...m i. iIl....... ~I ..1 il> U"l"o....n 2,1,
\....hich ".... .tai... m" I"""h .. io... ~ ,
Jl> ~ nd 3&. Th elf ct..\r,,.;r.ri9l1 c i.otopie
ratio or l: 1 ;/wold Dl3ke lhe rltmenl u " ly rocolfTI;,,," lu fr,,'" lho.: .l ~I" "r I ~ ble
1.1. :>rOle that the interpnobl,i,m . of "'.." 36 a> ~ l' aSlnml io n (Iou of tWO II] fro m
m-/I ~ R .. o uld he to' aUy m isl .."d jn~ . It i> hlghl)' im potl" nt Ih"t Y" ~ " ,,,,,,m,,
Iauuliar ,.,nh 1'" data or T ~ b1c 2. 1. " Ole l h ~ l ~ ho.: i .,mop. tif (1J ~._'1 ", ~." ,. r" lh
...".., Q/>uMlln' fOT all 11>0.- .. d en"' ''l';, q uite forrunJ rely, Note also th"r the Il"t"
p,c abuooances or the <k men!> "an be cla"i flCd inlo Ihrce lI'-"1\cra l cBtt~o rie;,
..... ~ IboloC clemen!> .. ith nnl)' " ne nal ura l ",m o t'" ," nprJl'eci.'oJt abundance:
. ,\ -t I ." lh" .... c1emenu (hat haw two isOlOp", th e so"o nd of which i. ,,~"
maR 1In ll hea vier Ih" n tl'l< m,,,t ah undanl i,,,lnpc, an d "A + 2," t h~.., tl~ mtJlt ;
lh. ' ha w ~n i,,, tope thaI i' two ma" unit ' heavier thall the ......"t " hu n d ~ n l
' SOtope. Th e ~ A -l T d em ent, arc Ihe ea,ic,! In Tce"J':IIize; '" ynu <ho ukllook
ro><
fi r" _We ",ill uSC a ' imilar clas,ificat ion fnr ma. n pectr al reak " ~ ~ '"
~~k il one who.. m ain element" l formula i, eom l'" ,ed of ,,~I y Ihe m,,,,t ~ h u n
(\Mn t IK'l Opeo; ih iA + I) I',,,..k i, Ihe JlCa k one mo" unit hi ~ hc<: ; . 00 '" fo rrh
,''''ow:
A ","clInd Isot Ope ma h . an "'flC'.-"ia llj' I' m m j""n t :lp pea.."'" in lhe .pc..1 TUM if
tt il mOIli th Ull n I\C u" i, hj ~h<-r in
th. n the most ab unda nt "",[I'pi" . !"-Ua.
tn."
ll ro mme and chlorme. aoo to ~ I~","" " <lenl "'Ii"... and . " /fur. are .."linK
eomm OI' ~ "l m r l~> I he pre..nce of Ih..., elem~nt, in an ion i. of' '''' ea.dJ
Te ",, ~ nj ..,d trom Iht ~ i S O! C>i'I ~ cl",,~
I'm dll<.U:l i n lhe "J'OClrnDL Thll. okmenrs or L: Dll1o ,"'n, 2 2 a~,1 2..1, M e Onkllo"' n 2.1. "" 0 be I~ Im m ' he
..."
"
<~ "ra<l"r"lic
;~n " r"
Lhe
;'''\''P;Ora li"
"rlit<: ion, , opn a lcd h)' I..." m"-'C' u" il<- (h ..- n....,
.th~ 1I I"'~k , tl .~\ l~
the l",t" one<... ..' n i" ilial in,peaion of tlle oor

\l,"ph il OftOll nn c".~ ."" y 1(1 id" nt i r~' '\l"~ ;\Qlo,.i<: d u\lcf'l , For ..mplification.
,mly \he m"' c"ula ' k' n J~L K ore md udcd.
Lin,u. lup" posill.... of Ilolvpk ,." .,,,. . If Th ;" more l h~1I " nc al"", " I 1""""
c!eme"t' pre",n l in II><- m"I." " lc. ' he "", ,,11 i
' ..n m"'" ,I n king }"m b~ tlml"-""
bro m; d~ the i<(ll<:> pi.: molecular ioll.< at ....it lI{l and S2 (11"'8 , an d H"' Ill) a re iJ:t
the relat ive pl o por11on , 01' foo, hl) I: I , Tile rna>l _pel.1I um uI D. J . ........ prrumne D! j1l ~lllC u l:tr iOnl a llU ~un I ~ ll, 1((1, ~ nd tl>l. <>f rc l~ l i~c aoonda"",. . I ] : ',
due III lhe i"." '" liT, . " U,' II, and " lIr 'Or, a M ' 9r , . rnpe<l ;"ely. 10 a
' imilar b 'hion. any ion Sll u"Nr~ oon tl ' nin~ ih, blom' lIC ~ l""" ,,-ill " hil>i l
f" LIT pc;, k, at ;n lc",al. "f l.." """'. uni h in l hc '~l i" 1, .1 } ; r , ~..,j t ho 3: I
i'UlU)'!;" rat;" of "0."" 0 yodds lhr pea k. ill IIIe rauc 9 :6 ,1 fOJ j"n ' p<'Cie,
c(lflt:l ; " i ,, ~ t""H-f>I", ;,1C ... "", I"" f il" ~ 2 I }
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The Ch~T~"'""'. ti c pattern. =<tl. ing ,"'''' .ombina t;" '" of II>< ~-h l"" .... b,omine. . ,,]fur. 6nd , iii con i,,,!o!,,,, k~ , 1I"i\ '~ tcJ by T" hie 2J (lu,id e fronl coyu).
atran!!""l in 'n,T< "" ng ord " of 11'1<' ."I~".c abl.ooa...,.,. Ilr (... + 2\ a nd 1-' + 41
' um" rica' . aJIOL"
cnmtHna tiom of~ A + !" ....-men.. M~ ~i ,"n in Ta ble 1\.2rho,", ",n. akttlaln1 1m", Lhc binomJal eXI'~n";"" ." _ bY' ~ a" + n~' - ' h +
n(n - l)~ ' ' h'i !' t- nf ~
l ~M - 2)0" ' h'...n !) I .. . T b... ro,. Ihc pc~k> cont~i l1 in~ rour chlo rine al,,"''' ,"" into"" ;I)' of thc t" + 41 rdan~ h' !' ' "l' UI<l be
4 ..1 . 1' -(U 2' /2 _ 0 ,61.1
f,,,
O. un> t1~tI ub.~J~~,. ~,"t:Ji"u'u.. n... IA + 21 rela l;". ab andan..-e 01 "' ~~ ..

II "NY low t(l ~\J. 'I(KI th us high An.u" d4...." .,'I;\lJ ~ CY i> necessary l" dc<luce tile
nu m bor ol .nnen J I",,.,, (ror exam ple. U nl."own 1.3). FO[ til. unkno wes in I ~i .
fx" ,k >" IJQw ble u l.>m . <" 0 ' or .L 11):,; 0 1 al><olute L.,...'" ,>I 0,2 (on th. <ealc
t hat the a h,m," nu: 011 '" bi!,h" l l"' ak - 1(0). "hictl"'"e( ,. ~re-41C" in th. ,'alue
or [(A + nll ,!:A] "ill oc a ..... mo!, ", ! ~ I (i njl. m an unom., of t ho "A + IN......."'n .".. OOn MOl
l""..:nl, p, od oci<lg " , ma ll <,.'(,ntnhunon 10 l h~ (" + ~J
IS u,... II}
1'lC<n' ."y ... "" ku la t. th. nu m hcc tof '''Vll<1J " Ion l! nlte, tho -" -t , .. ( I( _ n ll
'" " 'f!la<
0111.. - ,\ T ~ .. cl.me nt' h a ,~ 1>0."", " k nl,f>ed ,
",,,,I;:; .., "
t""
.It_.".
+r
The ,alu" "r - "" l!"-U'" infolm3t ~'"" . ",mld not
,"'crlooked. .~"o t l l( , ,~ ~ ..o n lor ch< c kin ~ fi", f,,.. the P1C5'ffiCe 01 ~A + 2"
. I.m~ n l , i , tha t one ,..., find.. ,hLm ' 0 hoi " b,.nt , C" n, idL~ ~n ~ pe<>k A (fragAb.nw~ of ~ A
~
... ..
"~
,. _ --_...-
"
""nt ;"D ~ ~ well ... M ' ) in '" m",,, ,peel,um And tilt pU k two rna.. unib.
~e, L' hc: (A + ~ p:ak ] : if [ (A + 2)l.'TA] < 3:~;~ the !'C al. A cu" ", >l """' ai,, Ihe
mo'" """"dll ~' il.Ol01'" of thc ckmcnl' Si. S.
or Hr III A ront~in. m" , e ' ....n
one ion form ",la. thi",ti" dolerm i"" , 1he proportio n "I i" n. free " f th= e1.mL"'''l- Ta ~l. 2.1 (i" lid. fro nt cover) "'''W'< th l if I""' ~ A oonl~JnS "no "Si
Atom. fl." oj ZlJi[Aj ;> :\.4 :.~, t..\OO u"" in nat u", 3.4 ' oS, at om _ mil"' "" r<l und
,,'ith cvcr} IiIO al "m. "" s, Th. tat io l(A + 2U/V'l] ..-.." "" p e,ter lb.~n 14'\
,rions of , ome otber coml'<l'>iti..... al""mn ln hule 10 lhe IA + 2)po_k
Cl.
Th<: lim.'" - A + I demenl\ ill Til bl~ ! 1 i'1'I: h}urogen. ca,bon, an d mtroi"ft,
I>uI IM ' I V H rati" i, '" ~.>'" I ~ KI "'" ,ball c" m ide, hydrog. n to be an WA"
elC'm<ol t-:..:h clem""l .. hib n, ill ilotopic "\'Iundance, in <kl'Cn<ktl ll~ : fh u ~ Ille
....rho>n ~lom in lb. C'H"Br molc",lIe ,,( Unon""'n 2.2 oonm \'l ut"" U ;~ 01 ,.....
,ntensuy of H'. miz lJ4 pcak {J ' C H, " Ur- l to the ",i: ~5 pe~k ( " C H , " 111 -). ,nd
"f th~ ....: % (" CIl J " Br ') 10 the ~ 7 I L'C H, OJ fll ' ~ C n kno..'D 23. wbich ~on
taius no " A , 1" clemen " , , how' [m,..-: 6~1.'(...iz 641 d ooe 10 Ihal e'l'<d c'tl I""
olle caree n Ibu t ad ua lly du o 10 " 5" 0 , - ;' 00 " S'Ot>f)'); lh2t gi,n lIS
~n"' h.r reMO " why"""" f. 2" clement< . h" ul<l he idenllr...:l lim.
l llc r~a \, ,, ~ the number o( = fK,n "''''m. 1tI an i,m ,nc,. ~ _ the I'", hahi lily
lha l "n o or lile," ~Iom, w,1l be a " c i>otopo;; Lt-' + IJ] 1A] fo, a C Je ion will
lhm exhibil tOll ti m ~.,. ,he I"'..... bil il~ 01 <:" (>r 10 . l.l~_; , '" ll /~. Thi, racl
provide, ;< Y,-" ) 1.<, <k<l...,. the number of "" , bon ~",m , . ""hieh i, ob,' io".ly of
l . ~, otnp"" to".oe in m l ~ fp' ~h nl: the , pa.1 Ta "I MjlJlni c c" mpouudl , Al Ihi, ' tage.
do IIOt " 'Off ) ~ "' ''ll ' '''1 -1in" nll, ogen a, ~n " A I \ " o l~ rm: n t the "n; ITog<n
lLllc - ,n Scc1 ~," l J .. ,II be helpful for rhi"1 T,,\'Ile 2.2 (in. ;"' til. f", nl
ta bulaf.. tbe p'{lbilbilit ~ l.... t =n ;"n of a , pecifi. d numbel of
",i ll
oo..tai n one
~''''" The lacIo ' 01 1.1'x, per carb" n lllom ' a'i.:, d i" hlly 1-2%
,d.ati.",) ..tl h IIw o, ,,_tijC bO U= . "Jch '" pclrolcUln (10 \11 "110ue) wn u, I co nln npoJaJ~ pLm\ ,,"","": "' ~ ",iii ;I<n"", th. sma ll cont ribm ioo 01<kUlcri"m ,,,"" lhe:
",,,,ll h~",,,'Cn "o ntelll of the iOll, fTh. 1, I "~ "' "'I ui. alen t I" I 'C/ 'c _ l ,O.8';~
'
" 'ttl. I , ~ H alom, pcr C "tom ; .i II..~ H,:C ~ h n g<. tile iolftl'ily of lA + I ~~ , "" I}
O.7'\ of it' ""Iuc, (A ... 2) b) IS~~ of its . 'al"", 1
In Un known 2,4. caklll a\~ l ",lk, ,h".... i .. 8 fur MA ... r el"...e nlsl t ile mad
mum " umbc, of c~, bon ah' n" in the i<>o.. of "'!~ 43 aOO ~~, 'The r""IIl< , ind i~"l ~
tha I m/: 43 peak is fe,med fiNn tl><; ",j: ~ by Ihe I,,,,, "r ""'hal gw uj'J'
~ or. th l mllny ""all 1""'00 in IIn k"" ",,, 2.4 ",ere ",Iat i\'ely unimport ant for
d<Ti,'int n. , tr ucm,e.
ptah . :"'cb clln be Imm~d fwm llb"n,l.n l l"-. ~ '
by 111 0 I"", (~ ~ yd"ogcn OT ",hi~h "'r ......" 'l d" ubly charg. d ions , In other un
~ n<lO, n' ",r lb" bc>oL_ ullIn'p<>r1anl peakl ..,n ollen be omirted, For U nhd"'"
2, ~. nnd fhe ......... "1;0] fonn uLt or ih~ m"lc~'utur ;"ni Ihi, ;, Ih. kl' ge<t ('1la",,~1
pe.o k in lh. ,['<:<.u um. indicaling hi~ " ' la bility.
W
""..,rj
c "I<"""
'C
"""' ;U;
,.
"..
.. .....".
"""rs
,
"
sc
..
....
"
"'
,",-, "
."
."
""es
"",
"
'"
"
"
"
,ro
."
"."".
.""...
..""..
",.
"..
...".
...."
"
""
""
u. . ... .. " 1.1
,,,
"""
""
"
"
""
~
ee
sa
"
.,.
,....
.
".
"
a
"
"
""
"
.'""
'-
"
"""
"
""
""
'""
"
"eo
ee
"
""z. o
'.
"
"ea
"
'oo
,.
"
!"
I
" "
"
"
o,,~h1" C_D. T he li nknown 2.5 ,pectrum "15.0 cont ,; " , a mino' . hut ' ml"" u nl.
p""k al m,,.'; 80 or O,2~-; inkn,;l}_ A"igning Ih;, '" tho "0 romrilK,I loli or Ol>e
IO n alom in mi. 78 would mean that til' l~lter rontain' nO m" ", tha n li...
u rl><m at"m,. wherca, \he m.. .z 79 Hbundanc< indicate s
Tn" peak at .n ,.'. li'Il
a<:tu a ll~' ~ri",s from C.[ I ' ions containing two J ' c: "t.om, and four ' 'e aWm .
11", a bun J a n ce " f , uch (A +
ions rolat ive to the A-i on de~lId. "" (he
number of car bon a'oms,ju" a, [( A + I)' J..'lA' J
111 . .. Kb llM . lICC. a ~
~ I ",) ta l1 ulalcd in Table 2,2,
0 1 coor.., (A ~ })- isotopic c''''lril1uti''n< "an aho
from "A + 2" t lt roc~ l<. .".rtcr Oil< 11 " , " <signed til. num~r or t.rfx m and ~ l l lOlI.n JlOID~ from
"t.
2r
,1<"""
",i
....._--_. - .- .--
"
'
the I.". + 2)' n lue m u, L h< "'ctIt:Ckod fo' Ihe

dClCc'\i<m " f ,.. ,~cn: ~ l lh"u8h tile " 0 /'0 v" l"e of (l.r~ i' , m "n. lh" ahundulllX 'l ""uT~,;i<:, . " "mcd ill Lhi' book (th" 8reat" r 01 U.l aOO(1 luL, or :!: I ~';
~ 1 ~I ' v~) u,u.. l1y ,In" .. 'm<: T<1 , alcul.t. Lhe ",}'ge n 10 withi n
I " IOn" fo r lhe
M"" I"'.~ If inf,. ",d or N~1R . peclrJ of the unko""'n ,,'" " ,';o.ilahlc. Lhe"" run
pro >lde definiti ve e" idcncc tor Lhc p",,,,n ,,, "r , pccir", o' n en fUllcl;o"alilie,.
F"r l.' ni< n",. n 2 . ~. <kduce the elementa l co m positio ns "f lhe m/; nand 55
rea. ,; d,) the.., suU "n its m"le~u la r ' ll1Icl ure','
Ille (A
U-
a b u nd~n ~ e v "l u~ ,
u. . ..... u
~
ae
ee
"
".
"
.,
ea
se
c.e
"
"" """
""
""" ".
".e.s
"" ec,.
" "...,
" a.e
"" '00""
"
"" "
..
.
"
00
1
,
"
f
00
00
-. ..JJL.
"
"
..
- - --
..n", Ihe n am h<r "f....... . ... + 2" . 00 ~A + I~ d . """"

m,,~ 1. ck pe n d; " ~
"
hI' hecn fi , o.-l h>r ..ti--
On Ih. c' rn "' '''''', 1 ' '''Ufllq~ th " to-olaDC< "" the rn a,.. "" the
",,"k m..., he d"" '" Ihc mo n" "" " " .,;.. " I\" "':;men" . The " " ill"m""l " fl lIc ,,,tal
elemental co mpotuion I" r of tit" ..' o ral plS'ibl. rom l'O"itiOQ , j is th. " oomh~ """ 'II n u"'t.;.... of 'hc...: clement, oo n, l>t<:n' with r ulev of ho OOing.
llIus tra Ling Ihi' ..il h Lite p"'.....u, , ,,",,, ra , , "" 1><1... rra k al m/% J6 .,.. C nl no"' n 2.1 m~" <;<>nla ' n o O>C "" IIlI '''''' No""'" on Ihe abotnd anco: 01 i1>; A + 2
Sul>t , ...1in, lite m"" of , " I" rinc. U . ' ro m Lhe """" . of , hi. """~ . J6, lea, .,.
3 <hlfere"or of 0' ,", ""' tCh of COurse m ust aT,... from
p"""""" of o ne h vdro"'" , The "',': W """ k 1m t; nk n"...n 2 2
(Ylle l>rgm;"" """ " nc carn.m;
"Ie",,,
""""al'"
t""
"
94 - 79 - 12 ~ 3. '0 the e!em."la' ,ompoSlli" " "r ' h< 00'1<' penk is C H.1 " '
Fur Unk n,,",,'n 2.3. Inc ~, . . , 64 I""lk ",a ' ~" ignc " tht elem <n" S( I, ;
I (2 x
161 _ 1>4. '" lh<re "f~ no " ,'\."' clements. For Unknown 2,4, the "'!l 43 and 58
peak> conlai" ed C , and C" r"' f'<"' , i . d ~ ; Ihn, 43 - 36 and ~ ~ 4lI ind it le th<
n um oc r of ~}'dro~u ' lOrn, in each . :-" 010 .h~1 "nl~' ny d ,oj!."" a'<>m< CIln he uoW
lu account ['I' ,,, .. diller""". until tb'alue ~ a. large ,., 19, tl>o n.....' ,,(
Ru",i"". ,"ddjlion all~ . t he O1.ml>ol' of hy<.l",gcn. COD ollu be infeTTed fwm 1M
p roTon N M R _peel'III " , and l ho: minimu m !l urnn." . of e~.hon al om , fr" rn the
C 1l NMR ' r"C. lruffi,
Try III", r;lfli. 1'peclrum r.I',,-.. ,:nliD~ a " u ~J~ fra~m<:nt ion:
mIz
Int
'"
100
126
"0
12'J
0.0
N o ~ A + :r OJ ..... + 1" <I. D1.m, <Ire ...."',illk. ,.,11 t he ' A~ """nmb nu l pho~
ph " "" ;off 'IIon o valelll; '" ,hi, S'UUPlDlI" "". be du e lo a , inllle IlK>no . ale nt (A)
. lom<"nl (...h;,.. h~'1. <>r " p.1ir, 0' a wmb"'a ' il>l1 (I( th.", with pn."phO"'~ (thus
H , r..
~.,.i gn mC ll t ).
r he r,,,gmcn t iQn~ of I"" l u, lh<; , exam ples Invor,c Ihe ,"line moIlof:<'
i' """'leei,."'"
,.
"'"
"
.. ..
,~
"
WI1 " t il the "'H imum num hcr of " A ~ T' den...... ' . , or " A + I " .le m...I'-' <IT
,I", ,J~ ,,, in the ro"'t rol"n",. Ille pr e, e"", 0{ Ollt a1, "'m ' ho,,1<1 be I\n "b\. ~ ",-.
P<"'6"bilil j" Ji,J )'0 " thi nk 01 ~ ,? Com!""i linn! rhot <.at Wy Ihe ,J"l"
c r, . 00
' '"t'
I' ~', -
1f}'
, """" J'f~d lLre'
" irll lJ nk n,""". 2.7 and 2.8.
"
'.'
'.
s.e
,.
"
"
se"
"
,"
----
I'
_ _ 2.
- ,.
,oo
"
'2.~
".
"
"so
00
O.
C.
"' ' ""oo

ro
"e.e"
" "
"
~
~
..",
"
" "'"
"
..
'
1
j
-r... >0
.. .
- ~' I '"
..,
"
I "
'"
,.
, .,..Io~,-T",
,.
i ' i
2.5 Ring. pl us double bOnola
Because of Ih. ,'al enees or Ihe e lem.:"I. ;" .., I. ed, lhe l<>1al nl,mbe, of nns , and
d<>\l bl. Ixmd, in a "',,","uk of tbc f~rm ul, ( ' , H, ' ,0 . ",ill be c~ u"l \0 . +
i. + I (pellegrin 1983). For Ins, IhH" ]<.1JIiII<:d u luc """ end in "j;" (ind il;"hn ~
. Il "e. ec-ek elro n i",,: SccLi" n J ': ~ , ,,d lhiJ fract ion , houk! he , uhlracted 10
l>h<ain Ihe It"" ,' ~ Iue_ " " .... l<l u"" Ihi, , h" " M be m",e " h,j on s from in, pection
o>f lhe eu mpies in Bo~ 2.1 -n .., 1"" J '..." ,Il<! fo, PFi<1 ine repre,cnl. the rinf
a n<l lh rcc
hu ndl. ofl h6 m~kc~le. Tile $.\ calcula led for the benzo yl ;0"
' ep" """" lhe nn g. lite IhJn: douhk Ix>n<!. " r ",,"LO"ne, ~Ild lhe do ubk lx,nJ
t,
"" , "Ie
"r
I _
''''I"''''.
, ~ \10""'" ''''''''' '' C,H,N,O.
",,"c,., <0 I,IJ.III,IV" ""."
I.H, F, 0 , 6 ' , '; h O. S; Itlt N,

T",. I ,i"ll" pi", double bo'd - ; 1 ~ ; I"
em, ,."
P;."" IV- C, s..
Ole ,)
'O' "" . ,",_. ,.0>'0' I"" ( ,0:;.,.",,,,,, ~ .2 1, tn. ' ''' " ,oJ"" ,,,".....'_ "" ";""
Ex.mpl
G .~,N
" '0' pic. _
b1Q """",,,
l"
Q ~ , , _ .
' 0, . .. mpl. oyridi, .' (""",, _ , 0)

G,H,O' ,Ing. oJ .. """"' ''' ","H" . 7 _ 15 _ , S ~
'''' 0'""'ll '0, C. ~ .CO',
\ _","",,0 0)
t>enz..,
the car bo nyl ~"".L!". C.ak ul... Ille nu....ee r of Ijo~ ~ Ild d" uble t>und. ror IN
f"m ,u La, tlul you loun'" r.",~ : 4,1 on'" S~ in L'nl llowlI 2.4
If other <I.me"b .n: pfL....,nl t"'-~ ~ '"
u dddit",n~l ~lom. " f ,h<:
~km "nl C . H . N. o r
hie.. 11It~ C<I(I~'J"'n,1 ' I' "ol~...",," n.~ .. 1 ~ "" mbe r
of , ilioo" alon" , hould be ",~ Icd ,,, ,t.: n urnhc, <>f u .ban a ' ~ m s. 1M ,,~mbcr , ~
halOll"n "t" m, l<' ,he hum"". of hy<l MtI' '' a'O Ill$. ~nd , ho; fium bt;T ,,{ rho;,
rhor~, ~I"" .. 10 the .... OIbo. or nilrogcn a'"m... 1'1 '''0 ~I,,> IMl lhil IS bJ,cd
on tll<: low"",, . alcno.c , [;de " r II\<: ~ I ~m tn l ~ 3l.,j J on D<>l ccent do ~ hlc h;,nd,
{(mnoJ lO d r:menlS in higher val~n"" >lat"'- Th"... rhe iom' ul. iod><:i,e\ ~ ne
double bOl.,j no CH ,'" O, (" i, mm L1 h ~ ft c). nO <I""b1e bends In CH,SO,CH,
td' mcth~ I,u1Foocl ami a _gut;"" , aJt>t. _ O,~, in H"O ' , Such . ,.,.,go,i, c ,~Iuc
.hould be nolN, be<;au~ it uri....... h" m , eurm nl"' ", ent M cbemicaliomzaticn.
Va h.., m o rt JM:;;;t!>vc th a n Ihi. ~ ,e no t po"ib1. ~ lId '0 m",t be due to \nC"TT" c'
8N "'.,.., "Fe1e...ental "om position M inwlrcc! ""ku l,,~ion or ,i o1'" ~I u ' doubJc ho ~
~mI'i ric.1
'" . .
"""liN
pm",,,,,
F. r " c "'f'CO;"""" ha, , hown that

i, n. ce" ,,' y '0 dc,'cl,'f' ,,,,,,' , ab'l
i, ) \" "'.. I "l ~ e1'lm m~1 com po, ition, from i,,,1opic a oo ndan"",. ! P~,h . p, Ih"
i, because 1M eh<omi'l m,," he""me accu"omcd to tho fact that the n"' II> ' IU""
lrum sho wl his/n cr carel'ully p uri~ "d """,pound to bc a mixt ur e of i"'tOJ'ica llV
di(k:. om m o leclLle.) It is importa nt I'h " I yo" undc"tand Ihi. l'rocMlll'e, , iooo it
iI the t el' prim 'lI)' , ' ep in in terp rel ing all lLnlnow n ' p""lr um , To ".oW ~,<ml".
1' 00,
lhe ,\~p ", i", p""redlLl'" beio'..., ...' hik you arc "'lUniog. I lIble lJ
illu, tralel I h~, pr ~dul" wit h dal " (rom ,nc M" ,eg inn of Ihe 'peet, um of
",,tlLllyl' hin phonc, C, H S. N Ol~ lh " l lh i, i, '>01 do ne roc the nth 10111a b.....
J ~n " c. bu" ~, .. e the
10':.~ accum cy in a bllndance i, rcla li ,,,, 10 the allU nda nct of
that !",uk.
'"II"w
e~f'C rlm~n l ~1 """, or "~"''' " n tloc u riginal dal3. in 1M

"J," eOlJlf ' co h,mn lon' " n l"" "",n.. I,,""] d o... of Slep ,i).
iii lo",,' r! tile e . f'Cc,O'd
. .................
~.
,.
'...'".,,
0'
es,
<., - G.2!I
1.> ..: 0.<
0. 1 = 0.2
"
malin
O.
'00.
00 rie
< 5 + 0.8
0,' J. 0.8
"s
....
' 00
. .,
"
'
'.
c,
0,
"0, ,
-,
0,
..
..
.
'
.
..
"'
,.
00
'00
eo
00
0. '
o'
IIi) N Olm a!;1C . 11da la (~ld oo m ll "' I"'Tin,etllaJ a<AU" , ,"J"I lhe ('tak &,o u p.
i,<' , muhipl~ all try II>< r.~ l"r nel'd.d to ""I l A] "<:lual lO JOlr;'
(i,;, r ,nd ~1l p""';blc "A ... 2" elerncn1< ILl>u tion. in "'paratc
coi\l mnl (S, an d (J , in the u a mple; "", ,,,,,II, . at Ihil $t. ao; up \0 thre e
ol Yll.nl ~.n be co m i de l'ooJ ~
Ii,') i'd""e t h ~ . lornent ,}'mho [" pJ.ce lheil ma., value" \0 guord . ~. i n " lhe
ffi'"
tot,,1 nc.."m ;n~ 1<1<1 "' ~h

(,'j A" ign tnc po <s,bIe own bcr ,,' c"" ~llS. 111 ow in~ IOC'OC in ,im;l.u ""IIImn..
Subtw :t lOn of Ill<; 'OS contribution to
141 places the caf b" n-;. C>I01'"
ront( ibuu. ,n in Ihe J~nIlC 8,2 lo IO.n .. leadiDIl to C. and C. :)$ PO''''
'"i.
hilili"" 11" "' e' er. 5 1and C. [oto1 140 nw", Uhi\'., ""... I IOlho1l o! pc. k ....
e.g i, a 1>;",1>1) unli ~.ly ion for mula. m"l i", C. IlK f~\'"rro ~ .. jgnn'~b1.
The L" lumll headed A I I . S,
W t ,w, ~ ~ ~
of "c, ' 'c " s
"'111 bo accompanied by .l...l.~.;, ~ 8,8 = 0.4 i"n< of "C,>" C ' S. pn:d; "t i n~
~ . o rrc, po nd ing conln l:>u,," n lo ",h J43.
(, i) ..... ign lhe (AI 01" '......... I>y d,lf".nc. , T!>c p" .lulot.d C ,S f.. , mula
,'CCollnt, f,,< % + ~ 128 of 1"'= 140 <no" units 01 po " ~ ..., H 12 IS 1'"
" hi,,", choi"" 1m Ihc T<:tna;n<!cr,
>.ho,,'.
io""
L " ng thi> p<, u dutc, can you . ";s n compositio " , a lld .~l ..'" ' a , , ing, pj""
<1, ,,,hle ....."ds 10 1'" rr"~ffiL'Jl \~' )' 'pectr a shown ;n U n~ ... """s 2,9 thro ugh 2.141
ns. 1"'3 h of l 'nh own, 2.9. 2, 10. a nd 2 12-2.J 4 conJoi" II>< m" l"cular jon
tM' ~ jII:~ ~ i in U nkn OWl1 2.11 ~f ;" 1:' k>$s f,om M ' u, ind icat ed. No,," "f
U,"",,' wnU
mi'
"
,."
''.. '..."'
' 00
'"
,
............ . .10
"",
,,,
.." .,..
. "
rs
. 0 1
"
mlz
"'"
ee
""
~1
"
. . .........
""'
'" '
0.0
~O
r~
I i)'
,.'" ,.z.z"
,.'"'" ""
," ,
1.'
1.0
.',,' ---------
00
Un""'". 2."
Unkn own 1.13
M,
11 ~
se
,.,m
113
110
'.1
100
no
111
0. '
11 ~
e.'
llA
0 .'
0'
,,'
oc
"
'"
'" "
"" """
'"
no
no
'"0
'00
00.
,"'
lhe, . contain nitr ogen, it. idenlllicatioll is discus sed in Ch ~pl" J. Untnowll
2. 10 m nlai",. me" , " ",,,,,,,,l 01 hi~h"t .. b,ol ule ,"ccmaC}' than tli< 'Imed O.2.
2.7 Com po sit ions 010111 p.. aks where possible
1'". ~h< 1'"'-='
" f lhu mole"" '" di,pln}'M in ie, ma., ' P"Clru m, knowledge of
til<: de me"t. 1com po"l;an, as "'ell " ' II><
i. "1\.0 very valnable in str nctural
rna.. mc~,ur"mcn t, unc can " flOll ' ''''riet lh e
elucidaliOll. E,'en w,thOllt .
po:..., ih,li\i> f"r u' . mc n'al.." m p",ilio" " " ignmem for impot'l. nt pea l> by using
i Wh'P ~ a bun d ~nct dall II ... the chid difficulty i. lll . t tll<: .b undancc mea.u red at R pa r\icular m.., ..J" e can . ctually rc PfC"'~t "Ofl(ril>uli() ~, (rom more
th" n (l"" ck mcnlat ~~""p<"i lion Such interference. ~re ""..ible e'en for ;'01"1'M; pcah of tnoloc~l ~r ;0,,"
,""t
"f'"
m.".
Uu j","", ~.",I>n' '1 -'''''''

~l,.,.,_. In cok ulu ing the . lemem .1 rom po ;,;l;Oll (It ~ reak . . a bo., we . .. unled rh. t th" QDlyrona ibuti<m, I" t nc ( ," + I)
.nd ( A. : 11"",b wet<: fro m ' oc rc... ~ ho.!nJ . nl iM:llOp,. of tile elements in A,
H" .. ~,"', ' hi. i, not n=s<.o."; ly I.Ue; lhere could be ; ml"" b nt . rldi t;"n~1 "" n _
t n b a llOll' tQ Ih. (A I) ~ nd (" t 21 ",: 0.1:. (a n " . ,,,-,,,,-,, on,,lIl , W (leak Al for
,,"' , ~ h C<>f!W'""" m L
" t he m ~ Jc h ,c I he ( il. + Il oRd(A + ! l peak.. the.. 00'J1d
HC_._.. . _._....-
"
ari"" r. um ul....., r ~"""'l1 i",,, (or impurities. backif DUlld. QI i' >n_m" lccu'" n:r." l he I!l, + ' Il"'ak these could "1' 0 ari", rn'", I>c h y ,....t"p" oonlrihtmons of ~ A .j. ~ M elemflll. , uch a, from the ( ,-I. _ I, l'u k. W u1tolJ, ....,h emlhe c a k" lu li ,,~ , l!lu' ~ i ,' e til_ ma .,i",u~ , numN' ;U<,)m, " ,f "",eh I}',,",
i" ,10" d enlllal c o m ~ os it i o ll .
aet~m,~
rfi,,,..,.
er
/.ruf~".a j,,,m "I."" fr-,_IOI 1M.. In UlllrOO.... . 24 ,,,kub 'in, the o"mber
" rcarhon atoms or mit 4 1 lw m t!>c :I", i.., a hundllllce of ]nn, in "'iz 41 Ili' c, a
ridiculo", ly high number ,of ul '''''n arnm,<; [ 41')/[41 ' 1 '" J.?/27 _ 44~~, Corresponding W 41) carh..n a luffif, ill TJble 2.2, Althw gh lhi, i. curT"l.'Cl lor rhe
m"ximwm n am ber of C aronu, " " h;oI(I!) ~ " Irru l calc ulat ion; lhe reason IN
th il .'aloe i , tloal m",t or I,," ....: 42 """,l Mi",s frem "C / H o " . aM I...... Iragmo;M ~ m th l m nlaill'. onl y 1 ~ Ill"'l J bu lldont i,o tofl'l'" Th i, re ak i, j)llrt of.
~n'.p or peak<, ......... "'P'" . U:d r",,,, il' neighhor h}' Olle lOa. , un,t, of I h~
ron nu lio, C ,Hn~.' ltnl n" wn 2.4. which i. the Ipe. lr Um of bma",,- C . H I13s
"",~ ,~ I " I....r f'l'al gro ups wh ich correspond t" lho rrag"""'l ""'" C, H. _
C , lIn ,_ ,11'" C. H" _", , The on ly (A) peak . to, ", hi< b Ihe co m ,r.pondin& IA + l)
an d lit 1 2) ""ok< do nol contain inted lnJl II U a~ 1 ion. a "" mfr l ~ 29. 43an d 511. c~ ",e"l' ondill g to CH.< ' . C , H , . ( :, H, . ~nd C. " ,. ~'.
T hul !he m""t u",rul i,ot()p;e-a bunda"u CJk u-'110l\ll an: 8'...." ... 1Iy th o..
that """ 'he ,i~" ilicant pe~h whictl a re ~ t d.., hi~h.ma'. end ,ll I"'ak group' ,
Can ~' ou dedu ce the eleme nt" l coml'"";li,,n. of ~ '" ",,," io ns in l'nkn own,
2 ,~ and ~ . 6 '!
Inte'f " " ":' f'- ~ " + r . ,, _ ..... '" ft,,.,.,...-... 1""'1<>. Th. full lna'-' ,,," otTUm
of mothyi hm midc tCnk"""''' 2.2l alio coOlai", f,a~mcn l i"". f,om tilt I"" d
H a[<)I1'" COr . J~~ C Hllr' 2~;'; and CH, Br ' . 4~'; (Wilh CH, llr . lOO:.Q, Tloc
",. uln o, ""''' ""","' . " m i . a lin eu , uper position of the'" " m mnln b. li"",
\= Fi~.", :!.2). E;fd. ~e. mu,t gi'C a I: I pa ir of ' "Or, " Ilr peab . and
t locn: m llS1 N ~ 1 . 1% " e I"'a k rot each 12C peak, SI.ltina IlI'ilh lhe -t'z 9 1
C ''' Rr ' """ie>, i" J'>f.... nce dem ands a similar inten, it}' at -t"'~ 9' ~nllLl rty. Ihe
C H'"B,' p"a k at ,~i. 92 dem~nJ , an "4 Ual. inten "' t}' pcok a t WI/: 94 . f'I..... ;"
e'al~ a l inl: Ille con tTilluti'm or ('H , " ar~ a nd C li , ' " Dr" at ..... ~_ \H ~nd 94,
1>1I" mu,t r.r,t , uhtrac! the ccmll ,l>uno n 01 t!tc . , Dr ;""I'>JI(: of Ihe l" ..... r-m,'"
' p<Xie,: so on e find, a 4';';' tn" t ~~ I "",nu i"'"',,,,, from Cll ,o ' Or' al "'i~ 9S, Thi.
fiiu re n"'Sl then Ilt s"hl riIL1c.J [,om , he mt3.~red Jnlenmy .al"" to c,hm~lC the
" m ,'~n l due [0 lhe "c conlribulion flom ...;1 94. H" wcyc", il ia much Ilnlpler
(an d !lc,e more acooratt) to c.ak U"'IC lhe "'\ + I~ eleme nt s fro m !hc ["',.'1 Q7JI
r'~I: % ] n,h". , ine<: "'-ir 94 .....1 W, "' ..., oomnin the . " me ~urnbcr "r carbon
a'" m , . Deal .e l~ I""CI -IDd" has ''''''. 1 ~ .," ""n no t con tr ibule to Ihi, I:A + II
p" .\~ .. II", l u. + II JiV\ J m li" cr U ?-~ co rro.:tl}' indicmes the prcsce oc ol o ne
ClIrh. >n 110 m . "pi... 1he mo<sl ~ ..Iul ;,otopi c .... kulalio.' generally .~ l b"",
Illal ~ .. Ihe sitnilicant pca h at the !li~h.m~" end or peak ~roul'"- Ha c a
pea k', "an ;~", n"" i, delc,mined hy lbe inten"IY YAluo, """, ,,<tey or the f'C ~ l
, ,
G B" ~
'"'"'~
r ... ..,
I' I'
LJ
- f':d
oo:"',, II
-~
11
102
9/
"
Sp. clrl>1l
"iI."
1.2. Linea r '''perpo, ilion
i.<"o ~ c
.
~J (J.(J9t~
c.r
pc, b in tbe 'pc<trun, <>l CH,ar
..-
. 00
10
00
,.
aa
"
lU U
u r
" "
1 7 3.'
0 07
' 00
"
00
-...
00
' 00
,.
,~
",
......=
.""'''Pi<: j"OI h
l",m or(., 11 0 ,
'" " "
'l'C""
I U ~' '''''''''' 2. 1 4~
2.0 0 " " ,
aa
~ "" c, ....r t' for lh< calculauon In UnknoYt'D I. 14 the ne.dod '" ': 1J1 poak ha s aD
intr.,.ily of 0 .0 o.~,;. ..' ,"'" L"'i: I J71Tm,i: 136l = "" ~'/~ <\f .o 5 c.o,b" n
at, ,,,,,,, If JfCJ" "".." ..1 ",, ( .' ~1 tile ove, lapping i, a topic ""n l, i h"I ~,n. lICe tbe
brraLdo" 'n in Figm e I ..lIn summ;o , y. if " "A + ".. clcmCtm a re present, the fA I II pc;Ik LanoJ "'......bly
" lhe. 1,\ - 2n + I I pea k<J will conMn iWIe..pi<: <:u n lrihulit>n< from r be IA 1)
P<'~ L rand po"ihly other IA - ~" - II peah). ln ca lrulatinJ: the .. urn!..,r "f
' '' loon " tni'll ' h)' usinE' [(A + I ll if At "Itt slI<'uld currcct rm >ur-h " "h' p' C iut., feTel' c",. Ahernativ"ly, u"," [(A .. 211 + Il l:[" + 1,,)] co rrt ' )X1 ndlng to lhc
pc.k~ oJf high"S! ma , ... ,i OOl: lhe (A
I] ""ak ",m o<>1 make Oil i.otopic . " nlri
butioll to th o.."
Errbl''''''oJ, ,,,... .-.J... .... J,,,..,,,, ~ 'l o n" l1 y a , i ~ n i fic a nt proportH>n of
I he !"'~~ A " llenSlly w~1 be due t" ,I>.; j"'L"pi' .ontr ihlllian of aD " ,\ + I "
.....""nl in 1M 1"I) ""o\;, Of an -A + 2" oJom eDt ill the ( A - 2. pea\; . r Ot
c, ,,,,,plo:. 11M: 'f'Ilrum crf hmylh<nzenc , h""" the g"' ap of pea ks:
""
..
~,
" "
e.t
T he ratio r"'i! 'l JV['" '; 9 ~J - 1. 1~," c q ~h' a lo nt te ~ .4 c.a ,h~~ a L", ,,,. allhough
M,/! ~2 is ma inl)' <:, H, " ACl ~a ll)'. l. r ; of miz 92 "nd n.25~" ,,f 9J ore d ue to
vc:..." eH
' + and "c >,,.
~ , H,. ,,"'~c
,'- ,i ,'d,.." thu, " c u'"H
'- . = 1M'"
" ' . ~nd
" C , Il . + = 41. 3~;" ~r"l lhe; . r~t;o i, 7,7~;, as expect ed r" , "",,~.. cubo.>ns.
2,. D.cIuc ln9 e le me nta l compo5ltlon .

Abo~ e W(
detiwll
p<:~ k
iDten' ;t"" in (he mn hyl tnomi<k 'P"CI'U tD Imm
~ n ow l
cdllC or .h ~ndaD ce, of particular ion c"",,,,,"; li,ms: however, lor aD unkntlwn
, ,,,,ctn,m wo f.oc the opIX"';1c p, ,,I'I"'m , ,.he l ugge" ions that r"I1 " ,,' . ho uid
i nc " ~ $11 j'OHI clf" " .- nq in ani,'in" al all rea"'D.,bk , ,,lulio", Lo 'uch pro bk-m.
I, 11ilt" " -.-, ~.1< .. 11.., r, ,,t lhose l"'J Ls "' b i ~ h , hould yield "" m po-<ilio n
.>f hi$.h . ""ufac y a, woll a, hi~ h ulilily. '!lie loa.. i,olopic <:0 ,'"
tamm.. liotl l" thc l l\ ~ (A + I ~ cl<,., peak< .houkl 'oe toun<l in Ihc pea L group
loomp,.."i",,, di li'",;n~ ollly in numb. " of h yd r "b'l:~,l.>f hit!..... ,nasr. (.. ~.
cioUy if n <" " ta ll" M - J F LlrLhe" ror aDj' partl( ular pe;lk IW"", lhe high-rna....
peaks ,h~ul d c"n la;D 1oc least i, oto pic oonl""" n..i.....
~,,; gnm. n l'
1, H~I>tSl ;',nuity ,.. Ir., Will'; D, ''''''' linll1>, , '''' ..." ," acy or ck",e"'al com-
pm illO" ""Icul.llou, oh,i uLLll y shouill improve " ilh
I nc re a,i n~
pe.o k imcm ity
J......~ qj'" .\ puIt. . 1he Je.in:<1( " ('<'-il k .... l"" p<'a k ~ruUf il; Ih.e 0"" .~
hitbW """"' '"'t~,b ",ml~i"$ onl, Ihe mOl abu nd. ul'1OI 0P'" ,such . , " c , ' ''0.
HClr, it i' also ""lied lhe " ~ '",i'01C pic' r<~ k. A, the r, ""l c8 ndida l" fM A, II)' l ~
large. t peak i ~ ' he lI' OUp; if the leo<md larj!.e, t i, ~I a rna" hi g h ~ r tban (1\ + 2),
II)' il in, te:ld al pc. l A [ no le iT T-ilbk: 2.3 the r arily oi M " poa" for . "i~ n '
""'Pl. ~ """'" IA ~ ~, po:ab]. Not, d" IIA - 21J.!I A] > ,l~;" chc.,.i lhe pu'>:ri ble
11/,,, irol o pOc r i tl e,n, IT ~hlo, :.3 an<.! .... 2) 1<> 0;0:; i f I ll ..., xre " " ~'I"" pc~l< . o)f
the ,,\ n1e dem"'l l ~l fornwlJ , F"e exa mple, lhe lary M !'Cak of th l Elr. i,otOP1C
c!u' lcr is oe\uaUy I he (A ~ 4) f'r . k, Hen: . " ",,[ul c"'!'dation i' In, flOCl \h al the
1M - ~ , ' i> u... . lly much leu . l>und'l nl lha D cilher ~r' Dr (M -I)', t",ca
S!o... lly. ho,...,',r, (M - JI' i .,,,,,,, .. bU...... Dl ' h,'I\ M -'. N<Xl, ".lLwale 1""
po" ibk . k m c N ~ 1 comp",il;"'m ror thi, IA) peak; i f~" assi~n~ " nl <:'l nno l be
round l h l :>ceOl\nh fm Ill. iu,.",il"''' of 111" higher mo" ]:"'. L" " llhm c, perlmenIal error, ul Ira.<t """ or tllese mil" "'man noni<Olopic ion, and (h""
"'o,oJd he """d " ' pe" k " . A' . n n"n, pIe. fry lho: ",it ~ ' W dalx h om 1M
OOl ylhc1\" n" 'p""l!'um on I h ~ i'fe v>ou, P"~". Bee"U", m/, 91 conn,,' co n!;l\n
n\ O~ th an ,,",ven ' " roo n " lo ms. no c lcm em .1 co mpt" ltio n [Of Ini, (A) peaL can
aoun l for the I ~UI1J """" 0/ "'" ~2; ;1 la lls 11' " '' be u>cd 0'
A
pea.
4. 0,,, ,,
( A) J'<d!.' . See .r u" ,f,,1 i n fo nn~ ll o n o n ok m . m a l COm", ,,illcn, C ~n he

obtained [rom low,,' ma" pool , itt each ~w up of l"' '' ks di ff",in~ by on "
unit. Il i. po''''~l c , h. 1 their ' ...mpo, i\i"n' differ by m" te \Ilan jutl \he n lJ '~ bc,
, >f hyd r ~ " I<HII' . f _ ~ n e'Ji '1; in ro "' n.1fion~ ~IO D 22l cu be helpful
m""
5. C~"";'Wtq "J <'" mpM;' ;n" W,1ttLII'." '>'n("th e!' ""~'C ll to ' \':<luce rhe e'e _
rnentol m m ro,il,on o[ a ll peJ h ,..I"u 1J'<'",ihl, ;, to " lIcek th",. fo r intel nul
.:on"' I,"11""}'. The d"metllal """1"" ;I;o n " f M +. ;;r l' rt"'CtlI) # ,et; l he mn in' um
m"n~ r of c~<h elemenl Ih ~, can be f,,",1 in ,,'y I"....,t -rna"' (>t.lk. SimiLotl;t.
tile fl ,,~me"\ ion ~"m ",,, il ion' " ill ll, ual!y , ho", '01\l(: mu tual conli",,,c;,,,; UIlC
the "" l" infer tl<o::
pr<>h~hl, oomp'",ili"n(,) i f n" ,ro \lla1\ one ag ree' ",il hin
e'rcrimenl<il ~I'li. C"mm" n differe nce< lu uwj bet ....," Il>c "'~" I""' il.i o". 01
a.. tl(r,l~m""l ionu rc ~'<1l in h hlc IL ~ and an: disc<lfwd m !.a:lio n
:\.5. C,,",n;on ' '' '''1 ,,, al " ",i~n:nellt' rOf (raj!.m, m '''n , ft" ~ YO" In TalJolc .\ b
(' 0" S~ct i on 5.21 T able A.7 gioes e" mj'lO" tion al """i~l1mon l> for IIlOlecular LOI"
.:on t ~. n; ng th' elc..-<n rom", ,,o d om,mll, ,,"" Ihi' tt, ,t.ec ~ if !"" have c<>n
"'''1'"
,,,,,lee""t
.........,.... aU """"lri hue:s.
3
The Molecular Ion
T he m()l"c ul~ , ;0'1, M +', pro ,'jd<:, t1>c m' ..... ~ I Wl I>Ic inlQrmalion m lh. rna"
,pcel,um; it< m"l1 an d d.mC ~ lal com Jk"ilion show the mo""ul"r h() u nda r~ ,
into wh ich th e , I T lI<-,~r..1 f' ll-nlems IIllhcaled iJl 11>.; m . .. ' I"'Cl, urn m ust b.
filled. Un f"rt un ately, IOf "",," C l fl'C' of ",,,,,,,,'tind. th e 'Q ole~\I l ar ion i, n o!
' LLlfoci. nlly st.ble to Ix '''uno.! ;" 81'1'reciaNe ~bu od " nc~ ;n \h e F J ' pectrum.
All jn"rc~,;ng!l la'l"l' ""'01"'00 of ma"' -'poc(romet r~ fa~i hl~l also hJ\'c "
" ",fI io ni<lltion "",hniq U$ ,~c h a' d ocmica l io ni'ation or fMI-. tom ho mhacd_
menl/CI or FAR. Cb:oplcr ~J . , ~; l ~~ Such dat a should be u>td I ~ . ",,,I,,,,,,!>, ,.~,~ h' """l:I'm~""l w"."," ~r ~Slblc , How",'c r. e,en ,",' ;lll ~,'<d<'1>Of h"'" ......
l(ln; ,~l;"m. l h~ ~,,~ncwll spectrum , h" uld 'lill be n .mine<! a. """'Til>cd in .hi.
~hM r>ler. "''''''' t hi' ,hould k....J I" u' efLLl ~t ruetu r. inf(l(rn oli" n ..., ..wcU ~I <el lflt;, oj I ll< M ' - ~"i g"rn "n'
Il ~ ~omeD l i on , rna" ' p<c'r omell i. tl .... 1<,,,l~le lhe molec:oh" ",,~!h , l",i. of
",Itt!" mol~" ul;, r-i on pea~ ) in tem" " f In" m. .... \lI l he rnost _al>un.b nl i, ,;,t opt of
eKh of tho ok mon" pre""n\. F" . ""'"",ne (('.. I I. ). ..lOCI> b' . u l><t ~ntial .~i: 7~
~nd "'I! ~O I"'~~ " rloe moloru tar lOn i> w n , idered to be ~\ rna" n (C "" 12,
II _ t ~ M' for ' M mDl<>cule HI, j, ...... 'sided 10 b< l~ ~, Iwice the rn a" "j lhe
m",\ . ~n "mla"l i""to pe. '" Rr. allhoo,h Ul ' h~ rn ~ ... . pectrum of RT1 Ihe mo stabunJ . "t lOn IS at ...:; ltll lSa.1 i<>n 22). Wi\h ill lh<Sl: com l"';" " . in tbe EI m. ",
"!'OCtru", "t .. !MIn; <'Ompoun<lloc m"t"""lal ion. if pn;,.n\. m" ,t be fo" nd . ' Ihe
hil.oOC-..t . alut oj II<!Z ;"l ~c ' l"'Clrum. There a", i" rther te, l, ",,'hi.h mo<l be u~
h .....,,,a m i[ , hi> ",,~ ). d.... not rCpT"""m tht m('>k"'u lar iOl~ alt oo ugb I""",,
1""'- ,;;onn,, ' J<mo",UJ le tlte con,"r,""
W
'i""
3.1 Require me nt. ..... Ih. m olecul IOn
"".k!
The foll<,..'inll a, e Ileces.... .y, bw "0 1 "u!.l'kl<,.., " '1ui,..".,nt. 10' Ihe m" k " ula,
ion in tht ma" ' peI....' ''m "r " pu" , ample. f, ~ ot cs tno n,:" ".
5uch as
11...- fro m b.lcl S"'u..u and ion-molecule ' c;"'tkm'l
Ie must b< Ihc illn or j,il'iI<:st n....... in the SPC<~ f1,'l'll
::. It mu, 1 he an ,l<ldcle..'1fo" i<>" 1Sc<.~i.m J, ~~
; . It l'll U<! b< c ap.; b l ~ 01 ) "", h n ~ \h.c inlpo'tJ ut lo nl in ,he hil' il-m.....
of tho ' p"C\f "m 10" ~ ... of logical neUlr~1 ,pc"i", (Sectiotl J. S~
~ jtI0 "
If l he io n in q lJ<'Sl ion fail. any "f th.,. tesl>. i t ca n... ' t toe , lie m olecu lilI iOn:
if 'I p" ~ lan the ", I",t" i t nlay or may no l lle t1" mo~ l ." ion
For Fl ' 1"'el, a, lhe "" mplc m" lr:c ult bt<:om. , io nizec! b,' I O $i n~ ~n .1<':lI<m,
leaving one .1""11<'1\ unl"" red. and lh. " w", the mo l. cula, i"n .... rtJJk al ' l"'cie., Suc h an k' n. c" her moln :" I'lf <IT IT.~m~nl, with an "nJ"'i~ eleo:wm i'
called an ~,>dd -dtcl ,,, n~ IO F) ion, and i' d ~"i ll "l cd b)' the ,}onb.>J .ne .>fl en
u>d'ul and ron ~Qlcnl on o, plaining and cl""if)'(" S io" -Jecom"""iti " n T~aolio",
10 d ill"D ~ ui,h kh. 'ecn sueh ' odical ion ' ~" d -c. eucl",: "'m~ n eE) iou., t ho .~ in
", h i ~ b ,he () ul.r-s h<ll ~ 1~~ t1'<l n, ore fullj' paired; lho _yn,I>o1 will be u""d ,m ly
10 m~ , 10 ovonelectrOll iOn!
f hi, ,"~m c o pt can be ,i, u. Ii....... in il ~ >impk' l lor m "' ito , tmcmre, (Equali" ...
'- I to lJ) that ind aclc
tlo<o Q~ lCrsh el l . k~1rn n ,,-
rile ease or
(11 1
1l,(:":CIl, '.
,~, c , : c ~,
0' H,c ....,...
(, ,2)
(3" ,
io nizat ion or Ihe"" eln.1 roll. ill ~n~rall, in the oro ., n 0> ~ 0> ~ K hol .,..,, 4~
L , uaU)' ,..",al ",,"onic;d tu<'n~n"" form' call b~ dmwn to ar l"" . ;nli l' , '''
el.Clwn di,trib'~"m in
ifni , Not~ th.t th ~ iymb<,li",," i' n"""-O I 10 iOOlo:at.
only "" km .. ith 'Q "~,,,"<J ~kctwn, nor a" ~1e.."'Nn ift tJd4iJ~", 10
,he
(" , milia ..p,nenh ; aJcli ,, ~ an dcuron tD CH. """",1<,1 tlI , ~ lleling lh.ir n"utr~ l eoun '" '1'"rt<, ioo ' coQlamiOi onl)' paired d " ot r"'" ~
(r E ' l ~ ~ gene,,"lly mOre 'l~ h le . "od th are m"," ....' cn 1M abnndant fr"~mcll l
l~n! In ~I m" " 'l"'ctra, For n am pk. d<. ,~ ~ of a C II bond in CH . ,. form.
t'"
t"'...,
.he 'table EF." i<on C H, ' a nd l L F urth<' , ,,,II iOIl ;L~lion n,,' hod. ,u ~,
," n'UrlOlI an d fa,;!-atom Mlllhardm. m lend wI'''' 1,;[ ' nl(>l ~ la ,
K)l ' ~ $"""~' MH 0, r<' ulling in the !n\>Ch .m ~l lc( tkl!rttOflr~iW<n l~ .i ()n
found in """h "","'1' .1.
If you call "' l ~ bhl h tl,. , kmcnlal GOmpositWD fu, ,he p"' f"-<d mol....lu
'on. 1"" rin ~' - I'h " " l " .. hl". h""d,, fOllllUIa "i ~ 1 . h, ..... nnmlialely if th. i ,,~ i . On
", Id '" o,o" -eleo , o" IptCI.... Fo r , he Il"",-r.l llo,mu\;\ C , H, N,O.. , h ~ vallie of
.. - j y ~ J: ~ .. I w,1l h< a .. h,,1< numbel 101 ~n y "d ,l.d o<lron ion, . lId .rnl on I
fe r "11 ",'cn-<;k ctmn , t~ , [ u m ~ are i! i 'e ~ in ll,, ~ 2.1.
ch< m i<;~ 1
3.3 The _ _n rule
1""'<
. '" m,," deme" " enco~ nt' fc" in " Trani<; oompou,>d"
i., a fottullato
belween 'ho rna>, of ~ n dem<:ot. mrt. a bundant i,otope and
iI' . aJe nce, ellh< , f+t),h ~,. e e"" n o ~m "'. ,"" . ' " bolh ~ ro ood ' nllmben:-d, ...i,h
oi'm"",n 8' the mojo< .":<:.,t... n I hi' lead, W lh. ",-""lied ",, ; t 'o~ rtol",W
which ca n l>c ' t" ,,~l ~, (" Uows:
1/ " (.'(+. '1"""'.1 "
"'. "" ( Of' "" " to,." ,"um"<'
nirr"Rt'" <It,........ rI,<.... ,It; .. lar
j,," will
t,'t" ,~, "urnh'" An . u rnplo. th< f"I1"... ;,,~ .noleco.1n Jic1J
. "en-m."" m"I.,:"ul~, i"rIS'
Ct+I ""f>O .>d ~ll<:C
"n
"" ,a ,,"
11,0,
CH. ,
(", II"
CH,O H,
"';~ 18:
"':: 16;
"'iz 2~;
.../~ 32:
c..H ,OH.
~" . .. 1114;
rniz 94;
C n H ,,('(J O II,
mi~ 2~ ,
O :U , .
<hole' te,,,I. C" H." O, "'i' JHt>;

H, N N H"
miz J2; a od
~m 'n"l'y r;djne. C ,H. N,. Hf!~ 94
An <+<J d num"," " f niIw,.,,, "I u"" ""'''se, M - to Ix at an odoj mas , n"rn he<:
NH , .
C, H, NH, .
q..inoli .... C,H,N.
m,.... 17;
"'1z 45; and
"'i z LN .
Thu s if Ihe ion ,,' hie""" "'.i<i, al an odd rna " " mbe I.. he Ih. m" lec"lar ion
it mil.. a mlatn an ood number of ni t ro~'Cn
m.. r<13liom hip "pplic~ W ~ ll itlns, nt>t j.." M ' ; Ih'" ll>c n' tmg." "'Ie c~ o
abo be sl" ted '" f"ll" wo:
~ " ,,JdledP'On ion "rlJ "" 41 " """"" mil." numh'" i{ " ,'o" ,o;n> "" ~,,,~.....-.Joe,
"">fb
..... '~':'='--_'::'---==
'4 N,
N. ,
N" N._N"
".
~ .
,,{ n,'roye" alom,_S'mi\" ' . . an e~d--eltc1rOll
IO n ~u n 'ai nin g an e,,,,,, I\I>m l:>n 0/

nitrogen atom, wil' ...pt'ar al 8n 00,1mil" n um ncr, Ym, m.y find lh'. n.n....;,,!
at fir- I, unti l you ~et .....-..1 h' " ", king with thi" it ""n pm ha bly be $Ier 10
<fed> e ThlJ from lllc fit>l ..mem. n!, re mcmlx:rin g II.." M - - IS all OOd--clccl'''n
ion. n ."", mary. _ T Ilw.. .1, t,
"'.... _ .... J .1. Imhca ' c wh. lher IOD. 01 lh. fol l""'lJg lomllll,,' an' odd_de cl' on
Of O\" D~k:~"" n' C,II. C, H,O. C. H."'. C.H,N O. C, H, ClB" C, H. O !>,
(">o F, . H,C , . lId C,H ...
" -' hiell oi lhe': ion' "' ,I] appear al ~.,-"" rna"
lIumt..,,;'
"'o.
oe-: ions h.;l~C a ' ped a l "'''''hani'tic .;,nif""... nce. a. <1;""",,,,<1 ;n ""clio n 4.4.
"r
fkca llS<
lhi.' yon . ho uld indk,de all ; "'l"'f1" ~' O f: ' ion.I, mak ing IIl""e di
rc..11y e n lhe specl rum (in Ihe r itlur", 0/ 1110,. ,IIo11pl<r lhe, . rna" num t>.:.. an:
,irded), T hi' i, Iho ...." Ile p m the "'Sla" Ja ' d In le, plOlatio" Prou d lln:- IInlOde
~",,: k e", c, ). The ~iml"" la n ,,,,- . .. ... peak, afle, o n~ ha. cor,ec ted it. a hun d4...."
rOt COlll rib ,,' " '''' "f i,,,,,, , o ll.a minil k"",,omnl on 1>010....... ll""""'11, ;.... r.a~
" 'ilh;
(" i d ",, ~'; n ~ intensily;

Iii) ,ocn:u ing m" " in the ' I"t' "lh;
(iii) illC,e a! lnH m ~" in II" puk i!(>lI 1' '1"' , liL',da, ly the mO, t or the = ndm, ,,1 numt.., of hydrogen ~toH ... IOJ ~n OF ' pea.)
'0"' . . ",
Iml>ort. 1l1 OE- '

",en k"" pr obll bl. in thc I""',.,m. ......d of lhe
' pectrum; lh ;n " """" .' <Ol-m" SS I"','h in Ihi' region an: -.ally due ,,, io n'
",-,,, (;t;n;ng , .>dd numbe' oj' ninoen alon". ",,~h as C H.N ' .
.111 (MUll,
. !)Il l t. S imd.o. J "~"," i n~ lead' Ie a com ll. ty 01 t~ " n;I,,'I\'-"" Ill," '
A srardty 0/ ,mJ'' 'r/ ,, '' t e"eII-Ina," "",,",'." .,..-ckJly W...., "'i: 0'''1..... . I"Jlca'~_,
mol,('"I~, .'",gl,,_
lhe ' ",'en ", i , no t alway, Iroc, the
I'IC'oC",,-" of ~ hunda"1 e" enmo .. io'" doL... ....1 nc.:eo n ly iDdi~"t. "" "dJ .ma"
M " , rhi, ", Ie i' helpful lOf l h~ "'~"' """,,l,um oIMopenlanc, molocu la' "''t''$.IIoI
which , how, no mok",,~la, ' Of) (Fj ~m . 3.1),
"'i'
.... nm-"'''''
n.
Hm".,u.
tI'
"
"
,oo
.'
"
~"" ~ft <>lll~ "'l~in number of nentm l ff'I ~"""nl' (Or I"... mas, ' ....1 u e
"..",,,,....1) 1,,,\ In .keomp"" ition, or m() l e " ul ~ r
The p",,,, nu: of an '":i"""...
"'''I ;"n "'J'd lnted Irom t he highe'l.n,a" ion by .1ne n<>me 1ou , ,,.. .,. ," <:knlt.. _
l~l f",m ula " ill ; 'oJ1 ~ate lhat Ihe latter ;" n i. not I'" m"le<:ul~J j "". Pre"", ,,,,. of
an abundant (a, oom r llr1 '<> ;" ",-~!,h b..riIll\ io "'1 j"n S '''''''' unit. ~ l"w the
ion of highe" mil "'"ukl h.. ~ lo "'pr=.nt lhe 1o,,, <>1 Ii"" hyJ",~n ~toms "
high ly unli,el l' d c""mJl'O ~ i l ''''' . Sm.a1J ncutnll rflljl:mm l' lot, fro m l~ . mo lecular
jon a", com mM ll' tl,,,,,,, ~tl ....iocd by . <Jnj.le bond. For Clan1pk:, if Figu"" J.l
hact l>ccn ' )/,l ~;"'-..t ("'m a unidt mified r UT< "" mpo und, "', . 57 mj~ht he
<idertd ~ , M ' - of CH,<,'H <. 'H NH1. with m,/~ 41 and 42 as lour. at NH, ~I\d
e ll " respecti,d y_Hm. "....... ~ , ;gIlJrlC,ml (M CH ,l - peak i< ,ocr}' rare, Thu"
Ilk- l'fC>Cnre of a ,,<>n""10~1C Ion mi' 4l i" dicate ' that Ih~ "'i: S7 I, ... ""Ill "" l
I'<' , he mol<nlla. i<m. e,'cn th.," ~t. ;L;. lhe highe' t- m"" n',.,i" ,(o."... I"'aL ;11 , h~
!{'"I tll"'. S-u. h " rna" d,rrel~llce of CH , i. "" mmon l}' cncou.. I~rl ..I.... lwo
, ur h "'-'mol"il o", ion, "'" I'mJ u"od by decomposition or a 1~'I'''' i,m. here.
C . H, . ' prodLl"io" C.H . + a nd C , II, -; tlli. e~n al>;o he dU<, I>u~r. lo t he
m, ,1o;.'U lar i,,,, of an un, xpocted itn p" l;t) ..hi,:h i. a hom ol", 01 the " n ~ "",. 0
j",..
"';>n-
c.r
compoulJd,
M"" 1u.. <> ul 4 Lo 14 al.d 21 .... 2~ , h~, ,i~< lml"" I"nl po:ak , a '" h\ghl ~
u n l .~ , l y, N" m"mlx'<" , hose u ngos: Ta ~ A. , ~ pn:....,.,I' " more comp lete liit "I"
lh. m, and of neulral fn ~'ncn" .. h"' h a n: cOln "."nl}' 10'1, Maximum e'l'C"tod
r. lati..... Ul" 'n d ~""'... no l'i ",n hy ~J'k 1l!l78 ~ for ex"mpl ". (M - 21+' i, "."a111'
mud . k a t>u" da..' IIIan m her \f ' '" IM - II " (Section 2,6,
If 1M
ment,,1 c.m>",,,,ili,m or Lh. fmgme,,' lost ~; m lx: OCrlu=.l, thl< gi....
an ~
~ ro..-erf" llesl, For e",,,, plc. thc p' o",: n" e ofa major 1M
151' ion
is common, l>ur "
(M - NH t ion j , prob..N)' an . "" malou. ion; 11M: loss
of35 i>; l o ~ I ' >n l)' ,1" ch10 rj". i, present.
Ca 8 lh. ion 01 h l ~h~'1 m"" Ix: lh" ltI<llc.;ulu ion if lite f< 'll ""';n~ are the
m".ior ions of high rna. ' in lh. , po" trn m:
"'''J'''
~I T "_ '"
Un"""""
.~ , 2, C , ~H , .O,
(' " ,H,.O, C. H" I>. c ,0H " . <.:. H,oO
.1.,1. C ,oll " . C, 0" " , C, H , " C, IL" C-,H, . r-, II ,

t d .n t iti'- ; " ~ and 1",ling t il<' nlO lcr ~ I~ < loll "rc impoMam l ey, 10 U ~ kD' '''''''
>,4 "n J B . Hint. In L' a ka"'''n ) .\, " 5<' [64 I].{6 3+1 al><! lW+ J,-T9 g' J I" <ak uI" ", lbe nombc< c. rb" n . lon'S, " n" m,.', to! ~ml 9/ al' o roll.~in ~n ;' 01 01'; '
oonlli..... liM [[(1m "n -'" + 2" , I, "''''' l in mi; fil l . nd 95, <l.-"f'<'1i... ly.
lJ " k"() ~, ,,
"r
- ..
u _
w,
ra
"
"es"
." ,
"ee
""
~ I. >
...."
'"'
""
"
.. "
ea '
" """
"
"
,. ""r.c
'"
..
"".,"'
""
ae
""
.,
""
~
~
'"
"
f, "J
oo -
~,
~
"'
,L L l.
oo
U'.-_ ......,
"
" ....nO... U
miz
,, '
"' "ee
," "
", "o s
."..
,s
""
" "
" '""
" "'
'" "
",
""
'"
'0;
,. "
'" "
i]
I _
"
.l l
IJ(I
' c>
..
f he ~ bU lld;l n"" "r I h~ m~ looe"l" r ion, [ M " J, Mpend' m oinl)' ~Il III stabilit}' ~nJ
Ihe '''...... unt .". enef g~ noodo<1 to ioni.. Ihe m"lco:ul. lTabl e " .3). P~rliroL1.r
.tmctura l fe~ll"C' tend tn sh~", Clo J"~"tCJW lc >at't.. or thc," pm """., 50 Ihal
lhe '''''~Il;' u,1c "f [ M"l Jl'I " ,i<!c. ~ " ;nd,callon ~hc . tr uctllre ol lhe " !L"L"UIoo ,
h hk A.4 $Ives typi,,,1 ( \l "J . all"" ro, " numhcr 01typ'" Qf "" mp.' u/lOh, li' led
In QIder (If doc",.,i"g a bu od~ n ""
"r
3.1 TJJ>i<* """.. IlMeI,.
r'l"'''''
3.2 tn .l :~ p, e... m ' f'CClr~ ,b~, ..I.... . bow , uoh tf,n<1. I' be90 ligllTt:> ..;!t
, .ftc", he , eferr. d 10 I~ I "' in the book. Tlte ' fl echanistio .~mh< ,1s helow will he
n pl.llncd in Cha pte, 4.
(])
oddd."" ""
Im('<" tanl
it '"
Impo " a nl J'C,,1 r" r",ed by 2H , ,,,,,r angemt'IlIC. H ,. _. It" . St",,, 4.to)
Im", "'I..,,1odrl-elo, trnn inn ....;.-,
I m po rl~ n t e,'<n_d cd rnn io" ,. , ~
r . "l lo, m,u by , igma dc<.1 " m ;"",zat;on
Peak IO l'n>e'<! b~ " 11"'"- cloa ' ~ie
Pe ~ ~ f" nncd to ~ ;"d ncl j~ e cl" , ," " ~"
'.
,~
fJ
! -
,&
~,
'~I .
-r;--r-r
.,
II
~U
_ oo
'\'
,J.J
...L ~,
-oo
,'t" .
..
,.
,'1".",, '-'
I, ,"eo
i
I
'f'
I ' I
I ,- ,
, I
, , - i
,oo
'"
I '
'-I '
,.i , ' ,oo,
. 1"
1. ., ] 1 lL
.. .
"
, ," r
'"
;
,.
,I
i ' 1
' OO
,,oo
'" I
9~
.
!
1.
.I,
,.
-I.
"
' oo
'.
-- -
,oo
,.
, 1'1
" -- ' '1
,oo
I
I
'.
-1
,--
~ , ,

_u - '.
,.
M _ ._ ,, _"' l~"'"
r.
j
-
.-, .'<oJ'.,
-
,-
",oo
,oo
,. '. '.L-
,. " , , , ,
....... t .t . 1-1_ 'p tt om <Of hUfl .......
"".,
'It' .. ....
,. I '
1'"
,.,
, , " ,.,..,
...,
"'"
:~
~::.
,lli
""
1211
'I',
. ' ~;. ,. ,
, T C,.
'<4/lr- ':!:r
, I
.~
,,
~
-
'i , ,
,'",
"
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<
,.
,,i oj
~: ~
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,.,. ,
,~
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T @dB~'
rJLJL
.. . . .
,. ," I
, 1 .11

' I '
'
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,.i
L
!
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j I
'00
'r,., 'f ,
,'~' I .:~
".
~"~
lei
, ~ , : < ,'r, 'f,',- , ,

",:l
".
'..
''''
.to
"'"
--r-t-r
'0
i
I
_.
i
!
-'
, i T"1
~
,oo
'1
..:'.:" "
, !J~
.f~~--+-;L;-,'
'. '.
. . . 211
,.
...
OIl
,oo
,.
'f '. ,
,oo
~~~~'iC".n,~
"
,"
'"J
..,
J
I
,f
j
.,,L
"
J ~ , ,. , ..
'IT
,"' -t. .'I!. lJ

l .-,.,"
r"T'""r
..
..
~~
"
-'
~ ,,tf.,,~--rl -,
'. '.
'f ,
'"
. uo. \d . .. 'f'<CI , ..... of di b..,....,Llid.
" ",
"" '"
'.
"
~ .
"D]
'
..
' '''
I
'!', "
...
~.
'.,..
...
..
,..
'I'"~ "'"' -~,

~ _
".
'"
' 'II
.......... 'T""""':""'", .,.....,... . .,

,..
".
'"
..,
'"J
..
..
" '.. ..,1".,,, .,.
".~'
I,_
" ' , - r T"" '-'
""
'.
,.,.
1110
:DO
,
,',' ,., ,
'.
, ,,~
.L ,
""
102M'
I" t OM Il. the chem ical S '.b1 ~IY " I lhe m ol~ u k f'iI .~ l ld, the sta bihty of !.4 ~
and '" i" , .flec:TM in i.OC all' LN ,l tlC< of M ' "; [ M '] UI ~ " U y inc , c&>e> ""nil in-
"re"sed un<ln...., i" n and numbe' ,>I ring>, as ,Uu""."" t by lbe >ottikill' " hu~
dance of M ' 1ft slr)'chni" , {Figure l !8~ l1>e d l'cd "r mol... ul. "";8'" ;" I~~
d , ,,!; incr...,,,, ng Ih" chain l"l~l h up l<J C . or C, g"nq ;~ll de<na<es rM" J
"'
D1 ially ('iCC T able A,~l bul oft>;n LM' " increa""" ~!"Ii n f... longer ' l,"i glll
ebai" . (Scc1 io n> g,4, 9 ,SI_( 'b. n.-br8tlch in g i \lb, \an tiaUy d..., e.t' co M' 'labilil y
_"... 11\ "1 its "bLIn d """,
If lei S eno'IU' "' ""l"'~ 10 ion;' " lnc 'Mol..:.,I. (t h;" i., if i' hal a 10......
"'" i"' I;"" cl>ery~ 1Jl(>I< m" lc.. ular iou, olio,"" , inlernal ell" gy t -~''' ,j ;,m, -,
can be r". ","(l. an d [ M ' J ,,'ill ' .,Id 10 be h ,~"",_ ' hown in T.llk ... J. I"" eJSc
or iO<' l.l3J ;OQ "' Inc o uler -.hcU lw n", mding ck etrOll i ,>n h,:tcro.ato m. m Cl~ u ""
in ll' ';''1'' d " ...n 0 column or til , '''' k rr in a rm. of Tb. pt, iOOK; la bl. T his
".",,,,, nlS for th e dramal ie incJ ..."", ' " lM' ") for mCf<". p,a", m oo mpar i, o n ,
,lie " ' rrc, po nd ing k!ooh<.I. 1~'i g u "" ),8 on,l ~. 2 1~ (>rima.,. ~ m i n (Fi g u, o l l61
a , mallc[.lh, ... ~h . igllJr",ant . inc " :.. ... in [""'1>."""' tho: c<m espond"'M
.It:ohol.
"''I ''
,.,
..
,
,
,, , ,.,
,
"
so
. '_ _
Try ,,,I< nlOre unl novc n. 3.6.

t.l<>..1la n,,,,,,r.
I'cl",~
l<Kkling
,.
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.,
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W,
m
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......
4
Basic Mechan isms of
Ion Fragmentalion
(Jlll imt la l .l~ l.m.nt (f " ' plcr 1) Ihat " l be m~", ' I"' ctr um . how. rio. m. ' 1 or Ihe
m" l<:c uit ;\nd t l'>< ma~ "" picce. b ~ ... jC i, o,-,,,impbrll , in that it n<Yc<ls
, ho; impo!t:,n\ .....'Ond <lim.;n;i on of a m. " 're"l",,"- Ion abu"J",,". 11>< abull '
rl~nr;. " r ,;p<cifi, fragment IV" trial;". to lhe a bundM"-'" of rl~ m~ "clll"r i"n
and ", I.. t h a~ "", nt ;O D' ca n toe n ,'cr)' u.d "J ;mti<a li,," Ilf l h ~ "" w,'Wre oj 1"'<1
Jr~g_tli ""J iI.' e'u' '''''''''''nl '" rltt'
I . H ow e'c r. I" ma ke U>c ,.,. 110;"
,n(orm ation, we m"'l Ut>d < " l ~ nd ,b. ,,,,1.or , lhal "",,1 '01!ragmenH OII abunda " ces. A I" climJnary, ..,,,,,,...'h~1 <.",p j rjca~ J ..........Oll of I h ,~ fa.... " " ,,'ill be
giw n h, ,,,- A mN . dCla,!l ll. " tl'l,ent 01"'cclu "" ml " prea", in Cha p ter ~, ~ n<J
\oc !>a,i. PI""C' ''''" in. oJ-al '" forming rna.. ' p"e'".....'ill be cumined iD ( 'hIlp""" 7. tt<'wcvcr. if " omportant tn ~ PJ'~h'l c tila t n",.. ,pectronwl ' ) " ~M
",m itiw to .11 .u" clu ,~l feal '" C''' " tid 1l1 at t il~ rom p]e. and com rL1 ,I;'" intera cti"" , of ii, ~ hcmi m }' limit <lur pI....nt cap. b'lily 10 imerp r<1 ' peelra \l, ing only
the... I:>io.';e f,lCIO" . T.. ~ o ~ ni , c fo r more: ""n' l' le~ molec ules wha t ~ I t em ali.-c
,I n.a.. , al !X,,,ihilitie<. co uld gi,'e , i... I.. the ob>e' vcd rn"" " l"' ctral k " luros,
..e n l",1 "ud~ l!loe spectra 01cl""",,y ,..1... <1 m<>'""u\es,
Such " nimok ..,... l~r ion -<lc.." "'i"',ition
eU~ be ,'iew<:,J a. allotll.:,
f,dd or c1><mi",y. ~" 1' 'l1 U n.l t ~ly roo mMI , " emi, t< >t ll(l ~n,-, this b""le lhen
M' ~ "", ny do ,. ,im il" ril;'" to pyrol>'tic. pIk'tnlytic, nl,J;<lI~'t i<. and " ,hor <'fIC'"""tic roaction" ~ OO l h e I~ ~tC e,'eo malll ge" era] , imilarnie, 1<, con tk llOCd-phm;e
,,,,IUhon ) 'l<t" "~ ," acdn"" The 1a ' F,<'SI ('<,i n'" of difference au Ih ~t ;nnic a",1
nlk n rad ic.ol ' P<'eio, a,e in""l> . d in ea ch ","ct;on in 1"0 rna.. sP<'"t",metcI, ~ nd
lheir C{lmtH neu effectl ",,,,,d imes "1'1"'" ' ~ nn .u al to tile o rp nic chemi. I, C n.m_
irn; ""'~ also ~ """" i()n the rcl'~bi"ty of , tT""tura l rcJ,.,t;on, hil" hued 011 'c.
~.,an gerntn( """ctlclJlI, Hmc." r, many nf tn. ~.", ba,ed on "d1-flI ~h ii, h ed
che mi' t')' an,J Can pm . ide t~ mnleculu inr." ",ati<m
.,,,,In...
"""'f"''''
"
_-
~la ...'
pK! r.ll r~.~I ...m are ""im"I~,ul",: the , a mp le r'~""'"'' in Ille EI ion
ker ' ."lTkic"ll111 In,.. Ih" t himoi:ul<lr ("iOll molt,,, I"") {" .lt ll<:r- collilio n ", ~c "o u ~ a re ...... U ~ ,,"'f,h~ i hk. l' " c' J!t'lk (711 cV) clcctum , ,n lcr<>ct ...';' h
, ~ . ~~""'\" "'''' I>!c m o lec,,1es al widd)' ," ' yLng d.. ld" ,,"' . ", Ihal lhe mok a , lac
un" rM 1 I ' e (,,,mal ...-i(h a ",iok t;,nlll' vi 'Q'ern~l energies, T ho," rhat are
ll ,lfL,Jelllly "",,1" "'Jl1 no l decompu... I><f" ", ~"I"'c\t"n, "n,1 will appear a, M '
in lllc spectrum. If ,u lflCieJltl~' eXClled _l hoe \1 ' in... (an li"w mPtose hy iJ " "iely
o r en<" Yji_dq ,endcnl rc"",,, it"';" ","eh ,,. whICh , eo<t>l1 . in Ihe IMma lio n of .n ion
and ~ "" utr,,1 , pecic" Ihi, prima' y r " ......." ,n" m ~ y h ~ , ulficie lll en", ~)' to
dc_ompo, . furt her, In the m. <S ' perom or "' bCU ll'q ""li",. " .It ,I>c ah..n_
.u,,' ce (II IICD ' will de pen,l on L'''' a~Cf '~ no. f~" or IhlolDLllio n and docompo
!.ilion. ",he,."" [ BC' ] will d' p""J ,," ("" rclali,,, <;dc, of .e.-er~I rompo; lll i~~
~n,l <~'nse<ut i w ,."ctiom, laome nz ation is " I"'"i!lk uni",.",-" I., f'C~~l i" "
[..n "" li" " ,,[ 'be (IE ' ion A[) I' in"lll, '", ' ''(lI'' a''II ''''''>!l (r ) or tl
ton.. oolld ".~
rdauoflSbip; of A lit: D " ,
", . ~ t<:C ....
"'OC D
---"--
", e GO'
A" ' ~ C D
,. , BCD'
L..
8 C' + 0
(4. ()
D ' ''' !C
L ... , ac-
- -'- "'0', e-c

.2
1I . ~ e "' ~1 o ' .
tba l inll"ence Ion abund..,.; .
Tht: I" n(>'l\'; "~ i"no!';,1 guidolllLe, Ii" p n: di ~\i " g

IW' II ~ .. ~ . " ho';"- d ",mioal principle<,
" n Lln "l oc ~la r ~ m
tkcon.po";.
..{ 1M I"~ ;IHI. T I.. mill;\ rr"p" rIUl1( gell""ll foetOf a"",,!i ~8 lilt;
..r a prod uct ion ill ;,. , u h,h\) Ke;- t;-re' ~f ion , 'abiliza !io n i"cluJ.
, 1'(1''''1 , I"",;"'} i.. m l~i .. ~ ~ no"b...n ,l m ~ orbita l of 0 hOlomal" m, . ucl1 . ,
.
ill tl", ~ od }' 1 'on CH , -----e --o _ C Il , (;=0 (lhe latter i, i,oe!<ClfOllic
",i,h C H, C,~ Nj. 10,,<1
"""..,"",.,. " aJ>j/;z..,;PIl. , nell a, i" th. allyl ca li"n
.
C ll , = CH CH , .... CH , -('H - CIl , and , ''' De,..,;- I ca l ~1l1 C, H , CH ,("ow. ,', the ph. n}'l cati(ltl i. m....h ~,,,. la ~or td . b.llL"" i, Ita. on ly"'"
,, _d ed "'''', hOI'
a,. tCq'Llred for arrH'Lati<i'rl Fm U h ' i ~ ", . ;IOI1M'rl wllh
""po, ,,' ed !'ad ical a " d ch. ,l" , i(o" i-d ;' I.....;e md ical ion;.~ Rado>m .. ~I. In 4)
ClI" be ""'''' " " ble 111<1 " their cln.. ic~ l W Lln l0'l"'rt" C H , CH , C H ,CII= O' ...
ClI ,C' H, C H, C H 0 ' H. C H, NH, _. ... 'ClI,N +H,
~ .MIfIJ
~h ~"'lll ,1Ct:
,i,
. , ~"" "o<." _"' ''' ''_''

To pIod;,.. Prflc rrctl d~ O ln po, i ti OT l pa.th.. ~ ~ " wtO "'til llse the ,in,pli<l " d '"
,um pt io~ ,11.1 1'" rea "l.i" n' Me initil<l<-.l ~ l lh. lawlr"d , il.<.... for 1b< ".I"'; d
. lectmn a Dd for Ihe I'", iti,t ' ~iU gc nI lht dt.omp",i nt- IOQ. '>ucll a ,i lt i.
" ;" ~ a. pr",id int- the d ,; . in ~ fon. lor , ped;, c lypes 01 , ,"c,;,,'" which .'e
, 1\;"'oc1cli, tic ~ f the ~hc m ica l " ~l\1 r ~ " t lhc ,itt , .4. lt" (><>!!h lhi. gives only, al best.
"n _ppl'o xim" ti. ,n "f lhe aet u.u clc' lro nic dj,pl.u:mem " it p"" iJe<, a OOO\'<:n;"nl wal' to cu " d ,,' t Mnd for you I" ~rlIelllbcrl ~ I_r~ llumOcr "f the 1'e<lcliom
of d;_"" " ""' lurnl mo ictic, . l'u rtht l, I h< di , ,,)C ia ll ~ nl "" ul lUl/t. f,orn radical
. nd d lll 'lt'-"; t. inHiali" n a rc, , ,,, ,,,"'i i, t ly, ho m oly l": ~ " d ... tero!)I'" , loa,'a g.>,
oom,non cl. " if,ca lion, of O' P "'" ch. mimy (McM urry J9 lt4}
'The mo'l fHorod , "'"",1 300 char~c , ile, ill lhe "'" .....ular ion ar e " .",m~
10 arise fr~m k_ "r lh. mok culc'> '''''''roll "r l" ..... t ic nll" lion ~ l iF.
Table .>\ ,I I II d . h.. ~... ~y ",~uiT<menh a", ';,niJar 10 tho".; (0' lhe elcf:l"'''ic
lfllm;lio n< a/leeUn! uh raviolet ipo<:ll'll; r..>o. a\>d,ly f", it,ni zal lOfl ICJlorall)' il
"" 1Mo.dc, "r <T. <:: x- " "...-Ic':I"''' '
-_.......- - ...
,,""
.,...-.
- -
T h. sym h< ,l , . II lbe end "r 1M molecuk ' itniflos a n ",lJ-<;lecl ron ion ",;lho Ul
~ t,i~l1 "t ing tl><' r'lld;",,1 . il. U sc " f "ill><r or' with in Til" lnol""uIe, "" '"
C H, " Cl I" Impl"" Iocali, "!i" n or I he radic<:ll 0,. lh. charge,
Dccon' f'<"j\loll< invol.in~ M ly th. cle" " !,,, of a .... ~l" ,,""'d in the ,ld.!",ln.u on
(( lE . ) mo"",,,la, >O m f1 LUII p Wd LlCC "'" eH Q-dul",n (EE') fragmenl ;"0 ~,od a
,,","!fa l ."di"" l 'fI"cie<:
(4. II
l'h e . ...0 flaprt. " ts eo n1flClc fo< tM d lil.ll" " nd lhe ullpain..-.lde<:f mn; l h ~ IIhunda ll"'" "f t ~. t wo ionic l"" oo.UCl. r.. ,m Ihil t ypo of ",....1 iOl' would be c4ual onll'
hy <o;,o:,.;.ne" (Sle. en." n, " u~_ ~Mn 4.2)
III cont,,,,t an OF " i"n i' lormed ffllm M- ' ~ d<~ \' * "I IWO bo n'" betw"en lhe N OO uc1,- Ke. " M gem<n l' and
im' ol.i n~ fr" ll"' "n lario.. oj "
tinj<. are two "' 11)-' i" which "bllndanl O E- ' '0'" ca n be pr",luu:d :
"'3<:1"""
.. . . ... ...
..
(4.4)
Again, the tw" fr~,mcn'-' "''''' pele for the eha r~e and radical In a ,;milar f. , h\(In. clcH ago . of thn'\' b(",d. of VI ' pr<>t!" c,,, an EE ' ion:
..i '
CH,CH,+-C"'~
'-
CH,CH.. + C"H, ' H;>
14.51
"
The tlrnn p,-,"ilion' "I c"cn.d cct Nln ion re " ",ngly inn...nc:cd by ' he poc_
b e"'"" /" , for ma lio n of .n EE + ion and E E~ ~ .u t ... l ll~e "ev<:t>-clect ' " .. ",It,"
Cumm ing, and Bleakney 194'J. F, .."'"", n .ntl Lc"'8 1953, Kmni and
1\!<Il>dclb aum 1990J. ProJ ucdnn "f an o r ' io ~ from an EI: " ion mu,( I:w:
~c c" m p . n i o d b )' formati on ~f . rodieA' MI'l r ool .~ ;n~ " I . i n g the o"" rgot; lly unfm'om blc .. parat i,m "f an do......"'n ~ j , ( a;q ua t,o lli 4, ~ ~
CH,CHr--O==CI1,
::%1:,
-:
<,
<
" " , ,'
.='"
CH,.--------;(;ot, + H6=CH,
" " , ,'
o=c..;'
("'a~
"'iI7&l'Oll)
(_rong."'o 'll, ""~"JO retentoo)

(una...",)
CH
CH,=CH, I....~ ' .._ l
C>1, = CH
Cot,
CH,
CH;'
/4,6 ,
I"""""""
; uW'. T.I . ( 1)72). In EE + ion de~ompo.iho", !Q[mi~ thc ....mc 1;[ - (l1"Odocl.
' he tendency of" \loulr al to k a vc n'ilh" " l tilt d lMJ!'l' is &""~ter I", m ollll: uk .
of 10.... pr o lon affi nit y (pAl. In Eq uation 4,6. the fOl1Wll JOD of C"H, ' wilh
o C H, (PA - 1.4 t V) ",,,uk! be ~a l ly r.. ...,rtd 0....,. I"" I,,,,,,,,,[;()l'l orC , H,
"'Jlh S=CH , (P A ,. 8.9 .'.-"1 !."m ( :, H,S ' -( ' H, _
Tho .."en main tyl"" of (:31100 f [~ ,mc n l;l1i """ ,1...""",J in lhi, chapt"1 lIr
rho," not in brackct . ;n Ta hk 4 ,1, f><kl-eleclrotl ion tlomjXlsitions invo!>'inj1
tho clca,'a,'c of",,", noM art d ,~Uf:lotd ,n Sections 4,5 ro 4,7. of 11"0 bon,l. in 4 R
~nd ( .9. 3nd of mitt bt>nds ;" ( \ 1: f E ' <:le<:" mpo , itio", clca .-ing " "" and two
___..... ,'""._--
..
., ..
~'
"'1M " )
ce-
N,"""',,"
~ tHl , ed
,,,
,,
[M - ')
". " >
"......,--
EE'
1'1
"""1'"1
H "
I' ",
IOE-r
"
"
,;
GO"""
, oten tion
mOll'"otl""
EE' ('1
0 [" lai l
IEE-I,.'II'
'"
[OE " )"
"" "11<'. ,,,,,,,,,-.
''''' ..,01....... ' , " """ ' , " .... 010" .... ~ dox' ; ><
,
,~ ....., " .......1. r"" , _
,_ I. ... " " .. '""'" , huQC
" " . ", ,,,,, '"
~ ~ollonl
.. "',
" = ~ ,,
,""'''''''. '',,,."1i'"'' 'I.,,,...., In " _ .
B, ock" .
""' ~ ".
N"'''....'
h<m J, aro co ,-.red ill S.C!;cns 4.7 " nd 4.10, r. specl; vel}', Note (hal OF' f<>Tma_
lion u fa vorN " " '.' for lh. ck" v. g, of [wo hon,[, in an OE ' pr""."'or; this is
why you . h" " IJ ma rk impmlan l o u- ;om (Seclion 3.4),
$umm"". Th.
i o nd.~ompo,it ion mecha nism' di, cu,,,,d in the r<,1 of thi,

chap/ or a r<llumm" rized ins ido th < ha"k COY, r for rc;cdy rd e", n, ".
(4 .7)
......oes:
If The oJe<:tr o n lOS! in ; ,, "il ~11P" ""me", frum the ". lurated bo nd f'Jlne,,'ork,
will {,f OO U,,", be favorod; ionization of ~ hnT>C inc""'''''' lhe
b<."J k ",.th by _ )0';.; and h;,lvc< ito nd di","''''I;'''' e~rgy (Bellville
I'l R2). TIle more...burx' "llt ionif",.j rt _b'1l10nt ".. ,Ube til< 0<Ie better a ble to >tabiIll<: Ih ~ pu. il;YC ~h ~rS" _ r ", ' a1ura ted h)'droa u bon, ' ud! ;" n;,otion f,o'" lhe
...!><,,,J ..>-l<m " Ih~ lo" ,""t ~ 'ler'j' V"""""" ; ,~i>. c:m then :t=l<,,,t rOt' r. "or!
~lb'Je h ~ ,nl<''' t" uon "I ~.,.. i:><,~ ~, ,,"" th l a n: nl'" '' hi, hlj' , ,,bsl ;tulw , "nd
wil'eh , ~<" ....,,'" .h.,~ (d m" ", ",adily a rry tho cha <gc ,n thc I'rod """_ ([ he
re=ma~ ya llK'1 ltI(hC<lt ~ the '<:'n a b"...!anu:: ,d ...
lO the ba '" pea k of m.
.in~lc bl'lxl ,"~" .ll'.
e (;
ti."
spll unL I
--".
...
IH_
"
""" cs,~ Se<,1 i"n .~.2 1 in H g ~ , e ~ :l.2 10 3.4, and in the 'pectrum 01 pl i. lno:, Fi ~ u""
.. I. Ho wever. 101 Ttt. ~ _ I>t , ~<! <!i.,,,dali,,,,, a, the "'In" e.trbon alOin. ~" ~.
lhal b dini' t<> lhe fo' mation of tbe ke y mi. 113 <tnd 1M3 flC" h in Fi8u~ 4.1.
lhe ,ul. lor I"", of Ihc la' Il"" alkyl n dic.o.l "l'fIlino; [1M - C . H ,, ~- l <
reM C, , H ,, ) J- The a bund' nt C, II ..., - io n. SOl"", as >II{' 4 3 and 57 r',""od
try- ",,"on<la ry fragmenlations \'ilO be- dilll.uW<>1 in 'lcco<m .~. I.
hyu. liom ...~ !O 4,1l SlImm...-i, . Ihe ho m" I)tic di uo<iatiom (McMmry
in Ih,. ",-"Cl i" ..
19~4)
dj s~", ~
~.rYR
~) ,r-;;
R-
,t,h "" (ally i<
c".vage )
--"-
CH,
' ."{1"'
CR
-"-
"
,.
CR, _
TR
" . O<. =CH.

CA=-:V
R-Q~ --"-
r
(410)
(4.1 1l
CH,=c ..........e>\l (4.12)
Rca"h() ~ i~; li . t ion I I Ille radill .;te aTN-" 1m", it, 'lron~ te llden~y for <'i,cIron pairinq ; th" od d ~I",n " J' ...a" J I" f"r", " new Ixma lo " n " dj"", nl al"m.
T his i. " CC()fllI'"n ictl " y d eu at" or aOO1hc' 00 00 to tha I ~_a!nm; Ihu~ Ihll II
,()fllm'jllly ""-lied I"," ~a ~, ,, te , e".'(i on-;
r: <,
,,,0. .
' O<.-. D-l,--"---<lc,..H, _ . '-
..
< '
. C>i, + CH.= OC, H.
( ~ .
CH,_ OC.... ~
(41 ) .
50'10 ICOH,- - 100'l\.l
.pc'Ie'
ll r " " "" ~.~~ N,u l ,"1 ' adi c.1!

u n~l;c", . na l"!,,>,,, ~-dea..... &.. IO re. n
I<)A(); Ci J lld Whilt CD In9J. A " fi .h h oo k ~ bJ lf3m , .. mlhc'dlC> lTaJl,r.,. 01 ~
." n~l. e J~ e l! oJl ' , ueh !lomo!y' i<: d CH _ge " ,U$I IU O'~ lhe ";Ic ,,r ,1>< unp:tJr"d
electron. A d"uhly ha rbed arrow " . 11 b uoe<J 1<' iM;""", the tran, l", to an
cJ,~l",m 1" '" ' ueh holerol)'I i.: dca.'al:" ",nO(> tM c"a.~" ' il" I:~ct; on 4.7;
Sha nnon 19(4),

The dC" lllg f" eu: i.> ill. tbat u nd<rlylllJ/l h. h" h "';I, I;o;'y "f neutral radical'
;n pn >cc, ... .urn. a~ d ll....,; ...l1oo and h) t1mgc-n ~ botra c ll O II Th. l,,"d eney IOf
th" rJdi.~l 'UC'" inil' .'., a reaction in comp" tit ion wlth th~ ,h "T~C ,i le j!.""" ally
I'aralk:b. tho radiea l $Il~'$ lend" ncy 1" d"n~le de" ~,,,n ,, ~ > S, 0, ~, R ' ;;.
III ,~ H . "'heu " WlUI,r. .. In Un, aIUT;ilec! ' ;lC and R ' an alkyl rodil l ITh i.
a.
~.,
-,
,i
, ;
;,
- -:" t
,a
~,~
e-,
, , , ,,
, ,e
,I
>
, - ~
.-rf '
_
-.
~,
...'d
"
oed" , irlg doe, no t mean, howcur, that II chlorine alom c_nn nt initia te _ nJical
,it. [",\Cli on in the "h,"~c" , (",nsoTuri d n, r" rc.) The dOllat il' t abihty of a
parti cular , it ~ ,,' nff"C t~d by it. molerul.rr en,'iron ment, for prod ; ~ tin~ thi>.. "" n_
\'entin nall'esonOllC<: and ; nd \1ct i~c cff""t. urc 1'<"", . 11) _llf'li"",ble
[oDil atio n or an a l iph~ l; " ether (Equi l;on 04 Il l ihooid OUr p~ ntia U J by
1o", of an n-e l~ c tron of the Ol}'gon_ DOOallQrl <It II>.: unf'ilirod d~u o n \0 the
adja cent C-O bo nd i , f"ll m. 'cd hy lr~" ,I"r (If ... elKlron from a" o lM r bond
or lhi, 2carho!l alom. The r""'ltjn~ cue-e lectron bond then o;k~~ to
all)'l radical and the re, cnanc" . ' tabi li""l " n;um [<on: lh. grelll.... l... d<>~ble
l:>ond "",,,,,c w, or ~hi, j"n , , he I" "ff .. ,il l he lhe ' "l icJI (ac l j"~ lIon l ener~ of 1M
",a u io". Note. t h ~{ only the nd ic.tl ~ lI e mo, ' ; fhe ehu lle " h,' .... .... i... ,m Ihe
oxygen .
"r
io?"" .""
[htk""w" 4.? ]" cdi<.:t which will he lhe "" " ,... hu nd~nl p ,, ><Iuel ,.... in Ih.
ma" 'p"C1rum of IiO CH , CH , 'N H: .
~ - C1< ",' a ~c a1 It.e "" ,be",yl gm up ClI n "" vi>..aluN . imila,l) wnll f">nn miofl
"f the , [ahle a cylium ....." as in Eq l18M" 4.14 (Stt Filu~s J II) .>nd ~ . l l ).
~ CA " C,I\--e=O
(4.141
,=
_, "' ;M.~ "'" ;mtJalc"d by 3JJ ,,1.-1inie <I" ubk bor,.j (or phenyl '<-Iy' tem) yields an
all) 1(<l1" ben.<yl) IOII lfqn31ion 4. 15~ he, e tbe radical ,it. can be on either atom
oIl h. double bond. An mIl lie-In '" cleavage ,ho uld hoc Ie", r""otcd a l
,
CH, ' .. CH,= I t --GH, {..... CH,-
CH= CH;, )
100%
, ._
CH, ' +
(H.' l
a c~ "OO IlY) do..hk h<l"J
he""""" "'>oM n c" , tanil i"a li"" or (hi, 1'""I"cl ""lui",",
p<>" t i,~ I;h~ " o locJ ~z.'tjon On a mmlO"al,nl a ll'gen. Wilh (be Qlh" ca no nicnl . l, uchlT"<;. ~ n ",ll~mcly unsl "N. a-a<ylc"roo niulll ion (Dommr.,...., 1 ~S1~
wherea v the t'l ' alent o,,,,,i,,m
C H ,...~).iC {C,fio;-~ 0
i"" j, lhe m""[,,""rOO , ilc/ Fq ual'" '' 4. 1h~
-:*-
C....' + CI',=CID,t<,r--O -
~--c(G,H,l==O
(4.16)
.,--_..... _.....
'"
ee
/! . 1;..,.... ~ j
1011 01 11 is ~ll
t: ,,1<110"' '' 4.3
...
"",
I ~ " I" ... ", ,lie l~tl""l ",I. yiN t~ l. l""dic'1' tha l ,hot "'..... ndanl
fra gmenlatio n path""ay'. Po,h,l. t. a muclnr. 10<
r", "hi<,.-h ' U" ~ k"' , ..
ll n ~Om m On
." .
_.~
" vZ
1,,\
"
""
""
""
""""n",h!<,
"ee
""ee
"ee
ee
.,
'.'
"
.... "..
..... ....
.."
"
"" "
"" ""
.,"
.""
"
i"
..
"
-. '"
..'.
"
" "c.s
ee "
"e.e
....
,. ..
..
n. 'z
as
r .c
se
"se
' 00
se
"
"
'00
--
" "
,.
'fl,,'
L<>,. "! '''' '"",,,, .lkyl ..,di,-.I.

r ule lSe<:lio1l 4.2) ;, ~,,,,ully ' W !icuhlc
(" ~ ....* ,..'.t<' 1="~U,,n,. Not. tb, ! th. ", uro two . -oon d' for Ih" "" ' OOIly!
RfOU P
,
"
-:
. ' ~ fff fur , " akOO ol HOC- or I"''''''' ' . m",.
. n ~ h", - C- O
I
H , NC - . ux for
. and ,lin. lor a "'fl ;nt} ' am ine N$C
' , . This rule
prfll" " ' ''''-I II>< 'flC''1 r un' of :l-n"'tllyl:t.-hcU llUI (tigun: 4.21 should , ltow
1<" ;' 1", I"'uh at "',' : 73, U , anoJ !(II. ""ilh .. hunJ ."""" deccea..m, io the
orOO ~bo.m in F<l Ual"", 4.17. o,,;Ole a l", lha t the . -d ",wogc k"", of ""1 allq 1
~l<"'1' 1m HI "''''' $i~t a peak tn lito: CN IUI"'n<,lin8
sud! a~ ttl,'Z 29,
4,1, S7, '" (or ald t h}des o r ket" "C$, 3t, 4 ~, W, . " (or aloo hols ore1 lten, .. ,,<,I JO,
44, ~8. " . 101 ~", ;",,"I. (Sc'''li"" S,21
.'1>;"...
i"""""""
u ,
"
l*
I]I
_..
..,
""
..
' 00
.,
>
." .8 ? ~ {I""
fC,H,ClC,H,I==6+rl
"U'OI , IO%
14 ,17)
'.
f,...."U. 101 . .. "t"<" um ~r Im 1>uI,a.m"",
The "Yor",' hcl min~
dll~"'~ 10= pm'idl by the nilro~n '.Qlll~ ol..nm n

abilil}' rna. "" ,t.... ..."lta va ~e Ieacti"n J mnilla nl in t ~ "!""'Ira of ali~hJtlC MlillC., T he t>nly "'81<>~P' in rl"l.hutl lamine a: "'"1." yls., 3"d th i, 10"'
yield. t l>o; majo. peal of lhe !"".'rum (Figur e 4.~ ~ II>... represent s SS':-; or all
LOll' ""I I.-.:ted. Th cr< ~rc (..." 3-melhyl, and r..... . bydI<1le,,, in dieth) lJ millo
(F i ~ u " 4.4t mdh~l l o ss i' . till d'lfn iTUlnt, )'idd ", ~ Y1; ~ ,orIll. lolal ion. , "". 6~.~ rOT ~ ... of II (the large mi " )(l p".k .. ,ti""u."''' In S..,lion 4. W~ For UDhranrtied all yl;I[ninc, (R N H , . R = C:H., to G 1.H 1.1. to" mi. JO is Ihe
.bundant ion I ii., ,.,pla"",meDI ur . l","n\lnal h}'dro w;n >h"" ill dod....,,"" by a ll
d , ,,, ~\in g
/''''''1_
.,
sa
- --.
..
_.,., ~-_.. .
"'Ii""
'.4. M~" ,pc"'um '"
olCth yh,m;OI:
ami" e grollp cause, the profound , peeua! change Ihown
b.tw~~n
FIgures 3.2
and J,16
Te' l your undeN an ding of the," . " ncoph with L' " klloW nl 4 4 to 4~ . wllkh
Hre 'pectra of i, omeric C. H 11:\ alk ylam ine,.
Unk"",," 4.-4 10 U
~.
"
,"
"
....."
"
"n
n
n
"
.. ..
.."" .."""
".
""
.
...."" ."""
.,
"
.,
"
.,..
..
",
..
... .,.."
'.~
er
' 00
o.
2 .~
..
"
..
..
."
lOt.....'"
..
."
""
..
""
.
.."
"..
"
...."
"""
"..
"
.." ..".. "...,...,.,
"
"ae
00
"
"
"""
""ee
""
"
"
.~
"
.~
"
"
""
"
'00
4,' . _ "'''"00 ,,_ _ ,
"
""kno""' ,
'OIl..,
,
!
I
<
.j
"
,.,
_
~
....
,.-
iI
"
.."
ij
, ..,1,
'.
-.
,
I I, 1
"". . ...nU
,~
,f .-j
I
~
1.,;j
,,"
~
"
f]:
LL
, ~
f' irs! .. nlc J ""in ,,,- ~ il'hl pOlsihlc am,.l\tS ol mol" uL.. ",,-~ ght B , 5",rt ,"' jlh the
four 'p"clra l b a l I> c a base ,...." k al
' x; " hoch ot your str lKtuJCSlIilll ' h""
;, tcady I",. "r 15" (Thu.. ",lu ch hoye un , no<lhyl l" M I" !l y , ... . hoo ld ha ..
.',i,
' _
00
".'
I h~ ~[>eCtr" of II"" <of II..", a,. Fi ~ '1T"' 4.3 01><1 ~.~, TIl<: nther i' om m C'
C. Am inel (If II nh" ' '' nf 4.4 th '-(lHgh 4, ~ oonra in \I>c rcma inilll: Ih' ''''
, -mc thyl"m "",, : y<i in on)) l" " i, ma " 5 ~ thoe hit ", Itatg. , tJ I"';LI< . Whv7 n ils
r ossiNe mo l""uJat ,\r~cmre,.
, hOLLld br ob~lo", fn m '
T" ao;;jU1 "'u<lur. ' to Unk u ~ ...n, 4,04 l hr oll ~h 4 ,~ , tt l' puJidin<1 ,1>0 m"j or
i<on< in tM
or a ll l h" ;,olnl',k C. alk ylam ine>. TI>c ' ,,",,' ru m of <one
'SOm er;, no[ ind uded in t hese un ln" " ,ns , Wh ich "nc"
'il"
'>""i',,
4.7 Ch.'--'M Inll l.tla n (I"d",,!lve
Fq ua l"_ 4. 18 In 4.2 1 ' U1nmal itt [he

Uio.cusserl '" lhi. , eclio n,
OE "
,,'
1I - ' ~ -fI
,
,F
R~
R-'-Y=CH,
'h" oaiUio' .. [M "M Uffl 1984)
44 18)
-'-
"OJ .' I,'('m", pair.
(4. 1~)
14.10)
(4,21)
V= CH,
aU,,, ,,i,,,,
'''acl",n ~J lh. po , ili ,'c ch a' F LO)'OJ-'C,

The [,""oc'''' y fo, ' be lilfmatior' of 1\ ' fm rn RY is:
tr",ial Lo n of " d ,'u ,'u!!"
uf
A---(;,----y
VH"
R' +
'1
~ . \. r ol y l lC
(-)-")
r-:
".... ~_,
h ~ lo
tM' " 0, S ~'~, C. f' lf d em. nt ' of 'he ""m. /'010' of , 1>c ptriodic table ' hi,
tend ency .... ' a lk l> ,he illd lLet i" o elfuc[ (" of 'I, H o",nt l'. lt ~ bili uli".. of [,...
eh" ri:< i, 1L' '''MlIy mnrc im!"''' ' ''l ' .....n ' hal .,( Lhe unp a in:d ,i<...1 ton J;) , doter.
m;n" " fe'~ C1~m p'0 d llClS [Sc<;t;,." 4.1) in bolh th e forma lion and Ih" Jccompo_
sinon (Or ,he l"I'ocu, >or; hcoou,", \ J..", hel,ro ly\ic .-It a\ 'ilfC'> Tt."le' fe' mj ~ ", 'i(,"
l~~ """,,rg,\ lhe) " Ie !!': nc nl Uy I~" /w,,,,,J Ih. "
1. rtnct ionl,
O , ygen i , in lc, ,, ledJat. in it- ~h dlly 10 in!h.c....-c .,1"'" ~ o r i rc :-1 ,,," ,,- In ;on
,11Ip h" ' ie et he ' ,'ll'~' Itm, "r all . I:lr<> o I... i. inil~'l ed b ) ' t he l o<~IiH4 p<><ili"<
<h~ rl'<' 0<, d t. O' )!'-'Tl '~ll fo r m t he ,,1\ ),' ion and 11>c al k"A~'l to d icaL in
Cnse
[he ( Il;org< , i'e .. mo ved (Fq wru <>" 4,12: ",e F i" ur. 3.9). l>;" ", [h~ 1 Iii< h Ol1 d
c1ca,,,.,J l it CH, - () )(J ;' _,..I l h.l ,1ca vt<t by thc ' 'loIl ical-sile inilia t;o[[
"r
'.1<1''''''....
,h"
es
CA ' oc....
(4.12 )
..
CH, C H, C H,----et<,----Gl
(CH,),.Ctf-CH,---c.
--, ,-
t"'-----t<Clf ' .
-'..
("'-
rlCl)
"
C,H,," , C, H,'
(4.23)
~
C, I-Io" ,
,~
C,H,
,., ,-
i4.24,
t il " 1 ( H, - -OK Eq ua tion 4, 13\, Th e I fa~tl o n
j , .1", ~,,,,,po:lili.e for 1nIl"~'

"'lr oallla,,", al~)'l iodi de" , c"ondacy and lorhary . 1< >'1 bron,ides. aDd Terti a.)
alk yl chl".;"k, _ hul nol for Re B, Y ro ml'OuM S of h'J"" C- Y hor><i
...",n~l h .. " ,eh a, llnb, allched alk""" I, a,," al k )" chlon d<o.; for IlleSt
[ , ~ - H Yj ' -l " [1 M
YI ' J " , ;n ~_ 'l illlt;', n n 1_ ~ "Ofl 4.9) A. i, ex
ro;o;l. ; u",,,,-: . h ~ lou at C H.C1 is
mu,h large r in F~ua(j Qn .H t ha n in 4.li.
Tni , , "ad i< m will "ot d ..., ., a m ultIple 1>oDd ,,, a 1>; 1 <T ' ''' l,~n , roor the c-a ,!>on}'] ~j O UP IEqu.hoo 4.2 S~ d ,,<:c mn-Jl'U' ~m a cl i~ 1l to the c h~rl!t' site yield'
the canon; , _1 ' .....'n;ln"" ", ,,,,,, lIt<:; ;"d lJC1 i ,~ c1ea\'a~ or thi$ then ~ ;'c, lh<: a lkyl
ion and aql radl,>~l H....."e\"er. l bC'><' prOO"ds "'" 1he "","pl"m"",, of <he alkyl
rodical and aeylia m i" n r",,,,,,,, hy 2-clcavage (l'qU aliOll 4,14), ;1' . on t, u" I" Ihc
,j- . n,l ;."'..1'..... Il ~ "" I ;on' 4,1) &nc kclOn,..
1" oJ",w j" ur maj or iom Fmlll clea\'J~e or the t ...o bond. l" the ""m.m yl ~ m u"
the I;\>'ored Heyburn ;" n ,"oL11d be o.hc " ....' f"'mN l!m' uV! 10M 01 the largot
oll yl ~wup , " nd Iho Fav ored ,a rboniuon j"n Ih ould be the mor e st"hle one.
ltllkn"w lls 4.9 and 4.10 'I e the l(>eCtla <Ii ,l- pcnlan, ,,,,, an<! 1.mclh)' I. 2.
bLllan" nc; whic" i, ",l1io"')
,I
j
_-
.,- _ .. _..
..... ....
, "1
,!
i,~.~J~
-'" ...
""
""
.-
1., i,..
r....
f""
"
"r....
EnH:/ec.l" '" " ,.." . " , d""",,;at in Sec,;".. 4.4. ,""

d e<." ",,,,"'; ' i,,n
F E ' i"n )'ield. "~"' '''T FF ' i"" lUId ;a m<>lc<;,,1e ~. the ne" t,al prodUCt F'rod lJCt
mo lec u..... o r Iu,., 1''''''''' affinit y a t<: f " n:J., . " ,h ", l hooc '" fq u~"<'0 1 4.2l>
4.111 U'A = 1.4. 6,2. a lld 1.2 t V. .....p. ':tl vely, r ,eld ', Il ule.
4~ !-,!u.8 I" ,n.
4.26 and . are I.. ",..,.",p I"' l h"""l"' fu t r" ...." ..s Ihe 'an,. I'I<'duCt1 prod ,O<! b y
Snol,,'"..
Eqlla' ;"'" 4,22 a nd 4.25. ""'f'C'-'t,,<:I, _ H " w~ Y<:r, 1M""
" ""blo:; by 0 ,<
:t<C "'' '':fg<;II""lIy !<M I.

0.8 ,, ~. (20 g(l H . moli iha ll l!lei. " n....Top oo unt erpam .
~~
~
,=
\ w
,~
- R'
'".
-, , -'-
-, - ,f<
~
~~
'",0
-- ,-.
, ,-.
-
,-
IU t.)
'0
(4,17,
. ,0
\ 4. ~ ~,
The injlial jon, prod llced h;' chen,;c..' j"nj,,,Ii,," (0) " re ma inly fE ' IOnl
' uch ", MH + ""d (M Hj": other ' Ofl ion;",,';o.. mcll"" b , ud ' a. r''' '-at"...
lx, ,,,b",J lIJe,,1 call ,,1>0 PlOO lLC'C " ... 10 .hLL..d a n l F.F + in... (.SO<ti on 6. 1). Fo r
d ecompo ,;lio", of t he M H + io n (Equat ion 4,28), the I",,, o r ",olc ~"J e, o f lowe r
p ro to" arfmily (Table ,0,..1) i, ~ . n e ra ll y mOT'< f;l>OT;, Ne (F ield ', Rule , Stolio u
4.4). The EI m" " 'Jl<'ct,u m of ephod ,;"" (f:ign rc " 5) , ho w, n" mo lwullir
iun: tOe 'f'C.lrum i, '0 domin" ted by the ~-cle" V"jl.O renctio n Ic. dm g to
CIl ,N +II=CHC lI , (m /: 5~) ' h I th e'e a, . only "'cok peaks ind icati ve of tM
rc' l ,,[ t h. rn"kc uk H OWCW[, tile CI ' pec tr u m tFigu re 4. ~) ha, . hu nd8nl ion,
at m/~ 1M , MH ' _ indi ca ';ng lOe nm l""ul"t wci~h t, ;md al 148. (M + 11 _
H 2 0 )' , Th. btleL for me d by indueli~o cleavage (tquali,,"" 2 ~~ lhLl' ;Tl<Ii""w,
lh e presence or the hy,lnn yl ~I<l U P, Dc,pite lhe 10w. [ l.nd.ncy for eharge ~ i l '
~ .
~1
i
I
"j
',
- --- "
. .1
, ,
I '
if? ,-
>, ,,",, ,
~
"
.. '.
" ,~
,.I "
~I
"
, ",,
"
,.
'
-t
-.~ ," ."~,~;,_,,~,;,_:,~ , JJ.'

-j "J
.... :II>
._
'"
..
U . Eht _ inouza""".ad
OIl
' lD
.,.
.....iDll..... 10 1.
,on
~_"""'I m-.
""'"'_ of
"rod""'"
ono.1 ..- of tb~ ~m,""
J[r..... p.. , he rno..H p... l

,ro ,..., a . poc1......1
_ : 1) 5 11-<1""00.. ... 291 ;.. ..:ry ,.:1.11. IlnaI It m.kates 1_ /11--00) 1 f.rOIIp.
"."'" IN t the ~'ft<1O " " loa. 04 H ,0
II . " CI-I , Iollo-n Fitld", .~
IPA ~ 1.1 ' 00 '1.4. "", pa:ti~el ~ ~
Il" bra
~ "'"""'tiool of an " )0:' rtUd
...1. ;., .., hJp.hIy <k~ "" 'u "' . bibt, . i1. f..nber <to,oo<;i:Mi<", ;" '0 ~bIc
('<'..t1lCf$ oftw ...........iLo' fi ",bR_i ;ol ,ta"JalI~"""'"
fr.I.I"'C"laUOI1
.......,1. f,om I ~ C ch. 'P' .,le tur._ l ~ ChaP'"" ~ t
.i,...
........
,..
c....-<.>ot---Q< "'.-"-#< ..p<,
---L- 4tl.~+ ~".

\4 2'>1
. , _ _. . . w .. ... . '
In U uk _ n ~ . II 1'" ""0 1_10 ptIl k ... ~ 1'" d t mtm al <Oln...."'il "rn C,H,.( )
1'" abo>t mO'd>ani, m, in tl"cidal;DK1'" "roeWre of IbIS molec ult, (I I ",,.
l'l>e molecula r i"" ,nfnrmal;nn f,...... T a... l. A.4 is ab." 'al.......I"-I
U~
.... .. "
_~
,~
"
so
"
"
"
"ra
"
,m
'"
"
"""
"
..
,oo
"0'
..,.
ea
"
"
as
..
-.
"
..
_ ._---
"
,.
' OO
"""
"
"0'
0'
0'
2.1
cJt .Q
4.' De<:orIlpou*GflU ofeydc a _ ....

The cle a,' a~e of Iwo bond. in a rin K ;' n=,",,'1' 1" [1 Ktuu:: a. r....@mcn. ioo
IE,! U-a, ion 4, .\(1~ Clea."a.gc of o ne " u nJ """',..,. nu ,'hallt<" in
pr od 1Jci n ~
.lI3."'"
.zs.:
C (;
.,"
--'--
o,'u ~
--'--
.
,
l--.
oWz !l'l>
j O lll
" nil' a. di , I,,,,i< r:wi",,1in n (RaJom ~I al. 1 9 ~ ( . <:O m", and McI .,.ITc, ' )' , ~ 7 ' 1- "'"'"
with a J r"woec bet,,'een ie, radical alld c ha r ~ e >lIe> , The unpaired tlec1ro n in
Ihi, i,ome ric ;on i, doo med 10 for m a new bond to the adj. cent caroo n .I o ,, ~
.0 0 _ 0
i _d
.~
..
,..
t .JLj,tL
"'" 20
.,
..
""
. ..... ' .1. M",. , p.,", u,n ."

")'< Ioht"' n.
"..it h con,~"";' a n l cleavago a no' '''", bond to thaI ZrC.1<OOn. Ah~"ug h t he

r:tdica l -';le hal Ino" ed. the " n~," al c)'d ic na illre ca ule\ llu, In',m,' M nd ~ l ea" a# 1<l place th. unpllired ele<lro>n on lh. chargM ll~ " nl>proo ucins "n ,>dd. /'. 1' '' " ion. T ht ma. ~rum "I cyd " lItxane i, , h " ill Fig",. 4. ~ (...,., al..,
H gure 3.6), ,,"Ptc I....t ,he importa nt O F ' ion C. II, ' ('~i: 56) ha, 111<. m....'
h;' d l' O ~C '" (S<Jcl;,,,, ) ,4) ~I . ny " on.i, ol;."", C . H : inn.
N"'j) ~/p.AiJ<y (Ma nddba.... 1'Ilt .':. 'r llk and Ho_
l~ ~ In cyd ohc,ene ,t.; ,,<:I.ctr ons p lO , ~ k a fa . ~ , e d , ito lor the initi al ch.u;e anJ radi cal
(1'" .... ,i,"I 4 31), Donati"" " I Ihis unpaired . k:""" prt>du......-,; a di,t" llle radicl
iCll\ "", mOl" by ~.., lca..l ~ a _ ond >!Ie h reocri"" d,mina,e, neutr al C 1H. NOle
Ihm the " Ih", prod oct n i" ni, . d U-bu tad ~:pc> ... !~ . t thi, corr c""l" or>ds 10 a
'"t ", .Dicl , .~ l<Ior ,."d ion . In re"~t il)'" )",ldilll an UI: ' product, lilt .. "bili.~.
tion of the unpaired electro n a, \0<:11"' the charge i , an In' j'IOl"lap, d, i"ing r<l=~
n"te t...., h"th of thos" a rc moch
slObllizcd in tho iou prod","" "I Equat ion
~J l ' han in t~"t "f " n 'ragn"'nt~ti on tcllCiions, Ihe l'\:" " . () i, I, -Aldo,
,t~"""'''' will b< iml'''',a,, ' ouly' il no l" c!t ll ble frarncnta liO!,! dre P'J'S"Mc.
Th" l the ",h11' ;,,,, of a fUl'Icti,mal gro up Can " .am.tl lically red,,,,, the abnndan cc " I kim from lhi, ' . action. Con, cr"dy . funcliona] g""'l"S ' hal can
01 tlx rin" ..u ylir bond, la m, tilt reuo- f)t . l..AI<k,
pro mO(e d ... . al'" "f
reacti. ... I ..uTeak and Hanu' I '>!l~ ~ Un!",,,,,,n, ;ol, , he struel nn:. a nd ' pe<1ra, an ,l j ",,' ily
) '0'" clt" icc.
""Itt,
""y'
,.. . . _, ,.. _0"
\ClJ'l,' lOO"4l
"'.,. ~ R . H, _
( 1 . ~l)R . CsH>.O
......
IhH , (1t' . I O ~ I , d %
R
. ~,
(iE
.t
41, 100%
"""",,w ,. .
"
i '""1
"
:I
,. ,... '...
,, ,
,
' 00
Unknow" ' .13
."
,.
,,.. ,.
4.00 "
"
'_'" _ _
....,...
'.j
o"'1tI
t:
l"l_.
:
,, 2'
,:jJ
"
C. arK~ migrali"". Tht final ~I~ P oJ Eq I" " 0l14,31 i. , I.own a, a hnmnlyt;" hOlld
cleavage, with ead of
", p.o '~l i ng frapocll" rt ,aining OIl< of the electr ons.
HQw",'el', heterclylic cl<a>. ~ t " I iJ I ll<> l'O'l,i blc (FGualio n 4..121- mm'ing It..
po,it i,'e cha rge 10 prod _ ' he i",.;;.,<1 al ~ " n e ( H ~U T C 4.8). In the tr an. ilion il l t.
Ihe .:tIl """ ~d olefin a,., rompt'n n, r~ r an .leetron; according to "St,'-'I"'" "
Ita l ~" ,he produ<:1 mon li~.ly 10 10M tht electro n is ,he one ",';In ,fo<, w..~ 1
io.>nil.3110n . n.rn. llE, T;<blc ,' d} T he!' ftl" It _ H. 1M ionization of bula<!ltnt
... f. '~""d "ve' ,"" , or <lil y ~"". However. for R -" pIl. nyL the "",ulling .1 1~
j,m "'''uld he fa ,ored. If til< IE ""lu e, an .'m,j"., tK~~ i"", "'"uld be 1"""'''1.
lO<'k 101 OOIh, uot. t ~,, 1 the ma " , um "f t""'" '."mpl......" Iary DE" ;,,"";,
c~ .. i,~l"n "" til<: moiecLLiar weight.
t""
v",",,"'"
4. / 4. ton;, ati" " from u ""u b(llod m~ d lT"n ",tn,,,1 can ahw
"iggel ' " ch ring fl'agmemutio n.. I' rodict an a loundan l " ,ld ,clc>clrO<l fragm ent
ion in th~ mall I ptctru rn "I p-<li" u nc,
.,
_.,-_.,_... _. _---
'lite", a re a l'" im!",,'. " ' ""'' '' 'f'<" u,,1 r....~li"n ... h :h r" ~I ..,:,, ,<on, .. h"""
. !Dms h..,c nof rel. ,,>1 the OOnll<'<'(;\'lt y ",tallo",h,p'" of rM ...rr~,na l m" lu!e;
r " f1 or ,1>c 1' 1,:<,; ut~J r ion ha. ruo"l';,J with ~ 1I0t h.l r art I:>efOrl (>f d u nll ~ dK<'mpo ' ition. s..'!tl<'t i,,,,,, ,,,,,h rear... n!",,\em, . re .... ". "....-i ....' ,h., Ih., ," . ~e the
prod\lct '<:In u..l<"" Co. m ,,1<ad i ll~1 for ded\l<'in ~ steucuee; IU' h ~random' rearrangement, ~ r" ,...' mmon who,....o n_( and '''f1",I ;m~. ~ _ I "'nllaIiUn .. 1ll;<>;"l'Uly
F"r"' n Ol.I~'. man~' "" "" "i<''''e"" {...." ul ~~' ""'.." of ">P<"'f"'" ","'halli'ln'
",f,;en a rc " m'" "'ell urK!et>\'K>J, .nd I n~...., p,.."Ia.;t ;<>n' ;lft rh u> 'a1ua t>k for
deducing mu clnr. 1I)'d w~e tl. tom realU ntnnem, 'nai al od >I a r.di~J I Iii.,
lOC mai n .,ub;",,\
hi, = \i,,'l , " rc a n 1mP<'rt"nt d ill Sof re,,'tiMI eth lbltfd t,~
a ..'ide ,'arj ol}' "[""\I\-'1LL'O. A, with 01 ', - [,,'mo',,'" from . cye'li<: m'.......... I" c
ion. the initial , o. l rangemem pr ool,cf il a dm oni' radI cal ion (IInmmen'm
"f,
19S5)
,..H rr" " " tWemn tr l<>.~ ~~" .f~r.fe4 1C"JMp ",il~ 1-..t'.'"J" An unpnJfed tltct>c d"naled I" f"rm " new b"n,1 I" lin "'\.i llC"11t atom IhW\ll:h
In m can
' pace: as in Eq ua lio n 4,14, the sec<>nd tl""ll'on of fhi. JXI ir I, , upplied by tran , fer
f", m ,m"l hcr h" nd to thi, ",tj .",m "tom, r ~, ult inl: ill its d e,w age rEquatloll
4.33). rlanerin gly. this i' u ,u all ~' relocrcd 10 ""' Ih" MMc L..Il l'n y n;"rc"n gcmC"I"
1\-lcLofTerl y 1956. 1959: King' tm, "I "/. 1974; T urc~c k d " I. 1'Nf1. ) ~ llr
pound s containing an unsat ur ated fUnCllOna ll1y sucl> u the carb<ln)'1 gr oup,
the :-,.h)'dmgcn a lom i, 'ram fetr"d hy "" , leric. lll r" vlJr.hlc " m~mt>cn~l.d~ ~
tran'itiml , lal e. nowever. in lhil prore" the initial clt avagt d~ 1 net le' ull In
"1,,,
c,,,,,
~~ "'~ '
"1
~,~
R . C ~ .. ~ o-..
IIE .e 1e V) A . ~~
m'z5a,
"U
14.3 ; )
-"-I:-~
Fl MC>1>I IE . &.7). s,-.

"' . ~
j<Nryo ...-_"i
III! ~ , 10Q'Jl,
(434)
4,' ....... _ _..., "'. ...
llle I"" "r pa,' " r ' nc inn. nut only in a cb. nge in lhe posinon of ll>t radical ..",
10 form tl~ i'omeric d i'IO ll i~ rad ical Ion. Th e JK'" lud"",, 1,i lc <;;tn nm.' inilial.
"ll ~-de,,,'a~c "'"ction rc, U1\ing in rcalC"'cnlali"n ,,( I ~ . ea rbon-a rbon t>ond
wbicn i, b<o,a ' 0 , I" cali" ,";'1 gro up wnh loss of an o kfl ~ or 01"'" "'itbt<:
mol ecule to ror m llle od d-ele<:lrO\l
an 0 1" ;,. r..rrncd hoaou.. Two
hood' arc ek. ,'cd ' n clTc-t:t rn b"" cnl ~l i ".., in M ' in Ill;" relrra n,,"""'l "'~cl1""
(Table4, 11
Part of thc dri ..i\1 ~ forc" r"c the ro n.( -t<:r ~ , H , j" r , ,, . idod b~ lhe (O(III.1I1('1n of
lOC ex',erncl)' "rong O -H ~)nd ,,'Iul-'/, m a~ ei 11.. dislOni<: intermedi" lc m.,1'\;
"able Ihan the ori~in"1 ketone ion. I'"n 01 Ihc <" i > in~
lhe se.:on;! ' 1q>
i' the "'ilOll"nCC " d ,;l;' ali" n nf the ra;!<.:.at <il e ill the proo llCl , 00. . 'bleb io
i,,,,,leelTOnic "'ith th. allyl ra;!ical (..,., Henu " b \ 'l ~ ~). Nole 1h;,1 Ihi. '"l ui,,,,,
/i-bo nd cka ,'age in the ",,"' nd , cac ti" " '<1>;p, "nd lhu' n~.n &lC$ , 11 tt~ M!"
IU prod "'" t he , cac, i>e inl1.'1"rtIC<li.o.",.
S och 4~dNf.en = rr angernonl tmo ullh a ... . m ~"""'-..ed. , ml.' ;n le, me<!lale
~'i.ld , ,'h."<utt,,./<tk'o 01"
i<"" 1M u " ,d~ r:urio:IJ l>j ~"" ",,,,, ,,, d J~ ,"" lhM I
~""' I'" ".,,~ ~,akk h)des. l ....o ne< \Fi &ures 3.10 :md 3.\
''' 'e ro , ~"illl"''' 3 I l
10 J, 15 ~ acid. (F if:ure 3. l 7). am.del; (rigme> 3, I'I ~,..J 3. 2Cl~ ca'bon~ ' ell, phosph"n;lt<><. . ulfit"" l ctiminc.. o ..md., hldr.orono< IEqnation 4, J ~ \' u l ~ ,,'e,.
~I k ylll.
.... and p1k-n)Lall a.l<S , E'IUalion 4. :16;
F i~ urr 3- 7~
i,,".
f,,,,,, f,,,.
'
, I'"''''''
--(J
e 01,
} '-"' .......
"
(4 J ~)
(mi. 85 l OO''\'1 90'0>
"
c~'cCb
,"'
'"
H .
"""
1'_'1;'
( 06)
"
(rna
9 1 100'l(0)
ma
92,
60%
V"lJk' ,,"" 4,l j , Wh ~l is Ihe mas. 01 the .h" ract"ri. he O E ion {ut io n"
which willbe Iorrned by lnis , i., ."",m bcn.:ri., ;nt H ",arr a"&emml (rom u dl of
toc roll"",--;n.. :1.1 " :
"
. !
,""'
" ' --
C H,CH~ >1z C(C H,} _. C H ,-
o
II
C" ,cH, OCOCK, CH,
L'"k""wn., 4. 11i and 4.17 The ", actO the ' JX-..:l ra of :l- and 4-melh}1-2I"' n l. n,, ~c;
which i, which?
Unk n. ..n 4.1'
I
j
100M'
"
'00
U"knowo 4.17
'00
f
i
"
"
n
, , i , ,
." I
"
pea"'
,~,
I,
' 00
Note thaI Ih..e j", m. r< ",-0<1""" the ",,,ne

h} ~ ~ H a go 1"' /' 4J ~nd
on<,! hy H:leo- age (",.it 15 a lld H ~ wh ere.. tile /I-cloang< r . " r r~n~",m c"l
mol es ;! pos,ible !<:> di, t i" Ku ,f<h oc\"''''''' tho i.. nnc.... by c h rocl e<;<;ng til<: ' ub>l;\""nl, " n tho ~'f'<"'l; o n_ T1Ic ' e" d ency for re~ ,r ,""" me ll t ;, great"" !()[ hy(tru~1I Oil brand.N . all l1ic. OXygOll, Of o t1>e< labile
~ }j
"t"...
.. _-_._.--
"
L....nown 4,18, Docs an i''' TX''' a" L"d d ..,lool"''' jon aid in It>. "" lulio n <>1 II>...
un hu,w'n"
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C har"e '"'8"'u ,,0 ca n al'" '-',;,,,,, ( E~ua Li "n 4 .14) rIt II" d", <OCia, I",. 'un";
. ,..... ..a',,- I h" ...,.., a l i n ~ pmducb call co mpete fo, the ionic
p.al:ltl1d in g
" u" r l"'''''f>la,)' DE" Ion formalio ll ;n ri n ~ ~I"" V.!!,=, (SN;ti.... 4 8J. The
r.n o l'(l(j ion p"'d",1 , hu"l,l ,,,i,e fro'" lil e fragmen, of Io..er lOnlLObon encrJl)'
II '"l I" "" ,,n.. ,n, Rule)_ Allhough th. opeet! um 0( 4 m e ' ''~ 1 " 2 - f'C111an m", fUn"
k.......n 4 16) show, 30'.\: of tho rca rran ~'Cmcn' r "'d....~ C H ,= CII( OllfC H, (m,"'-; ~8, I F. = 8,1 oV), fa, l , e.le, am ount IU " ,ha l'" , '''' ct>m pk mcnla, )'
{\H , (If. _ Q.1 oV I. ' ub<ti!ulIo-ll o f ... 5- phe ll ~ 1 iFi, ,,." 4,\1) "" cr"", lhi,.
)'i.l ding 100')' ('oH ,C H CH, ' (miz 104. no _ R4 t V ~ The 'peen" m "f
C,H ,COO C, H, , l,~ "", LC,H,CO O H+] \l E _ 10,2 evt [C, H. " I (I F. - 10,5
cV). ",hcroa' LhOlot of C,It,CQ(X, H, 1 ~- OJ i .. .. ~ , h" "" [C., H. " ] (I ii _ ~,1
,V) :> [C,H ,( "OO H ' J Allh" uth l h ~ cha, g< ten tion O F" " ",d ud ha>
gained an H ~, nm ,n lilt rta "an~eme nt, 1M ch a,~c miK,,,t;,,n Ill> " I"rciduct has
{o ,, , a It)' d rog e~ ;' h u ' the 101m" ,",u.ll) has t he mo't" alom , in ils pt.ok iJ O ~" .
'h"
"".'1"'"
.,....
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M." , pee" " ", or l-phm yl-2-pcnlano nc.
hLlL Iho l. lL<:r rn~} h ~ ,. . " ". b ' _Again, the , ,,rn or the;,. complementary rna,,",
cq"all that 0[ \1 ': in Figure 4,9, j ~ + \04 ... 161.
to .. _. atJl,u f~d hd<rnat",n ...i th QJj~,'"nt ('/0"'"/('. Even

if nt' "~ 'a l U ral"d fun<l; Ma l; \y i' pro" en!' ' '' eh all int ramolecular H transIer ",m
allo ta k~ pl.1ce to an jun;a l ra~i ,, ~l ,i l. on ~ ,,,t~ ral c d h"tcro ~l () m _ ' uch a<
Equ"t i(>11 4..\7
A$<lin. tl~ ullp"ir<d electlon is donmed to form a lIe w bo nd to a n adj"""m
HJ"'''OR ' ~ .",,,,g~~ . ,., . n.
(' " 1I 1'p ro pn " ,c ", m l", rna li" ns) H a lOm. wil h L" nc " mita n l d CHag c ul . no l he r
" ~-'--'
U
+
HQH"
mlz 18 , <3.,.
/4,311
. . ...",. 101.. _ '..

_._~
"
00 00 t<J I~ ~ t hvd rogcn. Howe''Cr, a """'''d radical- ,, '~ "'ac ti" " i' not f. "o.ed,
,inoc , w bd lZ.)u <>II of t ~e unpaired elu o n ;n I ~ c ",,><J ut l -CH.CH , 0 ' H , .. Il(I
belt'" ,.... 0 l"" t I" the imermedi" ,c ( ' H ,K llo I, O ' H, _ l,, 'l<:.J. ~ charSe--511C
""",li" " is HOW po.. ib k . fmmin~ i" ' hi, C<' $C 111 . (M - H , 0 ," P<" ~ by '*"'>~~
"f a bond to the hc t,-",aWftL (Wal 1...., i ' m uch mar< fa'ftr~ hIc f.... pr im a ry
" k" h ,-~ , lhall [", >a.'O<oda l)". ~nd U )'JI'<:la lly marc Iha n f'" , ~ rum y . !co h,, !,
hcoau, e of tho illCrCOWn!l comp<tition with ~ . d o ..at.e.l
fun hc r " hafl!C"'I~ ffil cIJ<>", ",in giyc >eco"dary pTod<><1. b )' d ea OJlle of.
n.m<i tha t is two o. "' Ote I,,,nd, furlh er from ' ~e beluoatom (Eq"a' ;" n 4 3 ~~
I'he prod u,*, 1" ..... <1 ~ ,t not 8 r<all~' affoc<c<l by .. hieh hydrogen ;, \ r ~n lleffl
ill (he ro,., '1"1' (a , Ix-moml;>cred.ting ; "termedl at~ i , n" t requlredt f u rt"cr. the
rL... uJ,,"g bel. ra . ' <>m-c"n tain ;,, ~ fl ~f"'C"1 ;.. "' turated. Jlld '" "ompct.... lm
-0 1"" the ChaT!!' ITa ble A. )~ m ~ ~ ;n~ charge migration lI''l ual i""" 4,:J&, 4.40)
"' ''cl> 1M I'e COmm on. 11>< cl> ~'Se nll$,a tJO ll rcacl;"n fa,'()1'1 tlr<:t ronc ~a li,'c 'fl< -
"
H.;:C-C-O
fIa'll" ............., )
(4..19)
.
---J "-<1
C.,H.
- ~
v
I..::'J. "XI"'I
(ctwgo. ~ '~_I
(U O)
cieo;
.. ru ra1<,t1 m"le<;ules of hjghc< ~ . n """ ; u ~ en"'i ), and I",... ploton

II a ble A.J' , uch '" H, 0 . ( -, H. (....-ond 510p "f l'.~ u~lj o " 4,3g\ CH .O H.
H,s. lIct at><! HIlr aIT "o"'1nonly lQl.t m th i-; ...'U)' (found iD f l ~\U "" l .8.l.W.
3.21,3.23. "00 _'.24, b ut not 3.1 t.~ h ". ch a rge ret en llon thc "'-'U'f>d step in 51 0.,,1
;n> olvL" r~ J ic . I- ,it e r<<<<tw n ' hot;" nll",h rna , " fam eanl. ,f It prmid"" "aniI;
,al ion of tho lln p a;l<.-..I d"Clro u 'E 'I U "I~Jn 4..19 ""rsus 4 ,31< The *"'Ih,.... ffect..
",,,clinn (E~u " ti o " 4.4 0 ;Jl\hcal;,'" or aroma!i. riD!: po..;l;"n muir. t'r<>m a
""m b in a tlon of ~ Illl:>ilc hy<irogen a;'"Ii<'hk l" r rearrangeme nt lind a "able ion
prod uct fro m chargo m igr at io n ,
I ma. ~
.ni n't~
., "'~---"-"-'--'
-'"
,
(44 1)
if
l,i.. k.. ,. .... 4.N invo l"C. ""me imp. orlUI 1"';"1' Ihal have ken ""w....... p"'" .
<m , ly. Fl<: "" e Y" " .. ,,<lo:I>14 nd ;l' ......';on belOit 1,.......-..Ii" 1I- 111<: "1 ~i l y of l h
....i ..... 5 f"'.. L r<>rmed b)" rneu., able ','n ,\<." ""","'U"" ..,11 be <llSe,, ",'''1 m
Soc1w" 10
"',11
fJi.,.l~u_ U<lcrU....." .J. (lnl} l><iri ~ n l;Oll

be mil<l e here 01 "II<' " r
"",,,,..I lyl"'" nf """hydrot.en ua rmnl:en~l l' . ..... e;.",-.i,'Il ~ .I 11 1 T,." ,ll" m, <or
~ro ul'" (o ~ u,,,,,Uy """ . i,,~ Ihe T"di"ll ';Ie) e,m re~1 lOu 3mo lecularl y: fo r m..'i"" ,Il !hi. no.:..' huRd 1$ a.:cotllP'l'Oltd b)" cl<',w, , ~
,.n,""" oo nd w
1M _ hI of th<-Jt &,Ollp>- ( ) -..i u nlio.m W"" nlio.m 4.42) I"
a di, .."'m chl,,,,' ",um io n with di<J1l.....-menl ,.. an ~ Ilyl po ul' &CCOlLnll 101 the \;\r(/'l'SI peak III
<he 'qICC1ra ' .... pp ropriaT. l-thlorl>- and l br o m o .~ k . ll ~ ' ( F' ~ ( ll C ' .1. 2.1, ~ , 2 4)
This redctlOil is m uch h..,... imp."'lan l in f>o-and ...lIl ~ al. ", l h .........nd rnr rUt1 Cli"nahh"" .... lh .. ml' h.... . len J ",,") for radlcal. ice ~ ."llOd. , Th e "" l ~S ~l-'t' <:t ro m
of .. -dOlieryl lTJe1'C;ill'lall (Tipme 3.l l) ,ho w, thoc r"lIo "' ; l'~ (:. H ,.>,S ' ; on~: .. ~
I. 2~~ (CH, su r""" ~ -.;lcan..'Ci; .. _ 2. ~ :;; .. _ .l. l ~~ : n _ ~ II ~; (fh emcm l-crud . ing); and n _ 5. r;, N oco tho ' imila' ~io n ..r ies" (So, tio n ~ .l ) ' 11
dodocylami"" (Tigm o J. l ~).
(}",
4. 1' C h.... g.-511e
r",,,,
0""
,4.421
re~rr~ngem en1s
E, ,,,,,,,,lccl' <1n acyclic io n decompo,i lioll< in which Ihe charl:O , ilo rolaln. ilS
~ ",at i "l1 and tho olO<:lf o m remain< paired. both of ,,'-hich al'O u.uall y M r.i , . ble
..
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froon an ~ncfll!C,ic ~"d"",ut. in volve r""IT~"I\L"mtnl (Se<:hOll 4.4), ik =u~ Tilt

.h. 11I" " ' e d" .... n<>l nlO"'. lhi\ . " " he l< lCII.<edon Itot~tr"ncgali v " fUOCllO""I
it-.. own . " ami"" N. an d m"Te~leootronq:.ol;-' < f"nC\~lnal itie ,,<h '" (1 ""n
''''''-0 wilh .,," """lral prooud lM<I.,.FIcr1) , 9H()b; King" "" <'f at. 1 911 l~ Ilt t<l
we ,",, 11 di"" u onl}' hydro~.u 'C;" r~hl"'nltll1 . for whi<h Ihi. "' ''C,Rm '" fa~(>fed
if I,,,, of a m "l ~ r; \l lc " I I" .., ptoton . llinl1 y i, in,,"h'ed; <:om"",n m."h~ n i , m
of th= p" " inJ. in>'ol>"" a l'J<>t"n. k<'ulld imOfmwi. tc I t - H' Z: Morroll
,9X2, Il" w~ n and William, 1%0: McAdoo 19S5. t The .... ullin. prod u. l inn'
can h" \'~ t hci < a,,'m_ ..crambl<d to a ""n fu.;~ g d~gr; lh' " tl>< , tTu<lural impli"'\lion' " I !k><: J'foOl' Cl ions mu,1 he ; nt"pA:l~ ..,l h ca ution . ll o.... n .t . tho;
F F ' ion ''''~JJan~""", nl 01 hyd ra~n 10 an unsacumted gro up ~o ntaln LTl g a

h<1.c:r.,., l mn ",; ,1> di mm ~ ,i , m "r ~" un" ,tuntl.d 11 . ,,1, "1, ~"n prov ide \'llluable
informalion. Th i. ,ea ction gi\'h th" ",",ond l a,g~" I"'ak in ,h""etrum or
dit.1h~lam",c. Fi~",c 4.4 (F'I"" hon 4.4}), Tile t,.ml liou-nate lize req ui"el on
em yl or
!'f" U" "" l he nit"'I!"n
lhi. '"" rt" ~ ll< n1 elll. T11 " , thi. nwction prorides a specua! dJStinclion bel" """ (("H, ,-, CN H , \ ~i gu," J. l),
((:H,j,(:H NHCH,. a"" ( ~ H ,e H,'ICH , I. IUnknowl1l 4.5 and 4.bl. Although
the ", 110 "", . 1"'"'1.... also . h_ a ""'" f"<ak "f (M - (H . I' by a-. k'''"ll':. l" oiT
" ./, 10
:u e m""l1 Io" e' 111 Ib.ll 01 (het l>~'Jam "le (.", te llw t h~ ' re Sh U
a Pflreci8hle. '10 Ih.al , ""... da la ", 1 he ulili,c" " " 11> ca u\kml.
".gcr
f,,,
"".d.
>Y='~
(U J )
V"l.lki.... t !O I' rodi<.1 the " "'''; f'ill "" ah in Ihc rna", """el r on, of
N ' IN t h) INiI.oprop~ INbuIyl.lmille.
r ven-elceu on '<>n_ ' a n " I.,. undc'co H rc..rr.n~n><"" ..hiel> do """ wvoive
, h hargo '''0 ("", a" un... lu'ated ....1C'''. lom~ _h ". ,c;Krion 4,44. Tl>e
r mtl ll n~ peaks s,h ould be- used ",jlll n "llO" lOr aW ~n Jn8 f.. nc:tj,m ~l group
locat ions,
h ow e ' ~ r' ll ot ~
~ ic h lv ", b u l ane
tlla l
(Figure 4.111)
c',,,,j,tJ ioni",fl ill" .
I~i:
55 is til. 00.", peak in h<>tb 1,3- and U -
Ilccau,," CI produce, ma inll' e"""-ctcctroll ions, for such

, ['Col' a it ;, "'1'';" Uy iml'Ortam Co reco gnize tha i r e " [n n~:m cn l i. "" mmon _
pla,e in EE+ di, ,,,,,ia liom (Ha rr iwn 199J; Kings.ton "t al. 19 83: eron,ble and
Ha" i, oD 1988). Alt hough 110 . , ite or CI """",," tio,, in a molecule . hould be
th dt or hig hc<l prol"n .ainit )'. Fi.ld-, Rule pred ict. that t"" neuleal k"l ...ill t...
that ol lo w", l PA valu,,; Illu' a" inili. lly r"rm<;,t ion H, N ' - tt - O H m ust
r ear r ange an H atom to lose H,0 (PA _ 7.7 e v j Imteod of NH J 11'' ' _ \1.1 c \' I
Figure J.,~ pro, ilk, an ",ample.
"
.,
!s
~.,
' 00_
L.
. 00
'- '
'OO
.!
K~"""It/(,,,,,,,,t uf ...u lIyw"l(' " .,""'" (t he MM cLo ffert}' I 1" t<:iIIU~ ~"MI i.
a ,,""[<!den , tic decom position (If
aml , ;m;"'t fun" , i"n" l ~ ro Uf"o thai a ll
"" ratioHIi' M 1!2q ualton 4.46) u.in~ a ,,,,,,rer of the 1<>00 h ) dl<'~~n by r,
moch. "i,m allnk'gou, \0 re actio n 4 .4.1. An :tct,kd ,If;Y,"!,, fu te" i, \he l" ..u na"..,
>1 al:>ili, al ion or f nc E F ' I'md uu ion ( Inn.'" 1>0,,<1. are cka,'Od ,n th" t'O"IKt Lon).
I, or propy1 . " d higher .,u's, a Olable aU}'lj" mdi"a l . an b< prod U>d; h O WC V~ f .
';gniroc.lnt C , H , an d C, H , 10.' ''''' 00<\l1 r",m Cln ) , an d i" ' I'"" yl ",1<:" to
pruduce ,-inyl ,adioal, _ AlthoLLgh thi, (M C.II , " , )- ion i. oflen rO'm<d in
relali , -.)y )0'" at>"ndanoo. ~."" , hould be a\>k; to, "-'C<' gni,,,,, it h om lh<: un " , " a l
rna,,,,, 27. 41. 55. clc.. 1",\ (Ta llie ....5) in it' for ma lio n. Th"
pro,jdes a useful cham"tori' tic or ..te,. (Figure, ~, 14 aDd ~. 1 5 ~ tni"" , t,-.-"
amide, (Figure 3,20\ phosp h. t". ( Fi ~"rc ~_ n ) . " 1>d C,'C1> ",Ifonc, (I(, SO " H g\Ire :l.n~ lhi, j , why ~..ou , h" " IJ mark importan t (M C.II , . , )- iom of o~y
gen. led compound . (Slep 4, Sta ndard J lllerp rciali nn Pmcedure)_Hc ,,"c>cr, I" r _
mation 01' the 0 c, ' pmdu<t hy ,in~ lc H ",~rt~n~emenl (c q u'liou 4.41) is ofte o
the domiuant proct "_
""en
.e_,,"ngrm.,,!
"
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,,. ,
', -," 0
( 1.
.... _..
'1
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4.1' Sum mar y 01 'Y1'" 01
,e ~c1 i o'"
"
mec"'" n.....
The . ~m"'ary imido; \l"K: bac ~ co' . r j,. intended to \lnd"T "" <>~ the ", L. ';" n, hip,
" I ,he romm,m ' }I'"' of react,..."", .. hk b i"m
undct ~o. "';ng example. fl"'m
tlti!. "h artCT. You , houlJ u'"' t lus ~. u "" "" kli' t .... h." y"u a. e J lt.mp lin~ 10
pnod iCl llle , pc'Clrum of a moln.,.lc; to uSC It e rl';~',c l y. h" w. "", you .... ill h "
10 " nd. "I" nd , n., ma rc" " l ,>I 'he preced m ~ _ , i" "s,
The loll<,,..inl com..ntio" , ha ve been cmph'l" '.J. II. indicate. on . Ikyl ~fOI lP,
bur Ihi, ,-,' uk! also e" nl;<in '''' nthel furu,tio,maliW LI a , pecic, "" nll ,n, m",e than
" nC R !!COup, ' h""" a~ not n=-.. ril} kle m ieaI. Y indicales a bele,,"' I<,m flme" " M bl} ......, it II nor limil"d " . ,he "alen indicated r. bu. ~Y R - migh' J el~. lI}'
be . "h l"'ine at""". ' I ' ndil-at.. a 1I;l\ ~ratcd co'U>ed in, "h ain of two <>r ""'....
al<>m l~ U indicald. a ""ble q dic or " n... ' a<a l<:J mo.>l cc~ lc. In n:aetior" In
,," ieh an al ~yl group ;" 1".1. ,h. 10;' ot t1>e la<ust is l"' neT~lIy r. voroJ . ~01C ,,1...
lha l III thl.! JU mm ~ J~." well a, ;n l h ~ ~ St of 111 . h",k Ihe J..i"", tinn 01 a
hom o.l ~ I c ....md cl~ J\' J ~c " I\l'' ' " milS lh. "'e,md fi,hbool; II . .... .uld be ~ l1d.r
" "..d '..... , tM second electro n of , he bond r.ccomc, Ih. tlnl"' in:d el..n on " f the
radical prod u. '.
",In
5
Postulation of
Molecular Structures
T he, e ar e ..,,.. ,,1 ......jut krnd. of ~. lle f; 1 1 ' [m otll....1 ;" IOI'n;lli,m ayailabl . \~
th. rna" spc.:tn.m f hes< are p" rli cul~, I) hel pful if ) " U "";'~ no jnform au " n
h om "ther ""ore"" c o ~ " "m iT1 g tilt llnkc(>wn m,*"ul<. Tho ,,,,,_all appear_
a".,., of
"",,;c leu m and Ibe 10...' m.. ... ~h can give a. l!-CTIC' roJ indicali,m
of the lY r< "I c"mp"un~ ; ~"" the 6l.'~ "" ill ( ' ha pleT 3 a , t U lTlJ>ln l<" 'l1.uJy.
h rl h.rmo re, the nCLl lr. 1 r... ~menl' 1os1 in f" rming the bj~h m... pea h can
prM j~ mfonn ~ !i "!l t>n .peafi, oln.clural featurea, Tl>o fragm..." a,Oon b<h ,;" r
01 the inJi"aled type of m"l,,",u te is then uocel 1.<, I"""lula le slr~c\u,", ror the
llnlnown Ilo: ' u... lo .,.amine ) " ur LLnkMwn 'PI'''l... m r",r each of the
Df
infon",lti" n defl:rib<d !>ere, a, outlmed in th" Sl4u,h rd Inte rpretati"" r rO<;/;d u", insHle l he ",",ck "o ver.
1'"
In",
A bri<;r in"f'<"'tion oj , "" ~n-~ r a ph ,pe,t1 al I"""'fltalion cart \.ell ,he expe r_
i "~d interpreter ~ . u"'ta mial amo un t ,,1k,u' . he \11'111>("" 1'1 mo lecule, You h". "
a l~<l<i)
ho,,' .he rn a" and rdat i", abu,""' n"" " f ,h e mol""u lar k,n indK-a.e
t he so.t atJd ",ocTal " " l>ihty <>f the ....
(Section 3. ~). In t d<l i. '..... ,he
Dumho.'T
~b ll nd"nt io n, in , he . pcctnlrn "n e! lhd , di m i1J.ution in . he rna"
*-",le ar e indi.",i"e ,,[ the l, pe <>I "",k eule and the fun~1.iom" group! p'e""nt
For example. .. [lJance al ,'''' ' I""' lr um or Un kllO" 'n ~ , .""uld lri1 you th"t ,hi,
i, a high I}' >table mOlcrul. _uedllC. il. olomenW oompo$it,on, thi, ' hOllld (OI~
, po nd 10 "1",, (OJ , mg> pi". ,l"u ble bond. " h",h i on, i, tem " ,;th ,his
" ahility _Nor onl ~' ate rhere no " u k bo~ in . h. molecule, hut apparond) 11le
n,a i.. fralJ"'Cnl.ti<>n par hway, 'Ire . " " l'J'tO'imately the '"me 10'" pro ha h.ih\y
W""\ i> ~ f'<, ,,,ib le . tl \l i:l ,,,d
." ,:>,
"r
""'uI.
..
I . ....
,al'o, 01 Mol"'''' ............
.,
Unknown 5.1
00"
eo
as
'"
"'ar
"'sa
"'63.5
,..
'o'
.
..,,
m/z
'ot.
'0
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""
"n
t.s
""os"
"'"'
00"
,m
'0.
,m
"
"a.a
"""
"
""
us
a.s
"a.s
,,;
,.
,.
n.
'"
ON
<00
"
o.s
,.
'00
"'
"' " '"

m
00
+,'" , , I
'00
'00
,.
"'-1
"I"
00
l-
00
,I
00
"'
'"
t, "'~~rl',"'::--t'rcrT"~
,.
'00
"'
.,
'05
A molecule ""mp",,,d or ,i"blc ,ub,tw<;\urc, conne<;led hy relali,-ely weak

bonds should gi... a specll'um with a few prominent fragmeut ions, such a' thal
of nicoline. Figure .1.1.
In tho 'reCltum ofUllknown 5.2 the miz 43 peak j, by far (he mo,! prominent
in the spectrum, Tho bond tbm is cloaved in the formation of thi, ion would he
c~pe"lcd 10 be the weak",t in Ihe molecule fTom it, known chemical rcacli vity
' .t
.. _ _ _ _ _ _ _
. _'
u_
"
-"
,.
"
,,""
.,"
"
0.'
,f,
"
",ee
,
"
"
...
' 00
..
""
"
'OJ
,., --,
"
_.
1L-
,,,
, J,
~,
' 00
F"k,w,,"'''" ,U and , . are tho 'peet,,. ort ~rM'=' In,,lec ,, l~ , p[(ldu ci n ~ only ~ k ..rrr<>ml"" n! pt ak l, In ~ '- ; , h"tI ; n g t h ~ ",.i~ Xi ~t>.l. ",,,, or a pe.ok
"-;lh w:"roa, ing m.... u wel l ""
<1,,,,,,,,,
with dec rca , in g
3 ~u n,j a n,'C .
_ .._u
~,
"
""
"
..
00",
"
..
"" ""
,."a ".,
.
.
"
"""
"
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,.
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ae
'0
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''"", ""
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"
.,
"
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"
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,
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'.ot.'' 'oo '" Mol".I..- ...."",..
Unknown '00
00"
ma
,",
" CO
"aa "r.o
"'" "
" "s.t"
"sa o.e
"'mm ""
"""m
,eo
aa
'm
'm
"eos e
'm
'"
'00
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"""
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0'
00
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ar
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' 00
,.,
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i"
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as
'00
as
'us"
,.'00
mm
"'m
,m
00
,
m
m
m
00
00
L
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00
'00
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'00
In unbranched alkan.s. tho most ,,~sily cleaved fxmll< (lhe ,,-hond, belween
second,,,} e,,,boml ~rc ncarly "qui,-alen[ in I>ond strength, The [.sulting mass
'[JCclm trigu,"' 3.2 and 5.21 haw mally peak, of regularly varying abundanc",_
Study the,. typic"l "pi","\ fence" '[JCclra <!, lhl }()~ can recognize them on
,iE'hl. "<o[e Ihe >triki<tg ,jmilarity of the spectra of Figure, 3.2 an<1 5.2. despile
[heir diITerence in mol.cul",' weight. ,\11 the "impOTlan'" peak> ",ccpt M' an:
e"en-electron io",. Th~ rale, of the initial decomposition reacliom of any
mok~ular JOn i""olving dea,'ages of the dillerem ""rbon-carn",, "o",i, are
campara ble to e,""h oth"" a, arc the ,ccondary decompositions of the primary
product ions, This account, for the TegulaT incn,a," in abundances witb de",ea,;(OJ ",," or the alkyl ions. The possibility of rearwnge,l product, or grea ler
stability becomes higher with the ,e~onJary "'"Clion" '0 that the structures
of the ,man"r io,,", ,uch a, C.1H,+ a<ld c.n;, are largel}' tile more,lable
i>ranched carhonium ion slrllctures, Thus th" di"n bUlion of inn, " maximized
in the C J and C. region of higher alkanes
Furlhe' ,uh<litutio1\ of a carhon atom increas es tho probabilily or cleaving
it> I>ond" compare Figure, 3.2 :lA and 4.1. Aher you reread Sectiou 4,5. try
Lnkno"'", 55 lo 5.7. which are C j611,. i,omers, Don'! forge! th,,1. ,,_bond
cleavages give EE- C,H, ._,' io"" nor OF' C.H,"" ion,. In tbese unknowns
ignore such important OF' ion" which arc di"'u"ed in Section 9,2,
"
., ..... .... . .. ..-.... .......

'
u
~
r
i"
"
I
"
"
-", ,I,

, i ,.J., , ."
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111
....
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I I
co
"
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Alkane . ' ~~.lL\ u ted ,,'ith electro negau ,'. group< ,I"'t do not sqrnificaDlly
10"-e r lhe ioniz,'II(>U eM la} (eil, C ~ Rr. NO" e N) ,ho.. . ery ..imi.... cffe< ..
of chain ~'a",,~;ng un til<: C. H , , ~>n al>unda""", (= f it'ures. l 23- J.25l.
! .2 L.. ...m...
I<>n ...r" ,
f."
;,<1''''
SUKl y tho; m ~ " "'P"'-11~ 'n .

.1.2 1" ,1 ~ M a n<l lh.. cha pICr
such "p;.,Ltl fence" rea ..,ri.... "",,..:iaU)' al Iv" .' maucs , Vou should find n~lny specll a
in " hich "" c,,,1 ~""'I" of p.:u k ' C
hy 14 ....... unib. olh<n lo~"e a
<l il'MI~ , ma ll., ....~rtlio" 11 2 o r I J rna" unils~ In F;~"res 3.2 10 3.28 I~
p"ak, b a~ beef> marh<l ",ith .. ba r lOJ'. S~ ~ low.ma,. /001 _ tl . ", ""l"" lan '
for pm, iliiog gene,,,1 ;nr.. rm 'I ~'" Ihct''D>3I,HII'" rin ll-"'f'lUJ-dOll b\ebonds) on
part icular .uMtruau...... T ~ . llldt.,du l pc;lh ill h'I"':' ma_ "'I"C",nl;ng
prillliu y' fn~menlat'''D 1"001uc" a le m",c ;m!K'l lan, n inJ ;'a lo " . of "fW" ifj"
, t<uctural Go"u''''' (, i"... "'ch,," l 4 Oil Ih. tclaliw ,mpolla t>Ol: of pc aks~
Altlwu~h =00<1.. '1' de<omPOSl tiolls cop'm only mvoh . ru ,ra nl """'OI' lEE ' .
SecliOf\ 4, I O~ lhe k' '' -m<I.. C. H ,' i"o .......,.. " , P',IJut:ro in Vnknown, ~J
In n i< a
Ind iCIUM of Ihe pre<e.- of a n ,' Ikyl d lllln. Uokllown H
~ c(U alt )' has CH , a nd C~ H . (bm 001 C , H,) lUo~," ~l1" ,~ ,d \0 'I tertia' ) car
oon. " Itho..ugh [ C,H , - ] > [ C.H. -] > [( H , ' J; il " lhe l''''''fl of ClI, ' nnd
C . " . ' thaI produ,,", ,be ~lmpoll a nl~ pcab .'l IIti: 211 and l ~ Q, r.IP' '''e l~
T ry to identitY any ...... ma.. ioo Kr'" before """,u1,,ti n$ , p,,,:in" . U",ture.
for higher """'s pcIIk . , At I"""" ma'
th<= arc ",,, . r l'O"'ik\e ion a6signmenls
10'- Jl flIll1iruJar mas> , a ln. (a oo Ih
an! lJ'IJ.Il~ EE' ~ " "l"bJe mil 2~ p""1c i.
usuaRy C , H , ' M ClIO , whe,u, mil IN "", li'cnlly h u"J,~J , "r isoba ric
pos ";biliheJ>. Th" , tho; inf",m at" m ro"," Io,, ma.. ;"n " ,"L-. ca n limit t ~ ~ pOSSIble ""-,;"""",,,lS fOJ h;~ --ru.l'" ion. ,
"''f'iI'.'"''
"""ble
",Y
CH > t " "'/" , 'ofany structuralleamre, give ri... to " siJl-ll,fi.

can l homologous snies of iOM ""rl; n~ al t~e lowma" end or the '1"'~l ru m,
sw:b o. lh. ronlin uou. ""ri<.o of "l k)'1 ion. C. H,. I L" in ~11ca "e . p.etro, The
hit h J"",hahility 01 rea,rangement on lorming the lowesl-m"-,, ions prod"""
a ",uch mOle m ",plele hmtlo k>gou' , .rie, with much I." va,i ation in ion abu n
danrn Ihan al h.iher ma"e" Th us a quick inspection or ' he 'I"'clmm '" \: n_
kn'''''n j.g, wh,,-i1 '" known '0 con ," in nrJ oxygen, 'lartin~ at the l ow -m ~ .. elld
ino:k.a ,c> lh. pre",n"" 01 nn alk ~1 moiety, Th. fact th"t the C.H , , ' ion, ""n
be Ir.:rocd f,om CH , 10 C , H lJ ' (10 C,H,,' "I higher , cmiti"ityl i, ~ .'aIH ble
1tl dic~ I; ' ," of toc m... i m~m , i,e or the ~Ikyl moiety.
.\rrin .".,.,...nJ
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" ..ho wn in hbk ~_ ! . rhe C. H" ., , "Il t'l <eoo 9''''' ' p"ak, at mi. IS, 2~, 43,
of a1\ oxygen utom l ,~dl as <umlit DI"," "r H by am g;' n l h ~ ...!~
J L. 4i. :99, ele., C. II, ]O ' "'0'\<'. ....hiocb i' ch" r~ C\(lI1 ~lic of , a LurateJ aloohnl.
~ OO c[bon; l ec F ig ure , J_~ a nd J~. S.
a lctl anljflt ~ ylf'k1 11>c C"H "" . , N - \.One
.,,/=JO. 44, 5., CIO.; M",' II><"", 1'1" iI are at 0"011 ma ... n "n, bers (Fi~lI'" .l lb
~" .1 .1 R). I nOJ'CJ llnj( tho:,; " um be, 01r inp plu, d()uhle-OO!I<k by ."", J,,,,,e,,,,,, the
mass by two un;b, a liphaTic aldehyde, and ' NOne'< ' " '' Ih. <:, ",. _1' ,e,'"
at'll,"'" N 43, S7. e1C, . Fi~u rc, J . IO ~nd j .l l ~ UnfOTl uJ>,u ely, rbi, o,,,,l ap. tile
':'11,. -1 + oeJlCS, ,.; ...." 1.:0 corrospo,,'" to. ( :.H . 1JI rna," . Be ' UT" y"u 11a' ''' tried
1.<' ~"i, n eltmc n\al "" m!"" iliom to ( hc;c pc. h; if [.w- l.-T 43 +] ... " nly 2~~ , ....
4 )' p<;a k .,." nOl b. pari
C" H", ,, - 'el:l,". Con\'cr",ly. 'f ' Ioe molecvlar
el:o , (" w rl '"..
"f .
" . . .......
_-
"
.,"..."
C.H,_,N'
CoH
~
..........,,yok,. ".n
""",'l"
C.... .
C"lt .C"lt,. ,0 "
C"lt ,N
C"lt..,O
A kl . ~ , J es.
ket o.... .
~m ; n
~ """"' '" -
.....,..
....,ao ,...len
G..... ,0 ;
Tn_,""_
'-
C.~,
. ....._
' ~.
C . ~, .C I
....
.... . .,,"'. ...
~ ; p hol ~""'
_ "' 1 ([>romo,
1>7""
' r., ...... "' " "", I "'~ ." ;0.
"".s. ,..,
00'" "'*'1 "'"

.." """"".....,,,. -,"
...
'- ~" ~
40 "" 6.l 82
41
~ "" "'
'j1
71
511T2 116
~$ ~nl 81
~ "'131J7
13 " .l75 W
-,,,
er
OJ
.'
C,I<". ,8
,W 010"
" """' ;M
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"
40 13 11 .,

13- 151I. 75_'" '
"
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-.
...,.,
..,
-.".".1, <ycm lkyl
Ch_
....'"
'
Fo rrr>J '"
.......n
~, 1SOl-~,
...
'
....
H=n'" ~; "'
", 01" -_ .
, ,_ _...
.. . ... '~ " ,. " P _ "~ ,
t>o ......
. ... ""~""""'_ "
i~ " m nta id' no o)~~-$en. th i, "'l nnot be the C, H" , O ...ne.. T ~Me ~,l >110"' 1 a
,in,ilar o~erlap ' n lhe ., 1. 45. 59. etc., series bel" _ lhc (:.H , . ~ , O inn, (alc" .
hoi.. c, h<..... j a lld th e C. H, , O, ~ inn. (...id.. '''','nt.l m o r~ complete ~s t 1I
!Ji.~ n ,n Tabl. A.6.
In n aiuahng ,uch ;<In ..."icl., """ ,be CJ'i e" ... of po.,k llnp<>n"ncc; don't f"' g<'t
lh;", in ~ "peak grou r " tcomp<>Sllion. dl!"'rn ~ only ;n the nun, Ocr of h y dr~,
t .... podk ",it b the moot H " t<>mo j , ,1M: ",o,t important. Th~ Iptr u <>1' al~......,.
(F;~ ur ~, .'.2 10 .1 ( , UnLnow.... ~.S 10
con t" in both C,H , . " anJ C . " 2.'l
;tries; obviou;Iy. I'" pI ""'-"'" or th~ f"m,e, , hould 00' be ime lp-.n cd ;c,
indic.atlOlI :In alLcnyl m cyd ' >dIL)'1 ~ro\lp tT abl. 5,1~ Both of ' h"", "", ie.. al, o
"f'T'dI' in lh. ' "",,trun, of l -dodooenc (FiMU{' J. ~~ ~<"" """. no w lhe C.H _I
"" lOS III n'O~lm port ~n t than C. H" , , , .,,"'" It.. former can K lo llow~,1 ap 'n
mw:h higIM-. n , u ~ ,
N 01~ in l " ~ d,><!. ".oc ,pectr um tl'i$ufe' 15l lhal 1hc Of. ' ",';e' C.H , , - i,
aho PTomi""n' , gon.ra U)' larger " UIll ,he C. H, . , ""rie> Ho w er, for an
llukno", n ,how;n~ impo t llln! I",..'m".. i""' .11 e, -. n rna" number<. do \
Met th"t ,he," ""wid 11.10 he dOle to DE ' - iol11 formed [TOm , pecific cle ac.et.
, a" h a, nl,. -' ~8 ill r ' $UIff ' .1 0 OUM! 3.1 1; h,x ~arcr~lIy 10 ... if t!>ere IS acI "" lI ~
~ seric, of wei> c ........""'.... io",., and do no t be 1o<>Ic,' b)'
l"""h (in
Fi~w,.".. l . lO a lld 3.11 lht til ': 30, 44, 72, ano! ~~ I""'x. I~ en' irdj 01... to ' -'(:
' '''TOptC ""ntri bul;,""} " wt h a ..ries of eveu-rna ... ions Can ;01", tl<' due to
Son
f",.
iM,Io ,,,,
.,-_. _..__-.
..
l! li ' i ",\ ~ co ,lta inlllg a ni trogen at om, suc h a, the "Ii: 3(~ . "t. 72, cl.<:.., [o:al.
in Flgn!'t's J. l~ ~ . 18. Here, a n'~ ll'fll'<1\ ~' ' of f'C"b in l!oi. .......... j,tdicatos rbal Ihe
res t " r I he ' f'I'clT Utl' m ll'l n. . 1" died cl rdull)' for otber
of t he p" '' ''''' of
"pi'
T\;lroge,l.
T he spectra 0( Unxno",no S." and ~ 1Il ;l'" ,,,r~' ';m iLo r. wil h. "':: 224 sho wn
to> he (" " H.\l ' iI' "" ttl H""'o""' . .....e i.< ul'lique in c.:>n'3imns an impm1;tnl i....
.." i.. IllO(" t h'" l l>n.e , ~ ~ , llknllfied h) "'''I,n ~ ~, Ihe 1,_ _m a.. ffld of
the , peot, um). ""' hl l""" i!>k ~ in"" "r m" k<:" I... ftU 11>esle?
"
.
.'IJ .
_.
'"
,.
,..
'.
'b' .... S.1I
"
.jj
_. .
. , .
1
,.
i'
,.
,. ,.
' 0-',
I.
t ..
-' ,
,.
,
1011 uri,. .._ ".ud "y(:H Ilnd C Compo und, wilh a hydrogen-to-oarboo mtio
mu~h 1.:... l h~n \"'0 c. n"" l show a significant seri., of ion' ,pu""d ~l C H ,
;nl<, , "I, (... Unknown 5.1, naphthaleno. C,oH ,). Tne ["",m ll" jon, of "",It
eomp<lun<l, .an " ill , h",. cha racteri'tic series, A very import ant ",ri<" ;,, tloat
'i1I",..n by arom. tic h~'droca rb o ns at mil 38-9, 50..2, 6 :1-5. and 7 5 ~ (C. H.,. to
C.H . ~ Heterocydi<: "" mpu und, conl aining ," ygen . tid nitrogen at oms . IX!
.. co._......_
,,.1<
W IIlp<'und, ~ onl ll i " i nit Ih.,.., d~m" n t;

an I&,,,,,,"",i. rin g , /low ~ \&h a l
,,;n,ik , mi " \'. l u ~ plu, addilionAl peaks al "'i> 411, S3, 66, aDd 19 I' '''' ""h igh"
arom~ lj~ .. rio." or rabl~ A,6l OOoau"" "r . e'J'lno.ment ef CH Itt' "0, '" CH , by O.
Altl ", u ~ o lhe Ilromohc ,~ r;"", i, Men of ulllli,'d y I"", I b~ nd.l n "., Ih. uniqaelie"" <>I" It. rna" ,"1",,, (l"ah le 5. 1l 1l,u an~' make< it q une ~",gni zal>le; note iI.
al>oeoc<: In I 'nkne wm 5,') and 5.11) compa..d tc 53, 5.4 and S.8. U",,,,, H ll u,,"
)2 ,,, .1 27 n< ullkno......... """ if yO ll call ded LlCC ...""'" comail' ~I omul ic .....,i.tie,
.....ng this seri,....
A! " an he ""'II In F"i~\I r"' .1.231 ...:1 3.1 4, l~ O cepla,-emenl of h}d r" l"'n alom,
hy halop 1&10111" X . e h a ,, ~ ", (It< h"",...J,,! (}u> , ori 05 Sp.:Icin!!-, h )' CHX o r ex "
cau' ''1l:a m a r~ed "h al1~C in lhc ~ f1l"'~ r a llO< of the . pectrum, Ad,li{i"na ll) , the
clc"t1' Outf.m i, 'e hal o1" " al""'. a,e m""h m<l..., ."my 1001 than hydroito ato ", ..
'" l h,1I ions ""pa ratoJ by X and HX in !WIn ~ ,e al." round. fo r chl"rine and
brom ine, (het< M~ ca <il ~ id~lll ified boca.... '" the "isotope: cl u >t e rs. ~ F luo ri....,
an d iodine ha , c ' 'Illy one nJlU I ~ 1 ;"'''>]"1< .~ ,h , or and .. T- ~ul the," oan
u'u alJj' Ix: """'9,,;zed by th" 'c' y unusual ma " diffc... , t = l he)' . " u,c.
NftCo>(.....; nx ion >UiN. o..,," i' l' qUlrkl}' """'>JIlt aille to Kk'll ify """ t>o uy'l
pea k< in lin inf,anod . po.'lrum or C H,
iu a prol" n N',{R . p"':lm m. Simila rly, you ...,11 led much mOtc "al h" me' with rna" ' p'tra if J Oll can ~,li ( l~
recoglliu ,he J'OS , ible ,i llnll'i ,'llnce 01 rna" _alue. , t;.... lhc C. II ~ , ",ria 1'2 ~, 4J. ~ 7, ,~(" ,11 yo ur rck... nee ",ak Note tha' in ,he I()()o; r<{li,m. , oj, i, onI,
,,,,,, inS"; umt, i" " e, ( I B, 127, 14 1, 15\ . tc , ~ "'"aulo< (CH , ), cnrmpond. ,,, ~8
on,' " " nil< (F ig" ... S.2 ~ the 200. f C~i,,,, ;,; thea 211, 225. 239, 253, and .., fort h,
,\ l>(', tl.:caus< C H, 114) can be rcpla,," by N H 115) or 0 ( 1 6~ one <:a n ostimnt<'
the t ot ~ l numbe, of C. N, and 0 ~'(l n' . ny' dividinll 1' 14 iF the ' I'<:0l, " m
contain_ . ";gnifi,,"" l 'a'u rs toJ ion ""ric., For u"""w' alion, . nch a, ;nd ICa ted
oy a n aromal ic jon .. riM,add lwic. the , +- do ,'alue U"" ~"y l. add 8, t>cf' ....
d1 \'idmg h)' 14. A, a h ~ndy ,,\1. of lhumb. 100 lila'" unit, n . "f' prn. im~ l~l y
[("+ ':': + 0 )"
In L nkn" . ,nj, '-I I ;lIld 5.1 2 notl<>: in l"'rltculJ r lbe go.......l ap""" ,,, nce of
the ' l"-"t1ra an d
jon "rie..
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5.3 Small neul,allosses
Perhaps the simplest and most specific assignments that can be made in thc
,pc~t,um are for the 'mall ncutral ,pecic, lo,t in the formation of lhe fragmenl IOn< "f bighe'l mass in the spectrum, especially those formed directly
from the molecular ion. For ex"mplc, important io", at ma"",' (M - n-.
(M - 15)' (M - IHI', an<1 (M - 201- alnll'" alway, 'epresent the losses of
Il, CIl " ]J ,0, and HF, respectively, from tile molecular ion. Becaus. formation
of such larb'C prim~TY ion, involv", lbe I"we" pTOb~bilit}, of a randomizing
,earrang<.'Ilwm, ;ucll ",maJ]-ncutralloss" peaks fife of major 'ignificance in deducing the m"l""ular ,Irucwro, Tbl,L' an abun<1anl peak corresponding 10
(M - 1)- indicates a labile hydrogen atom (and the ab'ence of olher labilc
substituent'). A list of common small, n.utr,,1 fragmenl' 1"'1 in Ihe formalion of
important speclral peak< i' ;et forth in Table .'1.,5: lheir use as Ie'" for tile
molecular ion was discussed in Section ),5, As di,eusscd in S""h"n 3,4. lhc,e
high-mass peaks are oflligh relati,' . imporlanee; ",'en Ih"se "f < I~,; inlen,ity
can be u'eful fDr ,truduro determinalion.
Tile specillc loss of" larger neutral Cilll al'o be ,Iruclumtly characterislic. but
ih i'knliricati"n "flen 'equire, di'lindion rrom adjacem low-mas> ion 'eries,
Thi, is I", a problem with low-mass odd-electron iOllS, since OE" ion 'erie' an;
relativel}' ," ro, However, carefully examine any FE I ion repro",ntinEl a peak
mo,c impurlanl lhan an)' "lbe, in ilK ion serie,. especially if il is nearly tile
Ilighesl mass in its peak group; repiacem.nt ofCH, b}' NH or a rai'es thc rna"
",'d u,ually lowe"" Ihe i"niz~lion enc'g}', In Ibe '[J"dmm "f bexyl formate
(figure 5.3), you sllould easHy idemify the c"n' .~jo ion series al mi: 31. 45,
59,73,87. and 101. However. Ille tiny peak at miz 47 i, e,pcci~lly irnpurlanl,
became it i' althe higb",l rna" or it' peak clu'ter m,i. 36-47, and tllere ar.
negligible peak, in its ion serie' at miz 33, 61, 75, and 89. Examining T"bk A,6,
we "an 'CC tha l lbi, ,trongly ind;,,~l", the pre",n"" of a 'ccond o,ygen or a
slilfur alom. Jf you knew the molecular weigill. }'OU sllould haw also marked
mi~ 47 as an important 1M - C.H"_lJ" iOll of an untllown tll"l could cOnlain
@
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......-
'" Yl'<-'fl t he "'/~ 47 1'C'l1 ~~lUa.I' aI. - 1- ,110< d ooble h yd, o*",11 IU lla"$. ,nc n t
I"" of <-\H , ,. a d ,araen ' h< <1;",....; ;"11 . of (," ma'e.. l"cc illm 4. W .
II t he - 1"b"",,1n"ut..1 ",,", . I.... ind lCateJ l l1.11 1ht peak of hi,ILe;, ,n.", " n" ,
the moleru la r iOIl. thi\ ill <~l m",,' di lk.......," then ~ I' ~senl, t be (lLft"... nce
het"",", 111 . ma , ses I"". from tlte n~.le<:ula , ~ m in r"' m;n~ 111,. .., ' " '' fT. b""cn h .
For example. if l!>etc i, on imf\orlaOl p<' k ltu IlUlfSoe$ blelow 1110< rea l 01
h i~h .'t mass, thi, could "'I'~nl ,t..: ~ _ "f H ,I I f,,,," . ny
bl a "",IecuL"
ion lhal '11'0 easily 1o"", <:H" An "npona n t r u k I J 1113
it- ",1",. the JlC"k
of higM ' \ m,,-,, ""uld hc <1"" ,,, lho; I,,,, ,of ( "l H. ..., CO f, o ll1 a rnoJtcUla r ion
thai a l", I""" C H, c .,;I ~ N" ,,, th ai il l'" n'a_' diflerft>OO " an odd ..umber,
an d nitr o gen is no t pre .em , t h." " II<' or Ihe , .. " r' ak"",,n\ po:;I k. m.... ' . "'.....nl
an O L ' ion.
Uo"" owtl l ."
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... ~--- In C lllr.n,'''''' ~ _ J:l, ~o~m i<oa l ioni""i " n and cu ct nla", ""'.l>Un'lll<1llS sh.,.., lIal m,'; Il ll i, f,,, mcu by the jo" of C, II , from tlle molocular ion: " och
neutral k>sscs are i ndic"r, v ~ " I 111 ~ , tm clurc. Dw )t>u iden ti f)- burlt '''' IIOn . ut
'o n "'tic","
._11
5.4 Charact8ri st ic ions

D"duClion of tl>< m ucr" .., inf"nn~l i"n ' Will a larger 10 0 i, more diffIC ult.
becau' " ,,( tno largO( " umber otl l>eole1 i<o"ny fI'", ihk assignments for it. De.pite
til" . for mall Y .peartc ma_ (a nd, C$ re-:Ja11y, elemental compo , ili"n) "alut<,
the le arc: " nly ... re.. char3",. ri"ic Slrll<'" tUl;,18"' '' l' inll' Inat commonly gi, 'e ri ...
", th.-, oor"""potldmjl. peak in rna..... ' 1"-,<1. ... . $uo.;h "character i, tic ion," JU'C .ur_
1'IISIIllth helpul in ' ''''gL'Sting po,,1111< fj'a ~m ' nti " r ~hc mo lecule. YOtI ihotolJ
.1",.(1) "" r~miJia . ,,'illl oc>me of tMs<, liko ~lIc '" ': .1\! rr~ ,n a mi...... m,,~ 71 from
r hcnyl and 11I/= 105 from mcth}lhcn/,yl '" bon~oyl (Uni ".,...-" U~ 'f Fi ~UTC 5.4
~ . c a n un1 ........n. l~ experienced interprcrcr ""<l ul" imml"' toly SWJI'ffI a
rh' ...."" " ' '''Ill l~ pre, enee of tho h" , c rc A ~\ "'/=149 Ilowe. ... in ~ da ta l>~",
"'l'~u ~m~ 140.1
);10 ,lilT,rcnl n,a, ,, 'pew a r\fd .... fl: rI~ ;011l tit CJ r efu ll ~ checked. PII( n><lm.. ar" ubiqUlloul imp"I'.' r,,~nd in
nU'" , !'Cetm... ~ "" the)' a re ~ommo" oomponcn M. , ... l'j~'" k.;,.. " (ml> i n~, ca p
ti",," . ga, l 't, 1and cll,-omawgm[""" Cf~ umn f",,:Lingo..
Thus Ih.. nOlf It ~p in \"" inlo'l''''la Lion oflhe ' pc-<lIurn ;" IQ n"'" to.: po",,1>le
,lruoLural . ilni r",a,,'" of ~ II imporla nl f'C<'h. \Ii,""," mot ' lhan 0'" poSlihlc
inlcrpretalion ~ XJlts. be , "IC I" nole an " f lhem: ff Ollie!' ev id .nc ~ ;11 10" '1"-'"
trum elirnil1" le, " "",,, ....' "' ,.h t>c.c ~bil i tie ,_ thcsc TemainiT1 g will be much
mote me.nin!:f"L r ,"";hlc ~ ";If", ... nu lor 10m are gin n '" P'lrl of tOe ion
..ri.. ofTahl.. A.... .W..." S,'<" -l'''/ C""''''lio'', (McLa lTcrty and Vonl atlrl,III"an
,.
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,-rTl.. -\ojo,-,-,-~;.,
'110
1110
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19821 shows what elelllemal compositions a"d ,Uutlun:" arc p""ihlo for a pcak,
and what the "elari". prohabilit}' is for oach of these postulation,_ The Important
Peak Index of Ihe Key;,,,")' of Ma.'," Spe"lral J)ara (Md.un.rty "nd Stauffer
1991 i pro\'ides a listing of compounds which give a particular m,/' ,',,-Iue 'lS the
mo,l imporlant- 'econd mo,t important, etc" peak inlheir spectra,
5.5 Postulating possible structures

Oflen [he 1i"1 '" ,Lep' or I~" Slandar<llnlerprotatioD l'rocedure (facing bad:
cover) yield a confllsingly large number of ,lruclural due,;, ,ince a rna" 'pec_
tTUm can h''''e hundreds 01pe"ks, of which eveu those of < 1;,~ abllnda"ce can
be imporlant AI lhl' 'lage it i, f>c,lw concentrate 11,,1 un the ,truclural features indicated tho most clearly. Review (or 'veir" down) the general type of
fragmcntali"m ,,,po",od (imide had oo"er) for the indioared substnlOlur"S 01'
compound classes. These product ion' will appear in ion ",ric, wh"", ma"e'
depond on the size and kind of sllbstituenrs: such ion '"ries ditTering by CJJ,
groups were discussed in Section 5.2, hut an ion ,OTic, oan "lso contain high
mass ions from sl'ec!/k cl"avag"s typical of functional gm~p'. Now chock tho
unknmm ma" 'pcdrum for il' m"'l important Deaks belonging to "aeh of
rhes" '"ries, and use their po,ition in the series to lin'it tho number ofmuotnn~
possihihties for eaoh correspouding Sll bstrllctur" or compound cia". For e,am_
pie, in L'nkn(}w" 3.1:1 there aro strong indication, th"t thi, i' a chloroalka"e' th"
alkyl moiety accouuts for rhe peaks at mi. 29, 43, 57, 71. and ~9, and tho
ohloroalkyl moioty acooum, for th. peak, at mi~ 63/65, 77i79, 91i93 and 119,/
121. Mechani'tically, ,igma-bond ckavagc at alkanc bT"nehe' ,hould be the
mo,t I'\cil" dissociation pathway: the important [>Cab in thc'" ",n" at mi. 57,
~~. and [I 9il:' 1 thus ,hould repre,ent the ,,,h,titueuts C.1I 9, CII,CI (loss of
49), and C,II" Placing these on a tefliar~ CH Can aomunt fnT the m/z 14g
m"koular ion, making thi,,, possible ,tructure of the unknown.
In rigure 5.3, the "obtcd mi= 47 peak indioalCd that this might be a formate
ester (S"ction 5,2), 'vI"chanistic.ally. the alkyl functionality w()~ld produo" an
alkyl ion ;erie,; both C.H'.+lO+ and C.H'._jO,- product.' at m.'. 31. 45, 59,
7J. 87. 101 would be ",pcoted, ", ob,er"ed, A<lditionally, a ,ingl.-hydrogen
mi; 46,
rearr.,ngement with charge retention would produc" a poa" in the
!lO. 74, of which none is "pprociable. and with charge migration in the series m,/'
2~. 42. 50. 711, ~4, oto. Hcro thc imporl,mt po"k "t m/z 84 (C"H 12). of high.st
ma" in thi' series, i' then a strong indication thal thi, i, a hexyl ",to" lhe 0 F. '
ba,e ]J<ak at mi, 56 does not misleadingly iudicate a butyl "' ter, SillC" examination of all [>Cak< in thi, C.H,.' "'ri" ,h"w, the higher ma", ""d thu, the
potentially more important C"II,: peak. Charge migration i' favored ",or
charlo'c rotonlion (ScOlion 4.9) OCO"U'" the ioni"niOll . nergy of formie acid.
11.3 e\', is larger than that of alkene, (9- 10.5 eV).
"'nOS
'"
'lk ab,,,.., '1C'p$, ;,,1<1 ~ II ulher H a il~blt mlo nnali" n, .h oul d be u lod fim to w,l
. 11st, uctUJ<." , ,,,,<>-,j.a bly possible , r-or """h "", io", candid"te ' 1' ....1 "''''. predicl
;t. , ,..:d rmn from the app,,,...-ialc di,"","allOll mcchani, """ =d compar. Ihi,
" Ah lh. unk now n '!"Xl, . m tarrlullJ . Th e d im; na l;"n of all bu r OPe r><,>.i l>i lity
Icr I h ~ molecular m UCl ur~ don nol, of cours e, p'OH tha f !hi. 0'" i. oor r . ~l ,
P ~ dlClicn 0( f[ "llJIICn l~l j ,,,, I'" l hwa ys becOmc1 ;n<......'ingly dillicuh with in _
c re", 11l~ ";IC or a molt",.l. F o r Ihi. ,c!crc nre '~lta I re p;l rtile;
hy fa, l ile lar@es'ayaik hk prlmod collection ;" Ihe ,Il <gJ., ,,y of M ass Sp<'("f. ..1
Darn t"'~ J ..rr....-.y and Stau fler l Q ~1. con l.ainint 1he spectn or rna", ,hnn
I ILl U l di rJerem co mpo und" of .. hJch ''' ~r 119JKXl " IT 'cpre..m! by . ln lct u,,,1
imdf';01, The e~p" lldcJ 1992 &!<J""-~ on ck "t",ni< media com . ill. 22tl,ln'l oil'
""'"lI1 m a"" , !"'ctr a. If a ref.,.,nce ..,..,..uum of }'o ur pro po llC<! ......."".m d j , not
~ > a; iabl~, tr}' I;Olldo t;.. ~ . he n*r. ..... . peClm or , imiiar mok.ct ,iu . R<mcmbor
thaI abuod om:c . .... ..... . can >ary by more (hon an 0""'" of ""'J:nit uJc bo(ween
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rn,lrumc-n. <; ..., yO ll mu.'1 measu re ~ ", k-ren", "J"'.1f a <>f .... postu lalnl com
pound "noJ..,. til< <;lffiC instrumental . ""ditian , ~..oo ..'il~ the unlOQWIl lD o rder
IQ h ' t h~ co nf>d<l\ct ," 1"" a n,w~r , Fv ~11 ~ I O, it i' hithly ;n,ponan, 10
W>Ik~l. nd the 1>IIml ' 1'<'15" of
.J'Ie"\ "'l'nc lr~ (Chapters g .Dd 9l s..w
as ,h. d o"", Kimi" ril) OCt ,,'uo lbe man spectra of md a_ and p<," ~ -fQ "'~ lic
;.. ,mer\, or rbe i..... n"'J\J1 y Iv chi,.lily. hod",. making ab. alme mU~T ..rat
rn."
."ignrncn".
Follow tli" "Sta ndard In..... fII''' 'a'''''' rIDe" dm e" in all""'pling I"
\lm c(m", (0 lIn ,n o,om, 5.14 a nd S,1),
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6
Auxiliary Techniques
u.e
fimi"" ;" ,, ,fllle IlnlClU, al info n n m inn in t he "..>tInal rna.. r.poctrum elln
he .,..rtJy oIJ~1 b)' l ~la l rna,,, pcclml techn;ques, _
" llho l' ih" ...,mrle " de-'ICIlplion ,,' l"'-"" i, t>.:) M d t he scop< of Ihi, b<w ,~ . ~(I~ . hould h... .... a bIo,;e
" m ; "" , il ~' \Oll il thell c.lpa bilitic, .
I,ow...,,,,,,!:.>' dUfF"" ~ja:,u... Lo"" 'll;I l l>< """"-n 0' the bomb.'rd in~ CI"" ITOn>
(o.g., lO \5 i V) ",~J also "'''..r tho . ""'''1'<' It>ul ,,,,1 1M mmi",umj ;nw rnal O1l orgy
allh., molocul", ion . Such low-ener, y M - - tons ,,"-n ai, ,, b< rroouced h)' f>~ l ~
ionil" uo n. cn.. ~ CJlCh.1 " "",. 0 , p/lo I01Oll;''''li, m (Section 7.4), Fo r ", w , la' o <'I " "
d d" iOll it is ""'1Il:tIIn<:>. d ul l< . ..hmina lo higher-.n.r~y r..",,1'''"' 1111' $ " "e
l<'COnd a l Y pr" d l>d io n, 1M' ~ ~ IOlICh 1<" ",pre,en tal; '" of Ih.. <>, i,li.... 1
' ''....1 ,..., Ho"'e,.,, Io",er .lectron ene rgle, i"" ",a.. t il< re1at; ~a ;dlundllllC\' oi
" rim a ry
rea l mJl ~ emc n l
, caeli" ", (1;eet ioll 7,2], F u r\h<;<. I.. ", <:ring d .. e~lI<>O
.....'ltrd <:C' n .... lite ub.",lure ab l1 nd :l nce ,~ 1,1' i<,n, ; . JtllOtlgh tb< "'&>Ii", ~" u n
,I;,nc. "r (he m<>lecular ion incre" ",". it n" . e"hel~ IS noo,.. d lfficul' I" .1<,.." 31
lC""f f eleeUOll .~c r ic , (unles. it h. , hull o bfo; ~ ml I>f fragment illl" frnm
a hi~her-ln ol e""lar.wcitht impurit)'~ Lo",~,int' (he molecu" , eneliY !s,,"h "'with ' urc'T, ,, no: e, pansio n. Amin...- t 'I'l l) I\di.n: ;<lnlZaho n do." "mJ uce M of
" 'en lower internal m "cgy, in~=a,ing [ M l ISec".... 1.4~
<_",... .
r.E' "'"I,,.I"'.f'k1 Jr- N O

Iiotu. T he mo,t ",,,,,,n on method
of p l'odncm~ e "' able i"n ~""' ta in inl': lbe .am ple m"k'Cule i. ta react it with ~n
ioni>'C<l li l" Sfl<l.- An ~d " ) e,~mrl.t ",a, l he me a t hl~h .~mpk l're"u ,es
under H roodjl[oo> 1<> p"JJ ~"" M il' ions from coml" ' und, Ilot 1ieldilla; ... ,.
(Mc Lalinty l ~ n,,~ ( hemic. ] i" niz"tion (el ; ,ee M unson ~lld t-i<id 1966,
H ~ rri ...m 1992) i$ "" ~ U'litui. in lhal mo,t (alth ough nol 01'1 'n<>lecu.... l hal do
. 00
DolLyield ....>lc<"u!;O. i" n, by FI caD proo ~ ce CI i""" jLK1 icative "f the moltelll.r
CI ronJ iti"m. r JOLlu." ~ b undanl therm a l d cetrons, gi v;n~ high ly em.
"""'Lclccuoo capT" . e l", negat ;"e ion formatw u from electroMga tive moJecllles
( ~i l'Un' 1.2. 1'1........"\ ;,;..;,,, l iJlll, l iJll3t>: lIo" io 1994, 19~9; Hite. 1988), Rntly a
!ride vari"t~ or po ....rfol mcrh""" ,'" 11>0 i"" ;...-. llo,, or l~rll" m" lcc.lc, (c. eTI " r
m<oIc<:ular l>t'd11 > ro- have been dcvclol"'~ : n>oo t y..ld st,ch [P molrc nlar
~ /!'.ct:l;,m to .2~
"'O~L
c.-.........
n-. ,..", ("I lhe ' ''''I:em lIilS R is introd uced tnte the iou SOU!QI1
( _ 0.5 Lun-. _70 Pal al a u """",n' r..l;,,n in I;o,~e e.-<~ (_ 10": l i to that oI tb
... mplc, .and is ion ~ by .""'ltOO ( _ SOO \') h"",h;" . J mcD I '" d ' >I:, rK; ,Ji""M ariC
(HUDI [ 915~ Thc R' ion, 1O'l' Iny fo, med can . eact f'ln hcl ",'lth ,-,tilt . R hlOle
cu les to form reaCli... ,,,n >p<'CM." lh. , 1I,,:n aU3d , he ,.,m r le """ cl:\llc M.
.. -
II" II
RH . ...
tA- "I U
(11_""' . . .
11- ....
li P
~"
f ,,
16.1 )
Ill. - HI' ,
II I,IH '
(1'1 - t>I)
lA - H)' .. RH
.. .,......-_,,,,*,,,,
IproI"""'",",
"
(6.1)
16,,)
(6 4)
II 1M HI"
("V<ftlo
l 6. ~ )
II . ", -
No ll" . ''''''''WC>
1M )
.\m " n~ ,h;, wi"" va.-ict) or p......it>!c 'OD'U I"''' re:>ctJooo. the mo,1 com11l00
a re: rroh' nau<>n (I!q ualit,n. 6.3 . Dd 6. 4 ~ ..hir h i. ra m nxl f", .."'pic mollX'ul""
01proton i<fflDll) h , ~ he-l Iha D tha t 01 flit "taCO,,1: hydridc abr.lu Clion lEqualion
~ S}, " hk h ;. "ornm" n f" e 1"""'I" " I" n-"," n;l) m<.I,>.:ulo.. l>UclI a. aft an"" amI
cha, ll" eXd llln ~e 16,6). which il fa ~O<M for rea genlS of high ionizalion """'ID'
U(h ", hd ium Th e ;nleTna l e""' gy , ,( th.o , ,,,,,lung ;OQ,nx1 \I """""" depend.
on the reagtflt choocn arid tilt ion ,. "",,"" lCftIl"'n<tlJfi: and ('''''' 'Ire {nnmbo... of
th e rm al i zin~ colli. ionst For example, Fiure 6,[ (Fjeld litN <'f aI. 1990) .........
the (:1 spcelm or b~and" yl ~c et ~ te (I'A =
eVI u,ing C H . (pA _ S.7 c Y ~
;",hUlane (Toagonl C~H . ' . PA of j. ~ C . H , - S5 cV ~ and N H , IP4. = 9.0 cv).
Furt hcl di.,o"i" tion i, nearl}' complete for the highl)' a otl>ermic Of, + reacl;"n. an d minor I'm (he N H ~ ' 'cae-1;"o. Such uoimol.l:".1.", Iragm e"lan"ns <>be)'
tilt mcoha ni,,,,, outlined;n Chart." 4 and R; til. major m.iT I J1 l' rod",-'t ion;"
formed by CH"CO OH 10", consi,te"t with Field', Rule, PA(CH ,COOH) _
~ . 2 cV, I'A" "H ,. ) _ _ K7 e V. The m i2 IS4 product ;n Ih" "IH .,/C I ' 1'O.:l rum
corre, po LK1, to CH ,COOH loss from (M +- NH , l" , Thul C l lpcctra Cil D pro"ide " ' Ul: tuTal a, well a' mok cular weight inl",m; ;oo. Sim;!ar Cl ' ......1. 11. <::la
-v
L' _ _ _
'"
'.
ts
!
0
'f
~'"
,. ,.
"
fr q
'. '.
,.
'"1
f
.
t,~,
:r ,.'. ,. ,. , ,.
-'.
_ 0.1,, '
,11' .... .
'"
-,"
,;,
:21 . 0.1 , 101.
<
,"
..,.
'"
,.
,"
Rguo- . 5.' , T1oo: CI ml.....pedro of [a,'a oouyl

u d ~ ll , ~ ,,''' ~ ' l !Il''''~
'.
1'"
, , , , r ,.
.",,' atc l lo.t ..., 1'/(;). m,, "! (:H <",-('. U,.'
b<: g"~ra ted:U mucfl l"",cr pre.,ur.. b ~' ,,.jug lQu1.-li,'ed tr, l'pM ion. in \he ion
c~'"k) lron reOCIII.<ll1"e (IC R; 0 Lehman anJ au,,",)' 1 ~7 ~. and Rowe" 1 ~ 7".
19R4j , ,. ion " al' (IT; c;cc Cooks ., of. 19911j"'troment. For dofinition< of ....
and gas-pha..., ilciditl' and "",ic~l1. "'"
l !1'9'l
Il,,,,,"),
. ' ... ...... r _
6.2 lanl ntlon ol lallle molecule .
For c".",. " tlona l di red-prot", ;n"...><1 ...' \ion. ~
"" m~ m U~1 h . ~
w lli" enl \'. 1"" prc''' Uf<: lOI><nna l Sla bilu) 4<> M >a l'''' ;' '.... m ,,'" i,m ..",,,..,. T I>'" "".
,'erel)' limi" tl>c awli,:ati" n of m,,~ ' P<'C! ro me1 TJ lO ,mponMI ';Ilm!,l", . ~ch ~ >
",,,lo g;c,,1 m""rnm " I",,1lk>, 'oo u" na l pol~' me r s. and pelra leu' n ~ d lLt$. I nl ~ 1>
, i"e ~m re;e arcll I'r"'8te>.< ha> ",." Ill..... in hight, u..,;rul mc," ... l.. Tloc m.""
widdy ".. ed brielly IIOU: m.l" y ucenl refe~ncn 1'>liO!l 6.8) ~in
e, t"n, ",'" del~ i l,
F~" 'I-"',,m h"m6"nJm<wl r f '-t H) , Inl!'V<l"""d by 8.J.rboor '" ",. lI 'i&Z~ FAD
parlic~ la,ly ' I\itahl. for po lar mot""" lc. I',o.i" ing Ion;,....' " molecIW
...
..,.a...
for m ()I " " ~I: or wd ~ h" "p 10 .. ~ U kD . j\l.-'lUlams rt ..J 1'ilI7: To...,... l'l flll). <\
. oJlllion of the ,~m pl~ ill ~ I" w-' ,,1 ~1;l i t), ,,' ul, i, ~"",h .. ~ly""rol is bombardN
with f. , l, h. :I>')' ;Itoml (e . ~ .. X ~ : ions I uc!\ R' C. - ~i .c .i mil", rL" ul..\ in the ioll
'><l u=. prod ucing l n ~ c"n ~; n ""u, ;" 11 b<o"n1 IlIMsary fm "",-nnlllg I,wrnm",,'"
The rneth C>d is ~~ ry con o~n i~t\t fnr ~Pf''''rria l" ,~", pk... b"t ma lr", read,oos
r md U<;<; b:l ~' ~r"" n" ions >II neal'1 y e"~ry rna" oa l".
1'1.o 1~'" Jt$" rplio~ ( r D )
":" " ni ~ ,,,,,
wtJ I~.~, Jr""p';,,~ II.D). TI>c"" 1"11""" ionization
an; p"r l ' ~u l all)' 1";labl. for th. tim.-of- nignt i"'lr" mrnl.... b ;c ~ ,,",
aJdll i<.>ll~1 aJ " "1Il4~" " r unlimile<l m:.., ran~ . TO F re",l~ing PO"""' of
:'\\) 1,oclO h", boM11 a dil,Id \'''n1 Jg~, but rec.nl irn~r", ,'-cmcn[, an; PH>m ;' ;'lg
lIj(n"i n ~ " ".'cn I ~~ ~, K ",~, '" al. 1999; Hill.llka mp eI ai , 1991). PD. pio nocnxl
by ~1 ~ cl~ rl~ n e 1 l 9 7 6 ~ fLr<1 , "owed ~!l" t m ~" ' pcelf:! could I:>e ohtaill.d rou li"" l, r, ,,,,, L,' lI" m" k ",,"' ,. Fi"ioll of " 'cf produce, two 10000M "Y pm<luc[,
1M ' .; ", ~ h ~ """u,ll inn;'e I ~ " thill_jib" , ample, aud stJrt the T al' d ock, !luI
pro:><l "o~ lillIe i(>n frag""ll1at i<.>ll, rO" i,,,:Hion of m" lec"ic, 'IS large a, 50 kDa
..i,h ''''''"'' " ",,,,unn8 c, m " "r 0.1'\: 11<,,'. boo. ll reported.
P,o l- rin" Jas< r dewrplion ILU 1eapa nilili"", iP,,,thum,,, <,I aJ. 1978) haw
hw n g n;~ I I)' C'I,.", l.;,11K ~ n" :lnd Hillenka mp 1988) b }' dissol ving Lhe , ,,mpk in
a ""Ld mal' ;, Iha t i. a higt.lJ enlei.n l :It>..-.Hboor ~f the la, ~r radia tiM . ", .., \ n
IOnIZe m<>lecnl.. ,.. LlrF,e ..,
kl)a (Hill cnhml' '" ai, 1~ 1 ), Tho at>.. n c~ of
m.... " . d lect, aDd rna.. me".." ,in g errors o( O.O!~,~ -0. I ~,; ma'c UJ " pan icuI.t' ly [lfilnu";ng method I",. pTl.Hcin ",i. 1O<rn lel",il rl aJ, 1990).
1M
3\_,
Lkn"",,..... imU _ _ ( f'. sIJ. !"i.,....,l. d b)' Dote (Dole <J al. 1 ~ 71 ~ Ii" ~. S J "
$oluut>n or . Iu; ....mr lc " ' l'Tl'Y"'-1 ~1 al mosph .ric prcm ,,,, thr ough a ." ," "' al
IOlOa rd lhe Ji fJ",,,n ~i a U~' pllrnpc:d . nlta""" to the
kilo. oI. poI~ "tia . diffe=
rna"" 'pcctm meter 4,>milh et al. 1m ). TI>c =u lli"t d"' r l c ~ , :1'" ck " rr". l:n i.
call!' cM rgN;:U the ...J.""' .~~ I'l>J~":"- ,*,--t, ost" h. r.~ulli~ u prod ucei "H"t~r
and , ,,,,,II, ,, droplet" no bl I'" macromolecul. ;. ~' l"'II",1 H",,~u"l":d" with
ch rg"" (h nn e' ",- l'IllIII Thu. a prolCln n bIr J protOn ro)r ~ , .,. ) 5- 17
amino acid>, yield i"!,, peak> ... ",.I.. !lI.l---20 ~ ' ~.,, 10 1 ~ U)" pN lerni tFent "I
......, _. "'''''.'.'.'
al. I'I<l l ~
I n.i ll~
~ i mild'I} .
."
P<, I)'llLICle<>tid.. Can yield
n.~"li,,, io n.
of .uch mi. val..... by
a propo,tionat e llaTl' b<r "rptot" n; , Thi, J r" m ca ll)<rN lIOed "pm hmit
fo r 'n/: mc.'u,u",. nl mak.i ESllffi<'o.1bl. 10 mO'>t I l'''''' of ........ ' 1""..1rolt\eters.

I' ~ I rna" ~~ctra hi ' -" bt(n meo. , u,w for .mol<uol<:< a, la'lt" ... 5" 10" D d
(Nohm; and Feon 1 'I<l 2 ~ . n<! ' tr""tur. 1 informa tion has b<m obl.tim:d rTIlm
alhunl;n (N) Ll. , OJ' tandO'm ala" ~u "",.u)' ( lJ...... ..J 199 1). U iing F ouri. , ~'alliform
(IeR) mn~ IfleCfro"",1 '~ \~l;"n l.l). [;Sol ,pectJ'3 of myotlobm
(1 7 kD aj , h"",
'Ii ~U ~ _ ) ~'I ..i'lr PO" "~
. ,Id <:0.001 D4 m~""""'-4.urinJl' . rror.;
(lk a d "I, I9'<J)
P'F",Ir-" ' . U...-Iul l!I"crurll in!o, mar;o ll "ooU

I ,~ .... pl miu " . ,.,. "r hil h m.,.
J. cub r ".\~ h l. ,..,; h .. !;>;o<.' c. i. , r L. nl .!"-'cimen.. ( O.flL high poIym., ... aD<!
"",'age . Iuugc. can be obrl ined rro ru I ~ mau ~l>"C1I. "" Iheir 1"'. ..... 1d"",m,
po, ition plOd llCU (Mttae" Ar ~f " I. 1,,!\Il, 1 ~1lU: St.-h uhe n 19'16: BaUislJ<ri n <It
1 'I'l1 ~ To ~. ;n; mi", "",..ndary ot'ac r,o"", small u mples (10. 0 to 10' 81 ale
r"*,,a bk. ,to . u rql<oouclbk Pl rol)"$i$ w ndi" oll>. ' " eh A' <. pid 1(. healln ~ af
wi", to iI' C U rl< ' en' f" U I" ' C l . ...T "" .k , a nd .>l h.,. ~.>1l he.lti u~ methN l
h" "e " I", hccn " ...'<1. Of raft" "lar j,.,erelt i~ ~Il au ,o mal-N ' r 'l'' ''' f.or "mt;n u
OU' pa ft id c beam sa mple iatod ""'...... ,.h C uri.,.",rin' r , rol)" ;l in tbe M S
, 'octlUln eh
llef. Tho. . y........ ~ n disUn3u,s.h d, ll"uem ~ t " LOS of bact. ri;<,
rCl")(ting ", It<..cry 15 . (Snyd er and Hard' lI IWll)
...1""",,"-""""1 or lhe mas; of an ion .. i11l , ..tf",;"nl .<>c"r",,} p",,;de. an a llcq ui, 'ocaI identIfic.olo on .~ i1. c1cmen.al i. nd ....'."ric) compol;tion, Th i ~ technique,. of..... referred 10 "" Mhigl> l'C'>Oi " IJ""- mass .peeIJOmet!)', , ince dnuhlc10000001lIg IFi gure 6.21 OJ FTilC R (Sct,"'\ io" 1.3) in,lrm" Clll< a", L\IUa U}' used.
H........' u . if inl,..-k. ;n" rna_.,. .cquirillg h;~h t.",lution JI . ab..nt. 'U~1c;"~ ll y
",-"u", lc ma... m."snremenl. 1_ 20 ppml can be aehio:; ,'c"d r", I",. ,.", . " ions
"'lib singl. loc:usinl or Quadrupok in,t<unlcnt< af l.iXlJ-..2,OOO relol"t;an .
n.......""" ",m he iJ ..,lir",d i1\ this way beea",. n",noi ,o topic alom; c ,,'c.;,,~ t \
.., n,,' eAl cl ,,'ha lo numbers, When we lake a, , ~ancbrd thc ma.. of " e
. , 12 0') ~1 ,..." T~hlc A. ) ~ then rn fo, '11 _ 1.007825035. for uN _
14,OO '.J07011ll1. ~nd 1m " 0 _ )5,99491463 (th. l.aot significant flYLln:. 10- '
dAll,m ..
9.3 e" af ener~}'~ f "c ry i.oto,.,., Ita, a nniq"e. chau cl c.
isu c "nlft.. drlccl" : "'" thc rna" or the ion. which , how, the tol,,1 rna" de""l.
J<knllf"" il' i""", pie and eleme ntal compo,it;on. FOT c<amplc. an ion "ith a
"'A" , of 4J.lIIM mu'l be C, H"O - ; it call no~ foe C.,H, ' (m _ 43,0547, C, H,N "
I'" - 4.H l41n CH ..N,' (m _ 43.02%). CH'SO' (m = 4.1.oo5 ~). or e , F'
I'" - 42.""X4t ' 0 d;'t i "g~ j,h thc compo, il;on, "'4U;'" an accura"l' in mea_
"" m ~ rna.. of 130 ppm ,
The ~""r"I """ o[ elemental composition informal;on incrca, es .x!"'ncnti411, ,.'ith ,.... f.a;Jn ~ ma... as doe, tho rcGuin; <1 ma" .mca, a riug aCCI\[<>CY, F;KlUC
"'J""""t",
,.
"
-,
,,.
~.
... 1
- .,
_ ~ O _
a . a
w. _
_ ~ ~ . '
" __
"
Ii
"l o , . _ 0 a . _ o _ "_ 0 " . _ w w O .W _ U _WR" . a . ' " 0 . _ ' o a _
':" 8 e e ~. u 1 C':: U UI :I =:I J I . n J II~ In i ~~ : :
01.1
I " \ ~'\ :
,.-
.'gu,. '-I, {'

ltJ()ro lh.> " , h
(:. 3 """":I Ih.
,,..__
M '0ll"n . 1""", .00 nOO
n~el
--
<>1.,....,,,< ;0'" of m/: ; 10 <""taining ea<boD,

m,,' ~
ll1 ." 1_
b~~ ", S't ...
Ml
''')'!I''8 . ,.......
ffi. '6 (If . ,-ariely of posr.ibll io:>n. of m Gl<cLllar weight J l0;

a m a"-m<:a..... in~ 8IXI1MCY of 2 ppm.
d i<, iG~lIi,hin~ tho:;", '"~lIi t'<"1
, . hndem rna... g ~ (MSI MS)
"Ooubl' (c.(lna""' locbru'l ' '''l. re _ i' LlI in ",veral .peClr"""""" met hod'" In
r",
mOl.. "I'''' '''''''''''ry thef~ ale an;,.I,'l!" u. MS,i\1S techn;~"""

~~"'fill ~ t ho:;
maS! .pectru, n or ~ pcal in a rna.. Ip O ~t rum , S"" il """" ndary IlmfJ>..."'.... l.ar io n
11"''''''' ' 'h"u kl be tilt ,arne a, til""" rfl>Jueing DOnnal m_ ' reel/a, MS/M S
h, 1"'0 m8jo,>r app/1 em iom (McLafferty 198); Ru""h ct al. 1 ')ll 8 ~
o..c applic-.,i"n ,"'" the first
'1'<,.:1"'......". (M S-I) ~. ~ ""I'~rat i l\~ device
fm m,"u' O'; soli iG D i Z ~ l j (m pm d ucn \t" . "" a , jrnilliT m"lt:c ula r l pe~i ~. fu r
c",",11 oompenent, All"r MSI '"'!'3-ralion, ~ln i . ~dded to MH ' 10 y;clJ J........
cialio n l',oo ucL io,," thaI ,,"" lhen ..., ... 'aled ill ),is- lI ; thi, rna" .ptaru m "
Ih"n u,cd for ltftJC{un<! ch
C'litalion of Ih~t mi,lu,C "ompoo<nI (Mel ..,tr,-n y
and Bryce 1% 7; K, ,,,,ge, ,II. 1976; \1e Latrc, ly and Bodholr t97 M ~ Ont or lh"
m" , 1 im po rt anl MSiM S "w1icali"", has been 10 I" uld n """luencinl, ""Ill ini.
liKI cr..-.nical Of ~Jll-r""' L;C d"~Tarlalion \0 " romp b .";gupepl,de mi,l u"" and
~ ft iallC !iqlII, al''-'''" ,,",t h IIt<l impure t.C [,actio .., ,owttd by t "" II. MIl' ion'
"''''''''I''mdi"" 10 "ach or rhe "Ii~:c'repiide. "re Kf'l-,~'al in '>1:5-1, fm gm"nlc'ti
t>r ~<Jd ;njl: .,erg)', ",,,l tne I',,>duct iollS ",pa rated ,n MS lt to provide n" arly
0011>1'1110 KG""""C info rnl" tion I M ~ I ..alJc.- , y el ,J. 1970; Wipl" . 1 ,,/. 1913;
Iliem~M "nd Marlin 1987; T"nlCT I'l H9). lbc I~ ml<m ,h'u~l ... lo<:".in~ m"...
' peetrn inet" l IMe La ffert}, 1'l8O;> 1 1~"U pro....n J'I'o, ticularly "Jln a1:>k f<>t th ~ "'ith
F T/K R pt<>mi'ill g [o r Ia"i"r pept i<\c' Llie u cl ai, 1993t The m,,,1 ",-jddy llsed
in,l,um e" l for .. <d1 MS/ MS n, i' hlle '~ Js u re m e n l, na" ~ n Ihl ' rirle '1....dr upe le i \'O$' ~ nd l'n k" 1m ; Hunt . f n l. I ~~ ~) u,ing 10w-.eoc'!lY I I().. \ OO eV)
colli";';, n. in ' hi om" quadtul'oLc. Such coll" io,,111 ~i." lion re M wilh a
(a~' 11M is Ihl
m mm on method of ~,Jdin~ energy 10 1M ""I"'tatl d ions,
allhougb roll;";,,,,. "ith a " trf"ce and b y ph"",n.. "lec1Iom., ;,nd ion< can be
m""
""to'
-1
.,---...
n.
'
..
,,'ICd . Hj~b~ne'n l~ .~ . 10 h Vl ( :A C~I1'C' di"ociat ioll (CAD) <If 'i ntlc..: h~'!l" tl
p<:ptidc ion. ,of "" ''Ie'> up to ~ 2.5 ~ D a Riemann aTI ,1 M ~ n; n 19Sn bul of
multiply cba ,ged ESI 'VlI\ ~' Jar~c a, /Xi kDu (loa er ",. 19911.
t he """.n<! ~ l'Phn l ion n'",)!>"" n. rJ Loni" ilion (En mal. spectla. m""'uring
MS-ll m ~ .... ' r-." u" <II a m <>Jt<:, ~. . f. " gm ~nl iom ", chalFLCle lilt' thrir struclUre , (Sh"UnOll lAd Mc L:o(k, ly l w.;.~ F OI eX;ln1v1o, ill LM rna" ' I"' clrum o r , he
h yp<)l h< l i " ~ 1 m ~l ... u... A, 8 , C. !he
,,1 i" ", ~"rrespon d m g in rna" to
AB' and ,, 1;(;' co u ld indicate "'I~er of the mo tt.:ul"" /I, II e R A or
A .. Ii R C , A. 1!00l,<t,'er. lite ""'.......,. 01AB' in 1l.e _ """aty ~ la" 'I"'e
pu;;e1''''
\rum uf the Aile fragJn<'n! ion ,"",uld Ix: P"S'iWe. b" m ng ,. arra ngemenl",
lho , Irud ure A B--C - B- A. In 11M; m ~ .. , pc<;'<lum 01 N-methyl-Nonl)
i>opropyk;" hutylaminc (Fig"", 9H I ~de.l~a*"e'S $"'" the "mminc~ \ ' on, ;01
... ', !ltJ ~n<l 114. and their furlher r" ~r r an !l':mc~ l dc>lDl'O'llions yield " ,htr
a1'><ln,bnt ." n, ~t mi: 44 and 58, "', pectl I)' (1.'''.... I;''n
If l his """.., the
ipttlru rn of ~n UTI KnOWTI , I hc compound .~' mdh~I ,"" ...1. h ~ I- "' -2-prnt ) t,m m"
,"o..ld """ hau 10 be co nsid. red, sincc il sho uld "I"" give ~ to t f>e<c, p...... k
(Lq.... l.i<>n b.ll} H,"" <\'Cr, Ib" ~ b"" 'V"l io " " f "',i. _\ ~ in toc MS-If .peo:tru Ul <A
"':: 114 ,"ould elimina te toc 1"ll er compound fro m co n, iderau <>n ; il, ' I":<:l....m
, ho..I"- . h",. nt!~ 11 4 "'i t 4~ .
r",
b.n
O<P'=J:C'fl,
-~
,.
(Cfi, I, CfiN C >< , C , ~ ,
!~
- C~
- C, Ho
,>
I"
(6,' )
~ ""
"
GH,-i fiC ,Hr

CH,Cfi;r
t ,. ,
'",
~~
",t
- C~
'-"
- C~H , o
u<,a<1,X' ~ '''''
",', ee
I"~
CH,=t
fll' z 44
11"
,
,-~
., ~
""',86
'",
I"~
nu i5ll
"''' ""
ICfi, I,C HN=CH,
,
Cfi, CH= N><
"
(h _~ )
H 1 = CH
'",
"' ~
l/"~' IQ .. n ~ .I .
Tty l'non"""n 4 .1~ al!am, u >m~ lhe me,astab le ion (m Ol dat a.

I, '" l h~ 'taelll1M m, ... m,.m' - m, ',"'' ''1'
When run undet the "" me c,pcti""'nla l ~~ m ol i li m l'" lhe nor mal 1mass speclrum " r & p&rli. u] at mo leelLle. "Leh os loillene. i' inde pelKlent at the sample',
source, alld can thul serve a, a u..rul " fJ n~c ,p ri n f' ror iolcn lir,t alion, III lhe
"'Ill< W&y, lhe hir h-oncrl'Y C,\ O , pce' TUn\ (Mt L&llerl)' e' oj. 1973bl of a particular ion i. \'inuall)' ilKlepelld<Dl ( c: 5:','; for pcab from hil1hcr-<:nerfY de
compo' Lliom ) of Its " " " ,,,, "n ,1 inlern a l enetf ;" CH , CIJ=On - ions from
(CH., ), (' HO H. {C H , I, CII OCllt(;l1, h . and 5o:-pregnan-l 0/J-ol-).(me (w hich
hal a C H ,Ctl OIt" . ide cha in) yield CAD ' peet", which "" iocn'i cal wilhin
~ xpe ri m ~ll t al errOr an d ' ub'l aotia ll)' different from Lha l or C H , 0 = Cn, - (Vall
"e ~ " nole " nol \1. [,alTerly I~ 7 .Ih). T Oe ' tl al" " ah undan"'" of produ ct' formed
by ' r oma neou . ", etastable ion di" ociation IM I ' ptclr", ~c,i on F IJ anol of
CAD N odu et, from lower-elletll)' p"",",, ,c, can Oe alTecll by p",cLlrSOr-iOIl
in lerna l enOtn; ' il u., for io" <tructure identification, Ihe peah found in thc ion',
M1 1ill'ctr\ln1 are omitted from its CAD ' pcctrum.
In " s pe~ l " l ", Ien, ion of this Lcchni<jue, lhe mass-analyzed primary iom are
tlculrali, ed to form a beam of di"oc.iating neutral,. who," producl' "ee re
ionized m form Oil N R ma, . ' l:>cc!t llm (Mcl.afferty Ie' at. 19~Oa: We'demiNis
,md M ~I ."lTc rl y I~ K 7; Holm., 19S9; "1cLalTefl y I '>90), Such dissociat ion of the
Unkng.. .
~
' .a
'"'
".
ec
" .,'"
.,
n'
0.'
n'
""
""
"
"n
"
"
"
",,..
'00
....
""
"..""
.,
"r.t
"
"
,......
".
..
U
'00 - ,
I,
!"
"j, ,
~
"
'"
'"
'"
,n
..,
., ....;<;.,.t......,
corre;;pondinll n<"lr~ l. call make po"; h l ~ l ~ " q """tilati~{ = 3':',. in Zh n ~ n a l.

I ~ g , I ~ ha n<: l tri:.a h.>n " I i,m. !hol iso",<'rll" e~ ..jly, <L1C~ ~. fi. c (', II ,' (Teng ~ ,
ul. 198Q) anJ r" \Il C . H. + - ""men i/. ha nl: N 01. 1989, 1 99 1 ~ ' flem....c..ilc IragmOlllati on" d"" l" pcd ,, ~, G ro.s a nd co .. "tkcn (Jen,en n ~ t. 1985; l ~ n""", ....01
G ,,,,," I Q~ 7; G ro" 19~ Q) " mila", ,,~"'c .. iromt r;;,.alion p,"~~di nll .lkyl-d\ain
"~8me " tn l i<ln hy 't~bi \i zj n ll the Cb i ft, t a,, ~ } I",m the site. For l (ln g-<,hi ~ e..tty
",~ d", hlhi.,ted calion ' Or c ~''" '"l ~' l e a nio ns a"" t<nc"'~ 1 1 y u....rul f or lhi'_
V "~ "" "Q 6.2, 1I.., the ",,~" n d ar y decMIJlO'il Mrn. ;n<h<;.'ed by tb" me l a "~ hk
ion . ",' l JlC8h 10 ~l;m j ,," IC aUbut one i, onw"" I"'" ,i billry I... - mz'/'", ~
I",lrumcot '~" l e m , con' b,nmg II ~ ~. ~ hrcml ,ll oll"lph and rna" ' p!lOlntltC
(GCiM S. M c L~ IT"ny 1957>, G " hlke I')S9, Mch ddcll 1973; Gdh a m ~' uJ 1\lM,
K3T. ",' and Cl~ me n t I ~ HH ; Md ..,lJn t, aoo Micll""wK;z 1<;</2) have paw ,,, t"
be of hi ~h , . lul; fo r analy, i, 0( oom l'l~' m' M ~'es, """h II", ,,,, rl'om human
I>'ol<>lI t",1n.ud\.. r l~n l e, traets, pollut , nl~ i" d.....ria l PT''''"''"'. and sam r b lor
fo"'. ...'" .t ll~. Wilb an on-I;"" "" n,!,u"l. useful
"f'n-" <a "r Ihe GC d fluent
c.ln be (,)11ectnl "c,,"T~ 1 li m~ " pel ' ec""J, The hil':h-pnfom ,jUltt li4Ui,1 I;l1ro11'l " to~rap" (LeI can ....T"l <. ,~ ml lt u~. not arnenahlc to (j('
l(; / M ~
i' ""w I'd " lt\'el~' roul ine. ..,,, h . v. n ell of ,ucce" r~1 i" l<...(...~n~ ledutiqu""
(Ca rlow MId Ro,;c 1'ilR9, 4, rpmo 1?90). 0 1 th ", e, P " lt l , ~ be. m , M ,U j lC- ,
""' ,n, ler er ai, 1988) ;, paniellL" ly , el. vant, ..tnc. ,\ ma.~ " . l"",ibl< Ihe m....ure
'nenl of 1I ' pt;" l'" of low .'olalilny RH>lccuk s .. lal~e J \ _ 1.000 da llon, . Ot ltef
'-"' Y pr omisin g co mb; ~ ~ ti ' >fl tech lliqlle< """ , ...... id S ' lelcctian with ,upon 'll ,"",1
0..00. c hH>m " lo~mphy (S'niln "' al. 1 \I ~5; Choil t , anti Pink, IOD 19901 a nd
"" p ~ l.1 ry - w"e cl.,ca" r nnr c, i, (Kuh r 1990). \IS- M S was de"" ibed d""c
"w..
l.ef>""" """
'.6 The _
......"...
Of!"n Ih. ,,,:k" l;"'n or a

11 ru",1i,,,,, L1 ~ I' O U p to a large m" I""'uk ""'b as an
a lb l" i,1 ~h~n~e' tbe 'P"d m m.,.el y h~ ;n,r.~,ing the rna"" " f ine .~f", ;"'n
lr~~m.m, ",'ni" n mn l" ill Ihi' fun"1,ona l gt<'up. !>u t without greally changing Lite
",Louv.: ablludallc", olllle,", i"n. ~",m.pl~. An ohviou, e~~ml' l" i, i' olo,,,,, m t>Slilul; '>n: deuterium labelin~ of a ",'ml"",nd iJlCf"'~ the mall of ea"h io n bl'
(>fit fOI t ac b deuterium a ln m tllcorpo ralN. but u..,h 'l'\' .'ffcct, CD ion I'elat" ,o
. hund. nee. al. jten."all ~' ,m~ l l. R"plac""",enl of a hyd,,,lt"" hy a ''''>Llp of low
lPO"",,,,,, (,w:h a. m "'b )"~ "'t tho, yl. or chl,,.-i"" l . , a ll unrea,I ' " ",,,,ilion (for
",,,"' pic, . ring. especiall) ~" a'olll "tic ring) often gj .~.. inn abundaIlCCS 'imila'
tn Ino", " f the oril" nal l peclTu" " I I, jng thi , to diloow r the nature and J'O"in on
0( " , ub' lituenl ~dJcd I" ~ ruolerole h ~. Ix: "~ l"rmod the ""hift = h ni<j llC~ by
r."
lIicm ~nn l . \l(>2~ ", ho, d<mom lr~t.J ii, 8"'at uLi~ly
\ he ind ol. alka loll!l.
Th e.., ,!Obit r;,,~ Sln lClUl'", ccutllU fU G~tional Jro~P' lhil ' lronyly inn~
t1>c <kw ml'<"i l;~ 1>, minimi,; ng lho clr<:<;l " n the 'IpL;;lru m "rm"Ioc'Ular .ub<.l ilu.
Lin,,- TI.. rn~\h <>d; , I~" USdlJ r~r n.., iule. conta ining I<' s..,nuwnal gr<m ps,
..ocII as t~lpeU<lS or l t ~, o ida l alruboh.
to nknown 63 . The spt<:lrum of Ihil unkuow n illdole alkalOId Imldd le) i ! computed to tho sped,.. <>l t "'C' l no wn ,lru ~t uT"C . Wh..1 r.....,Li.ma l ~ ",ul'> d,,,,, the
A, . ft;, .
,..,
,..
'..
Ii
,or ...
2Z>
-Woe
,
,'>
""'e,J""~""~I
,.., "'I"" ,., , ",,. , ,..
~
iJ"
j :
,
,"
i!>
'00 {
- ...
...
.,.....,.....
, 1'
""'~~l
,.
,., J,.,
.3
. alP. Il, . CH,. Y. 0
_ _
l"t... ,.,. ,. . " i,. ,. 1,.

,"
" '. " I I '
, . ~,
1 1,. " ,,.
,.., - .'" "'~'=~~=-".,'~_...:,,-...:,,,h,..,\~":~~"~'
unkno wn ..~.n ,~ i n~
W h ~"
a . e l"'y m_
probobly I""",ed , .., ' he "",I<:cuI" ,
.keI Cl on ~
(" hcm ;"'~, o.m,"",",.., or ~ " """,.u nd If> ~ n aJ'l'f''I'''''''' d t ri\c. l1~ CoI n >(>fOt"
11m... lmpT","e the r~ lllDS ma'l5-spc<'l . al <bta. c1thef by inCfea>mg 1he COlli"
pound", V"I")T I"",'u' e or by m<l1 m; i ... ~ ru m more edWy 'lIl"p~d blf.
f"mncr """ lx:<:om~ m""" leu imp.>l1all' " ' Ih the de't lopme" t of IOntul ion
mel bod, fo r .lOo, olatile oom p.>unoh (Secli"" ... .2~ Inlr OO ....1 i" " or a 1.."",jo". 1
~p ...1ucl1 ...-tIl stro ,, ~ly dum lbe rra!UDenlat ,O" dor e. ample, ami_
Cl h"
ylcrJe ketall ..dl , ubo<lat1' ial1y chan", , ... ma .'.' p 1 ll11 io(<>rm" I,Ol' (Anok,,"
l'lgg~ T hIS co uld be uK>.!. for u . mple. 10 .:.
(r~l"'""'I.I""" i" """ nr 3
""'rold olOlccuJc " bool wbich . he or~"al lD8" spedrun, ~vt hllit ,nfcu', MI;"'n
n.e
{Sa.1~ m 'oI "'~
a.
.,rue,,,... Ic.,u,,""
'II'-'"
Deri. a li"u ion ca n be: ....".

a d.... ",i... 1 ~ I <If ' 1""-.;(",
.of ":Ie uolnov.." rn<:>kenle. ,,it h ,"" mau spc<:tmrn of t he IUb.fqUCltl product
t1scd l<l mea ...", , lie reo.ul.... . !'lo"" th<. nurnl" .., of cnoli.'. hle h)': jl IS only 1M m. ss. (nol
the ...... 'i . c ab undance) o f the p",J IIct (ormed ..;, h lhe 1.,11"'" " urn"", ..1 de ul,"
n unl "lolllS tha I neN ' to '" Gt-r.e" N . Sud, e.chall~ lI\.in8 ("I ioni.<:l' ~.n CIIn
he ",,"le"""l y ",.n ,uo "nl fo, n = r"e, ... Iu, H,O.. l>,O "r NH,iN D. ". the
IQ1,izin~ ""'f"nl ~"'" Ilium ... I. 1972: l la lTl" , ,, l'l ~ l. Pr. 1:t9- I], I
Beckey 1977; Bud de 19 N ; B " rH ,,~ .n\ e a nd ('u,tag",,11 . ?R}; lIu...t. eI aI ' 'lKK;
C<",.. I?B. 1 ~1K De<Jra ee 1 ~!l6; facdlen i I ~U; Gu kfa 1'l 1\6; H.rris.on
19'1 2: Jen"-,, 1 ~ 7 ; K"ra;ck I~K.'i; 1...1 I ~ K K ; I ,,\>m;,n lWO; M,,<lo "' ~y 1m;
McEwen and Lm eu 1m-, Mcl'adtku 1973; M oU.ITcrt~ 19 K); Mc ~'" 1 I"""";
Merrilt 1900: Menzelaa r 'I aI. 19 K'); M o.-, il 19KI; Od hatn '" <d. 19114: Su ellcr
and Wat".., 1'Nt1.
7
Theory of Unimolecular Ion
Decompositions
To u""lc" l. noJ lhoJ ou ~h.l} lh~ oAl' abiht 'Q . ~nd peciaUy lh~ hmiu ti.:m" of
ma" ' pe<O[MflW'Ir)' for 'I ru"Wr~ ..h",iWtion, pno m u, t t>c lam il"" ....il h the ba,i.
Iheonlio:.>J . ' pc' l, 01 \mimo lecuLo. I, ,,, """omj>Qloition.
J, ' ~n <.l '. 2 are
,' rr"'l"i"tc ror inIl OO llCtOl)' "" ulUI d..,i~nc<J 10 In cll rundamrn,;>1 inler p"' li,'"
, kilO< rhe no mc nd;ot" n: . 00 abb,e"'" l;"n' ~d Oplod t' ..T< rollo", thoR <,of d..
GIANT mbk>c t Lia$ // " I. 1988).. ",Ii " .. iuu <><luetiQtl ,. rerommcnJul "",d'll&
,to ", d t " , lhe " ii:ttnl;O! at lh " end '" thi. '.....1'1"'_
*"rion.
Ionization o{ 1M " " " 1'10' m ule"" l.. ",ith 7tk: V elect",,,, pm<.l",-u IllQl"""Ia.
ion, ",h"lie ;,,1. ,l1li1me rgy valuu '.E) ro " " . b10ad range (010 ;.. 2 (l <: ,, ~ " r_
ag inF " r..-.. eV U e V _ 23 kea li mo l _ % 5 U /m"I). In til< appcr ""n o! t.he
W"llfh.rJ ig (1% 2, IQM ) di "gra m (Fi,iur. 7.11. (hi, d'<.Iri bu'ion Do J""""lbod by
l" "h~b il ilY funell"" r lE). Th. 'M" ~ or ener~ie6 il dramalJC;j1t~ <li!re,.e"I
from l h~ "" I cV tller ~ - ", ....Kl' distrib\1I;(>rl L"'.LaIly foll1ld. w oo n den~ - f'l''''''
reacoou 'J'''' initiaU) r",fMd M+- iOIl> I1Inse from cokl III ''t<d 1101"; DOl '~r,
flTisingly, I"",, Ib u' ~ h n,,' a widc I1Illj!.c ,ofd:ompo<li(ion be h ~" i<> r_
Onl y ~ ~;_ IlJlaI" reac';", .. ", 'e ",,">ltd. for th. gasoo u. it>t.. r" ,,"w b~ CI
,.....<lc e . he u . u~ l MS npe ralinJ. """nd,.inn. , Tl~ n at ~ ~ a.nd ~Il .... ,,' tI.c<e reoc_
tiun. d,pc'x-] nn ly 011 the ;OI1'l Sl r""'~ r" Hml in te m ~ l ~ 1lC 1Xl', il'M5pe<;riYe nf ,he
ivl1.a , ;on moth<>tl ~'R <"'""'t<>I:l " ~I. 1952), W;,MU. ~,, 1li ,.j 0llJl , it il rh. """'~)'
" . iginally depo l,lt d lD the ion r" m, lh~ io niLIIlimt pro ",,", {plus III. "ffiaIl
.m,,"n l <lr Ih"I'0...1 "'<:T&~ ori gin, ]ly in I"," p,eC\lUQ! moloc\,l. ) r""
,."
tb . JOn 10 <lec<>mp" 0" ;ooll1 eriu , -flit i""hahili l~ '" .... y .ucfI
c!lo n i,
.X j>' ~ a' lh. rate cun. ' '''' l k. ",hich ol)"km , ij-' mut>! ch~ n\IC ...,th the pm;yr""" Kill'. I nt . m ~ l en erjl:y, L. Hy pol hd ica l keEl fyDctjuuo. lh Q'A'i~ s the <'h an~e 01
Io-'fl l wilh F. or" al", gi.-tn In h gure 7.1 (I o""tt ""to. w!lir;;h 1",",1'" that io... vi
,I><
".
"
-.........__._._,._-----
,
,
,aM
,
PIE)
,~
_lEI
,,
..I. __
'. ,~
...... n . The W"',l\;lfu,
dug_ I:
,01...<.,,,10,1' '" 1' ( ~1 ~nrl .'.1:' I,,, ,m;",,>IOCll'"
......" ' mp."'Ii'... < ~ A BC n" . s.r Icol ~ ..- ddiniliom
110.
end
I W. ~ rfWlj g
1%2,
;"n
1 ~ "6. )
"',,'.'-1 ; ~ te rn al-< l'Ie r:y ~ol ues 10 ,11 not loa. " apl'm:i.~"le de.:omp<tOllioo rotes.
,,'ill arl"'at
in lilt ' l""'tnJ.m . A
,>I _ 10" ' ,,,,

'Of len)
L(l ~k ~ 6 on the en......, (H gnre 7.1. l ~ w er hair) f<lr II", ~ .w: , on M ' . ." 0
thus define. the minImum :\1" internal ...... gy (0' AD " fonnal;om. ",hiell ..
, mne,,'h t highe, than I.hc ' C,," ,ion ~-ril i "., , 1 .llC,~', "-~ (AD' 'J; Ihit te nn iooiosy
;. p, efe,able 10 "aetivation e ne rgy.~ and;" d efi n.-d a. ,"" diffNcnct bel ... eo;fI l he
' O"' I'"inl ene'gy " f M' and ,ha t of the adi". t"" <:0"'['1<-' for M' _ ",p '
(Ro bim on and nolbron~ 19(2). At higher M" e~~; e< kl ld ,. _ MI ' become<
~",a ler 'han k(),1 '
,AD ~.o thaI the formatio n of AD" Is rl~OM /\-lcla
. table ;0" dcoomjl<}"ilion" m', arc J i,ou,,ro la ll:'.) N"l o Ih. l II><: ""n i",,,,,,
r"a~'!ion ," te, producing m.asur"bl. frag"",nl lon, ca n "" much te....~r in
\ , ~ ppcd jon , ources,
I h. ""tu" l iou "bundallc, ,, a,c Jcl L,minoo! hy hoth the 1'(1;) an d Ih" LIE)
J< l.oli"", hlp.. Th~ rclal iye pr oponion of M- ' jon, lhat remo.ill undi!.5OCia,1'ld
i. dc!mined by th . lowe" encen teq ~irW for lOll 'ourtt di,~ "-;~t;,,n aM
110. ,.131i.. propo rtion of M+' ions for"' c<i ",ilh inlom ,,1 ennlj:iel br low lhll
.....gy. ll....., ,elal ".",, !lip" . n: , hu",n b ~' 110. vertic'a l dl.. he.:l I I M ~ in Fi ~Ul" 7.1,
5<)
a;; M '
nl k: "" ....... 01
~",a l"' i, ""~"'''Y fo, ;0" -'10\1["" ckornP'J"irion t1tW I"," _ 10-'
wilh I ~ . h" k.-.l ar~~, .>f Ihe Plf.) eun e rop'" "'''l' nll l'''' . d .lln-e prODorl""""
lormed. JI It.. ion izi,,!.......~"m < "" ' ~)' l' lo...n ...... rh;' wrll ",<l Hce the llH"'I>.:. <>f
~ + ' ;01\\ lormro .....Ih hlghel mor~~c. II Ll.1\' Iha ll it .. ~n rednc. the numhc' (
Iho,e form,,, willi ~>l r (no,. lht ~ 1I ...rt "'....., '<o l~ '" that 1M
projX'rhua ur M ' ion~ th; " do ntlt di~-.uci.tl~ .,, 11 iJl<:lea..,
N Oh: Ib l l j' e . o ~ d. d Jr
II>< Pl f.) c ul Ve l_pre ..,,1 ("" inilLal ~ bun<J a l ",",
<>f "' 1) a ,.u ."-B , Th_ ioruo l
d v..ith ",ff"'\cnl ' nlenwf ' '''' ' 11)' "ill Je,;" n, f'OU fm th. r: tho: .hu,,,b n= uf Ih~ r~, "lting p'od"~i 'm ", (and of Iht .. ndic.
socratc rt AI j + ' and ."- B"J "ill (\c pc",j ill luru on 1M P(li ,1 " nd q F.\ ''''',l'<01I' ,.,
A D 'an ~ A ~ - _
,.../d".....
The hYl"<" M ' l( al J>, Icm "f Fi~ ure 7. , in .. hi,h [.,,"B~ ] > [ M 'l ' ). illu>tr~ lt'
4,,,,11.... '",po.>fl onl ",peet .,[ " ~;m"I<.,-,,b, <!o;Olllpo:lsiti""" Ihe ~M-1 "m "r
Jo" 'nl .,,-i1ic-41~~"" ~y d"", nol nttl..:ml)' Dn xl" oo 11," ma<l -.abumdunl l" n. Similarl y. I"" t.mp;;;ratuT"O Olf 1 <'"' ~ p h ~ ," 'YnI1l..... ~ l cI>rm i, r~ i ...J II>o pti.
nUt.: ~ h. yield of Iht dno l'l'd prrulLJel ll' ,,"ugh '"killen. WfIlro l.n In Fi ~lJ.r " 1.1 II..
rc . c l; l'~ ~BCI)+ ' ~ AD- ' t1a , tho mOIf f.. ",~hk "~ll h nl py. bul ."U ( U _
xe - hJ llllIO mon: f~ ">T'n hl "'ro py. I'he lra"",iou ""'"' .I'll ",I'" io b ll'lJ.'"
7,2 roo' d .nc " "",iot>< ,.';""-.1 i,,, lh.. bcl, ~ .i<>r, 10 Ih. "' ~ ru n~". ml:..1 I'trlni n ~
AD ' I""",,,, bond' "rt r"rmed. oIf<cllio ~ II," . "ergy L"eq U" .'" 10 ""'HOA- R
~ rUJ l
l>. n oerilical ene'lYfor ,\ll + form1' ''''' i. h;~b.r. "'00;>,: Ih;. '"'1ui,..
B C d .av age. H o ~'er, . he . I.. requ i ,"mc ~t< r,..,. AD " 1"'0' 41'" '' at . much
mu t . " riel than t"~ ror '\!J - [u,m, li" ,,; i" lhe I .' mm " l, ~ oft~ n II IC<1 (" . , uch
lroll,il ion "'" ,""- Ih, ,,,, a re, j'<5P"Cti . d~. ~li&hC .n,I ~K"<" ""i' ~tro camp...."
FOI h,p.-r-",,",gy ~ lIcn ' i""... Iht IJ- C bo nd dlS"",,""'I..,u CaIl Inke pia
""1" '1"", ,,, sulficient "ner~y "=",ullo",. . ill II,i, hon d, Hu"'. "". (01 A1) " r"'rna lion, , "" energy r< q ui ' ~metl lll m" , l be "'''I al the , aIIte lim. Ih. l A ~ nd n ott.
'T"
' --
-1)"
\e= -e'
"'---0. '
=<0
..
1 / ......... ..-.. .. _
_ .h _ _
~_
wi' hm """"' 01: di. tanu:. whi<h '5 1"'" ror onl1 a .....11 pro ronion " ra il f"'l.<ih"
rook>""""".... of AOCU ' '1......, othctriDIl eo lh.olpy a nd cRlro p' - elk"", in ,..,,,r ,,,1 1c...J I" ~ ...t>. .o n.
lial DU"'bc.- " f com"... ;", pri",~ r ~' r"""" i, .... n "",nas the ........."...." >eCOOdary
~nd f" n lt .....ctio""' rh". t he rna", speeuu m of 8 Ll qo;t
~a D ha~
hnnd~ ot pca ~ .. lh<: """,peti, ,,,, ""lure of too..: , cact loJ'"
n ",ra n Ih. l
mol""" ,
."ut"'''"",..
rclo". e ly ..nail cha" gco in mo h "lo.'

,,11 ;n lo r", oJill ,\,n"-':1 in po,;a~
"""",lam"",. I'm Ih i, <e>.on , in intOTp ret:' D: 811 unb lOw n "J"X'l",m it i. horIpf",
(0
stud y Ihe .pttcra (I( cI<l<d}
<X:'fI' lJ<:lund...
1.3 Ou.as i....q whbr"""-.,

TIle 1am ou, qWl';""G U\~ brlum I bIl'}' ((.'I T~ ,,.,, i,,,,lI, r.o"" \Il:I\l t' Ro~L
Walle""''; ,,, W. lu ll aft;g, .. ud E~'nn~ ( 19n~ .,,,,. ide. a .' " y. ielll <1""" -;1'1;"" " t
m a",,-;;poc!rul hc h \<;<l, . ..hiell ; , no... lJ,"" . "" lly a=t'l l'(!. 10 0;1" '''1'1 {l( l ile fnOIt..
<", Ie, which u k.. p1>.", in al'pl"o lim atN}' tW ' '. ,n' ualll };.I ~, t he .' ~l\td
mol""" l.r ion with out cha Ll~e i" bo nd I.." ..., h (a ffa,,~k -Con dLltl l' ''><:<:>' 1 h
"""pt fur th" ",,,,110Mmul<,t:ub , l ", m i ~ ,m , 1x:1",... n .11 tt.< f'O'I" N~ ffl<r,y stat e.
of lhi' ioll. a rc , " ffi<1<: nlly rapl d IM I a qua ".
hililic", " f Ihe ,'"""u, l" "" ih1c ,1"e,..m l"",;li",,, of ~" ion ~d (o "l~ 0 " it>
>.InK'ILl,e and inlernal energy, a nd nO{ on the m ~l " od uioIXt fOI lh.llllllni ioll iu don, " r on the ,Iru~lu~ " r lbo precuL"lK'r for, 01' fOl mat ion n"",ha lli"" <Jr. \ be i" "
~lHk f ~ u i lL~ Joo" mp",il i"n. Th~, " n i"n ', d"""m!"",it inn d.."..n<11 only Ofl hs
iLl I" "".! t:I>Cr~l' an d ii' qEI fUn"li~n< , Wl>cn wo 111 0'1''' m""l1an" !1C4lll 1I1c me lecul., LOn wilh a 1'>ealizoJ char8'=' an d r:l,<\i cal ~; I o , it i\ not n ec~ " . r l thol th"
i o n ilat i~ n a "l~ any "" n" , o, an d cc1ro n " l l.h..1 , ilo; , hi, i, jll' l " 01 M" "' pt to
depid Ih" ground ~kt:lrQni" ' I" t~ b<fou deco mpo ,it ion, l " ~w elO~p1' "n , ha>'C
been [" uoJ IQ Ihe Q LT r he, e " non_c r g nd i ~" (\;" lXiatioll5 80,.." ally i"y uhe
'mall "'oJe"ule' (lewer, m"" o widell' ",parat<:d ' Iatc, ), o,"it"d "l"" I' on;" , I"t o,
lhal arc , imilarly "i",lal"U," and ""r)' [a'i d""omposilio", (", Hr " s~ 'I he
large;1 i"mc ' y,tem for which n() n . c rg odi ~ (\i" "";atio,, hal bee" .uabl i. hed
i' cn ,q -o 'Jl)~Il, --+ [ClJ, q -O') r;Il , J" ~ [( M
{; H" n
:l(M CH , )' ] (Tureeek an d McL affert y 1984; T urecok ~t ul, 1990),
The Iherll">eht:mical a ppea ra ncc cncr~y, ,~I f; ,{,\O " ), i, lh~ m i ni m ~m cnorllJ
n""",,"r}' to pro<1 lICOAD' [mm the w:rollnd-, talo IlOUlr~1 moleculo, The ~litj<::ll
ener!D', I:'.IAO' J, i' the minimum inlOnml onerw:y oj' M ' uq~ i rod fo.- lllo det:umpu,i liu" l" yidd AD - , ""d lhu, A E,(AD ' ) _ I E(Ml + E. (AO ' 1, (The' "
and olhcr rdali"n,hip, t" f>,,; di,"u,,,,d ta l'" '"" , h"wn in fi~~r" 7,3.1 Molecu
I", io'" ~ont,il1ing ilHornal o" rrgy "' L" ,,' nnut uewm"" .., , ej aN le;,. of t h~
amount of lintc allowed rur dccom i>Q.ili QIl , Howeyor, Ih. pr ot>abilit)' tht M -,
io", or im.mal e uef~ Y > t.', will p roo uce AU - in a LCiml , " u",", uOf"'nu, un tm:
--_._-
"".
....
'"
.-
t '.... ,.
1__ _.
_ ~_ ~
"'lOt.. !
"
' .
_._.
~- . co
, .~ I
f
:}
If lltD!
' f ' A llo- }
JEI '-UCV)
i , ,
e -;;-
A8 "
' CO
A",olA S' l oA" ,.-'CCI '
,...,.. U . l1lcrmod":lIIucool ,: IU:r lt ,....,.... . """

1ft the m. .. "f"d n .... C~'T.
"If"........1:<........ "'"
...-J
d..~ ............
I. ", c"""otanl. l: In[M '-:J..l M ) _ 1,). ,,C""'.tl dcl'iM C,l"D- l(h~ ...-. 7.1 ,
I "" In, ,,",""1~ 01 p:ra>no. iom . ~ h.o..., l'A ""' 141 ""-too,,,Jil, ,,(...........
,1.0: M...."' " ...... '\1' ....\ n- . _iol. , l, . F.,l AIt ' , ;,. lbc 0 ' ctlC1ll, ~NclI>C>Il5
~ lO.>l """",nt. '" Air ad AD ' TIl.....'" prodlll.l' " I>'
01.... 10" ... I"" 100<
f(JU/ CC ~~j , .. iI.Il etlCflY'MalI a\>o.Yn: l it< cQ<Tnp:>Dillll !tlUft>O( """' ..., 01"
l"",.na: """'!Y-11>.
"",....co
[ ~dl....",odI.lr.ic:ol
. alIOt by
tlw _ . J
.1'PkI"""'"
it)' 10 l>o: b;5JloCt IlI.o"

F.. _ f;'
~"h .. 1 ............ ttw
"'k "~lC , hiff", aJd.op Itt.. to .. finl < 0111 e~ . It .... q be u ,,,'" ". leV jl if"" ;..
I Q ~ !, R u.uo~ ."d Duo h . Im l ~_ Lbal lblt _"u",,Jc or 1M 1",_.. "'if!
<kprn Ollot , LIu1I I'" DIU' of 1(0""'" ..ppoa"' ft<>.:
..,h
. , ... ., - i.n FilOU1C 7. 1. iILO adJrlJ........ ~ ;u.:"e beiOf. 1M 'OOG1 per, " . ~ . hilt: ' 101",
'F~I\l.cilN l " l~
""'' 'fl.
i""rerr"", , h" lY\C;l' uro:! "r pc~ rII n,... ."'.,,. "' ~ " nb ,c1c,c,,,c to , (A8 -\ \ 1",(
MO' '0 '" ,,'I~""' '''''"' IlY "' '' 0Uf~,",1, I" ' mol "" 1""0.>.1 I", l .., 10" ~- ' fur M - ...
A1\ ' ...'11rlOC<'mP""'" in",,,,,,d '" pr<>d uc,/, AO- , l.incc .t lu. tbi. "'....1I<.> n i, much
O
b r~r_ r ile 'n l.... nal enc"J " I '-" ' l!l11 k .l AS ) 3S sh"",,, ill fi",~ , . 7 J III
>'.ld <'qual . ate> of fo rma lion fo, AR- ~ "d A I) ' _
"1""'.'
;111
(In oprctrMe<lrY, 3 ~rl><1~IUt>k~ Slale .. a ! .... ronodf"an'ioca ~y unslable 'late that ha, nol )~ , di"-Ocia,ed f..., k" "'11c r-,."",m.. i " <, m ll ~ .I , in MS a
"md .-ta b!" iun"i, Un<: ,h, \ 4_ , di -.;i~~, bul ...how dio.wo., .Iwn .. J.:L)-OO 1o,
\;'in<:ti, rea, uns.] n", dllCnm/'O';ti" I" of nlcu , u hlc ~ "" in a r.d,I-I", d, ill , , ~i un n" '<,eli" n, " r ' a l<:-onsl" " ' \'.l ,,~ jU$I t>fto... Ih. mm"" "m ' '''luim.t 101
) i.ldi"~ M I "I"'ct' 8 tbu. "'JII''' ''''! a
inu-,ouree dr>coml"'SlI\c>n HIC
l e ll aDd
nar ro" ranl;~ ,,1 If val.w.. ..1 0 ' 10" mnl ~ - ' jmu.:h ~, ....., "'"
iUll-I ,,,1' i" ' lr um enl ' l, In Fi ~Il ro 1.1. An " ", n, in Iht M I 'f"'d",m of M O',
(I",i l;"" led .. m (M O' - AD-J. thu' rr. l<t "'lilt I.. ~ ..I PIOMb rJily h o m M O
ien, " I' ~n~l"c, ~c r" cr n ..(1\ D O' l ~ n d F.,(AD- ~ a ' Kl (hdr "'''0,1.0'''' i. n:prc_
>. " IN hy Ih" ar<M"f lhl: CC"'C'l" mrling ""'1'<" '" "i nd" ,,' in 110" 1'(t) ""r....... T~l
"'-"'lp lc ~ "'"elions, which ca\\'. a larger k'""ti< '~ l f,. "" II tnu, le lld to Il''''' mOle
.~" "d~nL rn e L.\ . I ~hl . illn <Jewnl\lO>ilion " In the "une "'" JUter d te ll............bk
lull> mOIM- ' ... AB- ) ," u, ( Mri," lrum M ' of ene' g;'" cnrre<I""",f"'t h> 1 beI"'""" 10" "n<! 10", but th e p.o ba boi lity 01 mon ",n , ~conlflO:li,,~ in"eao:! in
t ile iun "",u' ce hi' M I _
i, nm,h higher (= Fjg" ,e 1.1~ "'. , hot
Im' I\1' ... AB- ll ..ill It. "n l~' " , mall In",(ion ~f the , hundll"''' iM i",,\<'<!
1') ,hi: rclool i," " 1\; " of thc ,Ofu,po ndi ng wind,) w in the p(r.l eu,,', D!' M O'_
n."1 (ur MS: M S 'lUodi., Ih. utilily of \11 ' poctra i, , e"erejy !imilc'ti b)' Ille
.1I ,, (imi,, ~ (j eQ "oI>Ii u,( hj~Ir -t:n.r~ y di""e;"li"n pmdllct , "n J the .. riobil;ly 01
" " ba nda n"" . Wilh prceur"" r int"rnaj...,nergy di<trihution
,...;oct"''''
f".
en-
'AD<tr htatl.."
of
"IE) f uncti o n ~
\ 1.,., illCIlk.h I(), llpp<m.imllling P(EI of a molecular i"n ;n>ol," me""" eme nl
" . ' L>loc"u1;n r nod",:ing M - from \1, t" ",h i"h must '" added lhe
"" trnal e"" ' IlY of M bet.. ioni:.<..aljun , Ikea usc i (,"; /,~ ( i ()n invol, '", ,, verli""l
tuUlOJhUIl. 1M
f...~ ""= ""'}' [" produce M ' < "ncr~)' of a " ",,1eI;ula j' <loelmn;" ,l~ l" ""n ""
,~lIe<."Ied in !he illlem al en,,,!\., "f M - pr oduced b)' iu nization from lhil , ta lt ,
TIu: "1',,,,,,," taUo n of Ihe J'll':' lunui"" of M ) ', . u, It u. '" fil;u ,. 1.1, r.lull~
from plortlng E for each ""alc ag.<m' l lite ,cla t;. e tn n,ili"" p,,,b,,hilily I F ", ",,~ .
Cond<>o facto' l (01 lbe . Im.. con .oIul"d ..ill. lhl: in lc ,~~1 "nl:rllYof tho nouttal
m"Itt,,1eI~.q" a l 2'lR" K, 0 07 eV rOf C, H , O an<! 0 12 eV fot (; 411,. ; Weilo<C1 ot
of l h,, ~~ ..."1&.'
._._ .
~ -
f, - Ll "
~
t-- "'-
j ~
... ,
-, ,
"
, --
............
..,
...
......... "
1
F",",. . P. ""''''''''' ron .!""" ,,,m
'* N, nor, v.r''''1
' _~1 ",ol,), """'~l>U"du'jj
'""'"",ic.',-i "fali0".1 """ illY Icvol . of r-" .od N, ' -, .. od "",Jc",,'. , urb,"'b
1~':l. ., i ,h permi""ionl
at.
"r ~ , (0 .." ,
1 ~1l. 'I11e phOlocled ron ,peclrum lTu me l tt at. 197U, Uho,h 1 9H ~ , MOIri'on 19% , Song \ 'J'-) which 'cp,,"c,,', 'uc h lr>t n,id ,,,, p",,,,, hilj,b fnr P""t, ..
ioni, ., ion , pro, 'ido, a usef,,] appraxim. tioll of P(El frolD eloctr o.tl ionizarion
IMoi'cl, er ai, 1912J. Pcnnin.ll ionization, lr. ,,,ferr ;nll . ncllO' no m tI' e 19 HrY
2"S He a,o m" i' 1ll0ro fa ""ra l~ o I", lh~ " u,o, ",,,Iccul. , ",nj,.I, '. Fuji... ",. ,I u/
19M).
"', a ,impl' ,umpl, I Fig",o 1.4 ), t he p hol"" lc ~t loll sp ct , ~m of " , 11 , lIo"11
with a ,."lIeal e" ergy scnle (a, in F igur, '- ~J oOl'rela"d with ,h~ e ""r~} d,IT~I'.
en"", he'w""n tho gTO'Jn ~ elo"tr onic " " ,. of no~ tra l .... , and Iho thl... 10lOi elt
N, ~, ,I,clronic <late , . Th , ioni}alion en,rgy UL ~ t h ~ amount e.f . n.ra Ylequ;t~d.
to T~lllO'-~ an electron from the l1ighes, N , elec'lo n]o k n l, 2j!<'" ' hou ld defj u~
the luw.c'1lcr~y limi' uf 'he P(E!) "un-. Although th j, omt e<l' ond' t<l ' he la'I!<'"
pe"~ (.10, ),
0, '", \ 1" ",. , en. rg;" ' wll " onl ha ml'" a'~ ,1i ,co rn ihl~_ T it.,. ~"f[ '"
' p" nd to oloelron 10" from vibra tionaJ\y excit.d l.v. l. of Ih~ ~""'MI'& ~I OUll(1
, '. ctronic ' ta te, wher.a, the ' ma ll pea k J ~ ~I above , h. 1 ~. value <O rre' pM!45 10
rurmin~ ,b~ iQ" 's ~ro\llld oiectroni<: , WI. in its fil:ll ..cit.d vibrallOno.l , tlte. nlll
i" [Iie ,-]hr a lK>llal ,pacin-,,\ i, 0 ,212 c\', ~ , m all <1',"a," f",rn ,h. 0.2'l1 "V "I the
gr ound N. ,t alc OOt ba nds, ' 0 tha l lh. 2 pl7, ,t alt is nearly nonbond,nll_f or tilt
n~xl band, eleWo n 10" fr~m ' h" 'lronll' t><Jndmll 2Plf, k . ol, 'lK: . p;t.l.1nll i>
m ""h low. r (0 ,229 eV, ,h"win~ jh" .xpt:. ,t:d Ix"".! w~a'<nin~ ,..,.u l l i ,, ~ f"'lIt
n,
a,
P ( El
,,
,,, ,,,
,, ' ,_I, ,,
,
f
,
,,,
,,,
,
,
,,
,, ,' ..._,,
' .- __,_.. ---+----- e'
-~~_~
'0
rc
'.
. . . . . 1.f, A f'f'ro1.,",JI~ I'l f. I ~ "" ~ . t. )
..
"
1." ",,1__ In, I"" ' .... 10" "" C, tl , Ctl , C H,
C,H,' ..... C.R.CH .... p-NH. C". H.CH,CH ,CoM : ~ "' H,f.:, lI.U 1, - + (; , 11,_
CH, . , and kI"l for c.lI,OC, Il, - _ { :. Il , O Il " , ,"m. llt>.l \10: " "" llY "".1
m.xhlicd rom t~.' of .''!t'"'' "I ,,, . ""'" \"" d hl of OMldin. th, p-NH, , ,,b'1;I>1onl
'"
i" ni/.aL;on. -r h. man}' v j hra li n n~ll"'a~, ar< also consi".nt with tho high bo ndin ~ char",,!. Wilh th. lll<JIl'-inlcn.c """,,00 pc ~k r~ ", L1lin g [mm il> more f~ ' '' r
ahl " ,'"r lie,,1 l'am i 1~11l. L" ", "r\1", H' )Inin a ll)' a nliho nJ ing 2.u. electron , ho,", a
,l i ~ h t l y iocr.a,.d (0.297 ~V) yibrational , pacing, consistent wilh bond mm~th
ewnl wil h ionization ~l hi~ her e llcr~i c,_ Th e 2~. ;md I. ckc(r"nio "rbilalo
' "'1uite .1 ~ an, l 4 10 "V, "" jICdi,'d y. f" r d ~ cl"," removaL
A larger number of m ~kcul a r bond, im;",a,", Ill" dcmily <if pllOl"cl"~'","
"""k. T ho "", u I( Jn~ 1'( tJ our.... 1m 1.2-<!iphtnylothanc and ilS r-amino derinli,'c ~ r< , how" in FigUl" 7.5 (Mc LaITeny ,,-. k,, ( r ~ n wni:<alivn. whorua, " ddiliun "r (he am;nu
~",u p <!lake; po;, ibk j"n;",alion al lo"er e nc l' ~Y due to n - " delooaliwtion,
Such a cha n~c in IE c",",cd by , "b, lilnlion in " moleculc '<Jeb "' AHCD in
Figure L ' i, due lU lhe lal'ge, , la bili, ation energy confened by lhe substituent
on ABCO - ' lhan OJ! A BeD (neutml). The IE .al"", or a variel)' of ,ub,tiluled
" ro m. lie ,'ompo und< , how a ~,,0(1 oorrdal;"n wilh 0 ' "o",IHnt, fe'r par" wb,\ il"enl> (T. bl" I'd l, .m d tho"", 01 honwlogou' ,e n.; ""n bo l'daled "",pin""ll)'
(H olme , and Lo " in.o, ENI),
I'o r " ",10 1"'l:"r rnolcl'uk. , Ihei, inili"1 inlern"1 ener~y rnu,1 bo "ddcd 1<, lh"1
.., ,,!ling fro m ioni.:olion (hot band , of lower Jl' <e",11 onl y lrom .ibralional
excita tion in Ihe electron.ic , tale tr om whicl:t ionization oo C Ul~ ) , Lo",erinj; Ihe
"m ple lemp"," 1'"'' her" , . io ui," Ii<'11 "''' lh '" ifl'''''''' [1.1' '] ""d alTo", prnd_
' '';1 " bund. """, (Maccoll 1 9~ 6 ; Bowen and Ma ccoll 1989; Braue" "nd von.
Huna u 19'101. '1ho moSI dramatic offecl' ha, 'e heen achieved with 3upermnic
n l'~,,, i " n " r lho ,a mp", beam (," ", If. Y1991), finding M - ' I", ak, with El Irom a
laro:e pr oportion of molecul", that do nol , how Iho" in their nOml"1 m,,,,
SPCClra,
T he Initiall' (t;) 1" 1\";01\ rot ~ producl ion A + fOfmed from ....1 ~ (,"" Figure
7,61.,.ill b< delerm in.d by': (1) 1'(1':) of \.f ' : (l) k(l':) for Iho To"cli01l lorm;n ~ A '
fro m '\II ~' : (J) kW) for ot her re:>ction, CClmpetitive wiIh A + forma,ion (M " --+ H' ,
M - ' C ~ ~ and (41partili ouing or Iho e, ,,,,,, onol iIY in :-1 +' botween the.\ - ion
;",d <he n 'lI I T~1 p"~ l ,, e\ to-... Fig",o 7.7 , hn"" tlK: P(f) "rC , FfoO ' for med fmm
2-h. u nono an d rrom 2-undecanon. T he much-lower a" rage oneI~' or the
lalle r 1'1f.1 is duo L11~l nly to Ihe p"rli li o ni ll ~ of II", e, coo, o"e rgy of M ", which
i. dh ided in l"" f'<'rt;" n I" the number of ibrational deg= . 0l" freedcon i" lhe
ion and ""unal products. Tb " i, """,n in the >o-calk<! "degre o, oH rccdom'"
ciTc"t (8<:nlc 01 ~1. 1975), "" hid, ",1. 1 lhc mota, table ion .b ~l >JaI\"" , [ m O), [Of
t he furlher d.romposit ion of a pU1i"ular (ra~menl ion 10 tho ' "'" elf til< molecul.r iu n tru m "' hlChit i. funncd, In j!;C1IcnJ, for a h<>rn ol"g" u, ,;erie, 0l"moleculal'
lun>, _ linea r tol_tiun i, rO~ll d [or log([ m+] i[An +H '"l'; u' th. r<:oipl'O col or lhe
number of ib... ti<>nl de~",,,,, of (reW"'" in til< m<.>lt>."\llar ;00 yicldin ~ "R ' .
M""o pr.f;'" ....,.h\ld. ~ r e a ".i la ~ 10 Ol" d;' lhe diswcia tioll 01 ioJlS for"",d
olmO<.W1I of inlorn al ..... ~y. Charge , xchlljl.c c ~ n be . pcc;flC, e.g,
"' Ith
I ~~.A r) - 15.15'11.1 ..t 0.10 . )( , ,r l ~-< M i - 10 0 c V. ne ulr..li... li"n " r Ar ~ (gn>nnd
_"""lIi,
".
, I
,, ,, ,,,
,
I...I.....IA ' I
,,, ,,, ,,
,,
,,
I
ta
,,
,,,
,,,
,
,,,
_ .'j
,",
I--" j~:M- _O-,

,,
J-
"/
.. " . C '
~ ........... w'
_ ".
,,
E.,,, ,
I'
0 :I
6 --- -/C- -."
I,
_ ,,"
,,,
,, [OI "'h ,'
,,
,,"
,,
of "'" ., ~_ _
.,
,,,
,
,,
,
,
r_,
.... ."
, ,
'
,,
.. .
_ . ' ~ N'
'-
, E. "
PIEI...
..
"
HEl. .
,,
"
R_ r/
"
"
9' _
E+
Io IEIr
e
s
Ion Inte,n.1
En"~y
,.... 1.1, R"" ,;"""h ip.-.I 1'1 ~.) a nd kit) for ITw],"ul.r and prO<!l1ot ion' ;n m...
'plrilJ "1'li",, .; ... l<xl for dc finilioJ",,_II i, ..",m! fo r tho procell M +- ~ A
, ~. , ' . 1" " )
' I, . Ild th.t til. ".,c,." in'm,.1 O""'~~ ufM - j , d,,'idcd <q", l ly !>e,
A, ' , nd~ ' (MeAd" " <! al. 1 ~7.; BOlll' d ",. 197j).
N'
.
.l~ 1.e)
by M , hould yield M ' with 5 _7 ~ ,\i of'Alta lll{"," .1 e.tle,s)'. /1'" loc\octm n
phol... ; ~n; '''T im' c"in"iJ c"Tlc" iPEPICO) . pe Cll'O' oop}' iO\lize. 1>1 w,th a. kno"...
eM , gy pllotOIT, rnoa,urinll the , />Cr ll)' ,i lho c~"iltOO pI\<)(oekctroo, and lhe r,,
, "h i n~ prod u. l i"",, in ~oincid o r= (j)~nna c h e r 1 9 8 4~
,.
,.~_
_ ,.. t(E l _
0; ...........
.U
=......,:
1"-
'I
-,
..
"-~-
"
. -..... ,
,"'
, _. n
n., ~
"nd rClU!<' ,or cakol .,i,.,,, rm 2hcxanon, and
2-un & ," n~ ". :
(>t ...... ' ''''I<a. nn ' 1"'C' n lm "f (he m<Jlee" lc ',". penmon' ,,] dalo);(b :, c " lo; u l~t.ed (uUelLe ""
In< PIt l" I nd Y(Jc " " ""'~ ' i,j "" I<ula l<d k l E) (ulliOl;ons for lil M -. C,H, O ' :
tiu ~ . _ C, J1,0 ' : 1"' 1 M' C,II.T; Id' , . Icul, ,,d ,'altie of 1'\,1,1.',"0'" [un cli,'m,
I lie . .. ,,,,,,1Ii". ., U . , . "'1',.... .,,, tbe "nxt""t, bl, window" jQ, C) I .o- _ (: , 11,0- ,
7.$ C.IcuIHon 01 k( E) function.
Soo", of lr... """"""ibk
""""l':J'
,tales "r an i<m can cm,u'l"md '" ae,inl.<l

u... I....g<,m1l d"" ,lm",,,,i liun>l; lh e minimu m CllcrllY "I wh i<h
, gdl an r""rgy ~Ia ,e can be """ ulMOO L'OTJ."pl,m<!> W L , fur I t.: mlfllm um
CDef ~y . caction. 1b: rale ooD!>laDl fm a part icular "~"lj o n "'ill be a fO" O(LOI' <>f
lb" "'''-~g~''''''le 1"'1'nlal i"n of ih aUlin lcd ...>nlp}; ' ",T~ l i." " , IhI: p up ul~ lj un
"r . 11 otloet ~"~reY <ta""- of the derompo1>ing ion. I h.. IS do.-. .... ibod b ~ \11.:
Ih "'. h m<l"" ger- K a9'C'l-ftoI m:U11 (RRKMJ Ihro. } IRoblJlWll ~OO Holbto ok
...'"'1'.....,.""I"'Hc " '
l ~ n) :
uu
"" he , e h il Pla n,k'! conemm, Z u 11" Pl' ttiti" n hlllW on I" , Ih~ adiah.. rie de g=
,'I I, c,, ,lom. I feier , 10 the lLeli, . lc-J "" ", pic ref.." 10 III" . CI;"" molco:ule
(""hich II",,, i! Ml ionie 'poN:i ~!), T'I(F . F..I i. 11K' " " mlvr"f ... '...., ;n ' '''= L"",,'l'~
ran~o E
E and I'(f:j il Iho " en" t) or ' 1"10'<, <l' .. ~Jnc . In c<>ntu <t tl! actIve,
(lc~fCC' of freed" ", ," nnot contnbure l!len
~y frl)' 10 Ihe d '...."'a lin,l
bo nd. In Ihe lei; , ,, ",o "'cul. lhe "",,/;, 0<1 in l~fn ,,' en" 'g ~. F:, ;" ,an<lmnly d;...
rributod ow, all de~ ,cc . o>l !l'I,>,1o,jo", In lhe ' C I1 , at~ w mple, one: del ..... <>1
("",Jom h ~, be"" I". "..ronn'<l 11\10 tlol ".'I ;J ~I '(I". I _rd'n.'" . ....u;rinl' ~. ,..
Ihat on ly I': _ 1':" i, a, oilahlc
J iw i lwn, ~ p'lfl llioll functi on indu.....
Ihe 'y mmcL ry r"cI",'. ","..-I, i.o t il(' llu,,, he f idemi, . l p.u h";j'~ by .. tueh I h ~
"action Is h, p!ae ~ ,
n '>e RR I( M rOf'" olthe IlIMr)' ;< fl rdtf '~ btQ"Soe If UU . "n " ' 1 ,,-,"m,,..' ''
1iOll of , Ill [,,,. H " " ""' , ""'''''
cl ma s.<-5pu'" reaeli"lI> "I L" .... 10
u'" til< ' W", im" '., f<lf' " ,.. li.... II,....,, ) .
f",
<I"",,,,,,,,,,
(1.2)
,",'!lw .: , . .. the freq u<U<'Y faclOI. E is the i",clflal t ,,,,'l' ) " r me ' ~ J 'l ifl i- ion
a OKl d i. llle number ... ,;lmori, ,,,,,1 , k ~.",-.... " r r~on ,. (The mJ~ni t ude of f'
IS " <d,la' ,,dy """'1<"<1 101M '100<"''''''.' ~ of llw ad;~,,,.,1 coml'k' ) n." I'",dk.
, ,""" "fl hlS theorj afe pool.... .. piolly for lo.... r.~'l') Ion drcnm)Xl~iliOl\I
........ "'''''''.,;Iily th ~ 1 ......... &-~ , ~ ffi.';,'" 1 Jr> U U~ r<ru;lion, E" Will ltlld. ' n the
.Cl I~ . ,,:d romplu dep<nd, on the n umhe r of acli,,, te,l-cnm rlc. c""'~) ,I . ,"""
. , ailabl. to, ener l(}" , n idcnce '""IOU' lilt number of energ;' <f Jt~ . eaew bere in
,"" ;,m 10 .. lPch Ihe i" lc..n",1"""Tn ""uld he dim i bul!. If th" .~~,~ ;nlernal
eneryy. l. - L . , i. small, Il ioc,"" "", fa ",,11 )" ""ilh i"Cf,,", ing " (""0 Fi~u ", 7. 1).
5in~ a n iJ>CJem~lll,,1 inc~a ", in f ,,"'ill inc'e,,'. p I rroflo, l;onole l}' much mOle
lh. .. ,... The . ale ,,( m.." on"" or k wilh E , ho uld decrea, e .. E E. bee"""..
Iorge<. "Pr' Odehi,,!, " enn<q nl , ,,It," '" f . hem me, "or;' , mati "",,,pa red 10 E.
mu , imum , . " , tinn ,ale i, limi,.d b}' lh e tim e .. qui , ed to ",parate Ih. 1" '0
0 10"". of the J,...." 'i..I Lll~ ~"nd ( ,_ 10-" ,ee). which depend, on it. " ;b<alJ<>n ~1
fr.-q" t n, y
f Al "ll I;'m 1.1 flnd",t. ["ti ber that a change in m uctu re can ;affect rbe klE !
f"nch on ~y tffecl' 1m ( I) F" (1) p1ir', an ,1 (:1) ;:1,...,.'.
( I) F., . If a , tr ucm ", l "hang,-incr,,,,, . lh e crilical energy , Ih. ex"""" """,~~ ,
L ... I.,. of lh. a"I;~ated com plex m....t d~"r.a,~. >0 that H' e numbe, '" . t. k...
rnu n,l n.er",-. ,.n r., ~nd F: , h""IJ . I, u Jcorca"". Thu ," ", jll e~b ibil . l ~,..w n lue.
,;nC~ Ih~ f"r nh,1bilily nf :lCCum ulatif\l: tb" , nerg)' E,;n IOC rca<,1io n ~"QOIdi"' I"
"'ill ~ dfCr.a.<cd, T h a .r~y Slat.. are q ua m izeod. , ~ that at Ii- _ Ii-. " n1~ the
gTC lLlnd . rKLc "l lh c ",eliva leJ "mnp"" i. u lilablC; Ille O<Jum;o n drmaods lbal
k _ 0 for IS -c Ii, . Tht mim rullm r" lc,
n..
12'
k~. - ~ r "' IE.) '
(73)
'-"
,-.._. ' -- '"
_... ......._.
will ~t", t>< "",ucod by ~n 1n.r';d . ~ in f., b<,", UW " f (he j llc r"~.~ in ,,(t' . ~
NNe th.ll ~ n increa.. in ~ . "" II inc",a, e bulh 1::, and the ~ in" ti o , hift. f:. _ 1-:
";n ce the ""'f<' "f 1(1':) ",'i\l d""". d' . '
II I P',/p. A modific;,lion of Inc m" lw ... l~r
' t , u~1 ut" ..-h.,h . dd. or ""t>In"" I, 't~I",. or chang<:' Ihe energy ,--,,)0(1 .,( IU t.5. WIll ChAng<'" p t: p ' . ~",l w;ll
lhu, ai,,, change lh_ li E) functioll,
n. while oth" p"rJmcl~., a," ""n , lan L. Ih, II ... ml",r " f " ,b, U lo WlI <JeJU....
of/Toed " ", fn) ill the Toacl,m l l" n i, ln Clea,""" I' " IL) ,,"'iIl lncru ,;:. This "'; 1' I" ....,..
1"" a tld will thu, u,ually iucro" "., l h ~ li/Wu, IM t. ",hodl It I'" amo" nl of
. xcc" inlem.:J one[~y ""ce' >illy l ~ rta<;h I. _ lO". A m.lj{'1 r",I(If llu. " e' <:J
",i"e, p i/I" i, lh~ nalure ("" otsr k ,cls and <Ic" "'I.Kio, ! of the " bu uoa al
de~re~" of fr<l om. all of ....hi<:/> "'"" d,",UII...,j (" I ", o~~ i,~, II is aleo p.....,.;" .. 1""1
Iho num l>or of ",rire mlernal r"l ,"i"",,1 o;<: ....' m pk ~ n if t ho.: num ber ..r i"lo" ..1 f(lfQlional Slala h.ve
inc, ,,. ><>J al Lh<: ~ .pe n>e or.ibra uo" a1 <La IClio,,,' cu'npl<," ,""cltin! " f .. Co - -- C
bo...ld " ' ,he .<cti' a letl ......DpI.... .. ~uId ..Ik>.. '''r'~ M 3\10ll of I ~ GU"'h<d
~I( "'I" .. hik .....~."""i " l\ lhe .ibJational l. rq... ,,,,~ of The " ,,,,d, 1\ 1'lI,lellOr! 1$ ;;aid
.... I.. .., ... "'t ig.l" oo",pkx~ If ro13tional rIo-~ICOI nr ff\-... .l" m ~'. f, ot"n " lit in lho
rumple of Ih" . , in<"i' , "" j"'T' .
t"" "lli"" .~Ie. llI e... ran""mtnl' a le a com _
",.. ; t~,n " f 3t....... d,...,a nded by , he u ansi li'tn "~te elkCli_ ely S((\1X Inu tlnn
~nn hn". an
. NuI thei r a,t"''''''1 ooDd. A """ . go in Ih. nllmhcr " I In.'!:
TIl1 ~~r ...m elko<t on lit< , . Ic c<>n<'3 1l1, sin. o tho dtn,i ly of r(\ld ti~ n, l ,T" "
",uch lorI"" lila" that of vib,.li" a.l 1 ,mle" Thi , )ll~di c" th31 r~3C1i01lI with
li{:hl eomplo n will "'-'"C ~ ",n<h ,l"w" incrca se ni l wilh inc, eos. in E
. I...po, .... li !.) in hit"'" 1.1) and W1U . xhihil a much borg., kineTiC" , niff.
t ~1 /. ';Z. rile I"' r llt>on fDl>t:tlOn includes the 'rmmef-TY f30tM. wni <k t3.l< !1
atXOl.,,1 0/ 1" " f~ ("I , h" , he , ,,,,, I ralc will he proporlional '0 the number (l(
i,Jt nuo:fll '~Mlinn I"' thw. yl, L:/L' al, o r.O I, Ihe mo mcIII, " r inert;" "I II..
n<:'\h-~ l eoi <"m p l e~ rd m ive to Ibe .<tive molecule: , uch n l"" u",.ll~ f. ll bl;.
i,,,,
"*'"
nO".1
I", C'''' 1 ~ n ol 10
COI'""l"'"
h.
A ,,,h"anli ol
,,f k,nk lhermochemi",,1 ofut~
be<o Llbuldai IL...,
" ai, 1 9~5I . nd I ll(~ d"',, "on "" "" im"tcd fo.. <>th.- (l'-'i (L<H.iu~ .ond
H olm... 1984; Holm... l~ ~~J . I 'lu ~ ! io n, 7.( and i , ~ ~ ( lIt
ple rka . "J:<'
an d rc"TTnn~etr ..nl ~&<Ii l>n~ of Fi ~uln 1.1 7,J . '"'" thennoclttroi...,] rol~llOl1
, hi!" for , nc"" r<",-";"" , ~r " . h",., n in Fi~~ n: 1 ..1 ..... 'l' ..dues for , ""
4BCO -
~D "
A8CD
All '
CD
-"I) ' .
+ lI-----C
vr,4)
i} ,5l
'"
corrosponding "ucl;on< of 2-h.xnnone'. Let il.JliAUCU) signify th e h.aI of
formmion of IIBCD from the constituent eloment' , and D(B-C) be tho di,,,,,,;~Ii"n "ncrgv of Ihe R-C hondo .~Hf(AR I I + ARy ( -CD) i, Lhe ihe,modwm,cuJ
,hre.'hold for Equation 7.4. At'{AB') i, the rl,ermochemical appearance enorgy of AR+. " .. that .11'{AB )
JEI,\R('[)) _ E.{ABCD'
.,\B I. The adi-
vale<! "omplex may be of higher ""ergy than lhe 'Urn or Ihe energies of the
pr('<lwel' in Iheir gWLlD<1 ,laiC';; Ihis nee", ell"rgj' is " rcllcction of lh. ,'lilio"l
energy fur the rever,e roacliun. [;,,(re'J Significant value,
"r E.(re,,) are more
commOn for rearr"llj!,emont reactions,

If L,,(TOV! i, negligibk, 1'.. for roaclion 7.4 i, <:qual [Q Ihc oorrd-di"oc';atiQn
energy of the iOlla.nd j, predicted directly (rig" 7.3) fwm r:quutiuu, 7.6-7,8,
17.6\
"Hr!ABj + IEIAB_I + AH!ICrlj -
AH,IAOCD) -
IE(ABCD)
(77)
N"lc Ihat F'I uali"" 7.8 u'os !:>"",l_di""..-iatio" c""orgic, "f "eut,al ,pccic, frahlc
A.J), w which Ihe organic chemist's inluilion and knowledge of mechaniSlic
p,inciple, should be dir<elly appJicabk. For two competing rcacliun, of the

,arne molccular ion (and thu, the ""lILe .I:(M) \'alue,\ I;q uali"" 78 predict' thai
,V:" i, determined ill' AI/-; 01the Te,poeli.-e mdie" I, (Steven,on', Ruld a"d "'J)
"f the ,~,poeti"c b"nd,. Further. a structural chang~ llsllaUy affects I HAD )
much more thun D(AB COlor IE(ABCDI. which is wh}' product ion stobility
i, u'Llally thc mo,t influential factor detrmi"ing product ion ahundano.; ISceli"n
8.2)
Potentinl-.nergy diagram, (FigUT.' 7.8 7.101 call provide a mor~ graphic
Wlly l() pre'ent the lhernlochemicul r<latiomhips for th~,", renetion" In thi,
representation tho reaction i, ,'iew.d '''" cl"",ical motinn of th. 'y,lem along
the re"ction coordinatC over a pot~ntial_.n.rg\, curve or ,urfau. Th e term "clas,i,al" ,imply moan, th'll the 'y,tom cannot ponetr"t. t.h. pot"nlial_.norgy ",r_
lAc. The r<"-"ti"n coordinat' in Hgur. 7.8 r<pr~"nt' tho changing l,nglh ohh.
D-- C ""lld, wbile "ther eoordinnles, sueh as bond-anglo change, due 10 I.hybridiz,tion, '" n,gl,oted. Throe regiOn< a.re important: (I) tho Toginn ncar lhe
,quilibrium jl,oom~try of "'ReD I on the hallam 01 th. potential-energy well;
(211he r"b~on anm"d Ihe highe>l_energ}' poil1l on the ,urfac which often correspond, to the tr"n<ition ,t."t., 'In" 0) th" n:gi<>n em Iho righl_hand ,ide "I
tho diagran" whieh eorw,p,)nd, to , quHibrium configuratiom of tho pfodllctS
AD + CD, ,eparaled w a diSiance al which their mutual illt<f~etion i>; negligible. The onerg}' ,0,,1e i, eh",,,,, t" r"ncel the ,clalive lbeTJ!",ehcmical <labilities
(All!) (}f Ih, reactants and products. The shapes of tho potcnti"l-cncrgy nlnl'S
,. """"_ '''''00''.."
..,. """..,..
"",,000
e
ME
~- A B 'cD
ABeD"
AS C;;.O' - ,,--
A B~D
AB' .
'co
AS"
co'
Aa:.t O
Coo r d i n a t e
,.
.1'''"1:1' "'"" kon l'f"".....'<l ln~
F. ... 1.. I........ "..... e",,," d....... rn h ,;",pl,

(.al.." """, aOO ,bl WJtb ."""" ","~i,.,iv n "",r_J,
. Il: m"oI ly ,m k..",.", .",1arc
dr." " . rbitrarlly on ly 10 i"dl<>lle Ihat the mOUOIl

. Io>ng Ihe <earnon """rom" le i. continuo" . ,
Tt.,; """pi< .oJ"'...!!" ,,,"c,j,m In Figure 7 . ~ (a:. i, charo.cterized b)' ~ ,omin uoo ily IIIc..... ,; n ~ potenl;" ~"n ... gy <:\''''e " hie" rcae he, ic. ma , imum in the I'mo""" "'tioc>n, The t'an,ib"n <tale, il il cao ",' eo ~ located, " ceu a l lar ge '< par..
Ii"" ." Ihe p rod""l.. and ilS . n<r~)' I, the therm ochemical thrn hl'\d or tho
.....el i"'" T q ~ .' ~}n o>" l be thcmlOchemiea1 threshold. Thu' the dccompo , ltion exhi bit
>ro""" ..c1i" " lMJn ""'''!~', wilh D(AB ----CD" ) lor the Il-( : t>mtd grealer , ltan
lhe II>c, m llC hermc. 1 ," It", " nd <k pcn<k n I "" Il,c rcadi"n pa th.
h l'~", 1. ~ ill u"l c~ l "" <lm ple cka"age ..eactions proceed ing by charge reten _
li" n a nd cha rjlc ," i"'lO llon , T he prod uct' AIl ~ -'- CO and All ~nc1 CO ' dIrk,
, I Th "
""
a
AS -CD
..
".'m.loo,'" I.n Do""mp"n,. ..
/;I, ,0
~:;-':~'t
Energy
+"
,
,, ACBO
: ,,/ .
AS-CD
8~-':t
AC"BD
-AC+.
,.
ABeD
so
.,= ..
Coordinotels)
.''''''' 7.' . 1"',.""al.c",cl'g\- <ul'I'acc, rO<lilting in r~)
the m,,~, 'rectra of i",mc,"
ili~h"
or .bllowcr ,imilm,ty [or
n"lv in the [ooa,;on of the , I. clron, and thus ~orr"spond to two different elee''''Oli, ,tatos QI the '''!,<''}'ICOl ii\B I- cot', 111 7.~1") the chargo is loc.,jized
largely in the AB pan of the A[lCU- jon "Old rem,;n, lhere as the fragmen\;
,.pamte (charge I.lennon), For example, ,,-d.a,'ogo in C,H, CH,OH- produc", m~i"I), CH,OH, If(CH,OH') _ 7.~ "V_ ",j,1l mud, Ie" (16:.;) C,H,',
11;((',1 r,' I _ 8 I "V, Thu, ,he gr,'und electron ic stat, of M+- ~orr"lat~s with 1he
p,C'<iucts gro\lll<i sl"to.
Alllwugh (a, ,I,..,,,,, i" ~'iguj'" 7'!(hl] in,,;,.alion i" (CH,J,CH-CH,OH
"Iso occurs from 1h. o'yg.n lono-p" ir orbil"], lh. ionization ,n.rgy of tho "Ikyl
radital(l H,.I,CH j, ,uh'lnnti~lIy I"wc, (7.4 'VI. N"",. lho ground 'late of \1+comlate, with CH,OH- I {CH,J,CH' [Ar f -CD in Figuro 7.~(h)J rep"'-
,."'..'"_... . . '.".."...... .-- ......... """.
'"
sl nnn, lill fir' t l 1C;I, d . tate of th. producll, ",he,..,.< the product . 1:'''''0<1
. Ia le, -CH ,OH (C H, :I,CH' . "or,..,l~t., ",Ilh .... <,,~, lJ:d <llolc tor '0/1 " . Uunng
Ji" "d~l~ln lhe ' y, I<1t' I\NI r"ll" " , Ihe ~ l'<)u,,<I - .l..ll e puteoli.ll CI...... b Ul al tho
I... lite <~ hcr 'UH" W 1"'" <1",,, CI~
interSt cllOn ~ Ia r~. fraction of \f '
8e t lC " t1~ f~Ynr,, " I . pr,,,,", I' . n u . !!" di, l,ij-,uli" n in com reting O l:~ ' lraf .... ntaLI"n, de!","<!> "" Ih. enef~Y ~ap l i' '<n by lhe IE <lllr... " O'
,, 1\;)
a nd tht d fld encj' of ","'e " up pi n ~ fur <'11<1l"" m , ~",. ion . "" cli,,,,,,- ~' ... !II Ii :>
n..l . \', I"" '''''Tl!rii",Uy r.,...",d p rud"d. pro:d.....UlI.lt. n Iorr,""" fI oI'. 1'171]
.toIl",.,
(Ste<em.,.,'
"R. nd",,,' rr"",."xr--./I. l lT u lead ing 10 closely li m ~a J 'peena f," iorooc"

4. ~1 ".., .lw boo ,i>" .al,m ";Ib " ""I'~ ",,1_= W'K"" -: Wi_Th..,
Ix "Ii ,,"
elfe, l, "an r.: ... '" ' plc . c" lIlllini" Il ..........ul ~ """I ",jn,ma an d u I" ...1i" n , tal ..
("'oil J $ ;onne .lral oolTlf'k~e.~ alld IU<lin~ 10 proo,>cl ;"n$,""1 .re cit"'" fF '
I" 1I","u) ~'f Of ' IHI. AIK:V' - .. 1.,Mll\".' -_ 0 .\' + 1I-"('., '1"0 I"'" "'" clk ", " ,.."di" 41.",, " , , ,,,,b a ,'8... "'" ,uul hd imonslOnal. ";m:e Ihey .vnl~w. I~ O
1e~'h l d the oollds k m, I:>f(\Len ~ ~<I ."",,0<1 ". ",en .,. ,II< ~"' .n g " . in Lhoc: bond
lell~t~1 an d doh<d ' al ~'I#' in , .... . "'1 d ,he oon. In these .Nl~<'llliorn i two'
tli",,,,,,j,,,,at d, ~",n .. ( F ~ u 7 _ IO~ the u ue coo.diD;ll" gre (X'Oj rct<>J into a
",,,n n,...., -.... "dina", ",hiLiI ""'" ,lcpi< b d in....,,1 ... m' Q "' n~ tho ",a.lJou
r "t h liM ocr<". rMI\'ly a< I graphlCl l mea ," of ~ "~y'nll ttl< ' In oelu, . <. 11 ;,.,.
mor;zaLion of an io n io; r a lr-d ."' lIn inU1 ~ IWill"' m. 1\1 17 ~ the lendrnq fM a
' '' ' '' ''''hl" fl:"",,,,!!,:m.:nl i. Jcp.:nd<"r un lh. Ilei ~ l'l .>f ,I>e bArrier sep ~At l n ~
1M ;..,mrcic p=u,<OJ' 1<110< ,,""~ T" 1'" \oa . n., ""; ~h l {", ,li' " "-;" I,,,n: lhe
i",mc rUal;on ih c lf n' a y be CIldo- '" e.olhe,.",k l'igu~ 7 ] (~A ) 1 ~0"'1 a re..",mgcm.:nl in .. hich Ihe ""Trior ht, WttI, Ail eD ' und !\ C 8 D ' IS lower than
1m, nunimum""""a """""'" I", d"':""'I"",;I;,," In
.' C..
p,n r,,,,. 4-poco "
alld AC RO ' -""" ",tereon ..n ....ro,... <I""oml"" ili"". whICh c:.; n c:<l\lIe 10.. of thc
inf" """li"n "", ri<:<l h~ lh. on8""'1 AnC O ' m ll(:lUre, A ,;mil~r . ""r , y -" all um
bas been u'"'" 10 ..plain , ..., d ",,: ';mib ,ily .-J Iho rJ ' 1Hl CAD "' ",,' 'I"'etra or
1- ~n d l -hulenc ,. ; ~ n < Went . , ,d. 1 9 ~ "l.
No.e.
IbBl ~ ),," ""mOIi>~tion t-arrie r d"", n O\ n<:"c'' ''Krily Jc~d III
, tTnelu",1 "",m ~n i ly. F'" <ioal hyd rngw r. aff ~ J1 i c nlO o t s thro u ~ h
a """Ollie ",dio., 1ion, ABCD ' ~ ' D AOC . I h ~l lbcn di " "";31<: l<' Gi,o 4" OF;. ,
inn RC ' <:;I n ha, . n
a<l ; , ~ li o n.- ' " O T~ Y h~ Tf; CT cumpc t;ti,'c vo11h dl$
. ncia' i<m; an O1 ~m pl o i. CD, CH 2CH , CO,H .. C D , C H,CH, CO , HJJ ..
CH D , C H. CH , <--o.V -'" -e HOC:H,CH,q U O), - ' ....CH U=CII , .. 0 1,=
q OD),' 1S,,,, ilh ~Jl J M d. ~ rro r l Y 1971~ causing H ;D scram blin~, How. ..r, tn.
neu1r..1 mo!ecl1 lt. rouDlorp;!rl ,'1 the' ,!i'll1ui" ,"die"linn i"I ~ ..muli HI ~ i, ""
unslaN. d; . ad; c ~L ,C H ,C H,C H ,.C (O H:I, . and lhu, ;, nol " r ~a , on" b le a ll"""'
Ii," I", I,UC1 ~ 18] a ...j ~ , ,, n ~ nl 01an unknowll molecule. 1\ --""mom ' rca rrnngc
menl, ",,,b a, Ih l of l h lllc'T>c, fnm " ~ "on,Ii,lo"ic i""Jlcr, "' hid, mLlSl inmlvc
;t m" lltpk.lCp J'I" hway 0' an JI1te,medi~te ionn'l11r~l comr ie"
"""",,n.
r.,.,.",
Figure 7.lOlbl ,how, a "arrangement in which the isomeric ions aro ,eparaled b}' a higher en"'-gy barrier, whoso hcight detcrmines the tc"-,,!ion "f
ACBD~ that "all <.,"ape revO,.", i,,,meri:,ati,," and dttOml~"e directly to
Ae ~ RD, To produ", .'Ie [rom ABCD' imtcad o[ ACBD' r"4uire, ero,,ing thi, higher barner through a tlghl actIVated c"mplex, '" thal the 1>0="
win form AC- at dit1el'elll rale;, Other ABCD+ db,odatiom ;u"h as AB+
formation "an now be importanl; Iho more eompetilivc these arc wilh the is,,meri,.~li()n_ Lhc more diITCTen[ the rna" 'p"clra of lhe i",me" will bo
1.1 Examples
The applicability of l'q uation 7.1, and especially lhe usefulness of lhe c"nccpl of
the "IQ">en.,," or "IL~hln.,," of the aclivatcd cvm pk" arc illu'tralcd by a fcw
murkl c"kulai;"n, Ihal h", bt;en carried oul fur largor mokeulcs 1E4U"lioTl<
7.~ to 7.11). 'I he be,1 agreem,nt btlween ltle experlmenlal data and ttle cakulateJ k(LI fum:liuu, (Fi~u,.e 751 wa, obtained by "ssu",in~ thallhe ""li.ated
~~HTlpk, und,r~,-"" an iTlc",a", 01 on<, ur lwo rree mloc; "Vcr the iOTl ror F<ja~
lion 7.~. a reli"", ion or on" fl'ee rowr in Lqllat;on 7.10, and an mcre"," of three
Ie. four II.. rotors in Equalion 7.11. In Equalion 7.~ lh. imporlanc. of pnxluclion '1a1"lily I'c~ Chaplcr 4:' ,ugge'l> lhalth, aeli,'aled ,-"",[,1", rC'~lILhb the
PWd\lCB mOl'e than the precursor. III such a mod_I the central ( C l>oud will
b<: suh>tantially d",ociated, lbus lowering thc balTier to rotalion aboUI litis
Imlld. and iner,a,i,,!\ the nUllll"'r uf rrce rolor, ill the acli"aled comple.,
(E, _1.3,
E, _I.B e','l
17.91
p-H,NC,H6' IE, - 0.7
E. _ I.~.','I
17.10)
17.11)
<0 >-C"~,",---@ .
.!)--- CH,O
GH'--@
C,H/
t.
C,H7
(7.12)
(,luile n d;lIc"nl <iluat,OL1 " indicated for the decomposition of p-amino-1,2diphenylerhane, The presene" or the p_ami"" group ,11OUld l"weT Ihe i"ni,"li..,n
energy..,r Ihe hemyl ",dielll, lowering 1'", and lhus lower ,he kineric shjfL This
is not obserwd, how,".., 'ugge'ting a suh",,,,ltial reductio" in tlJe "!oo,""es,' or
the adi"aleJ "(""ill<~. The pre,ence of lbe ami"" gro up will i"e","", Ihe elce-
... .._....
lJJ
"~0~~,", (0) ~
'" ( )="o'",-(r5)
F 13)
tr on denlity in the N - C bond of the nlC'locnl ~r ion; how.ver, in the act;\'ated

Iho p arl i ~l ror malion "f Iho " " " nanee ' ta hilizod p_amin"h<1l7yl i""
. 110" ld . 1'0 <odu"" Iho [,00 rat al10n a bol' l Iho ('{ar yl) Cll , bond, off, olTing
the ino",.,ed I'O tal io tl ~ bo ut Il", central C-C bond . Thi, indic.lle, that the
~~llf,~ '''" li<Jll of the ," cti.." lcd compl", fOT f''1,,"lion 7. I() i, , ,,h' tllntillily "lighler"
than tho t fe r the a cti,. moleel1le, in direcT conTra,t to the , iluotion in "qU"li~n
~"m r lc"
19
Th" "titio"1 ono r~ fOT f 'I"Mion 7.1 1 i, e"en higheT Ihan lhal for EqLllltion /. 9 ,,"oau," ef tho lowored "a lL,o el lC', and Ihore is an evon ~ ... ter inc..","
ill the \'alue of 11", oo", bined kinetie and competitive shifts. The significant
,h lm,t.n oo nf thi, r ro ~ l1 ct ion in the 70 c \' ' )J<-cITUm indic ate> lha l kiD lar
llq llali on /. 11 mUll ri", ml1 eh mo re rapidl y than th"! for ['luatioo 710. T ho
tr all, ilion-l tat e for Equa tion 7,11 mu,t involve an even greater ;"CrM." in free
tol,,'" Ih.< n for F.4 " .< ti" n / .9. ha,ed " n lho r~" l l hal the panial charg. on th
mino gro up and t h ~ adja""J11 ",omar ie r in ~ must now deaea.," in Ih. Immi
tion state, lo werinl: the doul>l e-bo nd character ol the adjacen t bo nd, . Th e aJlotMli, " 'orttl"l ion "f C, H, ' from an e,dd eiect ronic , tat. would con'titute an
ulIl1iuaJ ~, ce p llo n to the qu",i-eql1 ilibriu m 1h<0C}',
,"~,",---<>;,---@ ~
rl:oN~M.'O(-....-(r5)
M, fIe""',' ; C,H ,
(7,14)
S<lUlJl ch' Q~'" 10 . I<uelu'" <OI.n h,'c Jug< elJool 011 ,he mn" 'I-"""'",m if
t1>o ... mako l""'llbk no", ,,,,'>ct Lon, of h i ~ he r- ra t e co"'ta nt, ~ , e r on appr eci~ bJe
'lU Ll!" ,, ( I' ''.<:u'''' ..... ", ,"Ierna l ....-LC'q\...... n ,LO>- U\C dr.malic dilf. reJI<"" b.:<....""n
",~ 'ftU of d<:>decane and l-aminoooo=ne (F;~l"'" U and 1 (6) .< '" d ue pOm" ,ly t<l tM II;gfI <ale ~ (\n ~ t a n l 1M the new reacll<l/l k,"n ;n~ lit< e rr , = N ll , i" " . I "ctea ,il\~ Ill. cf; ~ "",1 ~,\c'@.y or R reactio" dec rea"" , Ihe :Jof'O o f the t{ EI
n.
cun'., >0 (h~ 1 "high~l-.Mrg)' r"clion mUlt have 3 1,,(1;ei.," I) 1~1 ~"jVillN
,omrle. in " , dc' 10 t:oc """,po:tirive,
SUU<lu ,'al ,ITeet' un Ihe PiE) runel;,," " f Ln.: m"h", ,,h,
con . 1' ~ f1OCI ' ~
",n
III".' ' 1"'''1." m, pan "'"l..rl) in (h~ ub"nd..ncn of lhe molecular and mt{J" ollle
iom . Addmoo of a ", ..mino IIN"P tu 1 . 2 -d I Ph\n ~1 ellu"w 1","'C1i lh. crillClil
cllC r~y for 1J<'uzyhc clea'a~. by only II 2 cV, " ui l" .. ,,", Iho inn;"'"'i,," ene' n to)'
I,r CV. lhi , rrn>J """ II du ul>l lhM "I lhe moleculal-ion abund ance. A!iding a
r- 01110 group 10 l,1d i p h c n~ I "' h fi nC m;,kc no uppn:l;iobw chani e in either t","
0 : 1". or Ih' mokc uk or tho Ai. al"e " f (he f,oTl / )'1 io" ( 10..1 0.: , V'I
H""'"eV<'f, ' boo nut c> g, oup g",alJy m"n; ..",,_ th" \IN'ulution of the PIE) curve <Jf
"' . "'ou nd IV.5 I V, Plolumobh tll,..>u\lh i""i,..l;un .. l [he ni lm b""' lUp. no,
""11m, ;" ~ ",, ",~I.(, , ~I ;"eTC""" in Ihe ion . hlLnd. nce .,,,,ng from til< m.U...hie <lecom~ (I~"'on M " __ (: , H,': in ~'igurc 7,S no le the low population of
f".H ,CH,C H,C. H, " '(I ll! III tl... "Iln~y ,.~ion wq uircd I", lhi. m cl", l~hl c
decolllf'l""1 ~ >0.
"" -er. IIlN , 1'n4; h ur. U 1 ~ ~6; G hOih 19 ~): Holme' 1986; Lov,cn 1978;
I
; "~ ..'. l H" I"'..... 19f,4; M~ rk 1 ') ~ \ M"rri,,'n I n />; Robi"'on and Holbrul,k
1'172;
T u rn ~ ,
19 7{\.
8
Detailed Mechanisms of Jon
Fragmentation
"''''t
lnlcTfl<0tin g ~ "' ~<o; '(1['''''' ha' lhe

ba<l~ ~Ili~ ...rol$ ~l u pl;\l nm~ tli<
prod \1 ~t ' of ~n y chtmieal "",n i " n. ,lr ma ..];ng ~ ." m ~,
lI",kN a ",b ~ ,~' ,II<:
, elevanl ,h~ m i<uy h, r ~ u m rl t. lht JddUlOn l'Jf a d " ~b l e bond h'> ~ ~ OOI p1 "A
m<"Jl<euk "",'II a> d i",. ni"" WI' ''''' 8.11 s""~1d m;)}; e oil!, m~th~11 nlmgf
l-l" "" ,-c" ~ ".".
"l.. ne<" to ;/< ;nf,..~...,..l ~nd " ...1"" , m~tnc' ;" "'.. "", n,,,
doul* " ..M rould pmt"''''dly ch3ft['t lilt dwo ml<lfl . 61 it d_ lOC IN" '!K'C0
lrum {Md ..aITe" ,-. L..... and 51aufftt 1 990~ Th ere ~lC "0'" mi\.Q Yexceu e nt rcvi"",~ or m ",-,h~ q i"" , " f ~ n i ..."l ""ul~. inn ":~ < I i "ft . ; 11",,,, . '" lj, t.<ol .. Llbc C<ld
, lit <:harter. ,\ Ihoro ol.'h di<cu""iml i. no, p<:lwhle boere: in tNI chapter, " , rn
Our"" J. the n.. '" ....' phasi s w~l be on rn.ch~ni"Tll that ~ r~ 'j pu,."~ lI t \"d~ 1
for ;nl"'l',,-1"-';".. " r 1'1 fID <VJ, Cl ,,,,J nl.h<, n lionic m ~ <.< ' 1>:, 1' Q
.",
'''''0:1'.,.
"r
.. 1 Un n.olecul _ ion decomposit ions
dnd reemph ocize th" "",i h ,'" ion , cac-tion, im pon alll {.:or ded \ lCUl~
. ,,,,,,Ion:. Ih e m~ "" ' l"" lrUIIl ,h"w, ':O/f/p<!Jjrll! and mmnUlh", uWnwk.ul"1
Kaellons (rJgur. S,2~ ['rimar y di"oci"tion prod ucl' such "' ABe' ~nJ co"'~ <n l J'l<'C""",, ,>I lhe m iginal mo!collle, and lhus provid. di.."t e, ido n""
of molenl l~r ' lrUcI"''' , Ex"mpk , "n' givcn in F'IL,"li" m K I " ml k 2 (ror 2.
llo , ~ """,,- ' "''' ~l"" F, ~ u ",
"nd Semi"n 7.3), Valu e, in . V o"el a rT"""
" -p"''''''l the " . " , all cndother mi" enthalpy chang .I"''" ,j" i"j ,id I'n ,, :IlI",. : th.
d<li";II", n c lin g)' in "AC
"'" of Ihi, "nd"lh"TmiciL~ (r" ..cr", f:. ) will be n hol",, l;~(1~ hl ~"",. lof ,,,~rrangcmcnl (rlj) than for simpl . de.""g, r, oct"''''. Vol """
l"' r",~lh
rcpl'csenl it' 11 0nt of fo,malion (Mtf l anti, in r arenth:-<e<.
II>c ~ >n ""I ' on ,mot>,) (IF) of Ill" """"'llOnding neutr al. h 'on if ,,,me nult C'l' IS con,,..tilJ,.e with primary di, ,,,,,,ialion , " ' tru ~ u r"l1 ~ inJ ;""'l j\", '00
cnn be lormoo by d is'o<;L. tiO\l of the i,omer (btu.. i 10). Such a ~ 'p: i flC re " rr~ " g~lI ", n l" C"" i"" ., I,'. dir. "t i,om. ri7.l1 lio n t o a di~,1flk , adi<:al iun fa
To
. ~ i "",
7.,
'1"'";,,.
,~
!:
-~
~.
, !
1
, I
.,
o
, ...... !
,,
0',
..,
f i
if
, I
' 1I
't,;
" " ~~ I
+ D
. 8' . 'co
. ' ,11'
. a , . (JJ'~
t , o'
A6C'
"" , B' , C'
~.L. I
I
.D
". ec
MH
81';"
radIcal a nd charge , ilC'<. 11>1..1,," , ... . ,1. 19841, 0.11"

CH,C H" CH,CH, q -O- HIt' H3 llvnl ~-heunOllC " 1 f.'11L~ li o n R.2: lhe
v e.ev b.1ITi., i, ~IJC In " In ", ,,., lI~ l; , a tio .. e.... ~ y 01 U . ~ oV): lhi' ion i' M t
nl ,t;Jut>k b y (lie"et ionin lJo n of ~ . 1~l>Ic .;<>m p<, u n,J. However, h}'dro~ n
", i ~ ''' l i n n ' a n al'" 100(1 10 an i"lll<.
vf another mol, cu'_ ( o, ~. (\H , ~ ' ;
Eq""i c'" ~ II. 'On Lhat l1,i. ""4u4 ,,~.m.m incrca'c. lh' u"u rM;n1r of
id.l1u r; Cnll ~n: tho lIm;ertaml~ ...ill ~.U4lh Ill: g"oater for a 10 "'0' i$OO' t r;' al;Ml
I'an i" [F i, a,..." i.I 0(a) .. 7. IUtbj), IN" undorg" inr ...,h " a, odo rn ~
" JrrangM><n.. ch~ l a~l."'-;" ' i ca ll )' ..eq uir. brllhcr ollor, "'" for dir1 d i<l.<>d " li,m
11.7 .~. r", f . 1I,CIl - CH, ,." U.7 ~V IN <', H. COCH ,+ t so \II.Lll sev.....al
i" 'm...-iY...,i",, ' \"1" tn, j,omo, ;c oquih"",' ;"nl Ca n "" compel.i,i "'i lll
Jb""""u"n. In r''''''','' " li,," di"-, ,,ci ~ [i,,,... tl>c runlw, ~c l ; on. or an cr:'
I"" dun iOll , ud, n' C. II , - ... C, H, ' ([ q IMli<ln S,I )", C..H,CO ~ , C.. H. '
J;"w...'I' be\',... n i"
'_ n
I F,!Ull l i' '''
8,2) ",'itl
~
~H,(IE ,
5,mO)
lt nd !o"''''d
.u; ...,c ,
- o~
C) o~,
.u.,
,
IIlOnI
;wme llzation: the
+ ~~(l\O"4.1
"
,,,,. - /II
"
88(75)
() -"
"
,~,
c.s
"
CoH'
11
1ol~ ; )
",
- 0'
,35%)
(45'll.l
91148 1)
9,3\lI. ~) Q~
.u,
""ollfldary
"
,~ ~
Cot<, '
II I ,M)
.,
0
) "'\00%1
9,9(g.71
(~, I
.,
__
~".," -' '' - ''--
co C>I, (5%)
t.t
"
"
-,-'
- 1.1
C,t;,,' ( I""'i + 0 =11,

!1J(801
- 0'
." ,
'. ,II
0.6
"
r f.!
1 l.:l 1 9 , ~J
l"'. ' I~O"I

8 ~ IQ 11
-"
.""
rs
"-"
G,I\,- , l O%) 1 H
i .&,8 11
aa
tlG)
" , <>duCi .,.-i lllhu, h ~ . < k " ' lnLc!uc,,1 ill\epll~' , .ta d , nn. " f:II,jicana: (>1' "'TUC~
l u,~l ~"isn "'<: " l " 'ill be much mol'~ 'J'<'C~~I'tI14<nl H' ''''i:,-,:ruch p<oollcn
art ~tlll m d ul in lowma" "ion
t " i~<i;,,,"( lho: l..,en.a loms ~nd rin~s
pl u' d"",bletxmd' or panicula r , ub.lr1fC(Urt6-
""ric,'
84>;( //0", ~/fecr;~!: ;o~ 1fh" I4/JQ""... r " h" ah....dM . III a m. " spectrum. u
frafficn l 1<1n m " ,1 be pr od Lbl ooonpelirwcly from (,"C M " ' ' '''' pn:eu,"",", .nd
IllU'! b. rolati.'oly " a blo 1<> further fral:m':DI~l i ....., '1tic rn"'l com peliti"e frag_
m, n luli~n putll ",~~ , of
n",h:cuLo. lun al ~ Ill_ 01 til<' lowell !'In-energy
~h"ng . noj Ih,,' 01 1'" m"" fa,,,,,,," I,, change. In <111 1>.11'\' .n ll ,-nlCOI'Y, Th.
""lh"lp) r""lt>' .. r~n.."" lI,"d'Il !he Sl ro1l11 lOndol"')' re, form the ..nIt -1m"" l"">d'~H. t:>{>o:,';~lI , d", "'''''1....1..... ionic proo uct. Quahfyinl: thi i, the 10 " " r the
1<trg"'l >ell }'l Sf" " P " f''''"rr<1 ~ntl lll < <n' m p, ,,,elm place" .,r,, ~; ".>IfI;'..... on
prod""l ro! m ~ l iull-
It."
"OJ
"'"l,
""",~/ili,, ~ ""'Cll O~ ' (l'igule 8 2), the relati ve 'l,milily of

",,>d..el. i.
,>I' J'J irna!) ;rn!"Jlta noe ill illl;lImll ni their [nrmal io n. ,.. .....,11 a < rtdllCing . he
hm f>c. diw>ci _tion 01 tll" r>TI ~I ~" L i" o. h lt ,imr 1e "', I>d--<:I"" 'Q~ . re""lion!
lhe "'.w~ activat ion e""tn i! UI" dll)' . "' . 11. ... ' .....1 lh< drivi nll Im~ i, lh<
enthalpy change of the !.~ c ti"" . 1't: llll iYe I... llIe !31uc.; Inr mher meh com peting
I"" ""''' Y' The Tclati,-"en lhalpy ,,!uI,, ~e i< dc..nDirocd b~ .he heal> 01fonnullOn.
Qd th u. the stabi!i' ie, of the IT!,,llinli i" Di< ~n" ""u" " I I'...~11>C1 !"ii. A, ,!",,,'n
in F il'.u re 7,J ""d Fqu atio n$ 7.6 1 X. Illil l<eq uhoalenll 0 . he d,,, ociatiQ11 energy
...
_-
\1). I . Ne .\ ..1) m lhe hond(,j d ca ,'cd in ihc ncu,,~t "'''' ''I'''pan or lhe Jea<1~"'
prod'."
pI..l Ih. i,' n,zaIKln e""r~y (ILj "f , hi, reaCli ~ll'l
th n '" i" n;A:d. Ih. f. el
, .... . 1f " h.K:' J"I",ml m ud l more ~n ' IruetlJ.f~ th... U >Il l..., d,' iT able >\. .1) i.,
lbe ' . ' l M' why pr odu ction ' labi lilY i , "r key j'''I'''fl lllOe ror del~ i mnll: frag".. nIM,,,,, !", lh" uy, . No' o, h0,,"O .- ' . th r ti,;, ~ Pr'''-'' 1<' , t.; ' ''''' f''l tJ.'><l n of
",,,eti,,n , in ...hi,' h " nil' olle bond i. dissocta tN-. w n,." ." " bo<1dl ~ 10 c\",l\'<d,
t w~ ",." u' ually for rn,;d. '" In. ! (he " . <:"dl ho.J J~,~t,OlI . ,l. ro ~an be
, uh' tanlially Il,... , ( H~" ", ' ,l). Th ll. O E+' ion. can he " ' d>" ndanl prod " cts
", FE ' ion. "'h.,,,. C(>fl'C'<PoJlld lllll ""uu a!ll ha.. II! ,'alue. 1 to ,\ tV 1<",,",
(Equ ution, 8,1 ""' '' ~.~~
In in l<:fPf<ljrl~ ",_ "ll"t,~. I<" u <h >mlX' r!an! prim. r)' p',"; lIo1 i" n ' e,m:m
bel' to che.:k
dbun,lonu: " f ii, "",,,plc,,,. "t. , y prod"e t ion: '. :r (CO I _
m/; IAOCD ') - ",,'~ . A U ) , h.: oomp<l1! i",;no", "r the"", prodacu "' ~ l clt;:o;lld
I1 La;n\y " n II", p, uJuel -1 l~b'bl, cffoc" , , iltce the .Ie,ic elTect, ....il1 u'u. Il ~ bo:
e<J uin lenl.
I""
,..;"" "Milily. lllu , ,,,,!inS thi, rr; m,ot)' ,;ti lcrio n, the I E(RI ....1...,.101 H',
CH , , C, H,' , ;,,~ C , H,'. al'd rcrl C. II , IT~ bl . S... . p;rn a raIl4'" " I I> '" ~ y,
,,' h<lc ~. Ihe ui ~';(",ia ti on en.rg,i.. or tb." bomb IQ .. l k ~ I I' Qlr I'" R'.1JlIt- :R)
<!to... a
af onl}' (1,9 eV Th. h"" i " f ("m'M I~ '" fA" , 1' MI""" 810;0 ill um ~te
the im port"nco or ,Iruelura l <labi lilalio~ or callO.... vcntJf> n." I' ""'. ..ilh i",,;o
" H, " . h"" , pa nni" g a rmlg. or S,li c\- ...btfc;l> Ihe tJH, , a i,,,,,,, 01 the co,r"S.,oDd lOg n" " I, al , a,\i"a 1, , I", ,, d """I'<' ,,.. ,,"l y 1,7 . V
Thi, lll(\oh-la r~er d fOOI oJ , tlllCtu' C (>n II' ~nd ,),11, " al" . , of iom Ihan on
t h,,!~ ..., nell'" \, ""li n . ,. " he >=fI rnr " I....' I" M h"" ahllr l <>1 Table A.J, For the
iOni.:At",n ~J1<'tS;', nat. tM! the ""W>luli" " " f a hck " ". " "" in l" "1' alkyl radi,.._
'."1;"
cal can fT ~ ble 8,II ;'lC[!'d'" IC"H.,C H , - .... C H.,O ,
~ ,I
...
~, 6
"Tt:""" I('H,( H, ... HOCH, '. 11.1 , 7,6 . \11 the IE , ~\u~
r_ ' ,f. ~flC~ ~ ", ~"np '6 r6d IC6i"
"
"II,.
'"
io<>C,H,
,..l--C,H.'
o.
.,
;1.7
.'
,
'"
'"
HVCH.
CH,
"
'-' l" ' I

O.311 6l
. Vj a, .....011 ~ , d""
CH, O' j;
I ,w~k:l
61'
A lk y l
, od ~, ."
..,
....1011' )
r.H,v
C H,V "
IEf" ' !
M '-,(A 'I
,.
.."
.e.e
,>
-...
",
S-_ _ ,......,. ...
M ~ ~}
' ,J ' I, ' I

0.1 (HI
".
"
""
"
..,.
I "".,.., , , _, . ,_
.. ... ... ..
, .
"",1;0""'.
and 11< Iri pl~t ~ - l ,1 e V I"" "a ble ,h' D C H , O H I ~ ""'1ill"'"

heteroal om ~d,Ni"" ~1k'\:I ' lh. !le"nal mNe th "" til< w'...... pondwf jon'
dJI} Ph -) - ,l.Ii,l l'hO ' ) ",',1 ~ . V, hul M ! / Ph . I - M t;4rhO , = ! .) c\i , reo
ncctj n ~ betto, ' tat-ili, ,,\i(l11 hl monM. lenl ox}'" ,n of lhe .. npooin>J <b:l, on iu
r hO - Ih, n ur lloe chal l!" "I PhO (Ph = f' h<:n~'1 1
~ '" ,; mple di" "" i. ' i<ln '''''<1i..", ;n ,,,l" i~ ~ oi"p" bond ~Jca . asc, lhe
mo. !-!'a ' o,-cd c"mmon l' ,Ood"'1S (T ~ blc. .'\3 . R~dll-.)'I ~ '" lbu, imlllonJu!ll
(K, C- N R', ) a",j ion",i" ;" ,,, fRC_ N ' K') i....,
nilro gcn-<,,,, nraining "' ''no
!X' und. " ,on; um (R,c- - O ' R I ~Ild ~ q h um (Rl : -- 'oO - 1 i<m< fo, oXY9t D('" T1 ' . i,,,,,g oollll"'U"d .. and ~ U y l beRo<)l I n<' ~r " py l1 u "" ions fo, bydr"". m. >n,
~t r\lCI U [al tffect. on II' .al""" ~'" to,.. " II , . ~ . e, peeled from ,he prihCll'l<'\
oj " h ~ . '<;,>I _o' ",n lC <hemwry , An '~ ~m pl " ;, Ih" d~" ic ' ludy of H. " ison.
Kef.., Ie. ~n d u-ing i 1%1 ) 'lbo,," in~ ~n ex.elient ~ o"d a , i on of ,l><o IF v. I....... <or
. ul;>$"'ur..-l h,:n,, 1 ,~,lic.,.l, YC. ll . CIl ,. ... jtb HammoU.. . II,o"'n ,,' .'ah"" tal....
..... I.,a' l ll~ ~, 1'_ )11. and Tur,,'ck (' j al. t'Nlil' l; II", ' ub>llt nIJ"" of p-NO , by
f""'\ H, dt<: ' e<I~ t< lhe I E value by 2.5 e~' 'I he d 't o n the I F " .1= ,,r Ihe
ro'l'fD' pt>,..h~ S m" l<:cub
YColl.C Il , C H, (\ H , .. ' .....th' ro. of ,hi5,
~....., ( ""' 013'C' WIth ,, ' .'alue, (Scc ~ "n 7.7: f<o' "" Cxlc".. ~e dj"u",iol' ",,.
M eLaITert i' ,'1 .II. 1970), II' ~o " e' a ). 'l l'U<tnral <11"'1' d ' ~ .. ..... ......., mor e impOT!" " ! fm 1': 1" I" all f" t' D E' i<>tl> IT <lbk A.)~ lor u~mpk, 4 IJ,.{C , II . " :1i,
2 ~ tV M
igne, than ,l./l, iC , H,O H' ~ ...hil<: "' H, IC1H . , is H eV hiil;her lban
~ H riCH ,C HO H ~ l F" I (he , o,,,,",pooomf """lm l. Ihe ,\,\ H! ,~t "'" a" 1.6
and 1.9 cV. fC'f'<'-1i. cIJ l
f",
"\I'
t."".
uf flU! ~~ .. .14." ",.,., . Thi, , ule c' the maj or n ee""otl In , ~c

impo rt. nee of
1 .''''' .,,,t>i lily_ tt,.. u," ubslituted a l~ }' l i:lOG!" "onded
, ,, the ... mc. Ol ~ '1 .. i ~I.n l. cJ roon "100* ), tho pmd ucl_i" n ~ ~ u oda ~ r rodu ced by lheir l<J;"", ...ill f ~ n~ ~ 1 I h~ "'~ of th, alkyl group, NOl~ l h ~. ( f.l" ~
li<>n 8.1) C, H, n .)( :H, yickl, 2:-, C . H.CO~ " . 100\ ', CH,CO ' . C\'tn ' ....."i!h
" ",on.,I;"" " r lh e latter roqui lo, {1 4 c V m"te ClK'<gj'_ l'hw; <In
1011.
,II H. >~ch ", fwm ICH, J,U - ' ot "h(,OH ~ , u"",Uy otdJt"dI". ~"',"" . ,,f
~lk)'1 qro" ~" larqcr ,h"n 'Kd ~l'l. Al~ )', ..... atld .lli: yI q an i.,. , at><! fluo rldts
(",h""" " . " d n-do clw ll> d'" mild>luI in,<ot,"" ID ;",.m.t;"'" Ih " ~ in l"', ~l.
tiel IOn-slabiliza lion: Secl"'''' 8 6. '). 10. 9.1 1) oflfl> j)Mide 'M exc'pt ion
T he~ , how ~ hj~ t>c, pref'....ooe f.' r H - 1. - I h ~n m,>,< 1 "" ",,po und, do, wito
[1M - H))" > r M +-I; for elampJc. f"" M",Cl ICS , [ (11.1 _ H) '] - _SO~; ~ nd
[(M - M ~)" J .., l ~~:':' Iou< H m.. """" '" nlmos l C.,lu,ively from the melhyl
alOUp. ,\ 1><1, ~II. ~ I loM<'. from <>I,,,,,n _' nm. ,I" no t alwa y:; obey thi, flll<:
p'''''....
Im/"'''''''''
( P fdTc' ~" , n ~ ..s_ l \l ~) ~
:r-"b(lOlUl<y i 198,:)h~. m"~ . oxm"ie ~u" nluati .e .. "diet on the ~ompetlli""

10.. 0{ a l ~yl l ~ d;". " (Inm \ 1 ' Th~ ~~undan e e r ~l1 o " l lh. fe>ultm,<: prod ut.l
..
ion, (pill' an~ of (h.:if rutl"'" ""'o ffi l'O'ition \iT<'duct<) is mu . U~' in'....",,: l~ 1"0'
porhnna l to thell m.~ ,I",. of d h)'1or l nr ~ .. j.1.dl~ ub ~ I ho .x-d'"dYdj:<l ~ ' ~t h yl
", ,,pyl hul ~1 .:arbin o.>l ~( I J tV (to eliminale lie':''''...." <1.'00111_1\"", ' ) \'>1'0dlKU p<-~ , b~' 12') , I I! . nnd 101 with re l a, i~e abu oo~ n ... "r n ~,; , ~ ~ ~. ;, nL1d
11M"'.;.. ,~ j ... jy; prcdicl"l! "h u nd~nce, arc lOl: l,N _ 1~~'; " nd I I ~;' 10 1 _
k~ ;" (AI ~I<" lro n "m:rgio, nU l tOOr a l'('C3no.n020 II", ,-l.okl. Ihi, d~ nol hold:
c... I"" t"" " r C. H.. from C.H.n.)("II, . '. I!qualion ~. 2, ' '''l UI''"' mor e . ".. ~
Ihan l h~ 10 of C H, l " Ili. rna., b: on<>lhor mo.nifc, hll' Oll of tl>< " ~ ~ """,""" r.
f.J om" ~U ...l, m ", lljch l ilt Ab.. n,h ",,< " r lh" ,am. m ~ t n l!~ h ~ inn produl1
from hom ~IO(:oll' rrccu""""" " f()" " d l~ b. inw rod y rnl~k:J to the nu m m ,,'
vibu li<.>a41 iklU "'- 01 ,,.edom of tho d cm mp (), in g loa (M, .o.d"" .., ~i 1974,
!ku, I ~. ,l~l i , [i cal dl't ribUl Koo <or tn" """"'oS 'a ~" .. 111< 1", 10'-'> [ ~1~ )1
~ ro u l'
J..nu"J"'''';''.''
(I ii '
S,.',n.,,,,, ',, H~ I~, 10 ~ ", p",)
ion, ele. ". Kt Of a <f'OciJie him" )'iclJ ,
pmducl<, only o ne of ... h,""
c~ n b< d.,ul"'d. i'>lew,lSOus Rule and lIS modlfied f"n " \I ~, ~ " ",, { A ....Le.- I !IW,
H~ rr i """ d al 1971; Tu rcf:ol ~nd Hanus 1984, IMle ,'''' , i " ni'l~ ti<>n .........~,y
. a lues ~.erll char:c , elf nllM "'- eh" rgC' m i~' " I ~.n in
de<." ml'O"i l 'on~
D"" ,,@' lh....; ~li on lh. 'f l' af~l i ".i ITagmcnl' "", m l""~ r..., I"" .1l ~",", wilh Ibe
..,,,,,or ~n8 ;ooi" d. If i" M I ' " ,"' 1J~"d is clc:I.td "''l Uat LOn> ~ . J 8,4), l\' "
illcipiom radical , peei
, h" chs,~ "h.r.~> ...i, h two OOnd .
('~~,~ , c"mpCl iri~ ~ i ~
dl~,.g.d
I""
0"'
"""'1'<"" (",
e)~ ,c..l-<rt oc>l,
8 ,h V
' 6.'"
e.,tt,'ct<,p: I1!
8 h V
69
ev
<- G,H,' COC"......
,,-
a.e
.-"
1-
c.....
'"
--'--
C,H,
~.
'"
JO~~
,W.
G1
OC".
,,,,
{ ~.3 1
x - c . l1<t
lJJ vV
--'--
--'-
(;11,.="0(; 11,
10J"';'
CH,;CO'
, ~
,,~
,ll 4f
n,ol~c> com""," Of t ho: ' ..... n proou cu

fh.!I.. ~"",n' "fl"......1 ionil~l.cn ont'l:)' (I F.. T.hle
cte... od Il:qu;m oo 8,5) 1"' '' in" 'J' ienl

j" dir~' ,h~' lI# ,,~rnlX'[i,ioll,
"
.,- _. _.... .....
'"
~
. .. ....
'
-'!'- ~
~"
~:tH
..
"'
,, ;,O., . V
"'
"'0.'
A
100"':'
"
~ .,
'.
"'
e
"'e,
(8.3)
~H
A ;' is b \'ored to ' CIUlU II>< "h~r~c and h' b<;c" "," lile innic Imwl..ct rf'l' Jlt>lt
cntro tlie dfe<:Is are d ist:~>,""l C
,,,. F'~ lL '" 7.9 and orbital .' ymm<:try <ffI> ror
E4" .... i" n .~ 6 hd""'l "l olt 1"'11 ~~' ~ll ,., n \ Kule Dredid s cor rect I) ' thot I f>~ ' l .,.
( PhO l ;n 1M rna", 'O'C\ru m of t' hO Pl\,
IE{P hO ' ) _ R ~ cV and I F~ I"~ ) _
~_3 eV. ' e" thoat h I'll ' ..
,n,,,,...I. bIc prod oc! ion: .i1l/ WhO ' l ls 2.~ ~ \'
lim-er in."<Jna" "" ,,"l>;li...... ) tha n ~",l t'h ' ) i'-tt ab<>vc.l Th u. 10 Il>~ Sl~\'en ."" '.
R ulo yo u d o not n...d I(> t \'31u.llC p , odl1Cl Leal > of la tlnal;" " , ,i nc " Ih o"" 0;,0 ",,1
nul for co m plemonlMj' h' n."' loIclitl al 1"'1<1""1'1. i \icrif~ Ihi; )'<>ur""lf UllMg [qua.
ILun, 7.6- 7.8 [,,, ,1", .." mpJ"m,;.. ' ~<Y (",m an o ", of AD' ..,. l.:U an<,! All I <':0 " ,)
1\, " fur lher " " ulm n. Stt\'t n""n' < Kule <Iflplico 10 o Dly the " " " I"' l;li.u r",mali" n
of J'f,x!UCl i ' TTl<; furt her di" oc;,tio" coald reduu: ~ 1"<.>d U\.1~ , ~ " ntiloce mi, kollljJlIl!~ , a" d . ddib" nal r,,~lud f",m"'i " n hy " "'f'I'no.' ptllh w uld ha,.., th<
" p",,,,;lc CIl'CI, ,\ppJ r~ nl ..a mple> ioclu<k the 11,,,,,n bk rOl IU~.""" ," CH,
' " n uS - L Ot:OClJ . r.nm C H,COC OCH , _. lunkll<l"' '' 5.2)
1" I <: , H , ' "" " , ,,. - CH,C . H..ltl l. C1 lm", C, H , CH IC,H , )(; H , 0 (ullk"" n ) lJl
Slc,,,,,,,,,m', Itu lu c;,n be u,,,,1 w mea,u ,"" II' \'J IUeIi. , '-en 1110'0: of w .. tablc
1!""'M'S fu.: h b 9d" l>.",. J iooc (ell) and m.t h~l .ll ._ y d o p l o ~ n" f..\ lCI') It m no.:cl
''''I'h. h~ k:"" ~dd",1~ (F ii ur e ~ .J J, T tIl: 3hu nd1nee. of the an:m, . tic (Ar l
. ,KI C,H, fr"gmenu l<'nd to lhe ...me 'ulue. lJe'Ju ' . the" e"'rOS I)f" ~j i "g U'
v. ILLo, m"t<;h '''0' . d o.cly. A plol . of Inl[ C. H. I'TAr 'J) v. "us I E of the
IUb. llt u'od I<Hl' h l lta l ~~, ~...
IFlC B, _ 8.0l:i ,V a nd l I:(M C Pj - g.~g . v I:Rn}'
" ' /Ii. 1 9 8 ~; ro, a nol her cun,ple. ..,., l u ~l <t <II. 119\1Oa ). Ho we"er , th j, ",.
l " me. ,hal lbo Ar and C. H. rC" IlI" . m. . .. 'h .t " t ni6.:anll}' ,li "mte~ away f, om
tho;, eq u jlib r ium !,-l"lll" cl , i..", in the ' It,n. III<)11 a lo IT mettl< ar>d Hana , t 9 ~4 1 .
r., ~m pk . in,lioalc (hM r hi, mcth.:>d $..... """'" .., I I: , at""",..'it h i n + O,O~ eY,
Slmil. rly, the rclro U,c!> Md or a~,li on " ' 4- .m~L..}clv"" ,~nc an d ",1>,10,1
die,," dim. " fOIlm Ibe ro", ['lcm,,"'. ' )' ,1""'0 ion, 1313Dd Ibl ll:quah "'l M./ ~f
n""rl~ "'l ".1 ., h",><:1. 11,""', ~ l Ih""'-'l b) i"'>lvpt<; lalxhnt:;, llu. JK'inN. If) Q .1' ,,_
"'w,.'"
f"" "
si"""
$1'''''
....,_........
J.
..
.,
1 ~.6 1
Ib i
.">1; /lK'\;h..ni .n of lhe ,,,acrioll in""l vlng Inn ' )''''m" lri" o l"'n- rin ~ illlemtedia'C
tP~ ....ii
a"d T u~k 1 ~ ~4; Gro;;newl>l d and Grn l< 19M ]. (btl l h ~ n:ad ~ 'n
JIfOU'Ul,\ 1 in . ,~ ",. ,,,lOO mode under N bilnl.y",meln-' ronm>l, ~ "" m d.:><ytli\'
1r-....I>J I.t! O
il lh~ ' i,,}'lcyd oh,,' cnc "'"l oe"l.... i" n "'<luld ro. relale ...,th OIl< "r lite
, -"'\>;1..1, "I thO' ~~""rc li" fragment (b,I IT~ ..:.-t ~ nd l " n,,~ 101M. "inuo the ' Hlg
doubk b<'nol i , \10" j"ni,n\ion , jte(IE ~ ~ ,9 eY. (,,,,,pared vil h '1.6 .V lor the
,.,
__ lUI "",' ," mil"'" n C. II 'J I ",
b(>Q..,JeJ<
'"
'"
\'in~'l I!OIlP~ ' udl w fle lali.>r, ..."uIJ r~4 uirc prd" entia l romt:lu "" ,,( I l>~ Coo c"ned n.1n,. llid ...Aldcr J<ac "~ ", ha' " ~ en dem()n,t r ~ ,, ~ Ma..teJ"" uu,
II~~ 1) 1M .pee,r", ca"",. IJft.<.<, .. ~ . , c ,,~w.d (1990) tho reI K l c~' rcri<)-die . ",,<linn_ of Toldic"1ca tioll'.
R." Jnm ..... lUi/tiPn rear.....'~__" . l. n 1'\..,Dmme iml""Unl rtccaul inn for thi>.
....., 01 I E va ll'"' i, l hal II>< prOO llCl io o ""'~ ~<1u~lI) ""I't_""nl " mo ro-, ta ble
iwlncf m tlle rorre'l"'nd ing . u h.in Jctmc ill the oniln41 mc>l <cu ~ (Rowe" nod
Wdh.am, 19110; Sd,,,,"tI IQR I; '\fortO ll 1nl:
I Q~ ~, Bowen 19911. T hi.
1< L...pc<.....u.y tJlK lo r Jo.. ..,nerg}' '" ,1",. ( m C ta I T ~ b lt lO"l <k:\;om"""itions. The
SCrmra l;ng ch~'l"-~t ~ nd n,,,,,,,1 (ragmen" .. ~ . tt, ~. t<:J by i" n-d ipl>l< l" i"n '
;",1" ,,,<1 ,lipo ic ' Oltt$. C....~ ling a !""tcnli"l " . 11. WI"" "", hig\1 ..........Ti' IU ljWt nrl
ra pidly ."",~po,: Ill<: \' fu, thn:Ihokl -.... ' gy rrngmenlO "" n be tr apped 10m, m"ulh
lo r j 'OlllCI' i.< ~\ ;" lI h. ' ''-'-'Of . .. hie}, ",~ n Ihl'n )'\eld A mono-' table ;""j~ (MINt'"
11<." " ,,1) p,, ><.lt w l(. :I, Fur U A~ ..'il }, ':'( ~~ V io nizatio n Ihe ;. H:/l-.:ka ' a,"
.....rro Qt<m.nt uf "-hcxanal ( Eqg~li"" RS I ei,'c, m" iniy C,lJ. O - ' (I~'A +
].(:.H ,n a c co r d a n~e wilh It... ... ...... ILIC H, -C HO H I _ 9.: . V an d.
1F.(I- l>ulco..:) - 9,6 ,.\, Ho w",'or, 11 Ie'" flt ro n eDefI'.i<,< It", C. H, I ' ion pre.~ , m ; I\;t ...... Will> ' ub; \an liul h}d l o~en tlehang<: loci..." "" 11><; t: , lJ. U ~ nd C. H,
fra8me n.. (I( la beled M ~ ' (Liedl ke " nd nj<o,"",\.i 19t>9 l
The<>reuca l """-... Iali,,'" lBulI <:houx "ai, I9g7i indl<'ll le IE..... I;,,,, ~. , ) Iha l
In" ~HIr"s"n excha"F Ink.., ~l~.~ in ~" inn_mo looll!c <<" npJ<c, 10 1"< c" <n-
""""<I,,,,
I
.
~.
I '
tu ~jj l' ion;""d 2b Ll'CM (IE _, 9.1 cV) " od n.u l'a l " ""' ald,,h)'<lc (IE _ 10,: .y;
MIl ll.ut,~ 1 t' H, t ' HO _
J.7 e\' , ~ I ('H , -C' HOII _ - I j ....., a< Ih. """",lahl" p roJ ocl' . 1'1 n simila r "h idd en renrr nllllcmmJ" , iO hi, ed ~ 1an o ic ....-..1
g;,'c. excl u, ivd)' the i, om,,' (' H, - q OH),' (I (f,~ ft l , u ,joj " ",~; I -C. H. ~ . :i'Xj at
li]i;tinw, o f 10- 11 ' . a, d"~nni,,"d b~ r,..,k1 i('>lmnl;on. ' ;nCl ic . " .d i.,. (\l,'t'hetd "I. I 9~ 2) . T he ,am" IOJi dominates the 7Uc\' m". l ~ t ", m. a., e. ptct<:d from
IE ,7 9.1 eV fo' CH-, -C(O H), ,,><1 '1.6 uV
C, H ,C H---('H , .\1 1.-" ,i'"
hfelime" ho ,",'c,'c' . lh. p,imary pl c.thlds, l>o "n ~ in ~ n i" n _m nk<:uIc co." plc...
undergo rCJnaJl~cmell t alld eharal; ml ~ration to }'>tld 1M l bul. ... io n <lnd
lll;L1l,al """ti c aoid l iE - 1U.7 . Vl ... ,I.. " ,..... ....1,.. 1......1'..... tl."u BII4' n a1
1987\,
Th,.,,, "h i,k k " ' C" fC, nl1"Jl>el1t." ,'i<;h..,,,"/ I?fIII.;.an a~o be import ;w1 in
7v-" V d eC\TQn ;" ninlw ,,- 'pe<t.a III lhe ope.crr" m (0/ ""'l h~I". iT"n~ ,1", 1"... vi
methyl I3j ';'~ abund. "",,1 d.... not inw,(w tile " ng,n al I'I>ef h~ 1 Vr",,,p b~
~d'"""6'C ~ " I'" ...h= ,I>e C 'l"""".. trd "xireo~ io u. $1Il~ ' hil i> a h1,tt- <JI~,gy
Slraiued -flng
rr" ....uk a nd Mel ~JTer')' Im l, In<ln J h~ }"" of
mct hyl i,,,, ,,lves a [ e:l"'Iflj!Cmeul to }, e1d e. enl..."ll)' llle ""'011 II. bole ",111, 1 ;,m
(I" I,,,. i'm 8,81 S". h .. ""'"""1':""....",, """,,",,<a'Y i" the I" "" ..r IIlClllyl f'''lIl
r.. ,
."""ies
-'"
n"' "
j~
"',. V,
2 . ,",,' 'I )' l\ ~ l r a hy d rdu ,. 1I.
which produ , a " . f}' 'tab le C.H , t r io n h~ 4 ,rcct

~ ,; l e u ' '' ie 'B uucholl\ Of "I.. I~~~ J . The nanallylic los< 01 ~-.lk yl radic. l, h om
un ''' l LlrM l~J ~lJ.:hrJo" l ot"".., a"d ~,t.rs proce~d. ,.j" a , . H ""'-fTlngc.......l.
""-,'I,,Vou, t(, pllol<lcnu,inli"n known 1m", , ,,ILllit'" cl""" iotf}, 10 . ,,'" tbe
nl<Jle 'l lub~ d'enul iuo (Van de Sand~ ~I 01. 19i6r. Ihi. ion thell "'"'" t" e ",""Ikyl
~,o" p b)' .l~ , ~ " r the u....ly allyIi, \>ond (lOQua!ion ~.\I ~
"R a n d om N41l'lln ll\=lll<,.-n I, " a'c lh. b.,i . feuo n wh y Ii>< ,pect, a o f Rl,l ny
i'ulll<ric hyJ roc artlO ll!> (!::qu ati on S,II, , ueh .. I ....1:w,ulen<. a re ";milar. Tbo
aeti"aliou e~l g v lor ;K>I'ltl;(Iulio"- of I.C. H ; ' is 1.0 . ...-. ,"'..,.. 1.Ii <V ~lT
ii' 1"" c, l. cr>eryy <li.,..~a t i n n. 'lO tMt e<' . n,i"" ""uilibrdtion I. C.II. ' ..
2-(:.11, - ' takes I'l aoc bcfof(: (l,"oci.tio n. "k" I,aIi",ti",,-reion;r.u ,OIl m=
.,- _
".
--
.. ....
'J'<..~ r.1 ~ mo rt effeCli ve in d ilI'''''' lih\ in~ Ihc"" ;"",rner. (Scc:oon n ~~ .... ~ lilt
isomm'3,ion an d
d; ~~ (lCIati o n
bmrkrs
0( 1 " " ll ~ 1 ! .c~H.
,,'" nn rly "'1',,,1
IFcllJl ~I aI. 1'.l8'.Jl
T" .Ir:WcI a ,.,.... l" m Of hklden , ~ art3 n ~cm cn t, remo,,' bcr tha llh
will hIo\-e
m1Jdl high<1" cnfJ"!'Y ' C<l",r_ ntl than " , imple ion Jcco ml" " ili, nn,' VI
. l><,uld be much m" C'' '''l ...... ili. c . 1 h,... <'JoelTOn cncrg ;", or in m., l a"'"
ion <1i"" ":'",'",,, ,\ 1"",~t "C1 ion ", h l'U .b u"da",,< m"rCa'C' ~llo" eM','-or
prolonged ructlon tome >uld
1I be formed by l'"nr r~"~",,, "nl . e' e" ir "
lllcohni' licall)" l'h \ll,hle . "" I,I..-d. ~~ I... T ~ " a J ,,, n \>I.- drdwn to :occnunt f<>r
;1, forllLa t i" " .
t :hU'I(t c(>mp<'/I/i"" I~ Ce- J~c",nJ'<'.mfOln: f'uhl'~ II~ . Ah "",,~h Ste vens o n "
Rw. j , . 1", a p r lica f>lc ,,, FE ' io ", . Qf "J diu",,-,I pn:d;':t i". ' all", i, a
propo '-li by fleWl ( l ~nl , nn'p1ifiod by /kno.'e n .., " I ( I 'P SI TI.;. r.,i nl,
om lite ..""~'1!" "td"omhili' y ~I' ji)m JI" y "
~ t1~ I",,' I'' '>too ,.g i>W ~. (PAl
in <I;'..... ,. " ",,, ur diITen;Tll E E ' ion, yi.ld ;n~ Ihe "''''~ U pmduc1 ~ I,' "
a u , ,, ~ "'ry
F.dd ', Ruk an in term~dia le rrotOJi't'o " nd romp!< houl d
.,,,,,,1,,
"r
<'I ;',n(. I~ l ' p~ rt ""'li " lly to
io ml tho;: l<:ower P I\ IlCUUD!.)

Corui.Jer ~ l'>ll h" til"", "f PI\(Y) on lh. one-bond cloh allo 01' ..., EE ' 100.
,''V _II ' . Y, l O 10..., lb. m~ loc u l c Y Iformation of th e ... di<:. t, A + Y
is not fa.".."./. '>cctio m- 4 4, 4,7, 8.8~ Aro,l.Jj"lll " Field (1972), the te Mi. ncy
r", Ill" co......."" "'. eti<>o. A- + Y _ A '" ."o uld depend on lire amnily ,,{ Y
foJ Ih" A IOn Ll!>e cnti<:.al .... f~r 'h... u~ t I", negligihk: (ho re""r si bill1y
(t: H., ),t:HO~ H, .. ((,Il "loCH ' + H~O II.. bft n dem"m lr, leoj, Tcrluuw ct ~I,
19$61. 'r lre ..clali ", a m nii)' "r a Y moiull' "". " J"'l1icul<lr A-io n ,hu uld IlC
,,;m ila r 10 lh, l for a prulun (Ph ' 1I11lC"> art "hNJ l~ rel~h"l I" CH : ~mni [ y
"Alae '!: H'"urnan 19 8 8 ~ ,u thllh. ten "'-"'-'Y rm diffeT..,1 AY ions \1> I"", til<;
Slim. A' ion .!l()uld he ~prf<>l'ma!riy in !h<' "" ""'I: on;I..., '" PAlY, of too
"'''JT''''''l''' nd in~ Y mO~lll.s tlJ~lt '\ ,3). Th o lea.i n~ a M ine. ," fhe 1<rn\.I;'mal
gmlJp" in rE ' i"" ' 0 t h ",. dCPM denl UIL t lreic p"' ~ ln . mnirieo!, Fnr U lulaTed
....
_-...
'"
l'l" i",.. I", ,,,,,tJ h. U . II. i , '''m hl !",--.Ji", ,hc I" "" " f H(l I I'A _ 5 8 ~"-"",m;o
" "" ""al, d ohl"'.....lh "" 10 b< m"m ~rtal e1 ' han , "" I""" " f " ;01'" lI"A _ 7.2
oV) f,,,m ' ho <..." o' p...... h..1; r' '' .on ~ . o d ;tJ<vltoJ, ~ n<J ' h" . lK>uld 1'< I~ rv< ' Ih;>n
1"" I",,,, ,,' NH, .,,-\ _ '1.0 < "~I r" ~11 .h" u"n.,..~"'Ji,,~ I'''''''''. ,.... ~", i,oo.
iI.
Quon l italivd ) , , It... i' < ~ ..r,,"<ecl<1o/y1;c
hon " J .. """j~.i(>n cne. gi"" f hhlc " .3, TIl(' ,:"",""",p<)n.lin~ y~""" .1. HU K.
LO. V, H ,0' ok . l. t> . ...; and H , N ' ok . 2.9 . V. F",... all yl jon> 11>0 I"", or C, H.
(1' 4 - 7.110":1 i. fu. ",cd
II"" of hi~ "'" ;o.~ ,"'" l " 4 I M oeH - eH z I - 1 8
. vJ "
" I JlCl$3'!; "","e. e,. r..... Me.<.- 111(' 1001. (>/ (.H.
(1'4 - 5.7 oVl i. fdn"r.d
1 or 1M uJl.... um.cd lil'- i ons. R- OC= U . K - l~ U ' , K - US::":'U ' . ""d
k -O' ---'-C H" or ~".I imem al ene' lti~ ' he Ios;es (>/ CO, IPA _ 1.':" . " LCO
(1) 2l SO , (I> I>L . "d {}--{"H , (1."L TC'flCdiYl;t)., . ..., ,,hl .IM" &"'-n:>t'" ",i, I> m
<rra";.. g
affrniry !>,,,,,Iarly, m [.qua " "". 8 IUand II. 12 , ...... , h,,"1d .end
to he more los ' of Immaldehydr lhaD (>/ ~ce1~k1myd .
'ho hiibrr
,,""",.cd.
""'."'''gem'''',
pro'''''
"0'0I ."" .
,H !)
(@
.1l1
"",Ion a lii",,;.,. of t"""" I1nsaruratrd n...l ra k ro D mak.. '-">ItIptUti. c , 1>0 "->
'<Iro-
t CO rca rr""gonent <IcaVIll: ",,' 1:0000' (!!qnat,o", 4.4J, li lL. ~. 13L ",ilh , he
t.. tde " . ! of III<: l>nld u~'1 -io.. pll,,",,,,,,, r '" ~"'p,un: til<: 1""'''''' d..pn ' '''=''1 ..." it>
PA v~l 11e. ...ilh F",,,al i,,,, R,1J fav""",, " . " , 8.11, RearTa n;......nt io ~"nlre'itivc
""Ih indnctl "" dra.a~ ( l' q uaUtln1 ~. 1Il and ~ 1::1 " " I ' ''e PrOOYCI a h""d. .......
a re a!k<:'<cd by III<: rel OI;' " o n{ro py n ""n a. ..,or&!, ""l. ui, e me Dti. .."J b)"
(,, <the.- d;"""-....Li"" tSa-..ion lUI: Hu n..,... ;md On". h 1 \l 1 3~ Fot e. "",ple. lhe
2-dea .'al)'
o f C , H , OC. H , _. y;.kl Ihe " ' I~ed. h i ~ ",. ab" " d. "o.
,, ( C l H , 0 ' CH " (~~l lha " o ( C , H , O ' (" HC H J ':'~iJ. h"" .-. ,"' t. f" n too,
d; .wciafl"" of Ihe forme r ([]qu ail"" KI ll }1r ldo 1.5 lim.. ito abup dance of
HO + - e H,. ... h. r..... d i"""" ialiDn o f {h ,- la.llef (Eq U lio" lU J l l "'ld> 10
;Is ..lmn<1anu: " f HO
C HCH , ( [his ...it 4-' i" n .. ...-It C.H , O ' C. . H , OC'
yield. ",,': ~ , 00 O ~
StlclI l':l + ",ar ra np:menl <o.<,", io ll' ..... m~ pi..,. al n llioi o" U;<IDw ..'"'tin
CI\n a loo;nwl... a I'roton-boWld ;n ",ll i"te I E:q""t~ ... R. 14L maJ.. ;,,~ f>.~ ,-" I"""
,,,act,,,,,,,
'i""'"
,1'>,
"
".
- _. .... .. ..........
-.. ...,
"
..,
(~ .1 4)
C, ,,,' O-'"I;H.,
dlte.tly u",ful fur PfM i<"tillll relmi " \-",udall"'" of prod uct' that at 11lgh"r
cllcric. ""'p<"""nl (he "" mp"liti" n "f i ' nd , H reaction>, The MI >pcclrllm of
C,H ,O-- 'l'H. - , bow, no C, H , ' , blll HU CH,.' represent. a major peak
(W;tb"uL 1'''loP;" l ~he lin ~ the prc><1 ~ " " ~ n:: tho ,amo as th", " or Equalion S.II;
Dowen 1978, 199JA' K ing' lon n " I. 198J: 7oJl;n~ .. an d SeibJ 1985). Even in
7Q-eV s!X'cT.T n, 11M/ever, lh. pmtnl1 _oound com pl'l reactinn can <til l"" compet.
i\i... W;\ I\ direct H '. Q" a n ~em.nt IO the "' Yllen, CD ,CIJ,OCJJ,Cn ,' form'
Cn ,C11 0 '(''',0 1, (1o",lin g t" c n, rJ l 0' II ;TI 25 ~<, ahl1nd~nc<) ami
(' I>.,C1t,O - (: Ii C I J" leadinl tn 1 4~,~ IIO ' =C1I C!I , a< well as :"2~';
DO ' - CIl CII , . Equa tion 8,B "" n form onl j' the laner. whereas both will
h<: r"rrr",J (F'l uali" n U 4) hI' Cn ,cH,O ' - CHC H , ; CD , - C H,
0' O=C IICTl, or CTl, DCO , O += C rrCII , <=, CIIO = CO, "[[-"'0=
C HC H , ... etc,
? rololllmund "ompk ,c; play a role in Ihe dcc"mp",il.;"n "f pml.nm,I"d
pI",,,)'! ' . I>II I"" yl . ' her (Fq ll . lion ~. I5) r" rmcd b}'exother mic (m'than,) Cl. T h'
d
/ . J....,'--"'-
IH 1'i)
'"'
"l H i" n. "'~ L~" " "" b;: !"<llun. l,,d ",lh . r 011 til<: "' K~ b"' n or in the . rOlllat; e rin g
l Wo (>oJ d ul. I ~ ~ J l. <earn,,&,", to a I'rot" n- b"",Kl UJ<Ilf'Io. ""hi<;t> ..,lit .. Ie<l " i~
tl>c pro t" " atl.odx4 IQ pbm " l l l' " '" g,5 eVi " r butadiene (pA ~ ~,4 . V~ At
[" ",,,r
lOl" ta ' lattle i" " ' i lhe IKU<'''''U:: (",. Ih" .. u,,,, tx" ie pl",,,,.[ l"
tela in ti,e pl'Q(on l>t,."mes even mo.., l" O' '''''n.:eJ (M tl' <~ n l ., " I. I ~~ 'i l
"""'l'''''
Q ua <l\; l.O li\l'IY. l l>e rompetition betweeo I"'" mc.>kc. b r" , I"~ ' ''''100 ron
to iu.l ,n a I'''"o~ho'und com plex ean be u..oo lQ de<Iu~ ' hriT ","' li\"" ~ .
ph,.." b<wol1~ \ Md .' ","" cy~' "I. 1991 ~ 1>\' 'nei 'U '" ,..;1...... m<u<lable ion or
collisio""Uy ," 'i vatM dJ" ",,;ation or (I>;; ,;o." plc. ,

" ",hm ~fTi n i li hB>e bo.n found \0 = <00 ,...'ilh i<m i,~ IK>n C'IlC,gi"" .. ilhm
a ",, <lielll" r compou nd ola",. ",.d . as aL:o hols, elh"rs, ald" hydes, ~ nd l e(,-..
fBc:noir and H", ri, on 1977,. Ilmila r ",~a l im"l. i l" ""lh b~se, have h= wu nd
(I >o K " cl ~I\d ll" rll" e!lYIl 1\l7\1~ '/ h" . Ihore i!; ~ qu"liu,'i .," in " ...", "'lalio""llip
bet",..,,, S"'"""",m'. ' '''' Il''\eo ''i,,~ O.E " dec(>Mp,,,,tionl ~nd lllu.l:: ror ".t.d""n mp"';\io n, (1'''ble ,\,3~ w>t h , lr ocluI'e gen' l', lly . 1fe<I;nll II.:. . ah.... mor<
Ih"! ?A, ~~h l< " H' lWC\ Cr.lo reltCml. , these rulb> oo.n be nriJJe.rdittl >r Tcac
liO!" Iha t f<>rm i><mlcn c ion ; or ""I1I f1, I, . Llr for tbo ........;,: ~,-,", ~ ll i .' . n "s is
~ ".,, ~d by b~01i c .. no t lhormodl.m;;try, A, 1"",. I:":yu~",,, . all'ill.lU.; ro,' larger
"".i,.... /C H C,H,' I can loUo..' tho ~"'l<'<lphihClI~ ;c-~I. !S:> N :>0 0 ) l'~tll",
Ihan 'hI ler prown "m"ilie' (r-; ;> s ;. O ~ as ' ''''''d lor rnO't'holi~. , thtomof ploolit>e. nnd 1,4 ' l h io , ~D(" IUl1 rin,ty atld C~ m l',ma 1984).
:",', ,,,,nl-pro.m,,,
[l"<,pn,, tIr. ~nua~y high.r impo rt" n"" "f rr,>du.~

ion ,ta~i h"" li o n a; a ...;1Cfion-d ri"mr f",c" . m"r.,l~b k n<uu.'. 1 prod.." m". l
ai,,, i n ~ "" " cc p,od,'o ,i"" ~ b urw:ia n,,"_ T' n, .X'lmpk. ["[ nout",l I;o"'"",.n
the hie' [, In i. .....~lly In",. ' ta bl. tha n lhe ~D ... t AfI;'CII "C H =OI .1H, (C H , - -CHOll l _ 0,4 . V, . " thaI lhc "" n'!",t;I;'" pn '<!"," 01 t:q""lion
~. S ~re /3>"'00 by nt~ lra l ~\ w.1I '" lho COnll I 'tI~ i,m 'labHiation;
<1H, ({"H, - I :HO H - ',I - <1H riC H , CH O - 'j _ ll,H . II WI." . th. po",ihle ;0,,"
M ""all y the sa m. , t"h; Ii ,y. II><: dr~"l " cJe.rn; Ih. ~~ l<l- prooJ,," "a biliry in
<l U~l lOn ~, 1 & fay"" ~~,r3~ i.m ,n' of lbe b~ d"uy l- H l)o ~\o rium la behJ1' is
,, ~IIi/i,y.
\ ~, l M
ntn"'S.,,~ It, .1 i flcr"n ti ~lc lit.," pwd "" u. hvwc".. A "",,,, -; m ro rt a~ L anal" lIUll>
,,,,,,,, i< t ~e <pecific ,.. "rran ~ """",' ;nd ica'ina tb. ,O H ' Uh<litution po<iW) ll , ,j
hyd, o,y-, ub'ti tut ~~ l~l l~ ~~i<J deri~ari\-a. (F'!" . " " n K 11): thi, yield, irnpo" >!
OF,- ion< a l In ,,'; 1j(), 144, 15\1. , . , . :nu 11\ the m" $ Ir ""lr a "f ll><: n...!I .~ 1 ~ l "n
.~OCH,
.ICI1i'.
1~_1 7)
., .. __.........-.-
.1\"
of 7-. ~ - _ '1-, .
J7 ll y d , ~ x y "' t u d e c a n o ic "eid (I>u t
u ,,,,,,,,," ol,ng flI'a ~ ,
a ", 0,,1 lmP<'II""'t
6- ..nd l"w e, Ilydn><y de, i, " ti,.....!. Tho: compo" or loogd i' tance n:a " a "fO.~1 "" ~ 1 ,.r " n all yl-II in an un m n.lll uted e,tet w"uld fu< m
. n . Ikne ne_". r., 1: ,,. n<g1igibk imporlun<e i, refle. t....1 ill 4Hr . ..I. e"" . ..,,1. ....
+ 0-' " V 1<.> 1 l -(:.H ,~ n.u, -2.4 . V lor C. H,CHO _
r"t
S"RJ I~"'I"..., Tt.<: k<' ~II-<l;" oci,, "on ene rt '~ ot . 1I ~m. ..r cour" , arc critic al ill
<lctc,nt illi na il. I-'~~"\.lll~tio" td...~~ .... 1'0 .., , h. i, "..... in inter preta tion i, cli , ~c, ,,np<= J . I",c~ u, " II",," "rc w mel;mes blr d,ffeunl I" ".. 1",_ 01 tho con . 'I'(l"d "t~ ll<'1l1,,1. l'Of eumplo. 11K: QI .soca" . IO'1 e....jl.y of tho n . ul r ~1 K- F
bo>1>d 4.7 eV, i , aon oll~ th. hillh. >.l l ll< ' ''' n (hhlc '\ '~ ~n Ihe ma" 'pe<lIu m
of CT. sh ~ w, ne molocLLbr ion . r " r I h ~ \x' IlJ -.,hUOci.:llI01l en...-gy of ' ~ e iNl,
f)o F.C" - F1 10 Ix < qll ~I L" L h ~\ Ill' th~ neUlf~~ DW, C - F), II>< ~. no /" L i""
f:n"'$Y of ,t.< rn<>k<uk; IE(eT. ~ lllu,l he t 4Ual L" Ih ~1 " r lhc ""',,, oon " p"OO
'n, 10 t he po:od '! i,m Il' l!'f , ~ Iru'll S<;ction n , rr:(ABCU) 1Jl." "'. ( U 1 ~
n. 4. R- c n , I " fA B' ~ Ilo.. e.~r. IEICh ) is > 5 eV lli9 f",r tha " IF.(' F, ).
"..l ia g UW" C - - t ) l><."lIal1:>l~ .m~ll . I" ",mira" , lhi, dirr"TlOnc"" i. ~ . 1 . \ ' (<I'
th. <oapo..d;,,~ CH al",...
rna.. 'p"ci n lm , how, [ell , j :[U ; , J _
R5 !(XI. Fu rther, tt.<; ab"oout<:. of 'of " I,,,,,, C I':,CI' C F, i, :)(fir, [Cf , a nd
C, 1", . , _ 100'~ ~ 1. ,ince it> ",,,i: allO" ..I<r ~ i> _ 4 <V 1",, Lh n lh>tl of r: F.
" similar .,a mple ,~Cel , ., ,...h j;h IF ICO .- 1 H .V , t! Ie" t n ~n
I EICCI,F -l. ~ .() ,,\' , I n" . h" ""."",,,. <l1 C'Cl, ' an d (,:U ,V JT~ :r!~ and 100':';;,
' O<p"',i ..ly, n .", the ~ U.c " d~lC(em:e ;0 bood..li."''''''''i,," "~cr,,ic , of
( - (:I and C- F is lur ~r""t"' II"" , d. e d il\:,.,"r"" in fr-~ pn m l rE , ~ju .., T he
M ' ahunduooc " no~ l igi hk TF-(M) _ It, ~ e\', n....,h "'l", I. n, III IE(C( ] , F) I
n le Cl) r "",. :,,,<lmal;,,, " ll:' di , cu " c ~ furll"" ;ll Solo l;"'n $,6_
p"" ".." ,d, 31 c ~ a'.c ,i te, in even-d . et"'" ;" m , '" i.. ~i" ".. i<: noJM:;,J ions,
bood-d l s;ociall ~ n ~Tl"'tle, " ~~ Ix; bighly d(" penr1< nl 0" d ,. ma n..rn>m (Lq Wl Linn ~. I *~ He'" '''' yl''' ~ olld d i " oci~t i(", a t a n U, , "~ <!e p<nd> o n lhe o::ati" n
,.It,,,,,,,
-~ 1tIC '
"
,/"
_..
",
R'.O".. ~
I\'(O ' '''~
, -~
,.
.. .,
I~- I ~ )
nll" I; I)' of Ihe lea ,j,,!\ ~",up (";d,, .'" fWd), .. ,h ic~ on ~ha'gt mieratioll lorml Lhe
,..,,,, 1 1',,,.,1 ,,,,1. How ever. hom ol ~ l ic bend d e.a\'38" Inrm , I"' '' ood- eleetfoll
1" 00' '''' '' and 30 ," "" II;' 'elJu,"", m",t. ~lO" eneri<Y (TOible A.J ~ T hh j. ",11nc..I:l , ly importunt 101' the reaotion RY - _ H _ R't ' ; + -H [ 0 _ 11'111; \' ,
I F.('HI + I'AIII \' )] III r ",r1 i<-~ Ihc Lc....1enel' f~r Ihe ""'eNe ' q, ... molo:ula ' reae ' ion. Fquatio>n lUI'. 'I'M hQmul) li<: 00n ~ ~i "oc i al io n ener ~,.. 0( \' Il l>on&
U OI.,., 'Ad"'.
.,....djt."
- -
' ff
1 ~191
in pto>'o ~~ted alcohol" "kkh~ .Jo; ~.1I'n,;.. ." 1" ' " chlor iUc..., . lId ' ~'Il n id>:s
(re' "," ,e,o nd , Iep. I:! G u ~ti "n l' 1910=....-.1 100 40 w 4,J -eV ,'a ll, nr C;- H
;,,,n,l, (fin-t " ''P) ill ' ....... lral a ll.lb<S
A.h T hi! impl~, thaI h~d roi.n
tra m rcr rcar raOl"'m"nl. ffUm "" .... m . " m.. III O . Cl. '" CN t o )' ieW do. ,j""""iI:
radical ion ' N " H e", ofu.-n exolhermio. onerV llcally fH" r; n ~ t"" ", p",h..a ).
Further. , e,n <c h01ll" lyI,e d ... ,'agc of II,",,, N- Yt; holld< .. .....
t h ~n
b<t"roIYli<: t.....a tc <>l lhe KY" H wnd tho' l e .,~ \ In \ "H 1<-.., The C'J\c-rgic,
r"r hctcm lytie "~,. lLolI of these bond . follo,,' the rul~ kn" ..n Im m "'ionic
chcm i .' r ~ ; ",ilh C- Y \>unt! , lhe <l i, ,,,,,i.., i"... "n':t' ~ d..:." aoe .. ilh branchin!:
'" 11"' ....rt>Im alOman<! the len' ill~ . bilitHdecn'.. si"t ,ir>~ ~lIin i l, . Field" Rule)
ill lhe hcto m,, 'om-comainin~ ~roul>; C- OH , ' ., C Ol l k < C NIl , '
(M" lI un, 1 9~2; Rein.., Han i.. " , l "' l\4~
n.b.,
,,,,,,Ie
8.3 &"'.Ie facto,s
Alt h<l\l ~h Ih< >"l>;li'...... uf proooc" Md inlcrmediatC$ ." ," ~ ..., imro" "nt fa. mr< ;n ~erm; nill" ion . bundancc, . _'1" 1,,
a h,,, affect lbe I"" l nen '~t; un
k;'ICll<:5. Sle reocbe m "t ,~ ..,n ,omel;me. be dl'd ,oor<t frnm rna,", ' pc;; I'4 (.G,oen
1976; M,,"dd ha um 1977, 1932; T ur"",,~ l ~ ~ ?\, t:<('l<'CIa lly ih he "pc""-r,, of "OmplemmtJl') stere ,'l. um. " " TO avai l"h le ( m
m. Stereochem ical etr~cl.
c;an'" dl1k,en l ror U I:: ' O" n" EE ' iou. a n.d ( -.impk hond Ji " "" ialiom
""" '" ,earran,ements,
."' , di,cu,se d in del"' ] in Suti,,,.. 1_J - i.i , II>< rn ,~ e n n ' l ~ n l rn, a gi. m rnx' "
\..'" I l~ ua li on 7.1\ "e!,",nds 0<. Ih. number " f , t.. ,", 4\,all.hl. in til<: u a "",IJon
eo m jl le ~; lhis i. detcmumd b ~ hnlh Ih. uorgy bamer fE. . E., I ,," '. ,I>.: d.:","I)
,i ' 1"1... The lIt,tc, (crm rclllXlj Ihe numhe , nr way' i ~ .. hich , be l1'3n" lroo
c'-'mplea can be fomKld on' lw " "y l" Ihe prod"".. , ~n d i, lf14lW 1" Ihe 5'eric
""l u' I'C me,,'" 01 the d,,,,ooau <ln. SIm ple bond clea, 'arc> "" oc "I,,,,,,,,~ 1Ill", ition
..a..... in ..hid> 11", " uml,., of .. t ~in " hk . talc, (e<pa:iaUy 'hou d... ' 0 inlornal
''' l ~ li on , l d ,ff"", ~ tll" f.om that in the fe. Cla nl ioo. It,. ." " I, u,l. ill bond",.l i~l' ('.If"",mut jon, (re"' m ni.ln llfl tl~ ....In<"'" 1hc llllern.1 1'Of,lIlnn, lUll" he
rfCrU''' IO " Ilnw for t ~o nnkrc,J ' r"",i liutl ",mple>.. t or . xa m pk in lbe ~ . !I"'{i
c"''''a ,;oo reu" ul1 grment ( Equations 4.33. 8. 2 ~ , "c 7'" H will be wi,hin ~ lX'nd ill1
"'nn"" LlI the rOld icnl , i1< in only ~ "",. lJ proro . tion of ,~c tot, 1 I"",;hl.
r.nnlorm.. I ; ,, ~,
' 0" ,,,, ,I,,,,u1..r ion. Att~inlll~ It><: " . n, " ion <tat. "" U red ,,"
th. num bt:, of free , Olon: lhi. ""bo'lk ncd , - .. ill ha ," all a dYe"" d ...-r 00 ' ,,"
reoction mt. {D<Jd<I n <Jl. 11/\14) Stnjo elI_cl, can n" ' \'1 . [;,n"" pr~ . Iahniti.,
in ,ktcnn; nin~ ,lo., "",nl..
or di"oc'al ion , eacT;on. Con.. tk, lhe 7\1-,(\'
ma" <peclra 01 ;;: ,," ~ ~n ~ fIC ( E~ u a l i u n U ) an" 24 oJe<-aDOIl<' (F i ~", e 3.1 0):
f",'"",
"" ",po,
"r
'ili,."""
'_....._-_. -._altoolljlh p" ",l llc1 'l ~il ; li( ic'" , ~ n " I ( 1 f" ,'or 1h ~ r"!rouged l , H.V _. ' 0.... b~ 0.6
c ..... lhe ......., ... an: oom inA'rd by , he C , H ,o ' iNIS (11)(1".,;) fl</nl ""'pi.: , .
<+.a ~~", On l h~ <>the. h~n<I. lI~rm och~ m i~a lly fa" ,"'.! f, " gn""~ I"fi"",,, ntn lf
, te" ca ~ J bmeler oo. ,Jon,i... le II", mel~,I" h)" ilm (VII) ' p'trA in which <,I "."
eli,"'...... !i" n. . ... 1 " "-c Dtr~y ion. ",." ", I..,lrcl (see F i~U I~ 7,7~
b ,,~.'I,J,_ .fllZt '
"''''''0In.
If lheI e ~ .c n" ni"...,l ,lifr~r .n ," ' in th e 'lshiht!" of

the com"" li,,!> p,, >d"<:l' md intcrmedla1e<. M';II IIw: ac tivat ion barriers. the rill~
, ;,'" "I tho r... rran~,monl Can he "" (I<" l" n, r ' \'e' Mot! ,i . -tl,,""nhcrc.! lramition
l t~t~' Ql e l!~"cr. ll y f"",,,"hk. [or h~d r~II ' l'3..u" .u ctions (:>.1cAdoo ' I 01.
Iq~4) , wherra' those ",ilh (..,UI .m el thlfCmomhettd ,in~. ", e <!i,r" , ..,.. d. Tn
hydr~ ~n r... rmJl~.m.nls to '~I"r. lc..J hc'c~, .>'"m. (Sect ion 4,'.i. reochon , 4.37
QM 4 .40 ~ the e"," lelll ,",Ii" , of the helero..l" m affect< , he pld t ncd rin~ size
!.\. F,limin,,,ion (fiv< -melll""ro:.l lin~ 1 pl'Odom iM l<:'S for llCl and HRT chm'''''
li.)n< I,om ~J k yl ~ hl ori dc , end broll,;de, (F.'lu."l;" n 4 .40 ~ ~ ,..l "'~~ ' ~1- ~nd
60"'~ 1,4rlimi"" lj",., " I H ., ~ !, ,' ~",r v,d Irom thi" I,. M:tinly Ll imi fl ~ ,i Q1l of
" " ter i. found fro m M O' or , honehain alcohol' (Equat!"" 4.J R. BIId. ik ic.. ic.<
t l Ill. 1967; ~,e , II" . , he fin" l prod ucl I'rom n-h" l>n" I' ;. "",' hyky..-J(>pr<' \><Ul< + (ll hmrd ~ otl , 9? 11 1,.1 "d 1,4dimi" a 'i..,,, n e ,q" . II~' imrorm nl
m ",>I;;r k... lrum , hoP F.f. ' ion n-C , H ,, - CH OH + IO f1T~ fT"'"
(n-C, n II ), C II O II ,K u.. cr 3nd 'Ocll>! 1~7 6~ fJllcrc>l ingly. 1M - H , 0 1" r...,m
"-C"H ,, OH --; \ I,,"ntd ...;' h 1~~ 1.4- "",1 63 ~';, 1,5-elimins tlon: h"",e,e.".
m"c h of Ihi> ~r pca '" t" "" d ,,,, to I" Mhe' kosb of ( , H. lrom lile 1.4_prodnct.
"' (M C, 1f,DOt oMM U ~ ' :47 for 4-<1 , . 5.-d , iBuko. i' L ~ " d RruI,i. ic",;a
I ~~ JI . $,mil.,l y. the ellSpl""""...." f'eIlCIio., n 44Z "I II - K Hz',
Y r ompo" nd,
yield, eyeli<: (M - R I' inn< ;n 1"1>"", I"" /i'....membc1v<J-rins ' PC'''''' pr. dominal e fo r Y _ C I. Or, J nd ~ I I . ,>nd \ke ,'x-mcrnbcfcd 101 Y _ :"'H, . T he " ",rer.
c"'-< "" -" " , .nl. l1l her. d lran,ilioll ' lalc . 1,,, ~ f'I'Iic.-< h ' ,I><; cl1 m i n~ t lo n of
wrmaklehyJc ft" ", 2 p1>cnylclh" nol, whiCh forms II><; .......l.ll bk:
n. ~ ~ V ) m.;' h)lcoecyc!ahexadiene \<>n (1 :qua liOll ~ . 2(l, Burl"u ~ l d1. f'.ll\1l
r'v'H, _
/ /
C() ~
~:D
!.~
I~. 4'
,,'"
-,""
~
C",
"
"X )
(8,201
lie
"
'"
.,c
'"
R ~ ute (b~ ~lOing c"" "'<m:.,I~ bl " loluOM j",~ " <h1f"oO'W """am" of , !'llhtet
r" u'-<JI.mbncd lu n<1llO n Slme for tho h j'<l"~n u .n, I.,.
~ lt"ri,: inl c . ~",j ...n, play aO h"porta nl rok m "~ fl "O " iTcc t " rc~ rr~ " ~tQ't.. lJ
(Schlll'u . 1?78). "" II .' Ie~ " ~H{>n 4 41, ' ''at invoh . hytirogo" tr and.. b:I"'.. n
""'d1 b.mnJ jn mp' on an .."""" ie rin ll- n",,, r"Hrran)l.~mcn ll. "~ Jf<'aIl~ LocH_
il ~lc~l hy IlL. rigid pIa,,", a n
~me>ll of lh. ;nl orac tin, ~l'I'u", Ib" l impost' n
qdic lr~ o .;liVll <l~ k .. ith ' 1_ M f",. r<ll" r> in I"" !l.>od, a ll~ ( 1II:d to and in
the awma llC,(n ~_ I his IS w ry ,,,of,,1 r"t the loc alj~n of "" Iu>- ... l lit" onIS, as the
Iarg. .. ,p~ti a l K PI ",.,on I:let","eMIn, ra_ " nd pu....... itu. lc..:l Y'l " pl wa ke, una lo~ou, intem" 'io,,. "" ",h.. . ~" kcr nr n<me, i, '.nl.
~ lc rio: dL.1; ,'tln all o ~ r i ," from non-bolldin, , In ;" 1..., <lar i"". I h ~ frag mentatio.. b~ 1_
'\lb' titucllt [o" ,ll. in >train
rd,d . ..him promote. tl1< <!i,,,.ciaI;,,.. jPih lMI M.1 ul. 1 9~2 ) . F'" u . mrle. , "..""""m ne<: potent ial (If I \ 1 . ('11. 1+ 1rom <>-di , ~rl bul~I bc<l""'" i. 0.9 ,V 10...
'T lhan llox l r", ,,, th" ... \d pl wmt:ro; (hi, ,"'", an n bm<;rt h. Ih< d jlkrcno;:e in
lho" . \ra' D<nerg;". in thc <:< " "'''''' '''<!;''.'I IlIol.c ul ~, ;ol\,lA mert 1% 7)
"r..
....n_" "._"''' ~ I '" _

mi,
is
1-.,) ,," " " ".. . if16~
....
...
"
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ro
.,
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m',
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"
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.,
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. .
.'... ."
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,. """
'" ""~."
1ll'J
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~
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"
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...,''"- \
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. ~'.
, ,
'
,,.,,
btr ",.,rJis ' , rr...,wJ;" . Qui '" dt1l:erent .lnw cIT",, " " 1',:1 ~l" III f, all LlJent ation.
pmooo<!ing , i. inn.......a..euk <oOlrle~c. (Motlotl ('ICo M, J..I'~ l 1 9~R ll"wen
. '
ol io' .... , ......,""
199JJj In (he\e di...,...,~ 'i ~n" tl'" pliula r)' i" " ~ n ~ ll\..." ral rr:.V"onh do n<'l
inunodi'lely. hul ", m ~ i n ongaged ;u, COn1pJe4 hold .. tgelh< . b}' all.o c
I;," ;o" ..li1'o'" " r ;" n.; .... u ~ ,hpol. forcc s. SllWe lb. ;on-,Ilpolr i" ~' ~ "lj ",..
r~ much Ie" d;r":l j(lnil.l ' ha n cov alt1JI oo"d " lll" j"" a" ~ "~ "l .... eoun lf "
C"ll ro tal . ",lal,l'e I<> ..,..,h "lIlL"T, and cv cn t \t ~Jj y react al , ileo; m""" ...
.... "'~ h' " ;" the ",i ~; na l strucr ure. Anal"......1 Iv (h. 10" or Cll ,O f", m
I'hClI , C Il , 0 jJ , ' IUl uat ;on K 18\ I'hOCH , RH _. Jose> e li , - 1(; I",w " w , here
the """" ",..tile I ~ H" _ O.~ .Vj PhOH ' ,. r,.. ""',1 , h' {t\'lIh on i on ltlol~o ul<
Ull" n ,,< d ;~ le ( I<1 . " I"~ I~ R2: H"m i, h ,, 1>(1 H"'m 199.1)..
0 "", <~ the roo", dmm~lic .,ample. of , ,,,,h WtHHnscmm" " lhc l111cr""tion
of te" ",l" lV" u,.. l,,,,... c~l in II>e .1- " nd the lI- or Xl-poo' lIo", of Iht ' lel'o ld
, kd eWh iLt< ngt'<,jallr 19l14 , l " ~ll ~ oll ~w;nil the ~'- Hi/l -d<-a " al!>" ""'ua ,,~,,,n "" )1
(>f lho 3 ~.'l~mj do ~roup IEqu al;"" ~,2 1 ). the mokCLlIo o( N.m~l hyf.1a:tamid~
,~p~m l.
"",Is
-r
I
I
(~.1 1 )
,.i
J "':>-\i
'0. ,
H, C
fr'" lOCI
CM I ",roam, lit 1"" "" Ill;I) of tho ion and mo,.,. Hcm .. lhc "'~ roj d , o: e ~ t on to
f",n, . 'I~b i "z( d h ~ d . ~", )- I-" , m l ""m1'k' with the 2!l-am;" u "",up. T h~, r"e" wall)' d;.....,j. l'.. hf ,...lca"" g~ 10 form the Inn "I ",:c !O3. ~"t" Ih~l "the,
r a 1h"'"J ' to bli n~ me r......liu.....t Il!OU!", 1"8<ll1O ' 1', ,,,, 1,1 " 'q ,,irc moch mo...
e" ergy, eil h., I ~ l>eltd (he r1!U</ . lef,>iJ ,r.ckt nn DI' tD cl< h C ... '..1..1 c..:--<::
'"
oon<l;_ In . n" ll." c'~h'l'le, 11>< CH O grCl UI' in the prnw""tcd ",-...~.ld""l'd. of
l:<i.",,1.>on 11.12 Gall "'~ I c "' ~, lho aromntic n nK tv reach ~ ...n",'~ ( .~d
" I"... ,\.,j"" itu=.., t>lC) m el ho ~ yl , fO'l1 l l; n ~ in d i",,,,a t;oD 01 mtthyl r.' rmat.
l Filfl.'o and G rulLmachel 19 ~ 6)_
,-cHO
'inli w olk
",, -- e,ti,
1~ _ 22 )
+ tlGO<::>CH;,
h",,,i Ji. ........!iNm. Ck.. v~ ge , or a l i ll ~ ~ b~ ml;n ~n UL - - ;01l ,~n be

I'" ;M1 < ,, ~ I ~im n_ '" " ,,,b' I. I. a. o:>tItroI dC II'>U I Ij, ~ Ot
~ .. m pl.. (M
H)' "'M form<d by ~-cl.a .. a~" lu.. , of II'" I>ridfldlt&d h~ d ro~ell
"""" ("~,, the 11'3n<;- , " nuIJ led i""mer a are m<>re ~" .. nd. m lhim ' ",,"0 fro m the
cl$';S<>m~r I>
"n d J.l . n ui I Q~ .1 \. In R.23ta~ Ilw n"n - I)"ndm~ ".o, bita! a l
Simp '~
,w," o-d ifferenliafjll~ if
ff''''''''''
(~ O' Y<' II
.tom [un. li" m a . a oontro l ~l<!,,,,,nl in lh. , -d "a v. go di.. ,,~intjon:

, 10.. " la,' m od , [ the djll~i.\ing C ~ H bond ~ ,dt. ""d ,,'ilh ,h<: control ,,,1>0\1
", ~c h i~ ..e mn ;,," ,n, ",..., top ill tho "....,;IJtJn . (~ I~ (MC",oc lcctT<>n ic ....,mroL
Tu r~cek and Hun u! 19S6. T u ~l 199 1..). The ~i$'~ n nulu tcd , ~elel on coi l< ~ 1(hI
mu, l ulld cr ~o 0 ( " " (Ya.. ~ enl 10 att ain a fa ,m~h l ~ ....,lIform<UiOl1 . SUdl lilllpk
h nn d di" ocialion. to ( IF.- CDD als Q be [a..iJitat ed ~)." N t _<r,hi131 millal;"" .
e"ell al f;, m<.>l<: bond. ( ~.~ r1<'l h.l urn 1982~ FOf eumpk . 10.. of ,hlm i"" f' '' m
110.: ch...."'tlOflro . ""' ~ o M ;"" me fl l ~ j to (0.11 in b ju. ' '''l\ 8.2" ;, ",,,. lp<onouu,,!
in t m ",hieh it Uln be " " llle\! by "" ighoorror r - c "'m.1 porlicipalion
IR<.>lh" elJ rl u/, 1 9 8 ~ 1
._.... __. _._o~o
IK 24)
,.
......,..""._111.
UIC - '
T bt . 1.t. ~ ""h . m ""' l , c<j u;,mK:nl' ,,[ Lh~ I, ,,-" .il;,," ,laic
for hydl 0lt"" ,~r< ."I";"","1 ""n h,: m~,'" "oun: n W"lU u, with un, a luratiun, a,
well ~ , .,"lh tM r."rlGtoon< of cycltc '1JuCl u",. - I ~. ",,,-, ranllomcnt nf ~ ~'- H to
on un" I "fa l~U . ll" " iO ~rim. eum""'. Th . , Lel" ' I.'...! .~ cl'"- were u",J t"
. how lhnt lh~ i -h" d, ,,,,,,, , d"", ""..l "" "" I ~ ... " ...... I ~ c~rbon )'l ~ro"p. and
1h" , Ih" nynm B"" ', "=,.i b ;l; l~' <:.an ~ affected b) \"" m3li. c m " r.gura1ion at
the 1, p, <lr y.c~ r l:>o n atomi {Dicr... , ; "-no! h . b. 1%6; KiA",.I"'" .I ..J. 19( 4). F" ,
. "',\lple, 01 t h~ st"eoi, omor i<:: l d u"..... i_I .Ad lbl in Fq .....i.m 8.25. <Jniy tll<
",J~ i>.u mcT ~n d c,g "" , the lan M m ;- ll//l'...:ll--a,-. Il" r~-a rTa ~1 tll;"l ~ ~ ...
nse 1.' the cydo~ntad ~n ol ;0<1 . 1 mit ~2 [ H ~I"""h. h <I <d. 1983~ It
., ;oh.o
~Pl't~ r ~ do ItM. l lhe"" rear ral'i'clIK:"t. J <l ,,,, I l'rtocccd by
~ .".~fl .~ 1
. "..
oifiD
,,--\ ..
,.,"
,.
,"
' ." -tt
"
'" ' ~--Q
,~
""
._.- .......
IDh..DJ:<Jn rr.. , "':-d.... ~I. I ')')(),,-~ thi; would ,e<Iuire planurl ~ for uie tr l,,~iti"D
. ta lc """u i..m~ on l~ O\1 e <1oll!>l. "" od_
lI yillOjl:< n If~" MaamCntl lD "" Iur utcd O lt" io n. U ll 31", n hlbtt "Vrrir.",,~ l
,*n"",,-t..'mi "~l . lTcct. Her. lile t"'''d-mak ing :;top . 100 depend> """ ily on Ill<
>paiial pro.,,,,ity or tile . c~plor ~ roll f' "" d Ihe h}.Jw l'P' ....>10 t>el!ljl tr4 n>rerred. In the molecuhu inn of tr ~ ~I.4-I<'f'I-t>uly ~rlo "'"""c l. lh< I, t li" , y hr
<lw 1'C1l al(J1IL i, [r,, ",f<:flN OrHo the hy<l..." l p;mup (LqlM,i<l<l 8.V; I, n "
, ,, -mcmbw , d lra n,i tian . t~t~, " ...1.""" 11 3 11 ~ 1o<.1 ~ ' ",ate. IU.een " " I. I ~7U) .
." - H,Ol'.
1 ~ . 2~)
rile Ctl crgy needed IN th. choir-fo-"""l < unl"orm~li' >1l ..1e. citati on {...0.5 V) i'\
compo, abk 10 Ibe "-jl,,al ."". .., for Ih. 10;, or waler IG=n rr "I. I Q7~). /';"1.
tha t til< !erti y.H" n" l .. ,~ ilo,t>le fo, direct [ransle. "ia a . i._ mcmbtred t r~ n oi.
tion , Ia,e in t lot .-rH . otmr; lh ls I><.>m<: , climina l. ' wate , to a nm.;h )e. K I e ~ te n,
a di ff. ,,,,,I.noch.lrnt m
The """"""hili,y I", I. a......, " ' , h lelal hydrogen alOm" can he ' ... $u d f.......
precil:ion molecula , moJo:!. cr lfl<Jl~"ul ~, KT~l'h "", program. TI, e n abililY '" Ihe
inw me<lJate , a" i<al , il. ;, ~I 'IO ;m!"'ft. llt [0' ,"ar,an~em<:nl GOmpdIu ReSl.
it... r"rmod by a bslraction or tutmry, Mllyli". or hcn ~ i1ic h, -d loae n a l o",", ~ ..
". """WIy >l~b1 ": ' 0 ,~i . pre"""", can f <:><n nl" , "'",,"'('lllicil y. NOlC Ih>.t 1M
' '-4''. '')I''",. nl path...ay compete, "' ;r!l %-cleU I (t<' of th.
hi<h oJ",..",,.,.
lh< ' ~ I",", h. 1Tl i e.d inlegri[y of til. ifOlll' 'fI _Th Ofefore t" b<.rituenu 1""1 inJu""
~ " k~v a ge in tbe mok cuJa, 'on, ~ n " ~ I the ""me- lime ~re poor k.,
i,,~ ~" oujl' lOCH" NH " cte_" <'ite.. ". mpu ~~ I""-~r", rr~gmcn la li " H'
I M "I~n n LaIlgc,c1d an d Nib l>erinA l'ill(o ~
.i.
''''So ...
'"",Ie
I::t;" ,.,..r"'''It~_n''. Stericdfm-. a... f'l" "'~.l.o r'~ 'l",nl'- in the di>sociations of
1:1::" 10111 p,-oJ>lCN b y chemical ionilali.on '" mulrifunctlo nal ooffil' " uIKI, . Th i.
",lte llOlty I'CfUII, I,,,,,, l...n ~ . I.fi l i, .....1efk e" , (i) I tll.btlilal,on of M H' by inl, a-
molu" J;,r prolan elldation. ~nd (ii) nelg llborln g g rc>~ p pa rticipa tion in the
d>mlll;llioo of , mall mol<'C ~Je , . For e. a,nple, prot on ~ to d. d.- 1,4-cydol1e.aned.iol
jll.17. a) sill' "'' m LLch It:s. Ira~)I)en lal;O " b ~ \0\' of
,.
tha n d"", ,he (Imt"" ..ll~d """,isomer ( ~ 27lY. Wmkl.. a nd
M. L"trorl)' 1974~ Fo llowing proro nalio... l~ ' ca n ~lIInO a boat-lih
,",,,,r"''''' 'i,,n in " ,hid. the I'",t"" (" rm h ~d"'ro..... hr;J1'C \Io.1 """,n I~ " lw"
0_1''-'"'' . tom ,. ,II", "ahi~zing I II~ ion Ill' (t2 ~y (Gutn'l[ ~ ill l'iHI :>;" l ~d]
stllbilll<l lion 11 ponible in tbe trlUIril.omer(bL wbll:lI um~ " oes ils t ehLll\nllti<>n
,,( ...;Ll~r. ,\ mino-, 1''''~ 1''' m 1l2lt{el (H.>Ur i<l .~ M. I ~ ~ I ~nd d,,~\>k; I>"nd.- in (d)
lh lonen and T a. k".... l'lg ~ call ,,00 'l.l ~ il;'" <tereollOnlCllC Mt1 ~ io m
'1110". 11 imtlll1lok'now- h~ ""~ ooI>din~
d. lhydrc>g. n or
w~,"r
I g . 2~1
M. j or stereochemical df"eu oro 015.0 " u5.<ld b;' Mighlk>rill~ Y""I' pant
eipa li" " iTl eli" "e ial,,,n . or MH ' [!Om eyehe ell",,, and ~... lcP; (Il~...po ndc'" fl
ai, WI ~\ In prot" " Mcd L~l-d lO c<:toX)'C)'cl<>ltcun<li (bInti"" 3.2'11 lite ,,0111<.
i. ome r (a) 10'" ~eet>c "tid 1<" '<'0 tin"" 3. <cadil) u do.;. the ci..
(b~ I..
(al the non' j>l oton" cd a<C1yl . rolup a",isu thc AcOH d unina lion ~y rea , " 11",'1;
mod<: 1',,,,,b1c by t he r.,"'''''''''''''s..", ti"". 'lott I....t <ICJic """"" dlOC10 hyd. ogc...
bon d .tabilinuN>n 311d DCIfhlk>ring-sro up pa"""l"'li"" a .c oftcn 'ylle,gill ite
,",'ith Illo fo".... illCl l-in. t~ st ~ bili! y or ti!isome.. 900 I~ Jalt or pm mol mj
i..,,,,,,,
di"",,,,iali.,n, ,,(" ...... ~,mc"'[)iffo",,,l ("' ; ""'"1" ' ''''' polh....,,), (0)11,,,,.;,,; CI (;....00"'...) m a~ . it r<'",il>k
In dlU;ngut... rtgio- a nd. ' I ..,.,;"".... ric o:yclC'l('mltllnnt phtl Mad d",," {Fqua.
li<m R.ll'll HCdd-t<","""d ....' 11>0... (al . rnt/l>l un.Ie.,-!!', r.."ik el"aV" 8" ,,( the cy d " .
La .""~,,.....
r,
rH
,
o-,
",
'
~In
,
{i-J' ,J-.
HQ'"
(2(""'
-0 r,
r.
..
" I.
"""'.'00l
A ",
IU9)
&r
.:
0
~,
,.
I'
.~
' S.:Jll)
'00'
(MH (,/\0""
'M'
,A
~,
"
blHflnono " h8 Ii> gl V< l' !'{IlO natod "ycl" r<"tenone. Th~ l~_l<l -ujl irom.tr< (")
. ' lLl (d) , h" w M"eo>p<'C;Ii\; t>.- h~. ior; 1hc , ,,dni, ,,mcc (CI rorm , a '"IY >W ble
MH + ioo ( I ~J "U~ 10 1"<>WtI ~bdalion between I'" " ' ~ S"TI turlCliolllo. The
MH ~ from the cxo-i""""", (<I) e1i ftl i ,,~ l e , .tlu ool to aJ~ (Mil _ C, H , O H I . ,
the 1>11.., peak nl Ihr S~1n ( [ u mo nt it ..1. 1<)1').
., ...
""
_-_. ......_--
FlimiM I,,,'" tor ., m ull m"Io:~"k", ,... n I-c ' l~<"""pcci r", =<."'" in MH - fru m
polylunctionaJ cOm!Xl undl : ror . xampl. , MII + from (l"nne Th)tatcd ri l>ol,,
r~nQi ~ , limin;ol<. m~ th """l mo l\: teiWily l!>;<n """'" ~ H ' (..om the i:,om ,,.ric
.f~ I,, >rU 'd "' ''''' 1f:<j u. I'" '' RJ I , Mc........touITcr lU,d BIlI "" - 19l191_
(8.31)
.Ch il'3.lily ....... n " l1 tn:n .h",..,. '" .n""l Ihe 1""" . 11" "r "" >1om -hound . om of o ptic.dl}- ' >ume no; """k>culos Ih lt$ a nd \~' ri lOh , 19n ; W i n ~1< , ,, al
l "~ li Suming d tJ. I'llt(,. :"l il<ob<v ~ l ,d. l \l ~ 8 ~
pl. ~.,
Ita", d,lt m", ,, in ;n'. ' r ,"ting rna"
Tlltrlltl>(.'M"lk .... 'iank ~Jfrrt. Th,,~ a

'pc<.1n. j . j ~ 10 ..ha l u tenl tho pt...cn ee
(>f all imllNtlnl )1<'ak \, due to

oleric r...., <>1. M a " ~ ' U rI an ~., n . ' l\ reacti(l Ll ' ao tln ou,h
path.. ay<; llw: lll..ora bJlily of "'. .." otIc cru:rgd ie
;.1''''''''
<IT
cnmf'l'liti' 'CIlCM of the , alc-<k' errr"n,nR Ole!'

Yet aD ' ~ """ J"" hl., ,, in prt.,jit l; ILR abuJ>dnn i, , l ~ . ffo.t nf "Tu. tu!. on
" (Al. lhe r ""JEY deJ>O'lliM funchnn, HigM T_mnkmhr.",cighl 2." 1>. " ,,,,
mow an u",,,ual C, H, O ' 1m,.', WJ ~~k_ which "pp" ",n<ly a n,", from a 10...
"..",,-Ift ,Jo .ubk:-H "",,, an~.m e nt , imilnr '0 Equ ati on 4.46, ,\l lhough lh. a hunda ",," of lhi> poat i, ~-. ,>I ! ~"l of lhi: ha", pea k in 2_ undoc3 n<>n., i! i. '" 1'~: in
l -bo u ,lOJlC. '11lc 1'111 runcl i"n, of I-'i gur e 7 -; off" an expb nation: then: i. "
..,,""'~ ' " lb. 1'11;) 1" , 1-h,,'O non., indicoting tnat rda li\'cly b. m()IOC\lI~r ion.
are ,,,tmed with ;nl..n,,1. "" , gic, in , he mn2e 1 to 2 eV, To reiter.le. for eithe,
"'lc' l"c l~l iLln or pred ict im, of mm, spectra. it i, im p<JItunt lo ' lu.-.Jy lhe . pecHa
<>I cl".. ly . eh te<! mo leculc"
. Ae...tion initiation.1 , .dlc.1 0' chaf1l" sll"e

L M: III th!l mech aUl, lic appro ach for" more-complex m"l ccHIc m nl,un;ng """ .
cral ...,." blo , it.. I'or the Ic>cali zed charge and l,npair<'d e\e.ot rotl r.qu"es
",cigh lillf " f IlLc rd "li "0 im!X'rlance of e ~ch ,i t., Funll~ r , at ench ,ite rae impe .-
..._... _. ._..-. -
'"
t.o." "" of the' ta dieol amd 'h arl o, relative tn eac h OlMr, i $ reacno n I ~i l , .t " ", on "",
....., he p<c.<Iic,,:.1. Th......, r""l"" will he di'o m ' ed In thl l ~tioll.;l.> ,.iII caS"" of
dcoomp<>\1tiMI <l.mtL't to r" dic" l or ch" rge_,ilc n,,,e1i,,n.....,ch do ,,'" fI.>r lly
II, ,,-e111,>1 illlti.alinil lite, How.:' '', impor tant fn~""'"t~ 'lOfIO ""n
u, ~,
po.><il'" m , em,,' " rmm Ihe ~hr80 ' ;te in EIO ' io.... 1>1" ,;....-.1 l h~t the ' "31"' ''
high.!}' ,t" bili"",,," (Tom er , r "I. I~~ ~ : CO",,,, l'IU i.
," o;n
R~latj "~ implJrl ancc of po>.ilok ..,~. , r OI a moJecule """ amlni r.On l n l~ la~ li!lll
functlo n" l grou p>. lbe li" l \I,,,.~ ) ">niu,i"" ono' BY (IE) Ll, ua lly " ,,"e. p.:lnds
I" the value d\~fl.e1eri>l. ic c t Ih. fun" ' ''''''''1 g, ,,up ~f tM low"'t I E voluc, Th" "
illu<tratM for the arnlDC. .ullidc ~ ,~ I ......,fi;do 8 r~u l" In com pounds la) to (g) ifi
Equation ~, J2 crab'" A.J). A pp.o'Ml~ the cl.:ct t"n"!"" ti ,,~ carbu ~yl .!o' 0"P do<'l
",,,,,,,,CI+,
C I<, S C H , CH . C ~ ,
fbl g eVI
:OI "oV
CH, 8CH, CH, CHINH , ICOOH

1' 1 nov
CH, SoCH,C1I, ClI ,

10' .2 oV
r.H,s "'" I,CI ',co '1" l,i COOH

1; I .ltV
nol ~~~i~bly
J, ,,,i.~ti,," wa h
;nfl uonc' the am ine IF nh", in , lycinc l$Yc, "nd J unk 1 %7~
7U_,V electro n, can oceur at an y runc< i"n~l l!">~p, bul 11lc
chari " ~ ~ n th<:~ be c>eh a u~cJ by I hf"" II:h ~p.><'e '" thr<>ugh-oo n<1 . ekctro n
t,an, l" c (CIU. 1 ,md VI ,II. r I q~~ ) ...,fficicnll y fao-I to> p~ fl~ ~melll ~W_>n , The
mu,t ~bul1d.ult I011i uf \11<:0< p.;>l}fu ortwnal mol<c ~k.. "","'.!" ," d In ~-<:Ica va ~o
p"xlucl' I'c,,'" ",,\ i~ I~ IO at the cllaJ !/;eJmdic:>l \.i lt '" I," '.. e~l ioniz. tlon cn"r~y;
the f,;"" pt.1h If' llte ~roclla . r" H, N- CH , ' far (h) and 'el. c.: H.,S (:H, ' for
k ) and iIi amI (,'H ,!><'-(:H, - Jm ill:' and (8) F or th" I ~t",r " .. u Ihi' I, tr ue
'ic' ri'" Ihe CKd tha I Iht apptaraoce ",,,,rgi,, at" -2.~ eV hlithu t n.. n i hKt fm
lhei r (M _ COO H) ' "",,1.. " f>P'I rcMl1)' becau>e ,o>oondary d..."mj)O!oiuo," of
tho hi~hc:r"""""g:> C H, YU I,CH,CH
NH, ' yield,
~ddit .:", oJ
CH r - (:H, '
",,"'N~ Jkfl1 , .'h.!:.....';t~ ;,.ili~';'m . The in itial cbarge 'lite ;n t/l~ ",,""'uJar ion 11M,
;" ll"ocral, th o "'0,1 fa--orabk m "lI vnmro l f" r .-abdiza.tion lor t ~ I"" ili, o
. t.o.b>ltz'l"on ;." r,., plOOt'"
ch,,' go. Olto n thi, i, ai, ,, In.: . ilO vi upll",,,m
ion, f:>.. nr ing reaction' in which t!>e J"."' ti,~ ~h ~ , I!"-' W>L1I n"r move, For O F. '
Ir>l" , uch cha L'go -'~tont iDn =<.1'0'" in,~ yt ,o,tum"" or the ,~d,c'll 'iiI, ITahle
4 I. ~"OT ;"\1 ~ .5) . T hu, .ad, " ",,,UVII>
lcfl~n Jl y mo, < o ~m m o n than ch",~"
<lie rC:>.CllO m (5.ect ion S,21, OIlthu ug h d ,"'.,ile rcaclJoos arc often t",'o", d ;n
M +' ~om:>.lnlll~ "nl~' cl""1ro.... ~I"e , u\'lJlit llcn" M "lbo, intipiom ion' '"
high . , ~hi hl )" . a,li .. ""ne ~I "' ~~ nlct h3ni.;.rn 01 ha malytic cl.mage [F"ig.
" re 7.9lbl) I. d'..... ,...) fu, (C H,), C HCH , O H " '(CH ,j,C H' + CH , O Il in
S\IOn 7,e"
,ha,...-
. ' 00..".... ......._
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or
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COfI<;"1>'l ol .adlc.. llctl .f ll"' ~ I . _ ._
Thi<",,"n,,1
";.,,, Il ~' Q weans te> for"" Uln.. dtr~ l ion 01p"",ibl. oJ..om,,,, . ;.
lion 1',.. hYt'~~" ami th.iel lliting proou~ . l.. hil" .... . ,,<1 . te. ic requircmenll
1 1K: Innit, of it, , ;,,,plify ma ;... wmptiml" howe"or. Ihoul<1 h<: rccognu oJ in
ma...' p"ctr a; inter pre," I;' ,n, S<>metifllCll. espc;:ially lOr m.,ltip k -bood cl . a,'~ ~ ....
en bcl ra oJ" al or cha rll"-1Oite illll "'l;'m PrIx[""", the: same pt<>dIJct. ; tf'.e cyd l<
ion ,1"""'''I''" it;''", 01 Eq.., l;<m 4,>11[ an al, o be wn U. n l~"I "" l l "' '' s.nJ a. a
cha rge_' ;te ....ao ion. Tk """" ~ n \ ", 1 peak at m./z 56 ;n [I ", 1p.....I' '' "' of 2--mr lhyl_
o ~-. C --'-- C
~ ._-_
l" ; ~ rid;~ e
........... .,......
'"
c" uld 3M'll: (lhld l; ~icwi<:l U oj 196r. p, J161[rom a rel,<>- Dicl, -~ Id
dec~ rnP'Jli I L~" 01 Ill<' ~' lunJC pr<>dI>CI ""n 1 .Io~uu lio " ~ .34). l hoest pr od uc"
c" u ~1 bl.., l>.: r,,''''eol by inili a! , -<:lea ,a~c in lhe ,in1\. followed by 10' '''' ofi..\ ti.
IR34)
.." "'56
~nO.J C H, .
I.. OOnll'M I. t h~ ",tTO_ nKl' _Akkt F''1woli"" 4,31 "" rine.. a, ;",'oh'ing
lndlcal-' ire mmution.
~. 'C IL ",ilh "" unp~ired ele'lro", 1''''''''' 1. c' on-decLNn jon, can llndcrgn
renCll0m lhou ~h r t(1 h< ch," . " <eri, lie " f a raJical , ite, e"en at , ilo, remote from
the ,hJl~e IU,"(1S' 1~SS I. Not. thaI \;milur r. ael;o,," o<:c ur in or!l~TlLc chemi't')';
i'. H,'~.cl"x ""~ ".Qlu,,~o m ."I' or "oQlral moluk, luh place in bo,h do'ed.
' hell (lelrO~1I0 re" eti(lll) ami " reno' hell (N()fri, h II pro<:o" j , y' ten" . while the,e
und ~ H decomp"\ll\,," ~ OCCur lherma lly in c,l er... ,,,,,lha le,, , ,,Ifo,;do:;, and
~I Ll j,~ r t"J \~'. f o' lbe EE ~ ion5 or Eq u~ti {)o ~ . J 5 (Kraft and Spilcllcf 19lJl ~
IX )5)
~.~
hydro ,..~ is traosfemd ~peclrlCid l, t h W"~~ ~ .. , ",",,- m l>.:<I. ,in~ illtetlned"' te,
J nd r;(> It ~ ") H teur" niffl1ont to "" " nw\".aled v w p willi p-deau ge" d "",I) . imiL" 1.< 1Or: ' ["". li"lI> 4.n , 4.3$, and 4.36/= >h<> I::q....llQn ~ !n~ Met.
SU M [ [. LOM C!in ~ho "o>d<:r lf ~ !I.,. r"" rTllnl'",,,:nt ",il ll 1Ii{!1I Iq:i<. .,..eificily,
~QI;O,.d Ul lto ZoUin r<f ~n ~ x ibl (' ~ )~ ...1>0 po ,n' om,
r ' , he ioci
,k". e .. ill. l E' I
"'..ell I.:......,. tllUl t!\at .,ith U le' ""' . '110<- r- 1I:,I1dea 'J~" ~.ran ,c ,. t if> t ho; ('I .~ttll ..r ""utumr ed m""""' les . 1;0 olten
.00.. """ olerp.o n ",. rt." lI"menl>. or ' he EE' l'f ol",,~ tc<I mr,locul ~ , i.... . MH .
11<'''''''''''',
..
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sc ""
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, I
I D ...,mc .. ~ phalJ ~ ..nd aromatic eti l~r . ~ ...I I'lK:nylalk.ll , be P"'ltioo rl i , l ri h ~_

toon .... ,"" lr an, b ccd h~d l'Q ....n il. qUllC~ ,nih r to the "'If' e>.po.>n<l'" l1 ,ca, ranio_
mtnt of ll'lc 0 [1 '- mol..." l.. iun (Benoit aM Il arril'OO [971\ L..'U"g WId Hnrn soe
1 971~
H" .... ". r, 'omt oI . h"", ",""I;,m, in ",>l~e ~I=";ve ",a rra" actn<:nl"
<O\'CI'
lhro ug h i"nm"k:L~ or pr':>I~n-t>rj dg.d rom,,'"'.,.... , ,,,,h tht lhe ~tOO u<:h altO
'tr uc t ura U~' rdai<'d '" i .""oric intcnncdia lt< ral h'f lila " In the ol'l"nal L1j+
ion (" ud~, ~I .. ,. 1'fT/: \'.... i" .1 ~1. 1<)$7; Terl ..... ," . 1 " I. 1986; H. " " ,," 1':187);
the role .>f lhe n ri ~ i n al churg<) sil. ~ "oJ immediately t v;<.lcDt ...-ilhoul d. ' ~ ikd
~1", ...Iod&e of 1~ , """li,, n ,,,,,cha QI ~
Readi" "' " <" ,,Ill \';, ua!i.ted "" l>e1l1 8 initiated .II d .a llc. Ii'e, can al, o !<>lr
rla'" in FE + io ns in .. hi,h hill e oJ' I ~ C ,'har~ <leo";! ) ~a ~ De at tm' , it" U
t ""u ~h Eq uati,," g..\5 " pOf1faycd a , a c ha f ~'c " '''01;'' <1, Iho , ok\llatro ~~.
t,,,n dm,i ,i<. indic~tc tholt mo, t " f the 1"'';1;'' <h~r~c ,n 'he " """'" FE - "
locahu <l ..... 1m: q O H I. ~M ""n I + 0.41 ~ " ,...." .". Ihe t. nn",.1 m<tbyJme i,
noar!l t l, <t,oneulr al ( - II n Il. T I", . lectron reuiltrl bm ion in
l<anlition >laiC
Ilndo.&btodly con lribme. t ~ ' he " c,i,a li" " en" ay of ' he I [
n ~ " ""' '' L T oo
Io<s 01 lin r",,,, C H,CH - { "H , Cll , Cl ha' al" "'''l been 1I ,~n a < ~ n ex. ml'k:
IE'lU:)'ion 4.( 5) H,...",."" "re mote -site fragnlrollali<>n' - ,,( EI; + ions, . l <,VCI"
'"ei ~ od and dc",h)pI l>y (1" ,", ~ n J '"u ...ork"" ( I"<>met .r 41 19R5; G"",< 1 9 ~n
"'m actuall y br mor, ~ ~ ~n ta geo u . thlln (...i, cha r ~c- ,il ~ f .a~t i o ns for o.."d , .oci, . ~
' !IUCt ure. All..., ,,, i",~ t ,thcr Ul! + . .... !Of' " , ,,ally , equi re 1m C"""'ID' lor j"".
meri""t;on o1lhc ,,,,, .. n1 dOlL b\!. bond th. n rnt ,Ii"",,,,ittli.m. m;UIII. " b ~ 1M
,1",,1,1. h.....J. B" ,1~ l>il Uin ~ 1M c h ar ~ e al ~ f~n1<AO o;le. ;..,."uUot;nn " ~n i'lc
m ;nlmilrd to IIi"" loxation. !"' oir" uO"' ""J.....i" OIlS ro. a vanel~ ~ , c nm~u nd '
F'l u.otion M,Y> J'f0yi<k. ~ d ~"i, ex~mpl" IAd. ~, . .. nIl Co"" I.' 1 ~39) u,i nt! FAa
11 i ' ) ;,"';', ,,ri,m or an u"' .l uraled b ltl' acid.
In S<>.:lk:Jll 4.4, Ulllmoloncular ion ,""",c"li" no "wo d.ssili. d b~' t ho ~ u m bn" of

bond' bwk , " I,..t"'~n the "'PaTlIti"", 1M dod noulral pnRloct, HOfe ~ WID
lW \;. in mohO <lal il ~, " ,monon r<n,licn 1~'PC;1 wi1h,n eoch cla. .. ," ill..."" kil
in T able U . by ' ~ hYJl'Cl' he! i< ~l inm "'B CD " IO E- ) . ad A lleu ' 1[ (; ' ,I 1n
wbid' lh<-..., kcners ~.ll reN <SeIlI an am mo" f~ln~<i,,~~ 1 ~",up, '" e""" ... ' er~1
, ,,,,up". suGh a8 an " lkl'l , !lain. Thus a 'Imd IouDd lor..."" ""....''''-'71 " ~no1 D
~ollld rur... ~ ,i nll1nCOl l'cra linll lk ir "" ,,,..1~""' I" as worl a, .,n A~D doubl~
1:><.. ,01 11", des ij(Jlal;ons ..~. , ~n d " i" ;l>dudc all Il l"'" "f ' ~ "" l i o ", forffiula lnl a.
'n...... in' initi" t;" ,, " l n raJj~1 1 Of "',,"'''' sill:. n.'SJ)<lCll\'dy, ~, di " u""eo1 ill tloe
"fe VIOU. ",olion. to o.e O(\~ ,i ""n, ",i,J, ", .., of Ihe'" II'PCI, ~ {)me react;o", m ....
hi; w".iderN a. ;"v ol>' i,,~ i" ilial ion ~ I ..,....oj" io" l , . o1 ienl ro r chm , e .,t,, "
All bill ,hi; r,,,,l lb= """'lion' lIm ..l>c lorm otion of . ne'" ho.... J In. ....r1'al
bv~d) fOI ....~b bond
1. iml"", ;ng Ihe energetic fa"or;,tIo hly of lhl: ",", (ion. Th " IIl<lud.. n:armnl!"...~n t !';~" I i , m , i,,,,,I , ing di<j~ ~n ", nr 1"(' .nd
climin..
It d _ Dif.placemenl rcarung e m~ nt . lSa.1i<m. 4.~ ~ n.l lU ll) ,an ;0. " 1",, cyclil.,o' IOll I" the radic . 1 oir. ...;' h d;'pla,~mrnl. j,.. II ,- ( " - D --+
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A ' ece
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In m (JI~"u"" II,ul do lOOt poss<"S l>ill~ ~ ~rgy = pied o rhi lu" , 0( ... <>r ;1ly!"" , ioni ~ ", i(> I) .IT<;d ~ Ihe ".-hond fr~nlCw (Jrk by weakenin, thc C- C
and C - H ",,,OC h a
Iken... 'UMliIU' c.J 10 111, - f , - 0 , CN , . nd - NO,. ""b>lil.,li~ n "'ttl, - Dr.
_ ( I H , UI - C=CH lZ"UC'roUy 1(>",e1"< rh" IE l> ~ ~ rtl~ li . ~l~ . ",,,11 a",(>ullt (0, 3
u ~ ov). Tho .._mhi,,,I, M l h ~l e h. lero ~lom . Of lho r. OI' b L I ~1l (If 11,0 lril'l~ hu n4
~ I ~ cJ",c ,n cn~'1!)' Ie ' ''~ hi ~hc: " ",,,-,,,picd ..-<>rl>il ~b oI 1~ ~ I k y l groups: th,"
alh"" rOf considerable orbitll mixin, in the ca llon ,, <l i"nl, la nd thu, qualiliill ~
III-; 'kcti" n 4.> rule thaI ' fa "o r ~b, lit y lor jcmil 81ion ~ n ... ,II ; i, in Iho o roe r
" .:: It -: ,,-~I.~tro" " ' I , Th",," clic<ol ~~lc u1s tio ns sho w t ~al <uc~ io~ , ~""pt. <' IJ<'
OJ mere ~ner~elka lly b M uMe fl n '<'\U I"" ;" ",'hieh , orne nl lhe c.; .. <: or C II
M nd. I.,.:"" m~ ~",ally elon;:altd IEkI. ill" ond Ba" kI ' 9~ ~~
~'."'l'le. in
lhe bUI ) nl' <1'ti<:>n 1"" 1,.......,.,....",o rllY '.tr uol ur< has a very""" Cll! ('.B l 1J<~ ,o.l
(2.02 A W " ' P3red ..i ll, 1.54 A in ,~" " L"""' U Ie~ Four <>Ibor >I , u,,",,'C! wllh
"""'1-. ...... ",ilhin 0- 3 i Ii ooo\' e thi, un ~ ha ve s.l1'<tel1td <":( 1r---c t21~, >o.l C t ~ l -tU J
,,. Ctll Ct } ) " ,u ' Cn ) C(4) bo nd. ( Bo\lI1\~ (1 aI 19~3:L On J",,,,,,i,II," " of
""'" a "'ta~e!led C C " b,,nd, "'''' " f (....
at"",. wi ll bea r th< ~" "rgo,
and I'" olher will
\hc T~dical ';U l Fqu~l i"n R__~ ~ The product prdcrr-., c~
",ill rdled I he h" ,,4 l'(lioriu lioll i A H - ' U ) u An '
CD I in Ihe molt-cula r
.un;...
F."
be.,
(.I,,,,.,,
' Oil, ' 0 Ih. t ""' Iher I.... ~h;,, !l" nor II,. unpalrl e1<l<:" oo n<:c<l 10 m ogra, e a ' " 11
oond kn~I~ , T hU" r". I'" ,,bo nd di" ,,";a!;,," " f C , H, CH ICH., J, ' [h"
1',,1.';""Uon C, H , '- +Ct! (('H " h , honk! .... fa'OI'M r ~ hom<! . " elch""
. r>d I'" prod"n uhun.L,,"c of 'CII ('H ,), ,;lwald he (tRftl ~ r lha n that of
( :, H . '. I ~"'. of rn,' fw m C)H, (; IJ ((.'11, h " ti'a. a pr(ld "d ,'( " H . ' ) whooe
) "" nd""",, '" <POly hlfthHl of C , II , - fOimed II) C , H., Ie... A' u !"""'od from
t ho "1M" of Ihe lar ge,t alk )i"" cuI<; It>ul "'~ fton) the Ihermoch ~mic, 1 dau;
f" . n",- Un" of ~ ., ~. and lorl(; . l1. - ) !'f r~ \'Orod by 0.1 and (l ,R c", tU Fli'",ly.
over t h~ t nr 1"n.C)H , ~
t1- Hond dea~~ g .. at pnllldr~ all'" ....., " !<.l,i ry Co, bo n atom l a re rel1 tt~lr hi glt<nerjI,J reactiOfll Wl4 lh.... ...-ty C(l m l"'t 'lj~c, Prim . , y a l k ~' l arboc~uolt ~t ~
inher en' l}' ......... ltk . pic: . ' hal ;romerize u~ irll y 1(> m"", <tahl~ """""du y 0'
,"n:iu}' ' ~ M. Th<: ''1I <I ~ < I;'' all y unfavorable c le oY. ~ <II the 1o",,", RCH, CH,R ' " bo ud ""n bo ~j 'c "rnve nlcd by . rc.rr~~rcmc". in .... IOB-a d i". 1 ~om
n.
"
_",
.... .. .... . .4.
,"
UU 91
1', 00",," ( W~ nde l boe n aI. 1'181j. 1Ie<:.. ,,,,, <:>f ' he "'-;hilit, - " f ' IOch " rand " ...
<e<l,ranll"'nlcnt"~ 1.... ,,"und.1~ <Ifal~ ~'l i<Ift< 1m... ouch
con be a",his "'.... ", ,'" utdk ll t," of .... ~Clu,e (Il<>rche'5 ~I <II. 1971; ~ n ] ')'3; u.vaodly
.... ., 1. I' '''j, r*....,,"" 'J""Cf<~ of <;m;I. , co ml" ",,,,h<
'u ld I'<: .....<1 in
1" "'''''''''''
lntc l"fM"'l:u ....n

~ ., ;.., /(NJIl" ,
lJ ect . (>D-atlr"" ting l>e{eroatom f,," et iona lilio tha i do
,lu;,,,,,,,,, thc i"tli,,,,,,i,,,, ""'-' < ~1 of "n "1..,,, Ie t , rr, . V, ('. " .
11,0; C, H, ",,0, . 10,8: C , II ,C"l, 11 2: C , II ,r, I U ,
h ll.~ :.<1di,io""l ofJfa,
lI<Jt "P P "", j. b l ~
(an
"" prooU<;,-i<:m " b umlallOCll. l\it""'lJ<''''es. R- NO , . h~", en han<:e<l. fo , molLo t!

of R- ; Dl R " 0 , 1 is low (2 .6 " Vl. The pre """...., , ,( an NO, ~m ,, !, ,l"'t " hil i ~
.n :<J k ~'1
the F,t':" iut! "'ri<o NO,fe H,I. " " DOt ,m!""unt. lI"w~" er,
w m" electrollCgoti.,. group' """ .. ,,,. i<1< .ta boJ;<;Ition 1.0 " ""OO~' of ion lypoL
Pfod ucilll!- imr><>rt am 'pe<:ual l""'b , R ~R 'Y .... It- - R'Y , in t:< , mpc l ; t i ,,~ ",ith
tile "' jl<lCktl " .d c~n <-", R ' R' Y .... R ... R'Y, N<Xc lha t 1M. is an example o r
t ho ~ ,o "nd .l"'tronic 'late 01 1110 proU LICI. co rrcl~ li Jll. ,.,,1 11 ~D e~c , IN I t~l< <)1
M _. [~'jgurc ' -,H II).!; t he =<= Wlual ion in \'CJt\'illt initial hotero"I '''" i<", i",ti"n
is typical c' f indu OI i cicH agc, (Sc" ti<", ~ ~I_ Til. h ~ilC p<: ~~ in II!<: m . ,. ' p<-C'
(ru m of (CH , ), CH F co ,,.,;ponds 10 CH , CH = ~ , . a lt h <> ~JV1 (.'H ,t:H, CH , t ' ,
yi<ld, (; , H, ~ a, ,he lar~c... [ I",~k _
Ekclr<><>egati w [ul>Cti<>nalilic", "" n ~1 1W appaccn rJy lead tv . i~la h(.m ' \If Ih<;
"lu" 0( [I", lKrt,c., t all ) l" ['uk (Section 8 , 2 ~ small Rll ;'l n u(".idcs and cyallJd
"nn ' II" .... lm"S,," lly lHr~" lIycl r<>~"n' "I"m 1", <1." (I''I" .I""n ~,40) ICMlioO' I<J lh<;
produo[ ion e~ ~ o l od on a lherm odynamlC basi. , Uo minanl ~ a'" ," Ihe .peetnl
i"". ,."
H'CHICH, l F .H I CH,C~ -F'
_ " H,- ~ "H,- F'
(100'/01 ,
( ~ ~ 'j'.),
IIH _O ~ "V
tl H _ l ,a . v
(H.401
of lar ~ r ~ I k y l chlorid e_ and bromi des represent ilalo11mm ions prod "ced by
lh. displacemenl rearmngemenl 4.42, lhi' oould ai'" aW"unl f", II", prumi.
L' ...... . ....."""(_ .....
," ' -""'l
'.~I
nc~ l
C.H , . , N ' ioo """'''''' ~l al'lilind by
'"
C~N ' -.
in II", <peo."1'" of alkyl
,, ~ .n ld '1 ,
I~.u_ 4{n...
In dassifying f Mct;"'no w~ "'" " ""'--..go ~'Honi l"ti nn ini tiaacbitcarily oh"""l1W ;nd " de ..,c/> re,lo'i",.. ... R- l+ _
R t " f h ~ 8 21. <llthough in M lhe d oa r... m,~ reside much mor~ ~t ltu,:
iodi nt atom than \11 tho C I 0000. S.....1> "",..1;,,,,, ufO rar . with tho r.f>I t uw
I..:lomatom, ~ , O . DOO f . om", lhc cone:< f'Ondln~ ,,,,linn< " re oith'" uIlltable
(RO' , R,N ' ) n, h;t..n "''''''I1~ ,,""'in(OH ' . "' H , , F'). Compound. coQ{,1lninll
hen"itc rn,toro "-,,,,, ,,, IS. CL B. I) "un si ,' ~ ie"" co no. pon ~ in! to .. -bo nd . .. ~~.
age wi'h oh"b" n:":nli" n h~ ll", h" l" l'Oatom, Alth(,\lih l,. gmn lts like HS ' IlJl<!
(1- oTt
mi t of Td;j ll'."l~ ill'" "bum1" ,,0;. l h(~ a.~ hiJbly IDdi"", ti,~ 01
lhl: l'T'e<en~ of t!>o IM:tor"" lvm ill Ih. molooule; n<lIe tha. Hi" . " d Cl' apptaf
~t
..,,1.... .. hich d" ,,~ t o,orlap w'ith t h<:>l M' O)lI'lmon
II. "I. 0) ' ion,.
Similarly. nitro compo und, ~ id<l ""'. II h"t dlanu:lem lio; NO, ' ~lld NO +
46 and .10) pou"'; nitrite, . II.ONO. Cll n )"1..1.1 " 1" , 1.'" N O ' ....~l. but ne> !\O, ' .
AlIh,,,,gh flr ' i"", "all gi," ,"ellappm, ,; gnat, or " Il " ~"d C,H.' 1,>, ' ' 8<"
and C.II 11 - ' thfllC " '" <.I i,!i..,..;. h"",. al a J1la,o r. ,olvinw""..... of ~ OO, 11><:
RO' u"oj RS' pt<>d lOcb lIla t ""0,,1<1 he 1",,<1 """d by thi, ""',-"0<, Irom "'hers
and ,,,1M ,,, ,,,-.: inhern nly IlllSla bl. re s ., C'H , O' and CH .~ I ; Nut..-... d ,,/,
1984), bu t hi<.I ,..P u,,,n""t.,,,nltll t< L'l!XU r to proouox lho m""$f~ ble iwm",i.
ions ie.1\. C H,OH ' " nd Cl-l,S lI ': Dill .. nl, 1979, DiU and M~lll1l'tt~ 1 ~7~,
R ~"' "" d ,,/. 19!14)
tion
w~
.....,
" "","-w h~ t
'< ..
'C.
"'f'
' .1 Ra dical -aile Inltlall on (g Jlllbond d u

DE "
~~
N ,. S. O, K. R
'"'i'
..d ... i......1 ,. ."angem""l)
Ai
:> C I .~r"
C=V
,11411
Tkc ,,,,,.,.."" '....1r..1 rea"I>011 l11 0~t eommnniy UoM in .!"Xtlal int" ,p,-,:ta tioll is
a-dt.<lf JllIe of ~n OE - io n. Tlti, i'l" ol>'" dolU Uon oJi , "'" un p.o ifeld elect",n
tn In.... " ...... I""'d to ,n .d,acont l2' OI" m (far = Tr"~ em.n t SC<:lion ~ . l O,
adj:>anl IhtO" ..h <p. c"J. .. ith OO'IOOIlutl llt 'l.-~yuso 01 " ""' holl oo nd I" . he
"-~tom I b~ "u ~ion. 4.U to 4 1S~ The ""'" li' m;, "" mpetili,.., b<: "a~ .~ th<- ....'"
h""Kl com l"'llIatol ~n .. ~ otieall) fot" lh. Olle do. vcd, ;n "h ieh l',oo:;ns a n....."..
tron ha' oc"n (1 ,""'1<:.1 ttl loell' otahi l..o lhe "".i liv~ ch.r~. (E<1~ alj"n ft.41~ By
Sl"vcn",,~ ', R" le ' he c1e.a' ~iO COIlI,l in,,,l,. ~h.r~. mi~raoo" .r ,.." ' C>ll'1.. t'"''
o ""I' ~Y (l EI "r It ... leo. llun Ihat of 'CR,Y (. ~ ...i".. ~ Eq...... tiofl ~ . 4' 1.
c or ~ ponlnJ'" .Jio:. ll ite, u,uan~ . everal ~""'P"'lil i.e ~--i:lo~'w~e rc.ctitm,
a t<: ....... ' bJe, sin '"
h
Ih. one or llWn, nbree m a ler tiary ~miJI.) 1
a t" nu can ha ve a! ma ny " Ih, .. , ubolitw: nb to "" 1(I.e 10, a .d~ n v al! . Am0ni
t"",,, .,. "",illiliti., th. lou (1/ the t~ 1buI1 ur hTp.r<l lo.HVlIKm enc,!)' i, "nor~ !:ti .
"r
110....'...._.,."'.", , " ..........,
CH,=V
(BAl)
R---CH,-----Y
callI' preferable. excepl thaI the los' of the largest alk,'l group i' favored (Seclion
8.2j, l\Nc tha( an abundant pcal:. from lhe 10" of H. (~" ,mall"'t .:Ikyl group.
lhu, indlca(", Ihal no other ~-deay"ge i, possible. (or indicates the presen""
of _. F or -eN. S""lion 8,6), lInkn<lwn 5,13 illw;lrat"' thc," rule", lry it again,
If ,"voral ra<.hcal ,ile, are possible ,n the orpre,'lrsor JOll, I~e favored
~-<;leavdge pnxlucl ;, u,ually lhe one Ior which lhe con.,pollding radical
!la, the 1"",,,,1 i,,"izati<lTl eTlerlolY [Ihi, i, true if D(A-CR,YCR',RjU(ACR, YCK;-ll), &elioll ~,2]. ~ ote thaI the radi""I-'ite prcfcrcnc" (S"ction
4Aj l" > S, 0, ", R > 1..-1 Br > H j, ~cncraHy the im'orS<' of tho II:! value' of tho
COTrc'p'",d'Tlg radicak for eUJlIpIc {Tallie A.JI, H J C\J-CH,', 6. I "V: HS-CH,',
7.~; J 1o-ell,', 7.6: C,u,-Cll,', 7 r. CIi,=Cll-CH,', 8,1; Cl-CH, ,8.6;
H CH,. 9,~ 0V, Item berg and Spitellcr (l 97(J) h',," mca'u"d the compelilive
cITcel "f sueh Iulldional gmup' on pmdud_ion allundances Imm a.dea\'a.~. in
the ,ame molecule, For the compound, C,H,CH(OCH\)(~H'jCH,CH,CH,
CY---C,H" tllo abund'noc of the C,H,C=Y~ ian "lati'" 10 (hal of (he
C,H,CH=OCH,+ ion in the sam' specll'um yield, lhe following values for
.-m10u, ::OCY groups: ~-=CH .C!, :>CHRr. :~CH-"l. <L _.::-CH-OH,
~; >CH--SH, 5: ;;'C=O. 50; >CH
SCH" 100; ::OCH OCH,I OO;
:>C(-OCH,CH,O ) (elhylene kelal), 500; ::OCH-NH" 1,000; and
>CH-NWH,j" 2,{)(Xl
Unknown 8,4 is complicated, because it de>e' not coot";n" molecular ion, 11
""'<IOW" 1.4
00'<
""
""
so
"
00
""
"
"
00
"
lot.
"
",
n
'00_
00
"
ra
"'
"'
s.a
ioe
,
"'
",.
fs
00-
>
"I, "
-, c'
-~ 00
...
" "- ........... (
1IftIt.....n
' .5.
...,.
"
""
."
.
"
rra
The pnnC>1N ' cmorittHtfll r>! 0""'_'" , S<JC'c lion or ...... ...illm....- t..<1in,; " '
C<>IeQPl1I r& ch ry """",li.,...

m
- ,.-....... ""
.,
..
....
...
..
.. ...""
"
..
. ..
"
,.
"
"
<
"
."
U"
0-
'.
~.
,.
,.
sa
" '""
,."
""
'",n '
. '.
"'
0-
.
U
..'" ...
,~
,
"'
"
,'"
'''1
,,f -j
. .
,,
~
)'''\1
have
b<:~i n ni n g
..l
"
'''''''t.",u,1djJIk uh) . u>C the
..
,ro
"
..L
el""".unl " "" ['< "';ti" ,,, ~nn ,l.1 If",
" r '~t ~n''''7,
ce'
----!.--
AS '
.,.
,oa+
CI, Dr, - NO, ..
0, $
:>
01. C
CD
1~ , 4 3 1
'"
Intlucli., Ii) ck m'oj1< <'Or .. <I11, 1e bond ,,:q uiTe' ehal ~ m;grnl;OIl tT3 ~~ 8 l ~ and
rhus " (I;[fo," " 1 >lruct uu l ~n., ..."' m<nt for the f;I1~'1'" in ' he pr",u , w r and
pw <.! uct jeM; Ille VI ' - d ""1.,,," " lI f~ u nd , \~ (e ror ~ l aln .. ifh loc fir, t Olcitoo
>late 01 the p ro;l UCI< [I'i , ure 7 ,9 (blj.
of I'" JDlP<lrtauco of cM r~, . I.hi.
liLlOI ~ ," in "'~' ''' ''D ; n Il,. fa"",.".j 1'<00 0...... of DnimoJ.xula r ""tion d"""""po$l '''''''' oint "' -oo n<t i ck " ,-al\c" ra.;" .,,1>,0'. 01,..1Mmf\<'titi ", ...rict;."" 10 001) ~
r. .. t yp'" of UI ,' - l' , eC1l t\Cr iom ale " 0,:1, i d.avages compffi li"C' .. il./> J;"'~I.
, iIC '" ~" lj o n., and in H , ' dn <>mpo<Ili<",. r....."..bond d en ull' . "" cbon, ""
jl,c".raU}' favorod """"..oe ' he ch rgc , ile does uN mi[mdc
fkc.o.",e
';."w-6<HN
OE " iJIJw,iot d.llv<o:e. . F"l k' W"I' OUJ ionizal.i<ln sue con' ouli,,"
o... ~ ;.. > (f . Kl' ",,, ;,ol;on prod~ R Y . ~ nd i" charge"' ;te dl>J<I<......ion
d",,' i nr " .... tloo nrl p",d uoc> R' ... -Y. lbu, l ~il ch~ lg.-mi S'" ti,," "...ct io n , .<j ui",. de<-omp"'i, inn from ~ n " ~1 Iw , 1,, 10 01' th. ion [Pigu,.., 7 ~ b ' l; 11
"I, ,,
be "~"'..c, l~, a n-l,,' nd cle.'-illl" ,4.ided b~' inducl;\'C dt ro n ...,11ld"".~J by lh"
d,cl ro nc~a ~, u bomruenl. R - Y .... 11. ' I '1" is<<t,o n ~ 61 J hi' """C1.i" n ;, Iho
," " , 1. ",,,,m,,'" r" r d lHmcgMi,," 11l r..li1."" " ," rur " I,io;h 1('1" J:;' 11 K ~ 4 C,
c or d ; lt ~ to Sl" , n.. ,,,, ru le. Th " c,,", mOIt ru lt nion ~l ~"''' P ' for which t h~ ..
1I ~. ~n.
N O" - l'N. h"I" gen "l<,m l. a nd o~ l'~e n fLLnet i" lliIl' 1. i< ......'b ... 11,.
d ,u , y 11-iO" ~ an",xy 11l() ~ form}1 1Il r O \ " ~rh , ,,y (HOO<.:j. ; nd alko~~ _
<:.a rtoon)'l (RO O<.
P"" ,hk rad ie.l-";I. r.~ c1i, _ can gr. ath lowe< , he oon ' ~' ;l i~._ ", "f Ih.
i_re_eliu", " ll ho,,"" IE(H1N I _ II IcY Ihe <lIa ...pec!, a of II" !!. ''''' dominat ed b~ ~ "'''' _''l!t ,.acn ''nl , Th. prob abiluy " l lhi. R-Y ' - . R' -r , y "act",," i, inc;l$l if the neutral II. Y Mud "' " ca ~ . For .M mpl<. Ihe d i,'ll is
,>h.cr'al ..:I"" if til< . lem"nt h<,~ ,Ic,1 h ' R IS ... ,~ .. I U" ~ as i<X!i~. or " mc 141.....
i""'l. l" ~ Ie"'. l .. t. nt, - S R I. ;6 C01""~lJ"In r"~di" t1 , R - y~ It + \" ." "
d a,...Ji. d " " 'l"'"i. 1","", or a ' bond , l""vage in Sed ,,,,, RI>.
Of the abo v" 'I' r"m:-ti<:>n/lli,it.", ";0 ,. - 1, and thMo:- e(llt la lllm ~ !lId,,1atoms
,,,u~l l y o>.h ibit the h,gh""t r<ndeney IQ
It ' (00'" R-Y " AI~ yl brcll1i<lc.
a~d chl", i""" elln r..nn halonium Ib)' d i.pla""""nl ....."ang. monl! alOd
(M c u- jon\., 1:>1, . the interprdi,'. illf" " na t;rm from th' lt i, ~encnll~' oow
r*''''~ '1a, y 10 lhal from 11.', For Ial",:et otkl l yau p,. til . pri",.,._ R' prod ....
<an und. rllo .~l"n '; .." rUflhc~ ,Jj,......I8IJOI. far Ih. ~,ultin~ C,H ' 0_1' ion ...
a , ,,......,t IL dim ih u t;on (mU lmum d! n - ~ n o' 41 ell n b. inthu tJ'" lse.:JJOll j ,2) of
an ,,.lIe)1 If'n ufl, ' uch as 'n Ill.: s~tm of I,d l" ...,_ and I -t>.om~dodecane,
~'igllr J.2J ~ ... I 1.24 1'....., see ,,9 and 3.n!.
Of the t. ma;nmg Y fune li" n. li' i...... th'" . " onil y ."'elronegati,,,, - F . Ad
- C N ~ ",,, p. can al'o 'Iabiha Lt ' peod ucr i,m, by bad . don allOlI of eb>1"""'" ~"ci " ~ '" ,,,,,kiI* negli" hIc th~r kmnation of 11 ; , he i,. " m ' 1flag
""'''''' IOon< ar" d l l~u ,oe<l ;n Su:1;,' ". 8.6, ~, l O> and 9,11. l II< hi"" m. ~"'ioo
.......,.1 ie' of the neulu l lt F, R - e N. "n,l R C= C H bond, a", al'o
" 01 WiT h Th<-~r h"o 1'~I.kn<} for ~ - r"rm3tion,
For Ihe o~YI!"1H'<l n l "," ; "~ rLJ "clionalitin, r,,<Iic:al " It lU, tio'1< " , c compet;.
"'It
Ii"'''
,i""
",,",i.
\i.,. , '" lhat 1M leo<kn~'}' I" , i.... u~Li,. cleavage ca n be ditr", u!t h' p dicl, F" r
0 111.' " nd II. q = O W "' " lem b r ;om , tbe ~- and i - e! . ~ ' ~ ~e prod u"",,
" ""1""1" f"" , "" """Il!", ~ ~ ull;"n ~ 2 ' howed Ihm Sleven" ",', ltalt- " >r' M y
pndi<.1,,1 1m ....C. H .-COC H , ~ thaI [e. H, IJ [- COCII,): th... "'<let ..
..., ." ".,d fo' " " -C, H "_.cOCH,' , M"", .\e<:lrolle~ati lur. :IOol'l.1lori. sur b
.... 'Q= O ,O H, -C!- O )O Il., a nd C(=OK'l , "'hic11 , h" uJd f or R " fonrklliol>
In"" ~. It - y ' , llCnerall}' produce i",,,,,, la nl R ~ ions ooIy for ...,,, n,,, '" 1..1.11.
gro"pi bee. u," ('If compelj li. " ,,,dk l ].";,e .... U lo~
For lalul" t"d ",yget! fun"li"nJlifln . /0 "nd "",le,. . ag"" di""",iat. d"ierent
00,,<1.. ...ilh R' - CH, - Y ~ ' ("""inll R 'ClI , ;md CH , - Y ". ,e' pte' iv.I )', F n,
R- 0 H ~ ' , II' i' ,ml""rta nt onI}' ror ..." d "' . __ lind J.,I..aJb no!s, al{h ou ~ h lbe
(M _ H , O ) ~ ' pea k o[te Jlllfo vioJ., lbe "" me il,ije!Ur1! informati" n, Tn. L n d ~
!iv" rtf"'l ClI n CoOn"" Ji.......ialioo uJ".. mut< pol.r,~at>le M M 'ha l i' fort!><-.,. a.... )'
( F~ ""ufl" ~,24 ~ for la l,~,C C H , O H ( ~ 4 "atJall 8 .4 ~J, the energy of lb. oil gcn - " hil"l '" ..n ly O..~ .V llOOV. th at of tbe hl~heSt """co pied r, ..or hi, aJ 0( the
It - 0
:
(CH,),C-
CHp "H
-"-
'<,
\CH, I. CCH, '
.-
,,,,,,,,,.
.~
e tl, = O'>f
.-
,"""".
(8.45 1
,~
6.1Q\I
'C MP<
1l" . 7.t,TV
.1k, I l"0l'p [I F. _ 'J.'J t V: It -' 10.2 eV for (CH , I.Cj. T hc "'oil 'n , l""enliKl
'''lh~ fo. I"" ",,,,,p1.m'".lI;lr) o,\eeomr<', ilio" , [Fig" , e 7,91bl l .,~ Ihe,d o,",
~ '1' d<>K 10 ... "1> <>lh. ,_ .1 lo.; "'il1~ lor effieienl , urfac. b oppin~ h . glve p. o<I ...1
abundance.. C<l ru..l""l "' ill! tne l' ,ed;"t;" n, of SleVen"",,', Rille.
maiJll) ClI,O' ...
F", 1I ' - CH , -OR comp ounds. CH , OC (CH , I, gi
q l'.' l l.), (I 1Xr'~), WhCrcll' C.H. - r.. p,e~nts <'flly 2~~
Ie jl~ hifh . '" b'b' ylE I\1e , C' 1- 7 eY_ No t. ~~a;n the c/fo... .. 0( nn lnl1 boJnd-dl-'CiI';"" ,~ ,~ ;.s,
PtR -OH) _ 4, ~ e ~' , and "_. Ihn<>!l yield lillie R . bur D I(:H , = C HCH , O Ph) = 2.2 .v, and C, I1, ~ ;.. fhe ...... rt~k in 110 "P'.~nl m .
.-k<l_ ,.
RF. ' .i"l(k bo'" u.J.<.1;~

TIlt m",n re" crio" dcu ing o!lC bOlld in .11
E1:- ;" n lnv" Iv<;, , he I..... or . ....11 sta hle mol"ule~ (Mcl afT. rt} 198Ob. H. r< "
1 911 J ~ Oy I-Ield', lI. uk Ix. llo" R.l) Ih" ,", "r the la"' . !! prol"" affinity (pAI e
c..",,,.f ... Ie ,nll I'r>u p< 10 fo.m t~e ",m< rmU1k.1 i"n. T h'" ~Olllllwn rta<.
lir>m 0( R OC- O ' , 11 .. --0 'H (from CI prolonOlrd cI1 l<'t""l k. n.. ~ Ret)" .
It- ---OS-::O - , 1t -nl , CJl , ~ , R O ' H " It -O ~ =CH , . R - S- H,., and
R -----<:_ ~ , H in . ol. e 1" , .." " r CO , (PA _ 5_7 . \'~ HO ( ~ A e\ 1. HR. (5.9/, HI
".
(6,5} co (6,n
so, (606), C,H. 17,O,
H,O
( 7,2 ~
C H, O
(7_ 4~
H, S (H ) a n ~
uc re
17k ,. Note that tl>.: I" " u' "r prn pcM lPA _ ' .ft eV) from R C II ,CII ICH , I' . of
""" h. 001 (7 .9 t V) from p' O!l"ln" rl mOThll . ' hcr., "f . tx:l onc (R . ~ . Vj (m",
R- O - ClCH, I, . an d " I' amm Mi. ( ~ , 9 t V] from prOtoo. IN amines are r",
Ie" pw nn unocJ, in .cl; ord.n~ wIth rho hi, 11H proton n m lll lic ~ Qu;ol,(ymj;
tl1"o predic Tion'_ we M I. t n" l ,h I'll ion. "" n i" ,mc, i", tn r,,' m m"'.,....tah..
mucture" and EL - ..,.t;nn , ; n v o l" i n~ rh. d,SloOciano n o f t ..." bond", di"'lI!>..ro
heln ...., can be highly com pel]ti,- . In Ilenrrill. ttlne 5in ~. bvn<J U : ' oJ:umPO<l liom
h,,,'. highe' ,,,i, ;[",1 <-"nC<g"'-.. t,,",n or ' ,lceo '''' I''.,.;II....' In Equa ti"n R.2 lhe ~-cleavag<:
CH I - (.H~(''O + (:H, l1.'<luiln IJII> tV,
whe..", the i-d . "' -"go C. H, CO ' _C.H. ' + 00 ...."d. ~2 <\' n.erounteTpn n c1eavag. , of "" , ~1 elnu, Cqu.ali" l1 11.46 aftd Fi.' lT~ )9 req ,nfr ~ 1,\'
~ll<1 ~ 2 ~V, =pectiv<:I~' , Fa r Eq,u.ianz ~ .2 ..n" ~.46 I I>, "lk~ 1 ;<>n. ..re (am d
"I.
c.n,co
c.,H.,o' ----:-(;t\
I
!.oj
,!-rr-c>\
~.
(8.46)
In"' )
l->' l>o'h the ,fira:t 01' " .Ii, ,, "'....'i"'. ~OO II>:: lW()..'IC ~ ~ath"'a\,, A lth o u~h Ihe
Ia"", u. . ....rgr".nUy 1= favor able I b~' o. ). o. ~ , Ill ,ho,n i, . n_ _I"1' "" " nl"r .
pen. in EQuauon 8.46 'h. ,,.o-, tep ]XI\ h , hould a1." bt im1"". tant, teeau a
. """ anli" l r""",i,.,,. <>f \11<: C. H j , 0 ' ~ CH , ion. art !",mod "'"h ' \lffitaenth
hIgh In'ernn l e....' g' '''' h)' M,,;ns 7(h V ekclmn... F urlhe r, 1'1',' i"n, h... ,c hi ~ hcr
I,nd,n~ 1<> lu ,.a ngr tMn do 0 u - : ions: m: - di"Mci a' icn in<lead to t~rrR
in f-'l ...
11.2 a nd 8,46 would 101"0' Ihoi' criticol en" ili" by 1.6 . 11 (n~' "
[R 'J in FiS"":" H "n,1 .1 11i
Mulrif'ly I\lll<:tional compo und, can provide a compcli li\'c "n\' ;",,,m,1I1
.. h<re ,n " "n mo lre",l.. ofhi~h pr"I"" affinil;- can Ix' 10" [rom JJI LL iOll A
ch . ...... ",aml'l " in,,, 1V", IlLo pro lonated diami"e,; H,NiCH , ).N - H , I" " dllli <'l
01, t 9 ~ 8 ), with the 1o" uf NH , a rna,irnum fur lhi; 'IC ri "~ l l y f~ \'O r ~ hI<; ,, - 4
"umf"' und (E~ u""t i"" 8.4 i ).
'i"...
"U '- , ( ~~'H
EE+ ' ;IViI...h""tI d <IlY<q< """ . 0.' </lturr fFIiv~i<M (.-." la li<sm vi lbc n nl _
d c"lm ll , uk"), O f lhe c<>m pl<" . " oI11ry <tm prod"".. fI"'" ble. I""'" from hd e",lytic bond dta~ait of ' h ~ EE 100 ",, "';0., cha rp; m' lP1lli<m, R- Y ' _
R+ I Y, art U' U4U,' la."Or" J 0_'" ' h"", (rom hom olylM.. blmoJ ,*",age wilh
M
11( 'on' .1
u "'
"
t " ",
,._ 1
chali e rel( lltiOn, R ;. Y '. T he hj ~ h di,ooc.ialion energ;' " nen rouud roc t loc:
hOln ol}lic d ea>"'!e ",1. di""u,,;o,:l in Section S.l; lhe c<>lliwtl a ll ~ ;u..,>at<:d ..Ii"",,""
cialton ~I'c ~lra er C, H,O' " CH, al><l C H,(.H - O' (. H, . h.".- O E" ron. a.
' ,;r ",,,,n l;ng ~':'; ~nd I O~';, "" fl<"I.1i", I)', " I lhe l01,1 i<>n abunJ ano.::. Ho""" er~
Ml J ll lonilJtion (flU ll)i V11 11 ~S of ladle.l, . '" b<:l"", \lot..., ,~- tlu: ""rTCor"r1J~
even-electron n(ull al . pe-. ici. .\rum, l,. m<lle.." k's <:3rl)'I"8 doct....' u"llarwc. ""I>,l;lnen l, (h "t,,~ .n , NO" C:1'.") . ,,, ,1", mo' l uClable c..
t<> t he ~e ",n
el.ctron lulo," Thu " In lh" m.." ' l"',<1U "t 1,3- .nd 1.4hnilrobeoze"". tlte
C.H~ il",~ llf ~ , 1). 1un~ C. H, ' I"," of li N,O,l r rodlJ<f> a r: <>f """Tly U{ua'
~ bund . ncu (onl)' NO' j>, mo.>re...lr" n<lot nl 1" " ' '''''1 " on. ,," I ,," ly heea....,
I I::H",n~Ylld <. Ili NO, ~ but al"" bo..~ "S<' olh", Te<lCt;OM .. J"d1 in, ,,h',, FF '
r",,,,a liun . , .... 11 "'" ..ba ll' ' Clc ulI"'" ,,,,h a. t ile I....' ,,' IINO, from
O, N CoH,: ((0 l" lm C. H 1 ,.,e ....1 " " .,,, " " "pe1illV(, \1a ..~ u ., mp"" 01
1i 1O ~ d"""rn """il""'" lha. prod ll' Q f ' ;0". ,..." " " Iie. l, h~ . ~ h....:.. ",,,,,p;;"d
ill a ley", ,,, b y KaUll ~ ud M " ll<k1bo "n' (l \1l1O).
,,,ption,
.. ..
"
............. 1.1
,m
rs
'"
""ss
""
"'" '" c......

"'" """
'"
'" ,.
"
'"
"
51, C, >I, O
, t
,~
""
,a
..
.
~
""
ss
,;
ea
.,"
'"
~
..
""
""
"
""
"
"
,
"
'",ro
.,---_ ....... ,
.....
S~ lll l' k pressure Itud,tS Ihow lhol !h ~ 'fIr';!I'I ~h"l\dan o:: ,wn m Un..........
8.6 il no l dw; h' i,m. ",,,!"" ,,I" ,.. ,...~ io n>.. f .. et moss ",,,...
'e<j lli,,, the
c.:,H..N a nd C, II ,O u6iC/lIl'eDIS I.........' Of ' "",I f .F ' ;,,'" "'. , he" pn .... 1em
in C ukn O\li Dij.7.
,,,.,,,,,,,ts
.', ...
Un".nw. U
~,
"
.".
sc
,,,
""
.""
"
""
""
"
.
"
,,"
.
,.
"
""
"
..
.'.. ..
.."
.
..
'
.
.,
".
,,,
,
'"
",
...
",
." n
zt
,.
"
"
"
,. ,
'
.
l+.J.
"
I
_.
. o. 01'" ".. '. o.
" , ~ o
,,'
/",: ,
/
'---'
--"-
~}o
(Y~
;Y
,
<: >
'"
l -" - D'(S 4~)

0
/ .....x~
-/"v..........
\ 8,50)
... D.._
_.
(~(
~Y"
..
..
'
18.511
18.51)
,
r:
_ '!.. ~
CJ
,) ;/-'j
QO _ c~
(K.S3)
--"!..
")
(T
--'-
("'
C__/'~; )
.} ,
(R.<41
C Ie3 " a~~
of al I~an I.... ring """ds in a CJldk ion is e ecessary re f" ' m product
IOn. by lll!o' fr ~ g "", n l ~ li ..n (do ubi. -rill>l d. ~,' ~g . u.ualiy demand> an addl tiono.l
""' fT ~n>", m.,n l .lc p in lh,""_rocm hcrcd rin g comp"und.. "'"" R' mdh ylu. i' R"".
Lq... u on a.a, <0 Ih<se a", not discussed he..,), Two-bond cleavage of an Or! ~""'''U'''''' l"Rd, lu ~n O E- pnxlucl ion; cbmi,"" "f a thin! b,," d i, "'-""......' 1
10 Pf..<hl "" an EE prodllc!. The ' lability of the latter, how. "", . often mu..
r,,",,~\1'.111 "r."",h prOO\&Cl. ruvorabk Maj"I rcacti"n-path u.:lerrmnan l> an; t ile
, illt\ .. <~ il.IId .. h<lho, too ioniLa lioJl ,ito i, ..ilhi" or adjacenl lo the n ll t
r.,.,""...t.
d....,...J. Example, ..eIe ~i" en in Section 4.8 in ..'hiel! the deav,~ nI

two 0000 1 in "" OF ' oy. li" ion led to lLhundlLnl p,,>dw::tJ;, n.... inool"ed
io"i ,,,t;",, in the , ing, . " eh .. of the ,,-eJect,on, in cyd ohe.,,,,. (I" I,,,,li,,,, 4.10).
n.el<lCt rous ill dI OUD~ (U" I<oo,,"" 4,I 4). and ~ -e l e etr on , ;n c~do"".., ne (""uoDieisAldc! reaction 1, and ;nn;7...li"n of , uhl<ti luenl' atlIl<:tled to 1!Ie r1n8 (Fit''''''
n.
C~ , '
;t<,
..<ell
".,C-O..,
""C.II- GIl,_.
(('
C><
',>mcCI' ,
IC ~, ' . '
OH M. fe ll, l,
...".
' o . ~
': ' _01'
i" r;
,,.".'.9,
G.
mI. lCl.
,..... ~ __
0< ,
..."
1M
H" C---<:J -
""' ,C-<) '

~
....,c """,,'-(11,0' -01.
--_
m'? :>ll. U
.
~ , C - ,," -
MoCH- NM. '

CH, _ CH""' , '
....,C- W>l-<,
<0
110.! ,
"CH,W H__-<.><.
C ~ ~ fII\'"
110,01
-CH,C... C.......O' ~
Cl1. ~ " -eo.oe ,
1011
I II
(; tl.. t:'U r
,.,/Z oo .... _
~
- " H,
...c ~ c'-o<,
v
ec
ca,
MOCH--C-OO...
' .7
M ~,C
'""
Q-C _ O' -'
C "0 '
C_-
CH,-QtCH - CH, '

~, 1
CH, _ """""
Do' C H , - ~ ~ -o
~'''':;-.:HCI I- C> I'' .,'_-,,,-_:c,--=:::::::::=,-
,'...
"
-0;><'<;><, " .. " " ,

".H I
C ~O '
,'$~
...
'O-<,C",Q'_ "-'"
" " ", bO, 10.
CH,-<: -<:tl. '
...
'7.11 "
CH, ~ -
.."" {....
~"
-",'-'
~-
O - e-~ '
_>r. ~ C =ff,<
- c:He _ CH ~ .- '
..-.
__.:::,-.:::,,-,.::::::-,,-::,-__
~,
;.
CHCH- C- "" ' "
4,8), T no '1'aC(;\ln is usually a I W"-'~l' (no n-c unccrtcd! ('1<"""" ill which the
r,r<! . tcp ;. f~ ci l c ITII",&: k Qnd Hanus 19M ; ~k >W<>oJ liltl4k d ri' ..... h, , " ,...hil.
ll~' of the " f'<"I1' '''' i ;" ' erm . dialio (these "Ui '[(l"ic~ I.dical i" l\11 al~ al"" formed
in tbe fu <d 51e"of hyd ro8M' l'u rrangomenl ""cl ,,~ ~,
d mm e funy in
Secti" " K lfl} Th u' n maier dti" i" . rom: on""'
tma diMooati" n pa in"
"' I ys i, 1M 'tabilit y of lhe !"". d hlc 0 (' +' prod ud., tooo "jmJ)Or tant O E" ' io ns'"
>!>olJ 1.J be eu, il}' recogniu d. l lo~'e1" lhar ~t>undancc, <.'~" I>e .lmrpl~ red uo:d
by IXImp<liti, e reaction, l!tnt torm 1:1: I pH..,h"'1 io n, by !Ill'''''' honrl doo;,,',,_
u,scus,.d bolow, 'IS \<.'ell '" It1 "'....1;,.'" Ln 0111 part, of a m or~ C(\m plc:~ mole. " Ic s, F,~ u,." K.l ~
r hc lypiCiI O lr ' prod"" I. , ",ith () M d N , ,, b, titution,
in T altk IU
" .. de rived l>y ,. ...<i,IL.,-;lIg II,. ~rrect fro m d "a " ;ng ' ,",0 n ng ....."ds. In un
un,u tls" t utcd ' l'doolka n<, thi, dC"\'a lJC ,,"',.]"'' '' (Equa tion. g , 4~ und ~ 49)
''''0 t{"ll,l. ' p",,,11K1 . socII a' <:H , - (:H .. ( "H, C H, CII , . and:"r
('H " 'H.f II ,ClI. ': lhc lalil" t "''' "'''lid he (Ofllled ~ c1i< ioos. which III fact
a re 0,' I ' V morc . table lhan 11", rin, .....,..,,6kn" '
II",... I"a~. l' isu,( 4.6)h ~ " . ", . i"h' I h ~ sa nle i....mcrio: , tr ",cl" re as ionized qd <>h",tane, WhOI' ''' m~,h yk:ydop<"II18n~ " yielrl' "",h m"Lh yl, yd op"opa" . ' and
f: H / -- H - CH C H , ' l F~n ~ , ' f ol 19l1'll. "'M I e ,'al~1 of 9.9-IO .j , v rUT tl""",
C, lI ' 0"' iom c" n he 1"." ..",1hI' all yl , ul:>stilulion to ~. ~ . V; p/Iffi)'l lUbstitorinn
of C, H, + ~i w.. l1>CII = CH . " , ! F, - ~ .4 ,V, "cCll unti,,~ {or til. bi>.c P':"'l m
It" Hta ,.,; "(J<'rum 01 j)M " I'lq d n h<.ane,
An u n <,n urak~1 ";, " ",,, n , hc r ~d riLlg provide, a ;peci.Ll . ilua no n
m. " o,
i.'
.....,.....
'"" "'n
,1>.,
..... _
.._
...
1'0..,;1>1e a <:o"""rt..... as wd as a ,,~pw ""' , di ,wd ~ l ion o( l"' o filii ~ o n<J~. 'I'~"
<e1ro _IMts_AldeT "",roun now ~r <>ducn ll:Qunl io n il.~5 J A , e..,,,,,, ,":. sld,il"" d
d ie,,,,- - in 1,lace of [he olorm-f ~ ,,,, , ;,,. llAIl., ~ ' '' ''' ''' lll no 1 ~.
In"
,.r
1''''''''''' ..,
,"
0
--'--
()
.Y
c ,,".
<,
",
C?r
III531
,J
I
~ H> '
corr.~po.>n tli~ n ,u lr~l
by .. I
~;
. v, Th.
--'-
(J" -
,pec,licity of the
, ix- llli:lIlbered -lih~
..ur
!o m. ..-hat ;llilueuceu b)' Ih. I.!llkr...~ uf hyd""",rb< ,n, In u ~~, " tnd"m n>
. ".Tl ~."",n l'; Ihc <.:. H. ' . bundance f, om cyd ohexene ,. ~~
25",,;
from m~th ;J[n.cydopt ntane and s: ~:-; from melhyk yd opcnt.""" t\.I1:yl 'u ""tilY';O" ....n nlake dLene ' - roundt;on eyen more rum l'diti ,c. l",.'cr;ng iI, IE " '"""
10 .. S cV. H"",c w' . ii, i,om,.,.;" ' I'" if,d ly can be di.>. ppointm.:; ,1>< th=
m<; thylcy,loh, xcnol, mcthylenecyc!ohexane. ami cydoheprene i'.I ve C ol L. -. aoo
C , H, . ' iOM of rcl~ti\'Cly eqoal import an"",
C" '''~ flfd !"elfC-Dicl,...A1J c, J coumpu.;ti,,,, J oc, <JCCor in ""c luhex. "" deri vau' -" l ~at ....af ' oMtil" ent, in the allylie positions; in , uch compound , the
eneJ'J!IS "f ol"'n-linll inlcnllc dialc, arc higher tha" lha l " f lhe Ira",ili,,,, , lot<;
f"r ,"" ..,,,,,,,,ted pn",""" which ('ICCtl CS near Ihe therm ccllttnic:1i threihold
and I l a~ l a <, 1~1l<>~ The erit kal ellcet of , ub' titucnt, on thc , 1 ..,0....."';,11)' the , ettc- O iek-Ald., react io n \\la, discu,,,,-...! in 8<>.--(;0 " ~_ ~ IT u,,,,do
300 I bIJU ~ 1?il4, M ~",l cl " , u m 1~ ~_1) _
I k l erl>;l10m . uMtna hon for {Lquation, 8 _~ J -~ _ ~ 7 . ~ _"'~ -~ _ 5 21 or On ( hqu
lion I\.j J ~_~) ~ ri-n ~_rH, can ~ ave " neg;llive .. well .. " positive dI."t
on D E' - prooU<l-ion stability (Ta hle 8. 3~ The nega th" etrccl ()f n'yg<11 .u b
.tilul" .n rnr ~" ~I"m ""acinI! " , ub,tant;a l pro portio n 01 the <harge i, lOen
1$
n"'......
""'<u'
or
'"
, "" .., . ......_
ill Mc , C - CH ,
... of ... " , _ , , _
(!lcu lr .1 I E " 9.2 " ~'l YO",U, 'l.1 c,C - O'
(9_~
,," J ~"J
'Cl! MeCllM.Cll , (9.1 . V) ""0 ' ,CH MoO +=C1 I Me 110,0 " VI, Thu, '\lb. lLtuti" M ~n U' YI\Cll fur ~ ri ng - C H, -, n.:" uld Ill " '.r tho pr~duct ahunda"",c\
vf t:~ lLlLl i l "" 8.48 and 8.50. 3- M.t h yjw ,. ~hydjoru mn )'i<kl, ollly 3>;
-( ' H,-fY - C H., . m.';: 44, b" t IIU :-; C.H, ' formed by CH}.l In". For it<
"x_membered _ring analog. m,ahydto p}'ron_ th e ' P"Clr ulli ,l,a <ho,,". all ahundam (M - C'H , O (', H .l'- ion (Equation 8.%'1, but link or lhe sjJl~le or
<I,m llk: _,,,,,I,," ,.~~" prod uct<
[~> . .
O=CH,
mlz 56, 55%. ~
",'z 30,5%
(8,56)
li a,,-ev<r, t he ,n " l"gm" nitro gen <u"' lilulio n (Table 8.3'1 ha , a le" del.ter;uu ' clfec\ on the oldin ion. WiTh IE(M eCH =KMe) _ 9.) eY, "ml .cILl~II} ,la_
bHi"" lh. du~-open.d ;011; ' CH ,NH ' - --C:\10, (II' _ ~_91_ In -Cll,MJ '=CMe"
rho "i!r~g" n ~t "m i, much mure c"ml'atil>le with the charge ,ite than i, ox}'gen.
~ lI d In ail llleh ions rhe unp_i",,\ d cctmn i, , tahili,-,,,l h)' aU,-]ic [""ma nce.
'C R. Y- - CR', . ,C R, Y ' C R' ,-: Ihi, accounts for ,he bas e peak in tho
m." ' p"c1 r" m "f J'ymllidme (D uffield el al. ]%51 and important OE ' ions
in tile ,peetra of ;N hom(~()g< _ P",!,mli"n ~_ n _ How r. I"",u," the " eutt']
(- c R, - ). rmmeJ a i,,, from the ring atom, mu,t h ,'e n > 2, thi, ion ""ntaining
:;""
~"
-,., .
... . 1'.
Ft . ~ ,: mz
~ .C+l, _
IS,571
(3, 101l"l'.
"' .H:..rz 57, tlC'IO>
... ""'.n, ..
'"
oo.
0:
,.
""
lh."" rin~ ~ h .. '\lI . hould oo! be for med read, I~' from a four-membcn:d ri n'll
U -<!,methyl'lCI'lh", " gi" , ,mly 1;-; ("1 _ C , H. ) '. hllt ,r< m:r-~ m:~ 4' ....d
1 5':~ ' n,; 43 pre, wnabl)' correspond to ioni,.,,! C'H, C' H- CII , (l E = 9.1 e V)
d" d ("H.I' - CH , fY,(, <VI, Iurr ner. , be .. x ~ ...lo;"""'""l' ;,.,.,.... 1,1di",. lhylrif'<";<I '''c ~i ,'c, (Figure 8,4) (\ { C, H. )' .nd 1M - C.II ~t ill . cr}'
I"", . bu' Lda IIGC: the [olmer iOll 'C H ,eH , "" Me-(:II\.le IS no lo n~e, r"'iancc' labiliud. d l" CX: L at i ~ lI to C , H.... MeN =CIIMe ' (u 51, n,ulral IE _ 9,J
,,'i j, and rhe I~H " 1 " o.>OIe",ibl}" lOt-med by I,..., nr ("I I,G I,ell, "'lIien i, Ie",
stable than the oIcfill ll'Ol ;n F'I"'.. ..." , II.S5.
Sub"i!u t;"" <of ~ !Itlel'<'afom 011 {F.quahn", 11. 5.\- 11.$41 ~ " IJ~ ca roou "'11'
ha yc ~ ra, mo /C d llllll;ll lG etl1 ,m 1""00" 0 <la bilil}' IT J bJe 8.3\ b<:"~ I1 '" iL again
c." mako all~lic ' ''''''.... n~ !"<",,ihk CJI, - CH v- ~ c.:H , 1. H = ~' - S'!U lated ",><1 unoa'ura red fU Ml;h,." ,. ~ TC "f neaTly cqual cl!c, I;v<:llCIS: ' 10,CC H " M~ ,C---{HOH . and Me, C= ClINIJ , h"v, IE ",IL, c. " r *.2, ~, .., ."d
-:cS d '...nd '\l e, r: - C-O and Me, C-C l'H haw YaIL"" O)f 1l 4 a n.1 _ ~ tV
" <>rmahon 01 .h. "" i~ " . /"'m lho , uh, liluLcc! C)'dobura,,,,, , h"" Jd he b~Mnl.
sin oIe/in;. T>eUlr al. at" til. oc-p rc ducrs: C , H. O . nd C , H.-O' -a re by fir the
m" " ~ h ~ n (t. nI ;"n , in Ihe :; pe<.'I1 ~ of hy ~ roA~' - ~ nd n",lh... yc~do bu l. n c. fC o
~lj Hly, Cycl" hul" nnft c, . h"" K ,i ", ila' b<:h ior, Eq.... hOD 8~, Otlloe! I"b
, I;"u,i nn can cause oh",~ e mi~' ~l\ o o . 3.3,hmc1l1ylc}"t'lob""'n",,,,- ), . 101. 100:'/,
R _ H ' mlz . 2, ' iIiI'I'o

R _CH,
mlz 10,
I~
,~
..........,-' -_.. . . .._""

,
'M
,.
'001
I 00
I
,,
..
-.
r_ u .
h
,-'
00
"
..
"(5
00
j
"
,-
M;> l poeirp m ~I 3.3.5 t rimclhyk ydohe" n<J<\o.
,m
... ! '" ..
;r
r I , , I
.
~
-"
,
T I
.'...
,"
"'~ I. ' \f... ' lJCI'l, pPl 0' ~~ h l )cyd" 1ltnl jllim "'.
C~H. ' (l ~ _ '1.2 ,.",. " od 5,}~ "'i~ 42 (9.6 . \i). Elll"r~in~ lh" r inll ..., Ih;lt an
dOl."'"
d .,(,,, .. "". pro.to -d

'mm tho ring . , ~ ncul, ,,I. m~I;~.. ...JJ i,i"nal
w lllpd lUW rc;oo.1 n. """l'i t>lc It><' small miz 41 in Figl1 rf 8. 5 " nd .,;! 11
IC H, - ( H!' He , H, ' ) in fj ~U I' 8.6 pro'ide exam ple, oj \h,.. I n t ile ' peCl . um
of di..."'Jn .... n" ~ y.;I" h.: .. nc. c,"" n the highly stab le ;an 0 I,=( ll " l("ll , '. .. (" nn,'" i" '''''1 15% nbu ndoncc I:alt hou ~h tll;, i, tbe se<:<>OO Ja '~ Il"a l ~
Wo h h<1cr""lc m "~ h\l "" , ,,n Lho I"", "r " ,in~k: rillS",..lion "'0 occur onl,
by dc ~"~gc <>f ill ~dja '~ n l fll'l8 bonds. T il< mast oom m"" n,,,ml' lc j. Iho ... mo;.
l im<,<;-jmp"'l ' l\\ t" ' 1 or <MOOn mo noxicl< from o:,d o al'annn ... I.:.qU31i' >!l I!. ~~
I r ;~ tL ro S _5 ~ Howe_'c" the 1M - (":0)' ~n ~ (M - CNCII, i- -JlC'lks ar. ~n order
01 m"inilud, b . impo,I" " ' rn tht ' ~C " <It n "ll_u", nM I;Cul<ol .."d "h<~a"' ''",
"nd 1\--cyc!ohexylidcI1 CmtIMyb mine, reore'crh'ely
Fm Ihe rolm l)joh -Alcl< , re, _"o n. heleroa ,om """ ,u ~li t uti<ln ll<.lt <lnly
enh" no", the "hu nd. noc , ,( cO' h<, r.. ~, ..d , h ill ~l,,, " ol uoc,," , andom roafI"n~c
'"
(8,591
ment" m"k in~ lh. r.",lting Jarge OU " ion;; usefully char~clcri,tic of ,ub>tiluted eyclG h..enel, The h~ dr o xyc~d o h. x.n. mass spectra show ba,., ]lCah
con,i,tent with the ~, cle"v"~e< of Equ,holl 8 .5~: with ,-illyl", and oI1ylic hydm~y <Uhl!i(ut;on the base peuk corresponds to C..H 60~- (neutral IE - ~_5
.V), and for 4-hyd" "ycydohc,ono I the ha"" peak rcpccscnt. C.Ff" -- [and an
equivalent " hundane. of 1M - n , OJ'- from 1,,-rea rrangemen, or the ajj~lic HJ
In the latter ca" 1l:(C.,H. 1 _9. 1 eV, and for the complemenlary pathway
IE(C II , - ClJOHj _ 9.2 eV: Iho C , H 40 ' aMundanc" i, 2.\ ~;_ Tn 4-mcthyl-4hydm , ycyc1nhcxcnc the cnrr"pnnding C" . ~C(OII)C" , - (neutral IE _ 8.6
. V, i' the mo' ! abundant, \I,'i lh ottly l(~'; c.,H , , -(Equation 8.Wl
(8.00)
:'>Jo to. ho"", .."r, lhat ring un" tllrati on and f\ll1ctio" ali7mio" ""n lead , 1' 0 10
rinll , tabilizaho n, In tho rna,s speclrum of l _ mc t hy l _3 _ hy d wx~ " ydo hc xc ne tbe
h~"" I'" al i' C.,H , ~ , the stabk belll.nj utn ion, a nd C,H, + i' of 20)< nbnndaoc. ;
lhe b tl"r [ M - 21)" , hardl y . "I"Sic, 1 I>CLlt , . , I",," [&ctio" 1.,\ ), emn;'pn",t< tn
("I - H , O - H,) , ~
Cyclic EE + iou, obo
llncler~o r in~
clem-age in a sim ilar manner (Eq"ation,

k ,~ I , K.~ 2~ EE ' pmdu~l i,m, att rormc-d withoat ch~rg" migr a,i"". "litre_
c}":Johexane - 10'"' NO, 10 yield 'he EE + cycJohelyl- jon, C, R,,' OO~,~ ' \>"n dan"e; the C. H, iou, of 100','; abundanoe presumabll an" b}' fLlnller 'O~I of
C, H , " n " l o ~o ". to E'l ""tion 8,"~ to ~ickj ;oni. ed CH, ~CHCl--l ,CH, ' (IT' _
8.\1 t ~-) or of it~ ~ y~li , ed ilome r (1,5 tV), Similarly. l _nit; ocycloh" . ne y"Jd,
[00'; ', C. H , an d SO'~,~ C ,H , ', "'iI h the latte; initial i, omer II C -CCH , CH , +
of "" "" ., IF _ ~.I) . Y.
Itetere atom <U Mlllution ;n th" ring ~ ~n prodllce t~ ",rr""ponding ioJn by
~-de a.' a ge . uch a , ( Fi ~Y re ~A ) the b""" peak ill the mo" ,pectrum of 12dimcthy,p;l"' tid ir.c, F4ua liom R..14 KnJ ~ ,~[ (the '1a' ~"' t ~ I h l )0 "-'" rule
re4ui= that the alk)'11>1' lo" !- T ho n:lru-Dic!>-Akl"r (RDA) li<;.. "~" 01 11li,
hl!:hl}' 'I~ b k ~ldi, ion )'i<; [d, a [0.... "bundan<;(; 0( C H, = C H'- Y+=<;H ,
(fn/: TO ~ OOlhj ,tClll ",'itll iI' fcla ti,'"l)' poo r r">eM IlC. 'I " billzation, 1n the ,pec-
I 0""''' M~' ."'.m. 01 100 .,..m_"'''"'
'"
CNl~",
H
'
r;j("'
--'-I
~,
--"-
<,
m'r98,
~H,
,/CH,
C", ?
10~%
(8,61)
fTI' 70, 12"{.
trum of the oxygen analog 2-methylwrahydropyran, {he (M - CI [,J+ base

peak on RIM decoml'",it;on }'iotd' an . ' -en les' abundant 14>;,) CH, - CHO' =CH. Ion. comi'tent Wilh (he dCClroncgati\'c alom <ub'lilu!;on a{ {he
charge 'ite. Tho lotrahydropyrylium ion rearranges ill part to the more-,table
2-Jll~(hyholmh)'Jrufu,ylium, which cannol do",rnp,,<o by the RDA (Murizur
01. 1987J_ On the oth.r hand. tho 2-alkyltotrahydrop}TyJium ion can di"IO~"ia(c
d\ the C - - U rin" oond. )'id<ling a ,(able a<ylium ion Il.!qu~lion, ~,5 j ~nd S.62:
z.,h"r",~; 1932).
e'
_R'
GlR ---
(8.62)
TN'" hrmds c/_a.ed. Th e rna" 'p.ctm "I func(;onalized cyclic (;, five_
memhored rin~1 compound, commonly show a ring-deavage decomposition
pathway Ica.<.ling [0 a hclcmatom_,tahilized Eli' ion which i, quite """rul
lor structural char~dorization (Figure, 8.5 and 8_6, Equation, 8.63 and R_64lRadical-Slle iniliat.d ring op.ning 'eparates the radical and charge site' to form
"
,
1
... H,
m'z84,1000/.
(8.631
m'z83.100'l>
(~_64)
a oJi,wnic fadieul ion similar to tho first steps in Equarions 8.57 and 8,58. Tbe
,"cond <l"P "r lh"," r""cli"m m<lvcd the unp"ired electr,rn ;;0 lhal il enjoyed
allylic stabilization: this can also be don e by hydrogen r.arrangement. forming
vorl' 'tabte iTabte 8,Ji onamlne or ketene Intermediate, (Equation, RA1-8.M):
tho dienyl" intetmedi"te in Equntion R,55 is tho hydrocarbon analog. E~cept
for fOIlT_membered ring, whi"h prefer ol.fin dimin"lion (F'lw'linn "_~R), ring
,iz. pro,'ld Htll. restriction for lh. I[-",arrang.ment reactIon: lh. mass
spectra of cydoolkyl-::'iH" -01-1, and -OCH, compounds of fl,.- to at l.ost
tighl.memhtred ring> (16 f"r RNA,: MoH""a and Lo"g"vi~lIe 199m gi,e analo_
gously C,H,N', C,H,O-. and C.H,O-. respectiwly. as their base po"". and
[hc 'l"-'Clra of umub,tilulcJ cycloalkannnc, with fivc lhruugh l,;n_m~=b"rc<l
ring, , xhibit C,H ,0' in :> 90~'; abundan",,_ This palhway pref.rone, i, consi,t.m with the resonance slabilization (clIar~e ,ite removed from o~Yl,<nl CJ<lXX'tcd
for lhew proouOl', 'uch "' CH2-CHCH~O'H CH,=CHCH -OH ....
'CH,CH-CH-OH ~nd CH,-CHC -OCH,-CHC'-O ....
CH,CH-C---O.
Althongh Ihc >, rH readi"n is charaClcrislic for particular compound classes
",ch", 'lcwid, and oillcr funchon~li,cd bi- and polycyclic compnlln,b (Secti""
~.6), il musl be u'Od wnh c~ulion in intcrpTctOlion, beca"", olher deoomposi-
"
&
!
"
.CrJ,CH,R
II,
(1
&
<,
CI-l,R
11
11
fr'("'C"'~ ~""
~
II
\"f
~
~I
~I
"
"
18.65)
'"
I """ " ..... , .,_
_ . . . .... .., . ..""......,
two, can c"m!,,<'t.c "';11> il< lh" :<loond-clea' ace p.' l h...~y IKin <!<lTl d <Ii 1975;
~h warz ", <11. I!U!h o r r~ r(j " u l a,. mecham<coe mln o, l i, lh~ 1'IX~"li.,.n.m " r
r j n g~ a1I<;) <o:li < ions to j M '~'''''' OT ,k."'.a, e the o r j ~i.ual ri"S me , lh.
"F eomm~"'-~f>l 'ca fl an~omcn l" ,.'ie-IM :lnd Ga umann I ~ ~J, Au"''''' ... ~I. 197 5 ~ In
Eq ualMm ~_65 lh c....,nd "~ d ,, '8,~ , ,e " fl ~ Llg . n_ t le~ d, 10 mO rln. li nn nr [he
~nd compc k" "1(" a -d eavab'" 1,,,, "r ~l k~1 (E<j uatl<'n ~.bl ). !;lnlctU1~ 1
[.,"'", lhl j",-~""", too la hllity nf ! ~e h}'drof"n l ~k 'n s pa rt in tltu = M>d
rearranj>emml fa,-.J;l~ l" II", 1 "~Ct iol1. Thh ' """m ili,-ily "f the ~ .
rC4Clton
'OW" rd n il! ";"'" and it, [li lt" """,iti. ily ' ... (he . patial ".i<n,~ uon of I"" '':In,.
rerred h~d.ogo n ~ lom iT", ..:"" 81ld 1i: ,~o .,1<jo l ~~O). iudi<:al e , h. t tnc C- C
bond alpha 10 lh. hCt",oo.l,'IJ1l d<'e' on. fully J j > ",,"~a.l e b<IO I ~ t h~ H t," nd ""
tF'l ua li,m &.M~ tbe inci",~nl - t: H, rad ical ~n n.--...~in \...", ~ Il bound to , he
""g.
<"
"
"~,:o
ooJt. ~
'"'
.....'-&1,')
(8 661
dl"'~cd h<1 ~romo m func tio" . 1 ;roup. n:tlu cillll ihe ' teric tequ irrment> or tlo"
hy<l rorcn lJ . " .Io,;l'. " n n' reed"" f<Mn-angt mcnh C. n la ~c plau ;n Ill. ;nlcrTno,H
.l ~ ,<>It, of tb ~ ~ , rH <C1C[j,m (I 1 ~J , ,, n ~ll d .\l c..~ <l oo I'ISJ . 1 9 ~4~ C' I,,", ,;. II} to!
' '''' la' lablc ion d","m l"""'i!in n"
Th" "nK I,,~a .... ". ' h...~y j'm c~ dic con.p"" ncl.... i'h heleroa' Olm iQ I"" rm~ "
10>; cffeoc: ti,... FOJ nie,,,",ne (Filluro S, I h~d pip<ridine IF ' l'", um, g fiT) lhi; t o" H,
10.. Jlfoo;h. = III< '"'"000 m""\-i,,, co.oe peak. but , II< ~1\.' logous >IIi , ~4 Il<:ak
(j) - -.
"
"
"
\ K 1
--'
('"
m-~ 6 e
'"
--,",
I~ ~i)
from Itt< >ubU;tUloo 1.2-<limo,hylpip,m din" t ~igu " 1l , ~ 1 ~ n ~ the mi. S? p""l
fro m ~m~""tl""1cd "l M"ydm p;un al"C , ,( oftly " /ev.. (lereen! intens ily. Th ~,
mu~-h
II", ,,'" ~ from piperi<!i"" could IRo I,ad h" fnr m ~d Ill' H I"", I"Jj",w~d
by I( U '\ I,," of r , H ~ (f",ualion iUh 1- l'yrid yt- I -,~ orhyll'~n-"liJin< iFill~"
Sol) dou nu' Yl.id the ~ ' poc1.Od IF<j ~ali"n &,57) C , H. 10, bul tn,t"",' g;ve...
"'~" ir",ant C , R , ' 1<>; rho I I ab! lr." h" n "f F<jua lio. n S,(,1 cou ld "",~t fro m lh.
aromatic ring l<> ~;.el d a bicydi . i",n
"r
... 0"""""'0'" of .... l~ _
"
",
Exampl... In Figurc 8,1 the addition of" double bond apP" "red '0 chan!," 'he
'pedrum dramatically. [-,'" 'he (JI..'+ ha;e peak; in bo'h spectra are 'hose expected (Equa,ion" 8,48. 8,50) from a cydohexalle,/-cne ring sub,tlwtcd by an
ammo group, a powerful initi"lor "r radical-,ile me"h""i"", 1J::'!uat;on, 8.68
a"d 8.69).
~-
CH,N~
--
".:z 96
r~
CH'N~
m', 125
m/2fH
OH
..
18,69)
When the pe'ticide DOE. CI2C-C()J-C6H~O), i, irradiated in '\lr, a compnL1Tld i, f"'mod wh"", m"" spo<:lrum i, ,h"wll a, Unknown 8.8.
.,_....
""
U. . ..._
,. "
,.,. "'
..
'" ..
Wz
".
,oo
b l
0>
0'
eo
-ee
.,. -..
,.,
,.
.' .""
..
oo
,'".. "
,.
'" ""
"'
'" "
'0
"'
1"
"
t-- ,i
". . - ,.._
"
0>
,.
."
"'
'.
,11-.,. , ok
'0
o
.,..I, ~ '" i ""
ea
'"
,oo -
.,
m,',
"" '"'
"
CO
. . . . .. ' . . .m . .... ' ,..,
I ,
'"
'0
'0
..,, "" ~ " " " " ,,,, ,, ,,,," , .. ............ . .. . ... " ' -" ;" h
, .,
'"
1"
~
Il'''.
'0
L " \;110""" ~." .. 1M 1pIUlm from. 1<""" ,,( ,.,hn~ powder found ," lhc
or . , usp"1CIJ .m~~aJ <r , I ~ (he ,na", ' P'Cl! um r.(l ""i>.lcTI l with lhat which
;'ou .,uWd....
f""" :Jl11l~lho-'l'c..bon) I-3P.""'1<lylcx}'lropalle, (If CU<...inc
1'<",1. ~1
p.-, '
WIt '"' ' K1"f'
..,
L}
I"
~, >c
. """&,......-,-,~
...
- -
,... ... "', I "knuwn S,9
....
_....
...,...
'"
'. "u
t} .,
~
.
......
"
. ,,
\ ""
""
'1 A
" D ,,'"
'/
y '
~
,
( U {ll
"), "---..
(8.1 11
,/--,
<,
~ P-.b~
, w
.(8 .12)
"
',1;
,'. - ,..
,""
-r"
II
-......v".. . .
A'
TM ' l lf>.' b, ~i "m "r cydi~ iun diu oa a llon, lind hI d' OjIeu n n~ I l gc m en l' ,h t.....
l ey . imijari!;c.. p"' fli<;~l~rly ill lh e formuio n " r ; , ,, ,,,, n ~n l oJJ-dectron iOM
;c 1:1:' ion l
.... ' h , ~ cka ' O;l1\' 01 1"" 1><.",01,. an d the r",m o,;"'n <If
<If """"ill) ;n,I"""
Willi the rurthco oI;. .......;;,' ;",n of a third hond. ~u ll h ~r
lanoc rnr tho"" ..",rrang<:mml. are hydrogen I. " ilil) . .J ' e ru..: ph. il y. a nd 1~1'ic
foctn,,: lM.se "' ~ ' lIl'r.xl ......,Jin S<:~ li"''" ~ _ 2 " nil 8..\
Of Ihe var iety of Iu , rAn!\l-"mCII " " bl.c:lved. lh n~ or hl'd TD:?C n . N ' he """"
OOlDmon. be' l un<lc""lood, ond l,,:. ..n llt mool u,",ful ror d",lu. injl l ltuellU"_
' hno"'......
.flO""
'"
O lLe (If the ,,"-ft.e- l oot op;C_Lltl<ling 't Udl~S 01 ~ m U " ""('CClnd I'U ..1 ;' ." co n"
lXrn:."<l l hc ~"~ nJ~", C, H. O , ' io l1 [ol1" od I>y I ~ I"". " I el h ykll< ,,"" " >n ni, od
bu tflno i<- acid IH "I'~ "nd ~I.c ", a r l 1952; Eq....I;\Ion 4 .3J ~ H yd < ul:c ~ ,carn0l\<"
r,, 't
Illelll' ha>" close ,,~wlnchemic~l ~ nal ogic>; f<l"'h<'1w1l ,1 9.~4 )

point. d O\1l
, ho; ."""~ J>Il.ra lleh bet",,,,,,, the NQr ri,h 1"yl'" II realT" ngem elll (If kctn n.:: . ~"d
\ooit Uln.. . pootnL Md
e",,_ (19.16. 1959\ d=ti~d lll. bwad int"pr"t 'I,~
.lln-
;U,
utillly 01, uch mecnani' ms lor a "" de vari<t)' or c"mpou ,,<.l, . ~ . ~rt h", <!<-talb
ill ""e '!!" O fe.'i.",', (1'1.. ,-...,) ... nl. lon3. K.ing'l on
M 1 ~ 74. I n s.; Sch,..u
1981, I( j n ~''''n d "I. 198 J Zolh n te r ,md Seibl 19~5 , H<' Lt<.M~. 1988l- l!e<"aUK
T ">J rr ~ ntfl M nt \, b ke cyclic "'(l m~n <l (.h.\ <.X i ~ lj o n . iD ~ol . t mU1hpl< n:~cti()"
'1"1"> ,r 4'ocll 'f'CdT~1 in lcfpr< l~ l i utl. ~lw,q. chock , et"",,,or .,..( 1'" of d o...ly
e'
rela ted "' '''(l UlU.
T_ 1><M;h d "41'<J.
Th~
~fl(' ~ ."4J " r"'~tn
Ill<: nuJi",1 ..."d
Iir"
,te ~
vi a" O l " rea rra n gflll en , IF.'lU~lio u. ~.70

~ha, ~ S11~ . 0 t",n 'M y can ... ,1 illu"!",,,
18.741
<I~n,ly.
Ii\;< ' he FLN ' lep in
IIn~ <:ka~3Jl<'<
(Eq " ahOfl'l 8 4 ~
~ ..\O_ R5 J -~.54)
1 )ff~ tt ' I\ il t he
en t w pi c unr~ .", ~ b il; l~ of . ea flon ~f\1 e l1 \ l , lh e, e J i,<wnic , lNIk ai

;OL"
ylIJ . KJn" with dlll r~ a nd Ilnl"'ircd d cctr on at 1l 0nad i;lOXfl' aJld
adj="1 . it respeo;:ti. 'cly (Radom r ' 01, 1984), "" n M fcm ~, lo . hl ~' more ~tablc
than 'heir pl
'" A. di..""""d in So"' io n ~.2 I:Eq uatio n ~ 19l tlJcir t" hifi..
tie' can be ..."
1<'<1 from 1M in n ~n,l n<utr al -bon d-di ' lIOC"u io ll ~ .... gie'l n a ble
A.)). T" dlo te. iIll ~" "" ",,c i< consi' trnt ", i. h ,,,,-,b ... .. <l'..i.... i" COn" o, 1 to"
conccrte<l. ......
(T urcoek .1 al. t 'M I>.; !orrin!",," ,., " I.
For lbe hy d 'o ~ 11 T ~ " rr" " gomcnl tlI .n uw .... uralcd fu n<-1 \(>n a h l)' 01 Eq u at io n
K70, l he duvall" Or a ll al iphlic e- H "' ....1 in Ih< hyu ""c. rbon ,IUlin remo te
(,,,m , he d,argc ; j l ~ le qu;r.. - 4.3 eV IMeM Llltn ~nd Golden 1 9 ~ 2) . I " ..,'c. e[.
,hi, i; mol" th~ll balto Dl'l tol lo"",n~ ~n O -H h' l1l d in Ihe iOtlil>t\l l "'",""
l<l ",Ie",c _ 4 ,6 . V. [11 al rmCIIl t he !lU, valu.. lo r 2h ".. "",,~ ' M"d
co u lll crp a rt ,tiM" nic radical io n a re 6, ~ and 6. e ll (l:::qull ti on 8.2). (':kI.~,-; n 8
...cond bond p rodu<;t1. an OF ' " ",d Ue l. fol' which ra d.i<:al " obi li:r.ari<>n 'I I wen
~ 'h~ rjIC .ra biliz<lb o n i~ im""tta nl for Iea,t ;"" /a~"r.. b iljl ) ; T 8b1e K.' 31PIn
' 'l<!
1..";",,
1m "
,I.
i a "" r~ fU. ' hI:': 1)'["'" 0110111. T he pmdl>ct ot b<j.... I)'-'t1 $..70 ;. !,~ e rnn ~n " c
, " bJ liZll'<l (l l , - CR YH ' _ 'C H , - c HR- Y ' J<>II ur><1 a n un,atur a ted
o",," ul Y'(; H -r-cu, wit h ch...rgc ~ lw ' i Ol' ; chn,~e mit rati<lLl 10 f01m the COWl
Ic'p"'l Y'CIl- CH, - io n c:w ",",,11' ,n romp<l ilio n. with ilhu"d~Il .'" l:u ,'", ucd
' .K _ . " ",,_._
'"
by S l c.crISmI ~ il. ule. The [10 ,'~ I""" or th e CM_I",ndiDi. " ,utml, " '"" ~ ,,,, .t
rhAli ~I>o>c of the . -d e"
r rodllClS; e.a.. in E qu ~t
~ , ~ (h. (' , Il , n X ' H, J>fo dum CH , - ("(CII ,J OH -' and CU,CO ' h"ve 110 _ ~6 and 7.D cV. re
. pn..'1 ' '''ly. How"" . Chew Me more thon " fllIt'1 Dy , !Ie m Ul;h-Io"" , t" llll h.-,~ d
,li"""""all"'" energy it! "" """ I C. IJ, LOCH, of 1.3 .\; '0 pnc'<l ~ C,H. j
CH, - (",(: H , \OA yo"''' ' 1 4 ,\I 10 ",od u, e C.A. t 'l"OCH, .
Slul, il;"," '''' vl lhe Me" tra l e1ll' """ play a role. al'!Irn,~ i k "" imporuo'"
or'" For ' ."mllk. 4 hydro ,y.4......,lll.J[-2--J1C'nl~no n. fo"'''' (hl ,," tion 8 i ~)
( -, A. O Imiz ~ Rl i ~ 1w,~ 3hund .ncc ~ D -I <&b<I i n ~ (Henn. herg 1'J' ~ 2I l1h~ "" th~ l
'"Ill'
i,'"
, h...-se ' CleMi" " ,, [avond . de-<pi le lite fnet tht .....1 h~I1I ,earr" n!:"ltL.." 1'",.
J ue,.. the "",m. C l l , - CI(:H , 1 0 1-1 ' ;,,~ by ella,.,., """. ..lian; r", the ",,"' ra[
,peeiel ~ H",.cet onel _ AH,b""I".,. ....oJI _ - UA eV /""'" " I..~ r lj\1 a liQn; ~ , 1.
~. [~. ~.1 71.
1I . ,Ir" gc~ m i ~, a fl<>n lo a . ~ (u ra t .<1 fun<:ri<>tUlhl)' IL:ll u ~hcm ~ ,n) "'m . \" ,
(" ,," a m" "'' l.l b[. d iit ~n ", <.d;c.~1 inn; tbr \>ond -di.."",i~\~~ c n<'[;)" wr t ~
" ~ve,>c [..,I;1;" n ,,( " " "kohol. DI.RIH10 , H) - 4." ~V. is ~cn", [[y [3'-10"' llulu
F-f't .. 5.~ c\' .
t hal lur . h'"'~''' but Ie" 'han th'lI fo< ~n ~";d. DI J(IUU j{. O '
Howc,,,r. wtthool the "" ~ llL ' al i ,, n I" ,toe Y grc up bl:aritlg tl ''''''~~ S. d hydoot""" , ub,.quem cLoYM~'" "I thai C v ' n b" "J i' layo1't'd. Thi< IMds 10
YH,- /~"", ~e Tc[cnri('ln,l ,>r 'I("A".' (.harge m;r 'a unn) p"odu~t'; til . I"ur , 8'"
al' o r..""ed in cyclic compound di ' ''' i" t;., n' (1 abtr lOt HV fl" rJ UL1< ,,'ef> U
HC!. U ,O. CH ,O H, n" d H jS ha' bigh ;M iI. tiDli
1I2.i. 12.6, 1O.'I. lIIId
\lB . r"l"" 1i ..,[: ~ ... (hat fiva 0' , ; , ...,,, rnl:'<' J -, ing fonlll l"," " Ill>:: (e H , ). ,
ch ., ~ c -m ig to l ' '' n ,,"'d uel l" - ~ or 4) i!; fJ'()~ if fin ~ d " , ~' e ~~ . .. tbe eM,..'r<>lldi.. jI. <Y'["J" " I'''-''" ' ('If C)'ct cb u l~ne ~ ' j<>,.... ..., .I<. l lE _ 9.'1 C\" T he: mo,..,
' l>ectru", .,r " ulanol _.hn.. ~ ""Iui'file" l " hLln ,Janoet of II>c % .c1.~ VOl'< \If,",,''''1
CH j ~ O II . ne w ~ f~ l I E .. 1.6 c \'. an d 1M - H, O ' - ; <>lktli n ~ Ihe 2.J-<e\'
dllkrm.. ,n I" IF;, ,,", 1,3) i' l!W WIIe""1 in nUll'.,.1 ooDd -<li' ......'~ li o n e,,
lJ( .... C,II , + '(;H , O H:I _ M c\' ~ ... l O ( ~ l [ ,O + c-<. H. _ ~ ,6 "V
Oi""lCl.tion wilh """fto ' e1c" tiun i' p<ln ihlt unde' I I"'C,,,1 CI.n<!i(]Qe.S:
110<-'()(H , <.1 ~ CO, +'("H , ('l~ H IJ"rloli lO a ul. l q ~ ,l ) yield, t~ "PC"-
.,"'.1';. ..
ft"'.e"
".
trum', b~"" r><ak. a. m(co,) _ ru c\', Ch aT~" rdcnli ')Jl I" form Lhe HY '
plu d" . ! ' ho "ld b<: "ntHor.hle ror RC1 ' -. 110" , ROR"
ROIJ ", or
asu- -. Il , S - ol lhe hl~h ne LLl,a] Hi o'ol"e' "ft~rmduct.. RSR ' --.
RSH ' - , twuld be m" ," fa ,'ombl. ; ,.-C ,ll j jSCH , - yi<ld, (hid.. 100".;
Cll , S' CA, ) 35', ~ lI s cn , ' , neulral 1E _9.4 .V, and 55:\ ~ C, H l u .
1I ' (E , . r . C ,H , 1 _ ~ _ 5 c ~ _ No l.
t hat t h.", O F ' ,"urrange moll! p roduc "
on . " ~"n undergo fun hc' d" ;oc;ull,,n; from n-C , Jljj SCIl , '- the third
m"'~' ab uml"nt (5 0~,;) fr" llm<n l lu n i' C , H o ' . p","uffi " bly by C,H . I","
from C, I l ,,"', Ab o n-C , llll SC, Il , -- ,how; <".u,,, us [orlh", melh yl I,,", yi<kl, lll< 45 ~'; AS' - e H , pcal:. Althou gh Ihe
reM' ~ngc:m .n l U J , C ll , C ll, Nil , " _ e l l , C jJ , C I I,N - U, is JeSI exotherm;c
lhall CH ,CH , CH, O H- '-CH,C H,CH, O+ H, fE" of ,, 0,4 e V and - 0,9 eV,
r"'rx.:,,~i.c1y~ (M _ NH , J' ;, TI cgligihl" bcca">;c d Ihc high h'lcwlYli'-'"I'on<.1
di, . ocial ioll .n.rgy (2.9 . V, n 1.0 . V for JI ,O - -Ill loti... 10 that
101' the ~ m,,~~ lIy j'~"' o, ~ b lc x - , k ~ va ~ e rea, lion; I l(C H , N H ., ) = 6.1 cV
" . 1I'I ' CH , OH I - ~. ~ C V (W"s<.IcHLi"li , . J " I. InSI
bot.",""
..
n, ~,, ~,,' i
" ~ ""(llIIf~ I>U'~',', T he llnp "i, e ~ electron nf the OF'
pm,l"cl
inn prnd " ced by ,urr ~nge m e n l can also induce a fnrlh" rearrangement. For
example, thi' i' p,,,, iblo in the onoli, DE" ions produced fro m alkanones
Ir ,!,,",; ,,"
R . 7~) .
<;,,"11 """ ",ce Ll t ;,e" , e" m ,%'CmcTI I, e,m "I,,, "ecur ror
,-
II
f 8. 7 ~1
'" "
~~ <T~n~od
EE' io n, (Eq uation 4.4<) ), ' uch os those fro m , arbonalo,
r.. H ,()(X) f)(' , H .,
: , II ,0 1]1'0"
.... r., H , OC \O H 1,
("~!.,
.... HO eJO H" ' ) ~n<! ph",ph" tc, (~-IJ .
JU O). r+ t.
f".,
P"....... i~' ...""1 rt'''"''~I1''''''''''' N, ~ c I n. t t he [1C< Lcnd ... 10

lh"
form, tlou ",I 8n O E+' ion b~' de . v . ~ ~ f two bo nd' in . ~ OF.
1'1W'U""'" ,., ~ ~ i reond. "" 1><,,.,..... I nc !""<enli.11 p<oducr<. A
,el l , a n,oem."1[I,a l i' inler na l to ,, ~ o of [he p roduct, d<>e' ~ ot count a, bond
tlc"''''d. .....-t- a. , H ~.ll" ,.'1.'" by ",-dca ,'a~ k"", "f R from R---CH,CH ,eH (110.) 1(+ I<>mt,nt (;1l , --C Il C n ---CnCX---O +1I (l:qlt.1ti"" g, ~j or lhe
.. " "
"
., .""
195
1h1'elhn ld fMT\1a l;nn r1f , he more-sta ble RCH -- :;H " i""'''''' fro'" IC CH ,:>I~ '
[Eq uQ1io n
t hr'l o~h Q "d j, p1 acement ,u ct j",," (s.,;, j" " 8.11). Suclt a
s.n ,
.<
(K 71)
"~Tun~em en l
Iho, efk<., . an i...,"'en...' i" n..r ....... o f ' he prod uct'>. i' ''' ~' mg
ns bld bjli l}' bur ~ompromlllnll Lt. dl>u"'~,iz;LllOD of ' h. "' iiJnal m<>l""","',
, t, ,,,,lun:; .~ Ien .h. ,,,,,,,er;,;1.(""'" of Ihi. l) P: ~ .. d i"'........:J uuder " Ran.:k>m
RunnlJ~."'. u,,
nl Ih..., oj or thil s.-1l" 'L
Tkrrr MNd_
' d~lI ..d. , \> "t.,.:n N jor , ~, l ; , c.....pvund dto:"mp:':l;,i" no, lt~d 1 l>
~." f.ar'fa, ~. , ,,",, ' . ..., .~ , .. ,hi' d b-"U<l h. ~ltld ~n ;"' ~" ul 1.1::' p<od llCI
;<>n (Equ.- ll"'" ~, 71-8 , 1); EE ' prW'M. ".nn,-d d,,-. 0"'l'" "f '''''' bonJ foll" ...J l>}' 'C<il.l1a=rnenl 111t, m ulling l L - "'" * ij! be d ilc .. ....:1 hcJeovl"l
It,
cw.-
>.i<: aulp!<> i" .... "" ..... r " .. .,1l.O'ueu' vi ''''0 l), d l O\llOI> aWJn. "' ~kLo.llerly +
1." Eq" . tio n 4.4611(> I"" Mm , 1'1".......,..., 1'h;" i. uod'" l r", Ch,I lQClenZlflll f" DC{i"" " IoI;"" <-.>nlAiui" $ , "".., "r "'Ore h,..reroa ,o ms. ' lO ch a' e"1O' "
~~'O
bonu "", 41l1id"", ...u.....,.. p bo,pl'"ll al''' ~ nd pllo" ' ~ a' co; Ill<: I'l'I3 U lpe~ r", m of
is<J.C,H ,OCO C , H , . h" .... ~~.; 1M - (\ H.l" and IS% 1M - C,HoI" ' (0..0
i""-<::, lI oU I,Oil 105M ( , 11,. 1<> y,e)d ,~~c~ H /"O H, ' , ",.:, ~ 1~ R .~rr~n~in!
l ...., H "w,,,,, uf K'OCOK .. r......,,-.l bc1;.. ~ ... 01Ill "" on J n, e 11 ~ M i z a l k> 1l of
loc l>rt.... ~d H ( J - C K _O ' H o+ H O ' ~ CP; _ OH , The he r OI O ~ I Ml\ . nu y he
..t.... ratro Ianh<r, C H. ("Ht O H f{ ' HIC H . i(:I-OICH,C. H. " ~~ ld' un jnt~ nl~
1 55~:J ~ I,,, 1M _ C. H, )' ' l r ",i, JlIIlll
!\ l h rec- bund ck-ov" o>:<' ""n il H ,u , u nil",,,,,m ;n , ycli, en"'pound< lI: qUJ tio". 8 6J- R114) yiclok r~ ....... Jl C<..... l~hit;"'J RH ('= CII ( R'- \ - ;0 \11. lhe ,~
can also ","ul1 frOll' ... . nan~rm<'nl "I I""" H alom.\., b LJ I l"""" ,"" l"""fc"",, d ill
d,IIrT...I di,ect i",," 1<> lhe orpo!oi lr rrnduclO . T h", !Il<: cnu n ter pArt p r odu ct io n
o
from IlC H, CH,CR
<:JIn he farm<d by inilial H !nm,I. , r",m ~ VJ ,iOI)'
01 ";1...
merhyl ....e' " F ' l,,,,rio" R .7~, Ihi. T"~cli"n i, ""luully " oer,,1 rcr
,1'""".,,,
Y".
=",
..
' _
on ....... ,. . . ....," "
<1e<l.K"i,,!" , Ir""lun,; ' ;'1<0 lhe product mdu~ ' he tu t:>,! i t Ll ~ n " no lMe ca, .~ .. , I~ ,
'" the funC1 ionali (~' [th o ,'. H ,'ca,nn~.nl ind.. ~\~, 111<= in mes-P""l,i<.>1l j
Th ". In >,,Ih m, u b, \,lu'M n lC(h~l ~'hr",a(c " th. l ar ~. OIl: ~ 7 pea l rt q"uOl: 3 1.\)
r,mn .1-11 or .-H ll~ n>fcr ,n I' quatiol1 ~ . 7~ (ni" h.NIl",..... <I ~j. 19101,
K" ,11 ,md Spil"l!c' 1'!6'11 n oe RHC- C H CR'=Y prod ucl "ao al,,' I,..
lormed b~ " third bond <:k. ' ago n" l in"ol"I"1 H , e. "" nllL..ncnt IEqllot i" n
'''i"",
,<
'--
"I
"" .~
"
.,. ~
,
00
(8.791
~ _N, In [ '1,,_hOll S,Y the ~rodu~ il ell, C HCH -" C H<:X- O+ H. an U '
;011 "" Ih . ....l11i"nn l ,", ,,nance Ila t>lli,.;1tilm
An unu. u.,l ", ample
!.,i pk.H ","frangeme nt i, iJln",,, '" F' I""';'''' 8.&0
"f.
(Ahh" n <1 "I, 1979).
"
.,
HJ.b.'Ji ~n I" biliry . Tho firM <lOp <Of . r.di"al likc ,,,a,, a n~. , ...nl m rn " (he , ile
nf the "or . i!"Cd eltron. T hu' ~,abolll"{jon of Ih< ",, *I~ r" m ",d ra dical ' ile
all'ee!> 1M en. 'l!~ " f , h ~ m te rmedi ate ~ ,,(\ lllllllCOC<" <be ow , ~1 1 comp.;lili' e"e",
of II><; "'"'''" ng..''''. ''l. Radi<; oJ-likc M;'dr" l\fll t",mok... Im m ' ~l~ra l~d "al b~n
" tes '" r........... "" '". "al " ,," Ofe usud ~' e. ... tho"";., ' n." 'erthd c,,, It":,,, c~il.l
both "'oer&.\' cnn"l"aint' dllc I" n",,, ,c~li~, ble ~mneIilali on ba, rie ll a ~d n ",'c
","', !Taint> duo 10 Io'i uf In.''' rQ(or> ;o .he Ira",i ti" n , t" le. Th.... e<:>nolf 4,n"
. ... ,el'.u d if the C -H b ~ nd b",,' en ; n", ~lI l has a 10.... dim,,-i ;diou e"el ~l ,
...h , ~ h , ~ n al, o It"d h.' hi~ h l ~ , ~r", rea,m nll.m enn , r or "" amp'" (Ta ble .. .1~
D,PhCH, - H:I " U. S e V Ie lhl!n O(R - H); thi, p''''' 1OWO 11>< ,ttlLen'lnUl'
,i ~n ; r,""n t h)'J[ ~~cn Irllmlen '" ,.. , o.'-, ub' tilulod . w n",' c" 1'..I.......lIect" Equ a.
tion 4.4 1" . lId ."'" .N, ~ad I() r~n .-mn~cmclll> (ht0 0f h 11!m ition ""te, ,)(
'"
II
unu'<llal ring '""'- In l'q """ on 8.81 ' hI' results in an -H In,UOl\C1II<'(I1 yi<:"" " 1l
II,{ - C H , O H) " ~nd (M _1(,1" f'C"h (MC'l:~' a nd Le"eh 1%1>1 that ate
"''''Y .. ,",(ul fo r identifying iu b<titut""" 8.t l-'",.6 in fa u y-.tcioJ mhyl ... t. ... :"I.... ~_
ho ",,,,,.,.-, tha t lICul ra l-p rod uet >la bila y "'III ai>o facdll"'C H lJ ..... &:" U! IC (}--- HI
is <1.2 eV h'1'/lw..- tba n n , R -H ~ ~'" the hy,l<" .,I_H C" " .1", "",rraa"" ... Iee[;,....y th m,,~ " oo;j, a lal'i.. -rID~ tnu";tlOn . Iate Uiqua"o"" ll. 11. ~ .~2' t>ox;o"...
1l , "" high <tahitil}' oft"'" n:wltinl ,,",!ra t prod uct RCHO r-'" lea n . ugen,ent
(ro " ' a
fu nctim,a!;Iy. a ...-ic:l j' ,of """" ... lal")' """,f i,,,,. ",,, I""', il>lc. Fo r
,h i-< = ,c!i<m h},l ro\1m <\cti.'a tinn i, .Ill"" cau ","" 1>1' jl.roo !'" l oeh a , letn. a m,!IO,
.1 1Ier. and Iri" le{h jh l\'lm y, '" wol' a , h\- d u .;n hc"""h ing and ,,".. ' ..... '<>0
",>Ita"t
lung _nUll" m ;b""alio n< of a ct ; ,<. t"d h)'d"og. " ,1 0 m , can .Ill", ",",ur in com
(!<lun d, wilh ~ Jl- u nwu nu: i n n (l 'q u t i<ln 8.K.l; rurnl'lf'e ...,t h E'I Un jo9 8.91. Of
~" :Il I Dn ~e r -<:harn enou.. (Lied tt e "t aJ. I 'H l ~
In iiI" itm. h \,J",!",~ mignt.li"", " '" o f,,,,, . """mp . n>e<l b~' <I<"l~ a l ... .
arH nb'WIcnts thaI prod "", "''''rJ.ll n"" med ...~, "ad, with ~ h ~ d r()~ ~ n IOh_
f",n , k .- i, ellCrg, u COlII}' fa'Drable {Eq U<lu on 8.8(, \\'",,, e! 01. 1 .Wi ~ \' uioa'
C H oood, til.." 1""",,,,,, acU.lUoo in lhc m un.c " r the . <:<,rr. n!"' menl "'~l" ~ _
".
I ...." . . Moo"an," .., o! "'" .,.....".,,""
a/-RCHO
... ...._,-----...
".
"
'0
"
r
"0
"
II,
11 ""
00
"
~
r.a
"rF
,~
~
0"
(~.&4)
na l ~r.
III th< orj~jn al H , + ion: such d~comp""ition, mo", low

In Ihe absence ()f ad i,'ating r~n et i o n a l group' in EE ion"
pr ~t() n -nc h ange reactioIlS can procwd in iOll-mokcnlc c"mplcxe, (Equation<
8.1 4, g . g~: T.d o ~w "'\ -,
H
.1
CH,
H,
i C,H 7' ~ CH,OH

,~
11
"
!
C ~'\..
ce,!
s,
II
"
ce
1",
\ e,
II
~
ce,
d"
be,
--
"
"
'\",
C,Ho
CH,oH,
~.
ce,-If
h
&"
be,
(8.8' )
'""
D" ...., .......
"'.m. or ''''' f"""",_""
are determined by lhe relalive prolon affinities of the donor ,nd acc<optor sitc",
I'A{C,.H", CH\OH) = 7,~. J.Y cV. Not, (hat lhe compl,(iw di"ociat;on. of
,"ell a I'ml,,"-I"JUlLd j"!Jl'~1 "f(Al:I _ HI" produce AH+ and BH+, who,e mass
,urn equal, "'B + 2. In bi-or mllltifuncti01131 compound, the charg"_hc~ring
group Can activate adjacent C -H bond. for ,peciflc proton transfer
(Zithon.L~Y 1988, Equal,on 8.86).
,,
CH 0
~OCH"
/
CH,o
~
H
CH't:,
'iQCH,
~.
CH,OH
CH,OH
~---,
~~OCH,
70%
CH,OH +
1,10
"V"
"
,"'
..
Sit, ,e""pli,'ity. A, di,cu"ed in S<:diUll K2, hydrogell lran,fer 10 a radial >ile

al a hdcrm,lom or mulliplc bond [orm, " now bond. m"king the ;ite c",,::din"llonally 10>, un,~(uraled, The strength of lhi, new bond I{ Y I H i, thu, a
m.a;" ..e of lhe ,ile recepli I'!ty. Thi, fa"Or> " tramle, lhat incr.a.,", lho "oordinaliun n<Jmber al ele"lronegalive "10m,; lhc homc'lylic bond di""ci"tiun
energie, of Table .'\.,3 ,how RC~N+ Il > RIo"
It> R(iJO)C-O- u,
R{ROIC-O~
;>
RiH)O+
;>
R,C-O+
RO-
RH,N' -H > R,O'-H > R,HN' -H > R(HJ~'-H, ~.~ eV --+ ,J.~ c\'.
Thll3 transfer> to all of the", ,ites musl be considered [or mo,t 'lerically allowed
H at'HTl<, ,ill"O D(al'yl_H) - 4,0 _ 4.3 o\'.
Ions po:.Js,es\ing enough energy to decomp",e Can al&~ undergo re,'ersible
hydrog<Jl migralions Ix:lw""n two or mo,,' l'<"<plo" ;it<" thi:; require, thai the
onergy barrier to the h}'drogen lr"",fer be lower lillIn Ihc ~'[ili"al ~=,~~ for Ih"
decomposition, For example. Jong-ohain ,,-alkanob; and cycloalkanol, [oydohonnol and I~Tgcr ring,) undcrgo h}'dmgen c>chan~ bel""ee" 1100 hydroA)'l
group and tbe hydl'Oc:ll'bon moiety be[O[. lo,ing W"leI (Ward and William,
196~: Turecek el ai, 1981; Bulovil> and Budlikicwin 1~~JI, Under fayorable ,leric """dilion, Ihe high hydrogen .Jli"ily o[ uAygen-"omaininl\ J'WlClional group' c"n induce unu,u"l byrJrogcn-lmmli:r coaelium, Fur eumplc.
()-hydrogen lmnslel' is opemlive in the dimination of i,obulene [rom ex,"",,,-!b~lyla(lamanl,mnnc, which prou:cd, through a ""e,,-rnember<d lfatlSition
slate (Lightner and Wijekoon 1985, Equation g,87): notc lh"t no ulbel' compoli.
rive h}'drogen tmnsrel" are possible. bcc~UMO of the m<>l""u!<:', rigid geometry
Tho enJoi,,,,nec I,,,,,, only c.. n o'
(M - C,H,!,"
100%
(S,871
Hydrogon-lransl"T mechanism, can be more complicated in mUfli[unClional
M -, io", in which the ch"r~e and radical re,idc at the fundinnalil)' of Ihc Inwe"
i""i/alioTl o"crn; b~,n"r"l1y Ini, will niJl be Ihe ,ite of higheSI D[RY' tll
val~e. The competition foc h~drogcn lhcn depend, on the rdalive pro Ion affinilies of the J'lInctional ~roups (Equation 8.88'1, Table .'1..3 slw""" that, [01' common
fLJHeli",,"1 group" Ibn,,' "r nilmg"" ,nn\Lld n"w be Ino 01'''1 1'I'<>'1>1i,,, ;il"',
followed by sBUm- and ox}'g,n-contaioing one," addilion of all amino niHogen
~l any of ,""eral t"""io'" ill >!-C..H,()H ' ' n",,,ly .li111I11"I., ils lal'l;e(M
H ,ot'
('""ducl. In Equalio" K~I the ground.'lale molecular iLl" ,hLluld oLlnlfl"\ lhe
chact'c in lOC "",mali" ring: IF.fa.1kyllx:menc,),, IF(moth~'1 este"}. H,'wev"r.
lb, ch~rged al<)rnale can [unc1iM a, " 'I'Mg add (L.ewi; I ~Mb). indu"ing p"OlOn
..' \
.. ... ,
l~
CU
I 1,
( U ~)
t.-lJ
tr~ ,, >Je J
frem
"';m;""'i
Hyd~
'h~
bcIuy Jic J><l" iha n a nlo the b~, ic e, l"
r ",~lh~ ....l.
~",u p. ..hkh i n i ll ~ te,
the
n. lra...ltr rMction, ~~n C ",~, ,...~.." ~, O E <-- i<>Q~ f(>I""'d by ""-i",,iz~lj"n. " hich fonn~i1}' ~ o nol contam cwrdl""li.... ~ll) u" ~tu ra'N [.~<plor.
For ",,,ml' 1<> IF i~ u~ 808), tile tern" .., 1 ..o pr<>pyt g.oup. or 2.m" thyln" nam,
and I, J-dim et h ~' l - oc t,m " ., ~ ci<:ao1y indic/lIN Ii, the importanl (M - C , n .l<-'"n,; the 3-m.th yl ~ lV wp of Ih" l. tlC! CO"'I'",md giye, the le 5 ~ lmpwl;ml
[M - C , 1-1 ,, )" . T hi> h ~d",t''''' lI~n.r<r !>ttl''-';>;'' \...0 rorm" Hy ""h .. ~ l<.>.l p.lJh ;"
",ado po.sibl" on 311 lO1I m~ k ~'U k m mpJex Wllh iUl el"",t!"aIM ~ nI ", 1 C- C
'"
bond IWendcl bool: ... "/ .
I~. roaoptor
""rl
1 ' ~ U l h ~l
W<l ".li,, ~ ~.~n
,e nto>-. ' coo rd;" alw nl l rl !ur.t;on from

T heor etical calculatillJJ$ for CH , ~. !rom
~~
-J,"
H'0>
1 WiC
,
1889)
acetone" sh o w t ho.( in k,w -<:ne'I!Y. Silllple cl<..1' -d l:" rkcom po , itin n,,-
I.~ c
""(i,,,,
" nd r." Ii,-. I rr ~~1f"",l> Uo " <>l. """""'ariJr Uy . "' ~, In lh. direction of the or;~in,l
/J' bo nd, bUI ra lh<or ca n olip .J""1lC;o.... "l l~ , . be i ,, ~ bo~ ud by jOll-dip ll~ ; n tetl ~.
tiDl); thl:l Ul..I........ I ~ prubBl>Hity for h ~ d lQ ~ Oll tr" n, kr (Heimich " , <J1. ( ') p,g ~
!It""H.. ;/Iu hi 01': , - ,.....""'Ii~ m. ~ t> .
,ura lllcln....o ....,. e dio;ru"ed in Section
L"" ~
"';&"11;'" '' ;"'li.ted at
radi~,j
Ilere c>d ., n, ;olll effect. <In II ... _

il, ",,-;"'w i1 l'ecommmded I n ! u_
M ~ Jl )
~_ , ;
site, (,. dleallike
f<.Il f<~n""",cn"'l
"'......
6-;> ~ ,. :l-_ mh.:" ,d lram iliUll .lale" but 4-mon,bcrcd 0.... 8'" renerall, en..fuvor. d (Wf i' kt and Schwan, In3). The ].,n"",bered lr1l Dloi!ion <tat (12", igmlLO"') 'c.u ll in hll h. r-cnerg}' proces..... hill ",,"""Ily r..,n ro oyer Iho, e
pr(l<;e. ding ' n"'ugh \~, ~ o=r , ill ~ " The hlgher cno'!'t' U~ Te<l" ire<! r{IT radical_
l i ~ e Ll-Il mig, alion. t><:"w ... ""c da.1.ttu, musT be Ill_ " in ~ n anlihonding
",bital in 111 . t,~n,; ,'"n " .1~ I hIS b.uTicr ""n he l" ",.",d ii l l\c~ i. a n electron"'; lndmw ing 1'.""''' d ,,>t hI Ihe mip~ti"" s.il. 10 dinllni. h lh. ~1a:1 t()~ d~'n>ily
i~
the tr an, ition . laI c ( M "" ,J, ~ , <I ../. 1 'Ji9 4~

U.ocmll r 1.l -migr3' ''''''' MOl \ -':1] '. cil<: in F E ' ion. (, at ion-llke lu rr ang<:mcnl'~ St<:ric ' '''l"""men.. . rc lllwch lc.. ror II "," rran~.TI'Ie'" In... ", ~l1
bound oornrh:~"", but ll",,, f' '''ll ~ t io n is layored by tow int..nJI M~ oud
I"n! ~m li'".iJtlM. rho ).1m.: i , l r" o or I ~T gcr po , i ti Y e l ~ ' !w' 'lN , .o w ~
, - 0 11: - _ UO HI, " - CH OH ' ) who"" hm~-u i" a l\"" ",ujl,tAlions .:><Xl)1 in
lon -mul,,"uic ",,,,,plcxc, ,Section 8.1~ th. .. "lien """, II in nonspecir" ht .... <'lI\'n
c "'....ngc between th. oountCTp. Tt~ ' "~ .mok,,,~le .:omple.. .. ....e h. l", L"S 0l!lc,
It) ion -d 'p<>!e or ion-mduad dil"'k' IOI ~ .. h"'h ~ '" ,..",1 II..... " Jl,ular d~m
i<;~l bv ~ "';, a l high imcr1l.'lJ CllCf ~"'" ' h"
a p,"y d l" OOllIO, <,l,mini,hi~~ lh. i, ~ompcllti "l"''' in fut (!<In f(>lu'<l ,L"''''''I''''; LKm, """""M ill lb.
n", mal ( ~_ I ' " e ll Ina" >v<ct,a
1'''''''''-
"'''''ple.... .
L n,~ r ""'1...../, rf/m... " how.. in Figure 7.7 lor alkllIlun. bighe r homologl
, ho w a h~bcr .eb..,." a bond. na' of J~ .. ""e' g) M [fTO III T.<1""i"" \he 1'1 1
"hokn "..d lb lle, t (H <."Un ( _; ,hi< can II( viewed as a <,l <i',l c ", - u f'(,,,,, d. ,,, ,~
dT<:d l"'~''''~;''[l. 11\( M ~ lifelim e b~' red ucm~ Lh ~ "",babibl)' of e"""l:J flo..
into ' M . ibral,(l" . J ",fH1e. in.ol"cd in ,im pk"" l e k '. ~' <1....,"' p ooitio as . lbi.
inc.le,,- t I" . ..... rllY M ~' pro ba bih, y C:In . iin,frC)DII) b.u. lo->..."""" l re....8n!:" ' '''''' . ' " 7O-cV ' f'"OU:I 01 large nlO.Jeoulu, l l>c <J"ubk'-b}"dcogUl .c-
~n ~ "I"""''Il ' ILq" . " <>" 4 411) e"n ~i "e ' ;S".n.:..n, j)U~1 for compound, "," h no,
c.,.. ""'ere"" om 011 the c l ~a\'l'R' j (CHI,P
()1I ' ""'i, ~~), .. id,Y\("'h ~I ",!C.. (II> R
C H,U,X><:!l ,.' --> R t C, " ,O, ' , "'.'J. 7~t Tho ehm,nah"n l of .... a..... m d.h.
yk:n<: from IJrllt:r ~I kan itl; . ..n ~;,., n "" '" "hunda 'lt PCOO;l(1 ion< nm in the
'pc,I'"
1" ,, 0< hornolop (hd"" 1le,~nall, [qll . ti..... 11'10 . \1 ,*,ol'>on er ai,
I ~70J In t" ~ ''''''''l '~ "r primM)' " nline, tbe C ., Ho'" ~ abund.tl~ inc'"" ' " ' from
1,,,,,,,,
"r
.... IX r,'r "'" ~ I" ",i" e ' 0 30.\ for d<J<leq l. minc I Fi ~1"C .1. 1 6~ l" i, be<:orno< nwr~
pwm1nOlll at k>..- '*eImn c~," cl' , e, (Bowen """ :l.1""""U 1 'l1l ~~ Thi , '"p5Cud<>-1dCm' ng,;" Ill""I . c:< a mult i;tep " )"<1,,'1"'" . " d ,hleial ,u,"3n g~m<n l , ""u lt j"l
in " n ~'''",I ''~ 111~ ylo mi "" ,tru CWl t ...1", 11 un <kJ~ '>C'" ~.d tHn ~e 11:: ~".tion 8,91;
" "mmen,," " "I. 19R.1 ),
~
.... - H
..,",
"
.''''-,
-"r.s
-,"
t.e
~,
r r"/""-.---.r. / '
'
r. ~,C ~ ==U-I,
If... U
EE ' U>N " um"'l.t""'JU'. "'" mO'lt 1"",lily r""mal EE" lOll> a,. gcncno lly
for t h~lr furt her demmI" "" li, ,,... ;I .",i.ly c>f retho ", or Jug.h Ild,ility.
"-Jfan g~"""'tl ,~tl be rom..,ti!; { M" L. rrcrt~' 1 !il!lJb~ Kt a C1l00> 8.92 1<.> K95 are
TIt".
1 .10 " ......... ~_
..
...
com m.... I~ "",,", ,"od ut 1M u..... l u' ~lUd . it. of lO r, ' lollS. ," uh a. th" .. foImcd
by :Kl.~""g~: . n .nml'lt of 8.94 (Lqllal;M " .....) \Ii~l di l~"'''''', if the un",,,,," ti..,, j. in Ill<:- rir>~ or the ' c. tr; mgcm""t If. n~uon ,ute. the 'i ng n.. <l~ ,0 he ,ix-"",n,l>.:red . 0 lh l lh.
do" ~1e bond
~w,,~' f. " m I'" H"c'CCrlor " to (8.\02 _lid 8.9:1). Will! onl,
.. " nile bon d ~t thi, .il. (.~ ,94 .nd ~'~' ), cle. \'. ~" ..r I h j , bond il rr quired (1',......
hl~ j" , .. ' lOOn wilh H rea lT~nll"m.",tl, ~lld a ~.n.'Y co! tr"", it io ll _ $I: ~l>O ring
1< o"" ervud
In ,ome fa . .. , ~ hl " "a'e, lhe,e 1'[:;- k'll ' ''''Ha [] geIllO: DlO clo"" l ~ ,~"",,, bl " lheir
0 1:+' oo"" '~" I"" '"'''' , pe<ir.~ H tr.ooi.... ' h,,' ugh a >i X, ,,,,,, ,,N .ed rin ~ lr"",i lion
M.lt<: (bq ".'I <>Q 8.9 2) j, ( " ..nd for prNo" o'" ,1 cl "~ 1 ao:elo1l, [E qnJ tio n ll. 91a);
8 9 ~ ( h- .r), Po, he, k In<l Dnn n ll In 4l Spo;:itio: 1). 1ra n,!or t, \;C, pl. .. in ("J 1, =
N ' RCH,CH,en ,(:H , with <: ,ll ,n eliminalion (EGualmn Ilo.~ l, "~".i l" "I~Z
and tl" ltl 19'1 1). The r,E' ions ot I:G"allon ~ 9Mb- tl) (R '" H 01" C , H , : R' .
CH , Of C~H ,; llenoil . ml Harriwn l ~ ?b : Loun~ on" Ha m ' Oll 1 ~ ? 7.1 ,M....
"''l'ri. inl!l} 'i mila r bth.<..ior, 1'0111> C , H o 10" invol .ins the tan. b " r
-H, - :!lJ.\ il-H, and _ 50':;: r- H . Thtoze i. per'''....' ''' ...idence lh:o l l ~j. " 00'
,"'I " , ull Ir~m II "'1"~ ..,h1jng in lht (', II. ~"'''D IHim l ~ lhe II-tr.mk '
....'l:u mpan ~'inll C,H. I",. For , .." h ''''ltlMlKemenls ;n OF: """ that invl>I;'e ", ' ur_t<;l!'.,ing "a lUi'; ~ n ..a' e, lh.; a " .l o~ o lllo C , Il . lu;, I,,,,,, Of "'
1""1')1 phon)1 ",her ", ,,b 'tIla/ lOI1! ,how, ~ , ;... il". H-. "'e di,tri b,," oo , B'
.,.JI ""''''.
'lZ\1'
_)if.,.
R"--C, H. + fl V=CttlCH,I,I'1'
(~ .'M)
(1'195\
,""
,. ,
I .., ,,,,., ....._ _ .. .... r.
.,
.,
,,'
18.% )
dl":' C.H. I,,,,, flOm CH,CH jCH, CII , OC.ll,- ""mp.o"'d 10 1..... fm m
CH ,CH , C ll ,CH , O ' " CH , (F'IuKli ull R.94; B~k ie", lCZ ~ I uf. 1 % 1 ~ eve n
the f lo" d.>pIP,"",,<!11 1 ~arrang.ment I [~u.ti"n ~ '17) " r Ih"-...J' ''jd........I ~y ions
r",m ' h ~ 1''''1o ' nil ~1n "r djet h~1 other ............ ..it h h,j'.h ' P"Cilicity.
-,"
A l t llou~h .1buDd~DI pfl KI""'h ~,.o forme<! b~' fO~ '(l M fi ke f:qualion; 4.44
'" A.9J ' ha t "', mall) . " rr elpo.>ud to a fo" r-mcm hcroj-till , lnl..medla tc. tho"e
~ r . .. nf~ '"JKhIc: rrum orbil. I_l y"" "" lr)' <:on,idem" on. f ~ .. h"" k and Bullill
1'174; Wllb"m, J977l am] "~ IL I" ",ff(! "';111 io voh('ll">t"n' rJ lon- molccuk cumr lo,co I Il~m ",n 1 ~~7J, T he ~."Cfll
for E<juation ~.~4 vWt ~ .'1~ ror
"",i"". i ., rul fO f d.du<:jo~ , (ruc! p", II" gI" . 4,4 .,. Unh ",, " 4.7; tJ,, ~ 'lQWlIS
4.20 and 6.2; Buw,," 11
' n kpi u ~ _ ilh lhil profe" nc., fOf roct iUldb l~ ;, m
d<:<oml"',i tlo". U( <<H. # at 11 97 1) r"" " d \ h~l CIl , CD ,l'" H <:H , "pecllically 10'1 C , H . I>, \ b ..... tioo 11 94 ~ bul th" l CH , C f) , CH_ \Ur,. (EQUal' OIl
8.92) "n<1 ( :[) JO ('H , 1- NH ,' " "okr,"c"! ~Ofl\l'~le IliD ><.n mbhng no,he I"",
IIIe\hyl.."" Fo r (" ~'Il"""I",1 ' nn" four i'''mom; C,H ,O ' i"... _bow Ia.." e<lll' \s
orC,H , tv y<c:W ('0 11.,- . For CH,CH,O ' e H, 400 C H, C H , CH - OH '
,hI> k"", >hould tlt due to F.~ ,,~t i o n< ~ . ~ 4 .nd 8. ~. m ~ I; ""IJ; f", (CM,j,e =O H ' aa/ " I'I'rn pria le ,\ ruc tu~ un cl ~<l EQ .... lh>m ~ ~~ Ihto llgh 8.92 pi", "- num.
~ r of "lhe" . l'" r e<ilmf'k R C HR'- S' "'''' tllnt would be lomtM b~ ...
d eQ \"u e in sulfi(\C, n~ un. ... tIle. re..nanging I" R-CIl. '_ SH ' (e. ~_ Eqwllion
~ .77: ~. " ,k Gr....r..rut M ( L;MTell~' 1m ). Tile lorm ation of , he
;,,""1.......
rAlc -cI<' lerm jni ~ g h t.tTO ~'" rC"' '' ~'' !lC m"nt to ""oid f"rm."..... of the hlh.ncrg~ R Ii ' 'pecl. . lll~",'m .,
I ~~41
l otraooni~ 1"'' '1''0 IrA" , fer to ~ oonl, nMio"Ally .. t,,'3I\:fl run~1j"";l1 ~lOUPO
II><> rad lO'iol loileJ Iffi lllonlly ,," cu," ito Eli i<>nl prodnced by CI ( M . L ~ lTc r\ y
1%IlI>. Ha.rilo n I ~M 3j, ome that "",h w.el"'''' h~ ,e II() Analollle:; in the c!le",;,-
f'I'Ck""'"''
)') .1,.
"'''eT
.,1.
tr y nl d""""I , hoil ",,,inn, in , ,,Iulinn. Th;, H ' 'm mf~T <:an ,,,..., Irllm , L:kLd
= rrJng..m..,m ()r lnto..-action, in ion-mol<ru l< c ompla.., For e""rnr/o. Ibc
ubiquitous 10' 5 o j' wilter j', om proto n"ted aMeh)<:\es and ~ Ot<>fl'" r. pn:u:daJ by
hydr<l ll"n Ilr ,I.~"'I ..I ",~rr ..n ~""""n l' Ih. 1 Ir\<"c tlte I" ",id ,o cha,,,,,, iiI. a..ay
Ir0111 the C-O H arollP IFq\l;lIiOn ~.~~~ the .......1y 10......-.:1 ca mn "" "",,,c <MIl. '
U~1 ;" . IU' prt OlU '" in ...Jj""""1 l'" ,;\iu". C
<>' . ",,, ,,,, """.. th.. bast< hyd,myl
uou p (Bo\\ en an d Willii'Oll 1~flI) a. ,,~ .... ~I " ' ' ~ \Io'"lk."" 7 f'f " I 1 9R~,,-h}
AlterM tllely. f/'lTl," ng a" ;" n-m/'llu le C<l"'f'le~ "') .... torolyhc: bon d d,..>ciaIjun. H P: Y _ II H - Y. "'lea.... QI... wo' dina tion <P. ,,' ' h. "" . r<>,1Wnt. ", k,eh MW C.l" 4i'l<IC.lCf a p.....IM f..... m ' h. l(1n'C co u nlerp .on \l'q""tion
8_8 ~\ ~" e, omple, in C, H,O H, tbe 'd.a ya~ to C , H. I H. O ;md IlK ,.
" rra,, ~.nvn' In I<,,,n (', H. f H jO ' _,~ "' .... pcl;' i, . ,n cr "' nl!l' " I i"lr:rn. 1
( Ha m"""_ I ~ kl~ fl, e <1ruc1 uI'3Uy Ilcn iflCMl elim"'at~ 01alla ne mol
<cui., RH illtd R'H from IIi000 l",lf'd alkanon... II-Co 0 H I II
h ~ll lll b'C n llan, fCI .. . ...... ,,,lil\;l ' i ,, ""'I ~ 'o;<lu' OO c,,,,,",,,
(H. , riw n I?l!Jt
.,,"ttt:<
.1<"".
~.
in_",,'
."
"
(S.9~ 1
CH,.=
Ctl ==CH. HP
In "" ,j ' ~m, fm m hi f~ ~ " I;" tl ~ 1 ~u ", pou , ..b " ilh l",""j~ible " elic oon. (,o) i"l<.
I",,' on lI an,lor "" n """~Lr lx lw",'n ro.;CplU' ~ lO ur'. directed b~' Ih.i , r.lill;".
Jl'I0lon ~ffi nl1 i<;, I~. poinlcd mLI [0' 01.:+' ions, Equarjon 8,88. th. , i,o '" highc"H l
O (RY ' H) ,'a)"", will nol be fa,-oledj, For exampl e. in " icrn ul ~m ; "Ml co hoh
1M . mino a",,1 hydlO, yl ~ ro up, " ", in;li.l1)' protonaled jn ,j mila,- proporti on.
by """11>;l1l' (:I , rapid proton transfer can take pi""" Im m R--{) H,' lu II..
JIlO'C ba, i<; R'- NH, gro up to produce a mMe,table CE o ioo (l<Jn~c . ; .ll"
'" " I, 1919) Hm.,,,,,,. " ilh ,uilable steric constraint'. di,,,,,,,i. ti<.>,,,, 110m III.
KO H, ' IlI nOlJon"I]!}' ca n he "", ",voll
F] n~lly . hydroll. n rearrangement can occur in an EE' ion to a ,itc th~ 1 h ,
" ..........
~_
. . ..... ...'"........
""" her a charJ!<' IWr a multiple 00",1 (E'I"" l.io'.. 4.45, ~ ,99, ~nJ ~ . I r, ..... SlIr
........pf" " f in lhi' . ""Iion ao d <_Ie""i"" C'~"' p1., by z.,ho n:z ~y 1 9 ~K 19K91 HY
d imina tion in 4 4~ amI K% p",d uctJ a doable bond in <~"'Ju~~ll on ...\th 0lM' '"
lhe r<"""""r ioo; produ ct 'IIabd ny a Pi'<~" 10 be lbe rna", dr;"in~ I,,,"," i", A9 1,
to al ka ,... "'lrni"ouo rlS from pro ' II"''' I..... l . lur..'1 lHalrison 19A l)
"""log"".
r8, 99)
- 6'
"
IA 100)
R~"oIt>tn """"~t"" (~ 1100 ~i<>n> ~.2, lI,(O~ A I&d of I'U< l.iYC .." n" ", ill
all i"o r~ul11 III hi ~h , rill,al C'IC,,~jfi (0' tbe dis><x....I.i"". ' ha l u.., tol e pI..oox.
and m,,'" ""m""ti li ~e r~le. Ior I.... l"'m\lk plior . Itd ooooo""... n. ""'' ' d gt"",n il , POlenhftl-eMrS)' 'U <fI~1 for ...:h ru"."; cmcnl' bdo~ '0 Tlu: lype
,h own ill FiaUle 7,I(lja); tl...,e mOl" be ",. eta l local ",ioi", .. "' ''<l.-'' p<:InJin~ to
' l..l>le in" ' ''OCI"",. which "," ""r" r~ rc<! 1')0' rrl . I'.dy 1""" isomerinuioo lMr. i" ", (W' Il'"m, 1977; Dowen 1991 ). lho lIiS""'" tile tonJ.;"C}' k" ;uch 00fI(panying r<' ''."~ ~g" nl e \l h, the tc " the proouet ion. ",ill "" chat"""-"fi:dic " r lhe
, ,,,:oj! 'c ,,(( cu rl<lT ' l"yew ' .; h" wcw ' , the f\.."" lting "Iow-rn. .. ion tene<- 1,5 Ii,,,, .1, 21C,ln . ,il1 indicate 1""em l . Irucl llral featu,e,. ~ ""h ~ , a n <illm "'arra nyemenl' " 0... tj'pical N' ,n olecular ion' from hi. h-ioniul liun-eOC1'!\Y m" lcuo h ' ucl>
al'unes. ;no;lu dinp thn'e .u ~ Oli t U l "d wilh h"l"g" n, "y' M, .nd nilro y o " l"' ,
n o.; ,!"-'C L. ,,m "r (CH , 1 ,r~ H , how, a C, H, ' ion, and th. 1of O '::I, FG-':'-' ,F' sh"",.
:I CO, " ion; 1m . ""ak , "" more ahundant, I",,,,",'or, in Ihe >pec t,. of n-<:,. H,.
o.n<1 t't1, Ct1FI , ,.."pccl;-.ly, C ha ;" hra",hi ng and un,at malinn rlca-oaoc."eh
....."T4ml>li ng le"d" ", i", I>u' ,I" nO! noc."arily . liminat. them; ' >e"pcn",-"" ( F'i~_
",. 3.1) yiold, Cl ll,' and C,l l , ' peab lInd pcrfllloml>cnr.cnc )'id d' C F, ' ,
H1J " ,&"" '<"TAm hti n ~ i, "ven mo.. common, Th. ""0 poals in the . peClc. of
m..1 hylc)'cIoh<13n< and Miu.,.,. aT< (M CH,I ' and (\-1 H)' , ro, pecti,'dy.
u' cx\>Ccte<llrom the ,"" chan;, m, ";t.d uhM" }Cl from C"H J ,CD, the pc~ h
IM- m n , l' a"d 1M e l l, D) ' ar. Ia.", III"n (M - C D ,)~ . and from
C, H , C'D . ;iIt _ 11,- i' mo ... a ~uod a nl [huo rM OJ"
In alb ..." 'k"" ' a",JoID hy d lO ~en land halolten) milt""ti" ", ,,<-'Cut in i" n,
'hOI ....~ e no o. hita ls a , aHublo ror H lm",b kg., F'l "ati"", ~ ..W ~.~9 ), P. "li,.I
,..."1co.a~c of a bond 10 th" atom ..1.0= one of its coord in. lion sites fot proton
a b<>l ' ao.1 i"" Irom the alkyl pon ion of Ih. ion. For EE' ;0"" ra pid .xd, ~n !",
1eado"t' to H -r~n<i"mi"",,t"'" ,>U:m, ,ml)' if ''''' pm,'m al1i nilie' of Ihe l.a"ing
. ro up ~nd thRl of tile olofLni<' . oume' p;lft do nOl diffe, by mOle th~n 0.5 eV
(H.t"""n 1 9~ 7) """"" Iu"n lly, ",l"n,i,,, ~ yJ",gcn ",,,han~,, ;" ,>Il ,",,",,,d in pm_
lun" ted eth.mol PAle , H.. H, O) _ 7,0, 1,1, and protonated melhyl i",propyl
et ~ or, PAIC, H" <,H,O H) _ 1.H, 7.~ cV (Eq uation H.H ~ ~ hut nnn< in pmtonatod
dielh}'l OIM' (quati"t' 8.97; PAle ,H . , EIOH) _ 7.0. 8,2 e \'~ or p,o l<ll,ated
am"'''l; P.... (1\ 11 .1 _ 9 ne~' 'Such rea ,,,, n ~ m en,, , including Lquation, 8.9] and
H,'I4. can ~llern"t"'ely pr""eed th ..OU8h inn-mole,,' le comple.., in which lh e
di,,,,dallortnhheC .. ('=Y R. C Y' = C,o rC Y' HR hond,precede< the
hyJroi en-milOlm ion step; lhi. lowe" the 51eric re, trictions a nd J llow, fo, inraction ,,{ di., lant luoui"na litie, (L~uati,,", 8.2 1, 8,22t
Little 01 nc h~'droien " ra mblini is ob,.r, ed for , hort -lived alkane molecular
;"'0> an<1 pr",l<>nalt<! a l ~ an . , (I louncl 0' al. 1977t Th i, i, nO L" t'lL<; h()"",.Of. for
EE ~lk~ 1 ill'"~ IW"lk"rr <l ~l. 1985) nor fOI loug-li.<o.l O E+' alkane ion, (EquariM H..1J. The C. H , . ' ion. form,d by ,hc m i,~ 1 ;oni'a li" n "f n_C.H co undergo
tot~ 1 t.o:rambling ~ri"r to di."oc iation. T hi, pro bably involv es roaclions StIch as
l1ydI ide ~"u"rC! \ 0 lb. ;~l u' ~led ca lion , il' combi".d with !,2-mill]"ati"ns oj
C- Hand C-{: lx,",h, nnal" g\lu' 10 ,,,llllion n;~ rr~ n g " m ~"tl L" ' ( u."an,h~ " a!
1979), 1l0 mtric ~ -oct cn c OE- ' moleeu ," , ions (Borc he" er ai, 1977) of ,ufficient
lnler nal ~" erg~ to decompo>e llndergo i,omerizalion 10 a mi,lure of intorcon_
,e,tiAA ItrUCW"", ",atin 10- 0 " wh",e.. isomeriza tion 0 1 the Jlolldecompo,in~
ions is incomplete in 10-'; ":<Xlnd, Thu" ",di<:"I,ite H. mig", ti"m '.pflC" r to he
facile ill II"''' Il",a\~r~ lod OE" 10 nl. Similarly, 0<:-' ion. from l1 ll<atn .. ted
. 1~'\l hol l and ethe t' und "'80 e~t e",iYe hyd ro~en rearro ugm enl' before 100ing
. l k ~ 1 gt(lui'" IIl" Ll"" " u, . t .. 1. 19~ 4; M"I "n ur_ L~ng""old " al. J 9~ 8t
E" mp ftJ . The ma ss , pe~tr um "". butan oic aci d. firl l Itudio:d hy Happ and
~"''''arl ( t 9 52), ", ill he 11",<1 hl illu' tralc tho multiplici ly of wmpe ting reaction
~.thw~ ys rossible fN even " si", pl. mol.cul" c jon . TN large' ! I"'" k, . i>< ,,'e m,i,
27 ate due to the 1= nfe t h ~ len ~ li m ,;,. ) and of methyl (2 ~~ ~) : a lthongh the
r'>rmcr to Il><:trno<:" cmk.oll}' tavore<1, lhe pathw ay, yielding th~ latte< are OOnl plu ( I" I" o, ion 8 101; M'<,A rloo ~' lil. 197~ ). A f" vnmhk: i><md c k:"" ~b'C i, ,",'"il
al'>lc rilC The inle""edioto from t l>< 1.5-lJ , hUI "",t Iho I,.f-I L ,ran, fer; by 1,1-11
, hill the l. n er yield. the I!oble one- I,I-<liol iOll. whioh finally Jose, tlI~ terminol
.....~ ~ ~ I ~~ " f" t" .. k: "'fm ini ~ g 1) _H ,h il"! (M c!l.d'Ml Knd Hud"'M' 19f'.!il. For
lowe"cr~" lon~..ll>ed ion.. ~ 1 .2-mi ~ratioI' of t l>< protonatod "llbo x~l ~,oop
" n,1 (u"~cr 1-2. a",1 IA..H mi~"di",,,, clT,:rti "d~' ..,,,-mn~c ....rhl" pmit;", ..
2- .r.d "- a nd. [0 a 1"' 0<1" euen t. C -l lhrou ~h C -4 h)<lm~o>. alw ,,;nmbJin<:
I ~~ h.,I"'8"n, in Ihe C i t, --<:(0 11)," product ( McAd<>o et ,..'. I" ~ ~~ S<A:h
h f'<l ro ~n ~ ~ fra ni""""' T' t<...... II ) ,
.I~ ~'I I"",." fmm ,,'o i,ox! <:a<l" ,... lic
l1Ci.:lq !l.u ~ie r d al ' ~ "-l : W~I<~e a ~ d .!>eh,.,", 1 98 ~ ~ ~'icld Lnl:: m(lfl: ' l. bk pa ll!,,<'t ions Iha t a re of\eu uxM fOI de<lUCilll .trll<1un;, . uct> ..., Eq ..al;o n KlS.
11.....ow . , , he .",li",,1 ,; ,e ...-cah:<! ""n inil<alC .. c<>ft,p.:tlli\", . kelctal [""rra ap:ment prod ucing 3 It ~ ble U ~ io l ion {Eq" ",l' ''' 8,102, " uti "--..- ~ ", I Su",,; l'l IU,
Wellkt an d Sdl1';arz l ~i>~ A " mda r r<:.1rntft""""nl in io~i.r<'<l J ~h1Ibu ta ....1
"_,,,Ie
,,,
yield. 42':~ I:M - (;, H. )' at 70 ~ \' . bul This il ll1 . b o.K pc . k <>1 ' he "f"'Clru m at
11.V (M:~ccoll and M ' \l1e" I ~~~).
'
.. ~~
+.
'/
C>i.- {
CoH<
-'"
u
"'Y"'''
. A!
H, C
~~
y-
_ _
GH,
+
..
. .""
(" 101)
...."'. "' .
..
~~
,
,-"
an
~.,,,."'-
H,C/------' 0
--
y-rH
U <:]
- , .
l:Jl

~'"
,
r- ,
r-, ..;
r(
CH,=CH,
\~
..
"..
,c'
(K
Unk""". S. , .
',;,:,
'"'
es ea
au
"sa ",""
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c.nm pk-. " ct< ltivcn . ;"I ~' In whic h thc "'N" p,,,, n ..
of a Hrenn angemenl ...A. 1Ilq:dy due tn pro duct IUtbihty, S;""" ' '''' " reh fur the
1" "''''' loCne' llY p:>l.h lal c. mnr<' time fm ":"",, n~"" l' th;,,, fnr l1mpl. bond
c1u '> , GS. ..... ... crf. d' me abo cril k;U, U '" """.." Iry oxum ple, ill Se..1 ,QP 8 3.
In \ ln1 """"n K) 'h e Flo, ' , ,,,,-rra,,,,,menl ,-=.H." ,!\' O - .... C. H.N ""OlIId
hnc ~ n "n lm po n anl indKal<.r "f hJ <I"'xyl in a In ial lInkn"",n. ... fIIII;l..
R"~ch(ln <;Kll Kiel in .l"cidatin~ t'n ~ _ n S,10. whid , ;,. I n ~,,,,,,in" ""id i"'lJ led
f, om " n,(\uul 100 m,'" "" . he "thyl ..t ,
8.11 0tMt '_ '""'i!emenls
u..pta""",cnt
iJ
,"--\
,.
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0
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.'. 0
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i, ~ . I t )
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Fb ", ina\ ~", :
..,
'I')
>- - ,
>~
"
'\: j
"/'-.
...
/S,Iil6j
8o.;au, uch a ...i& ra ",. <>f in tern al eI", r~, I:. 15 e \' ) is. dep""" C(l ln mo!ecu,
1, ,,,, t" n nc'<l by 70-. '0' ~ ron ionizati on. " Il"'''. di, -enitJ ' T'u rr anllCment
reactio n '" ,'..... , ed. A. " ~.l1eral ruk . the nonhyd'n ~n rea rra njlel1J<II\' """
u""ful '<>l ded ,,,, in~ ,t ruc lurc "t "u k""., .. 'l'tt'nl only if lho '(lCclra lor "'_I~
,,:...ted <:<l1\\p<lUOOS a", a v all ~ ble: lbc ; n .e r rre l~ f Inull be on gtUlNl dl:di"
dra "Jnl: "' ''' l.:lM1 i<l g oon d u";"lI'llf""" ion plod uct. " f , uch rC<\C\i<J.... M ~n)' of
I~r
,....
_-_.... ..... ..
,' ""',
hesol' a ~ " "P' in "nnil"n, fC..." .." l"" ...." l>w ~. ~, 2, ~.lU), ;>n<1 .0 a~
"sdul ' Iru"t" ",l1y Onll' for " ion ~rie.~ tl'PC inJ,,,,,,,, ,i,,n. ~ Il' cu 'nple, a lkyl
i,.... ~fl<Iergo lo"ile ,kelel<ll a, ~ll ... h)-.lrogtJl .. ~rtan~rment (T." ',"neh ~ ... " J
1979) ThO.. " " ' If. ngcmc nl> " '''" h ' 8n ~ u ""fu l for ded\iC,ng
lIa _.
"roc.",.
be.n ,,1~s.i r..<1 il<:re a, "di, pbrem<nl' on" clinl in~ li o n" l',ar ra ngemenls-T .....
in", I, c a hond fonn; ng ' '''p bel " '""n . ....., put! of the ion in = mhi"" ''''n " i.1I
the cl""v, ~" or _ ....,",1." ., ,,,,1,, " Ul"",r P,llt er tlte l{>ll (- <1" r lac",,,e," , ,r ~
or the c\<:ava jlle o f ."-0 bon<!, 1<> "jeel an iTlIC'
tr. grnen. f"elimrnati<>ft, , , '''\.
i,,,
n,ne
fJi~_8I'''''''''''''J.
reactions ...rc I... orabl<: . ... '1;1'1..1111', , incc a new
.....nd IS fo rme<! in "" m!'<'n. ... lill" f.." lh e <)tIC cieaVd. OIf-otling Ih" a re the ,feri<:
Te<l" i' ntletlll fo r fOnl'\ing tlK' ne", h'JOO lba l ok,",,, ,1 eriL ......II )' .o n the deg,.. of
. uh. tilUlion of the IWO atom. in. ohed "" ....U a. ,'''' nlher f~"I"'" iii""",",,,,,
earh.,. Th", IhcTC i, ,,,!>-I. ,, li41 >Ie rie 8 d~ anl<l l:. if OM I'>f Ih. atom. is m Ol><>-
\ alent, a major ... <on for IOC 1' t'!''-l,riLy fn, niher
h yd rn~ n
r rnUlj!eme nl.>.
D i'rlOLeeme nl .. action> io '''hing h)-.lrogen mig,.';"" c.n h.: im,," fl4" . Ie"",.
r, ~ ' ''' li " n ~ .n~ b " l amo nalhe mo. l \It , ~n n g example, of r d r""eli,," re . h",,"
ill" Ol" ing Ihe mono\ 'm O lL cl,~,~,, " d, ~" i l\e and b, omi ne ("""Iio" . ~ ~ 2 . nd
R.i 03. y . Cl Bfl to )"lCld lhe Ita b," 7<'l<1 . yelit: halu n i" " , WlL F.." Y = l,.' Ihc
C.!l / '1 l""'\ l"'!z 911 is the boO... ,"'01 fM R _ C,II, tbro~Jlh C . H " IFI~U I.
J .H 1 an d 1M ""'molog u,,, C, H ,, (1 . ro ok il " ' ",,Ily S 10 !/J'\ . , OL bunciant. F <If
\ . _ Dr. h. rorr,""""nd in g m..'o '" . . 1.\1 i<'>fL' Iti.", m4ju. p" ab ~ ti ~u.-e 3.24 and
I lnk D"'. " R ,l ~ Equation ~,1O:1 reo,em!llts lh. H ""'" a ngc" "'" L in pr ima, )'
cblo""",)hn,.. t hr" Ll~h r." C~ rllembeJ ed- ril1' U . ""'h.... "al. (Section ~ . I IIl. Inc
..... l ) T<q"lrC~ r<>l dem'in ~ the ",,,,, I ;,. "',,'" ,I.. " uIl'. O\ b)' lbe formmioJl of tl~
R n +R ' b ~nd nnd l ~ c ' La h'/uy of the <.-yd ic .-t,l""" "",n inn (Van cl< 5.allik
and M e La llerl)' 1 'J1~ I , a ,oln h ra nching or " t,," sllbst,n,ti.-. n ~ , o " i a<1 1 ~' .....
clu~c, II", dj,pla",, "'~". ,.,."e, j"" . irn;l~ r In Ih< eOecl <>" Ht.'l l~, (rom c hln rnalkanes, r he re:u;unn can be ~ 1 "", 1 hy , ,, bs lil l,"nl' which >tahi" ", , 1M: R
p""l uc~; the " ""'. 'fJe""~ n( rnc, h~ 1 ",-amin",l" " ,,," "" . h" ... ";g," r"'''''t
1.\1 - 'CIl ,OOOC"H , l" ",'~h.
Tho 'l""'lru'" I'>f , nd tc~ M n u ri l ~ . (F i ~ u, e .1 .2';1, , h" ..,. an in' POl1~ ". ;Gn ... ie,
Re,"eli" " S. IOJ "a ll Ol.OCUWlt 10. tho ..n e'! ,'" , imllm ...1
I,f " 1.': J!, 'l6. 110, 114
....'z II U , ~ _ b~ wit h the Ia r~ e r ing ..'" n,f!o;;Li"l'- lhe .." de C ' ( . hond angle
f", ('. (" :-N, The tcndcnq rur ~ Cll" n 8.101 t" pTI><:cod t htou~h u l;w '
"""n ~I"" (Y - Cl, Rr, Sil l " ,. .i....~ , n ber~ (}' _ N il , ) ring ", di""Ll, ,,,J, ;a
Secl km ~ .~ a t h ree- m.mhcred r;n~ i "Ic' '''''d,~.~ C<ln " Is<:> be iml'Or la nt. , " ..... n
in It.< f.m nnt i'l Ll 01' " yolK; C , 11. SU- tJ"TOIOI..' cl"l ' h iit~n" ) [tom R C H.(:H ,:;H
(" on de Gr...... i. '''\~ M d .alrorly I \l nl 4 <iln.r~nt mechani<m i, clT""t j"c. h" ",.
c ,'~r, in fornl i n~ (he . na l" l" lu' C, H.).I- inll Irnm RC II ,C li ,NH . _. IF"',....
tion g.91),
I, I N 7lI, 1980) ha \'. pointed o,n that tlli, re.lCIl"" do "" l~ r~ t~ l kl>
bsh tll1 iun at ""lural cd cadx'll l U (~ . adt cal oh, mil'l')', and invok-e<> in" " '" ~ r conr.gurat ion ~t the c........n au "dr.d, Solution-<; ....'1'll>.tl')'
...... ..... ...""h ," " "e i ~ hb "r i n~ ~r(,)up !"'-fl;ora tion~ or - andJim<ric a,,; , t a oce~ al t
also ,i milar 10 tM>C ~ a, -p ) ........ di. pl """"' ~n l " sij' h 5lu eo, peci!ie f'~F m.,;ntd
Ii"", are treated in So.olion ~ , l . 4 t", in d ...... p" rallel lo , ,,lutio n ehem.... ,.. lltt
oIi' rl accm~"' l 1".. of Dr lroPl 2 phcnylethylbroPlld~ ("nn , tho olhyJ.:ncl>t:l>l.J!lII_
ium CPhcnonium'"j
l ~ u"l i",n 8,107; K" ppel and M ct.ffm j ' 19'i6~ f ......
tion X.1 0X(Loo. ""n t'l W. 1\177) w;o, , h ",. ~ 10 involve o;yc hl ~ ti ~ n t" oilro""" flOl
(I~ ~ll""; note lhal a . illl lic ho,>rod IS d,av. d, The prolimilYof IWO 3rom;tlil: n nll'
1<e.IJ> \ <1 ~ lad .... di,pJ3ccm.;m dccomp0, illo m luch ~ $ lh , """ in IOq uation
~, 1M c;..-bukrL G , u!Zmacher I ~80) .
G ",on
~ n m " I)-nc
i""
In a d" .oni, I'lldi<:al iun, di,p! ocem,, "' cu, ...."<".11 rrom an ~t o m othor th"n IIu:
" "" .' llb:h ..J Il, the migr~ti l1g grnup r OT n ~ m pk. lIe" l\< d ~ I , (19"74) h o. ~
, hewn that the ]" " " f C, H,. aJl ~ CH, C -V [,e m ethyl -'-phe~ )'lpr"rWNl1 e
im'olvc, (e4uI!\i"1l 8,11 0 1 ' di,p1uuncnl .1 ... lyg: Jl thol mo,'e , ~ o " hl<>- hrof,,1
ch. Taelcr In an ndJ ~cell t (. 0 bond I" cI:t,placc l h~ ~I ~ yl ~ ro u p oolhat o' ~',e n
Noce lhal ih" ,it: . !lt' R'- OCOII ' _ 1\' + OC O II i , l( , u.JI ~ unfa. ...m le
t:1 "OCOC, Jl , l rro'~ r , H, OC'OC, H, >. is -< I',\~ Sinlllarl). in rq"" litlll ~. I I I
. n o ,i ~i ll d )' , 'myl", ""11<:1 i\ ck. ,~ (] (Toji"," "' ul. 1')$71
f.' ~ "l,.,... il....ru.pI.o """' e lll I'N <.li" ", tak e place ;D F.F ' i. .... lf.qwlI;on 8.1051.
'"
. , -
..... .. ........
"# , -
I~. I
WJ
", . OCQ .
(S.lI l)
,uc'h as L2A-IC H_.U I, C, H, I,CH _ (CH , OI, C,II ,e ll, b 61Il"" bc rr<l.rin~
H.di,plaCCH'Cflt a l tho i>crl 'Y1ic ,,~rbull {C",. ulu"1 " I. I ~I ), U, u~ ll,Y lM EE '
prccu"or i , bifunctional, " , that the . it. of the c h ~ri' moy e. ( Ly u~ Liun ~ .J 12,
Seilcr and H~"o I'l6K,I . The ,h~.~c\eli.li<o periodi. ity of iCH, I. in th. C.l l. ...,0 , +
ion ' erie' in the 'pectra of fall y-acid deri, "li," , (~.a l k)' IC(l() I() "'n,V ' " p.,'L
he dnc to di,p"' cC"'""l. ro"ot inn, com hined v,il" fa\'Qrcd iJ and Ihyd ros~n
tmn .r~" 10 the radica l sites. T h" . the m ~ .. 'J'Cc"um of "" 1~de ~.ll~1I: ~~l<l
{Figure K~; sec al'iO F igu~ >.111ShO w, mal;ma in thll sen.., at mi' i l , 129. I~S
~nd 24 1, Th e met hyl a lka~o ~[c ' IF i~ ~ T" .1 . I ~ ) . h."" m~. i m" " I ~' / l ~ 7, l . ~. l 'l'l,
2\5 .
!.Jven "hid do n ~ di 'l'l ~, ~m"" l. ""n ,..,..IlL III Ill. loss of wa'er
C I
pro lonated o' ime" H , O is di,pIKc",o
i",mcrs were found h> u",k:r~ " ,hi. type " f """'1i,,"
r,om
,.G)
V'N
(~
,
-, .
.
0
)"
'y~
,
.s.:
o.
,
(~
11 2)
'"
I
-f,
",
.:c
,
f
i
-"'
-s
>-.: ,;~
,
!
,,
,
_....._...
,
,,
(8.1 I.1)
U"k"ow", 8.13. F ormul~(c a di,plu"fficnl rearraogement which will rationalize an abundanl iun in
lh~
rna" 'pectrurn of {J imlOn., l: nknmm 4.13. {For th.
am"", '"0 Equalion 9.29,j
E/iminat;an " aclimt. with gm"l' migration". Th.
gon~ml
mochani,tic
f"rmlll~_
(ion AHCD+ {OE+- or EC-j -+ AD+ + BC (equation 8.106) would include hydrogen ,..arrangement' for compound, with A ~ H. Three classes of non-H
elimination ccacti"m will he di",u."cd here: ""me Iype'
or,~
gro up' exhihit a
high tendency for migralion, ,mall stable neutrals a" common!}' eliminated a,
Be. and the new ,\D+ ion can show a substantial in~rcar;e in ,tability ovcr the
,.\,BCD+ precursorR"~rrang"mcnl of u"ygcn function"lil;., is relatively common (Le'-,cD "oJ
Schwan; 19~.1l with mctho,yl migration probably beim; the be,l du~umenled
nUII-H rcarl'arll.\c"'e"l. Tlli, ha, bt:t:n ruuml in a ",ide "atiety ur pulymcthoxy compound;, ;och a, d"rival",ed
"Ild olhcr aliqcli" compound,
IlJuiliibewicL d al. 1% 7: Winkler and UI'litzmacher InOI. In eycJoalkanes with
lhree ur more molhuxygroups, Equaliou 8.114 ~i,'e, rise to a major po"" in
Ihe 'peetrum. Trim elhyl,ilyl g;ruup mig;ratioru; arc common, allhough the,e u,ually ''''''UT thmugh five- l" eighl-member-ring lran,ition "ate, (Iltooh 1979~
the l<ln~-ra"gc reanangcmell[ of E<juation 8,115 proceed, through an iO/lmulccuk eomple, ami give, ri,e to a ba,e peak "r I.he ,pcclTU1Tl (L""gevialle
19B7). In di,tonie- radical ions even carl:>ene, can migrate, ,uch as: CHOH
Ihroul\h the eyclopropa.o.e iUlormodiale in E4uation ~.1l6 (McAdou .1 "I. 1ngJ.
"'gil"
CH,O)
1-'/--;
. (CH,I.-,-6 H"":"';:CH,),
(H.114)
C H=OCH,
CH,o-~cH=6cH,
m'z75
EE ion. <;;<n .I so lll'<k'B"
, ~ ch ~ roUJI n "V~liom
in f 'l"a l ifml 8.117 - ~_ 1 20 (8. I IR-
w.w <'I " ,
,,j,h
" \; on ;n ~ti oo,
a, . !town
lY'll;',l
"" (~
,
t~. I171
rC><I,
~o .
6S ( Cft, h
(S I U)
F./h .u_rl"8 <if......If ,I~hk ,puN. Small H Y mG lecul", or h l~h ion l, mion eJ>. ' SY",. Cl'm mo " ly 1.....' from M ' I.hrmlgh hyd rog<n r.'lITun~'Cm.n l. . The In" "r
<lIher . m,,11 'l ~ t>Ie molem l<" ,uen '" Co, N" CO,. nnd SO , I. IE _ 14.0, 15.6,
1.1.8, . nll 12." respc<:ll, ely) can alio be highl~' fH or. ble OJl a n energetic ba , i,.
R""KU,," ,IH.= gr<1Llp' CKnlH,1 he IOClltc~1 on the tc-rmini " r a molecuk Iholr
fkl n'e" rr~n geme nll ",. mu , t occur f,om " cycli<: lI\()iety (e,i" Eq ua lion 8,59), In
spec l.."l il1lerp retfll1on. however, their 10<, i, 1101 cletil1 illvc for , ring 1,>c "l on;
> I",,~ il ca o ">rnc,lrnes ,>ccur by ellmlnalloo from acyclic po, lll m", despile tho
hillh enlN py rc ~ u i rc lIl<-"Il l ' . Thi , elimination i. ul,u ob",.Y<:J for HY mole cule,
an d f", , ma ll r:wlc~ 1 'l"'cO::." , uch a, l-ICO' , 'CF, S, " nJ ~'<I' ,cn" Ihal cC'lllaln
element. Oriilll" Uy loc.ted wit hin the molecule,
A prl",e dri ,I ns fmce for such elimina tion. Is Ihe . 1" bililYof th~ product Ion.
T h" mo,1 CommOn .." mplc. 1", ,,1.'c rormallo n "r a "0'" bund b.tweell larg.
llro up" fXl'tku larl~' aro mali<: rinll', to increa se th" re,,,na ncc , \abllizallun or
lile Innlc product. Be~' Llo n er aJ. (1959) lim pointed out the , ommon lobS of
CO ftOm llr",u ~ ' ic cmnl"JUnd, meb ~, quiuon"". F UJ' alllbr aq uwone (Equation
~ 121) allea't the .e",nd CO 10"' mu,1 involv e a nc", bond bet",een Ibe ,ing,;
the IF. of the J1eu tr ~l prod"",\ i, 1.0 0.....
ra 121)
SHeh dim;n"!;" ,,, a rc rd " i,-ol}' m mmOll In e" m pound , with ,"'" "mm ~,ie
ri ngs \Wl:r.olek '" " ,- 1%81. A var iet }'of l'-u "benznnillde, ....ere fouoo (Broxton
~I. ~I, 1971) to ellmln"te CO " nd Ihen H . n", Initl. 1 C}'e1 i"'lion belwe. n the
"",m.,i< , Io!,/, l " <IUK! iM R 122t , he rlog nllro gcu I"",'"i"" ~ n.dle~ I l ikc ";te r",
the initl, l all ""k, a lK1 the I"r~er nn~ .y'lem [onned pro,'ideo .tabilin,tio n
r"r <he " u!",irud ck,d r" u ~, wcll ~, chile....... , n.... c\i m lu~ l i<l1l " r H , P(}.
from t rirh en~i I"!' o,ph~ 'e m" or ;m'ol.. " mnllir 1le;t}' nf "'ch ' Iep' (l'<j"" tlon
~ 1211
" r" m ~lic nilro C<lm fl<l un<J. elln be idenllflC<! b ~' ch. r il<Ol<ri. tic 1M
"'0)-, ..
.....ll as iM - NO,) ', P"~ h ill thei, m ~", 'l"""'"' Th< hU"go cnlh..lpic ~(h'an t"*'
01 .. 1 e" for the fu rTiln gement I"", ,-,( :-. 0 ,,,. <lmI* dea" "te I"", of NO,
fro m 'he mUcllhj~ her .... on~llce .t~bili""tK'll oJ 1\,-0- th ll <>t. 1\, . (Ste.Ii"" 8.11 Th ... 'lO d ; m;n ~l i "n "" n h.: c n h :rn~,--..I ,, ~' an mlh"..iluatoo fund,,,,,"1
! ""' r (Yi~on 19_1. IW2~ l.O<I of ",0 ma~' . "" oc<;ur Irom ar'Jm . lic FF. ' IQ~',
,u.:h '" rtOlo nal e<l nll t "beuzc1Ie (Crom bie and Ham "'l1 1 9 ~ ~; Iiq ua l;un ~ . 1 241
.ri""
... ao,..-al '0""0<00
'\
(8.112)
oP
H '~M' ,llk"n ~I' eiim,na" their 2,J-c ho"", ., (" H. (12'l Wllion ~ .9 m a, ~ "'..
i... l..,,},r cyallid< IBw ~. lma ", 01 <II. 1_,
i8, 124)
T h~ . ",. 11 , la bl. molecule, '" .. ~ic. l. ", ;",;" alo:ol ,or" not noceuali!y prcteOI
... OOjJJ1U ~ blod ... in the or igma l <tru ctUTel. TaM< 8.4 .,;"", lu r '~c r s mpln of
. hmindlion l\:" rr~ "W'",.n,",
'-c .''''"-", 1978; \.klalTt11J l lj ~ : Howe ~ r al 1981: Zw,,,,,,,lman . , .. I.

lI a rr;",n 1983; k ;"'~'I"" .1 ai, 1983; Zol1in~'1 and Scib1 198'i; Tl\f~e~
l ?~ J ,
1 9~' ;
222
" _
Ib mrr>tnom 198M,
Tellouv. 1989.
\1" ,~d (l(l
1988; Heinri "h
~ n<l
_ ... ..... _ .._ _

S<'!1 .... ~t>: 19119: B""iol'$ . 00
"ou',.' """IM'od
"re
CH,.
J .
00
"
CHO
.,
$ , SH, SHt
"e....
RSR, RSAf,
RSS Il;
C, HoC'ICH,I= N- OH
ooI!_
CjH ,.
00,
'." - -'- "

'lew . '
<"""""'''''
""
" "".11
IiCO,"
se
cr
"
C.",
C" '-
CH,CH.S '
ASO, P'. , "'S(),OII;
9
M ass Spectra of Common
Compound Classes
N" .. "'" ... ~Il au ..." ,.. to apply the prin,il'b .,,, rurll' d ,O\'e to rloe inlel P'~I~ lio.>n of COIDmOD Type' 0( (lTg~nic "" "'I"'utld, . 11 II im po rt ant rOT YO" to
~ a ' D ;Ul ~I'p'c'\;i;" ; ",, " r th< reliability_and l" ,~ ot r,h ~ t.il ; ll, -_.. f lhe ~ a,io llS
lyro-" "f m'S$-II"'''lml information in I'f(l" iding c,idt""" ('tJ1I~nunl YaJi(l~'
..ro<1 ulal ! e ~t ~rel. Nul, ,h i lhere i" all ,xponcllti.:J1' nCle"... in the " um"". or
I".... il>l" " "8'''''",I\;On palhway, witb an illC"""" in I"" numhe. of ''''''l ion", ili ~l i n g sites: this CaD t>e ,een by ""mpa, inj!. !he IIrh3<k>l 01 t ~lel l .. , '~ l~ " l of
either kctonci <IT ~ I ho." .
Thi" chaptet is ;ulen<led to illu. tu lc ho... II.: m .""h ~ " ",,, .. cau be . pplied
to particula, cornp'JOn ~ ....." '" gi.~ a com prohen, i"o ~alu lOll "I lh~ rna ,,
'fM'clra l och ~ . ; n , ,-,( " 'lamc ~ttuct BJ". Del ~l! cd ~,mc l~lim\, ha,., no w boon
publi,hed of tb. nIl" spKl ra <A ll ~ <k ~3riCl y or mol,clLlar cla.ses, In many of
the",
illOl<l1'icb heling a d 01,"" , ;;ptci, ] techniqu . , ha,'c boxncmploye<J
to ducidatt mtdta"l$l\C p.lt h"ayt. An ", . , fi . nt ,urnmar y of lhi; ltlt r~ tn ll' , ,,
1% 7 ;' a~ailablc in 11>< ';""'l"chc',, ,iv< volume of Dudz' b . ", ioz. DJ"... i. ...J
Willia m. (1% 1) W. f \lJl1lntnd tl ,II a ba, i. rd , ,,,",,c ; the (X)rnfl'Ound d aloS,flC.ol '
lions in lhis ehaplCf a p;,"""",d " fk r it. '.. wealt h of ,pe.;ifio IDaI. ruI1 i, I\> he
I"".nd j Q the , ......., . 1;,0<1 rc"' rc n Cl" ~ 01 S. ction 1,9,
In d.."I; " l' with co mpo und. th at COD"" D more , n3n on" r.. ncTionol iUOnP.
rt memb'" , hat rbe,c "" gnoal <lirr".MM in tb. " "" rail a bihty of 3 1"'.1...... .
1&. lul>CliooaJ ~w u p to i n~ LlC "'-'C lh.: f' RI:mc:ma ti<>o of a mol. ...ula' ;~ ... Fnr
c' am pl., in the
, ' pec!fum of C,H, CH IOCH ,HC H, l..C:H, I"" ~ -d.~~~ g. po~k,
C,H , CH - OC H \, i, mono tha n (....
high u a n) <>1h<T in lh. 'pettru n,:
"""'c,cr, II i' "" 1()'\ 0( the bei: ht " I the (: , H. C:H - NH, ptak in the 'pe<trum
01 C, H , CH IOC' H, l(CH , l. C H( NH. )C. II . ,Seclion 8.7). I\!s" , ,y ncrgistic . f1,,"1, a, c c~m mon, mol...." 1e OOIItamin, lw" (unci " " ,. 1 groups can u"'''' ' go
reactions that ar ~ nol (o..n<l rnl"IIM_ ...'ilh titlltl group alons:, T" reiterate tllt
l"cc" uU<.n< , i' cn a t..,... al..... Y' chock Inc ""h", l ma".,pectraJ behavior IJf
mmpnu "d' do",ly relattd I" your prov<"",d ,[cuet" ..,
",,,<I,"..
k< .,
1I)'drocarbons, " nrnn"na lcly, ,,>hihil ~ , .. I>-'a"l;al '. ",1"" .,. I" ..~ J.;r ~o:> Modm"
rearra!ffl<'l'le!U' (Section 8,9 1 in ", bich Ihe "ydro~Il" lo)fII J'<'!';t;OIlfi, ,d. III a
b <er nlcn l., ,he ClUt.. ,n . kelnal a mm ~e menl ~ ~ scrambled T il;" .. tha m". ~
pro noolflced in .Ilanes. ill ',; II..:h lhe o;""i"'l;'m f" llo:> ~d b) C-C boll<:! cle ~'"
a<-,", ISccti<l" ~ , 5' prod u"" al k ~' l [ [ . ioms .. hi,:10 t., , a hi ~h .. ICndcn<;y for
i,o""" izati"" an d rca.rangcrn.... , t.:"""'l'OfitLOn, . Thi~ " red~ b)' Ille r rc"
enee or ~h"in br"m,hin~ a l>d UllUlUrauon : Ihc . dd;li"n "r .. pola r 1..,,<;tiD"''"'
gn,,'p c~ " n~o, tho 'I'"'"ttUOll dra mal;,:all, ("" mparc ~ ig... .... J l a ,lfl J.16).
Sillurllltd Illip"".i<: ~yJ,_",,""". , _~ h, ... n in ,he ..p.....1 fa '" <lOOK"'" Ir'lure
.1.21ami t.." alria C'Jnt ~ "" ( F i ~ u t e S , l ~ s.lrll, Iu -dLa,n , Ika no.. . . 11",. ",.,.k m.....-.:_
ular ion, lind t}' pical ..,ics " I ( '.H ... , ' , and 10 ~ !eue. n lent C. II"". ion,
wilh ah .." dan"" max ima aro und C, ' If ('. _ ( :h" in h,,,nehin, 1F"'Il" ' ''' 3,3, 3,4,
4, I. ~.~) c".."" " ,j~,;f'''''; in L~ . 1 ~ Ild d'arlCler.. ,i<" ,nc...~ ,n the ah.....
dance, of C, It" , , a"d C,H 2, '
t~ rr"" ,~ .... a . <tjle <tnd cha'", r<tcution at
Ih. hranched .arboll, ",'i th the 10;' of t h e llf~ a ll yl g'o Ufl (a....,...;<1 ( ~ -<l ua tion
9,11, Lavo nch}' ~, "I. 11 97'J) . h" .. th ~1 ~~ v{ C, H, , ;011< in tM .pa't f3
j"""
c"Hz.., R-,C + ' Cl'"A"
Y
(9.1)
C'>!ln" R, C ' CH, R'
~
01 C~lI ,~ " al_atle' a rc r" , mod by direct ".dcava<-", ror" > 0.' m, but th" t
' ~ l S~ ~ ;o n; formed ;n thi, wa y for " S 0.5 It" In F ign ~ ?, I on ly the
,CH, J,(' ffCH., ~ . (mi" gg). (C H ,),C ' (m/= 57). and CH, ' p;;ak , can occur b)'
dlle-:-l " .dt' I.'all", The " arrangement C,H, ". L' peah that a" larger tha n half
,t.,; m,, ",:o; ~l aT W e a r. olw io...I}' Ie" abundant Ihan tho,. of ,maUer maos, . uch
.u C, . I, - and C., H, . Peak< , c, ,,llin fw m , ec " n d a ry oloa ..,,.. a,. <v< n k,,rd iahlo indi<alon of , tr..<I",e lor the,e reasons; nevertheless, the lerti ar, '
ea r bcni..m i...l (UTn' ...~ 1 b)' inil;';Ll ~-cl.a ..aM< "I " full}' , ub, titul<,j carbo n Can
un dt1-~ a ,"",ond"ry .>!cfi n to", "r , Ignilicanl , pceili"il}'. ~, in F~ U' di " n ~ , 2
,,,,i,
(,~, m p;".
Fi, ,,r. k,kl.
-"-- 1'1 '.
-"
","- h 'en;ary I RR'WCH) ;m<l qU" tCfn;lI)' (RR'R' RC) alkane, with R gro up.
laqter than "'''thyl yield negliphly ~hu ",l anl M ' , hut thoy do produce the
' .1-
'1
,f
T """'r'~'
ld
.
.
I-rr-
" ,'
~
' , r"
imporMll ; ("',( ~ - R.l- and (M - RHI- ' by c ~~v ,, ~ c at the br ~nchl carblm
(Eq " ,,\i.m a, ll'l~ l-'Mel~ l'b\h",,, Wilho ul L"~OT R ",b' titulioo us......y , how
lhi, (M _ C , H.:,' I"'" k to be n lmpe:'lUlnl a, IM - CH, I' (Iig..re 8 8, lop' no
CH. lo,",
II _ e n , ); M d;n ~ , hi: l- meth)'l bI a ~ c h i.....""""" jM _ C, H, j''',
H" ",e. er, ionl eow " po nding 10 C.H, ., "n d C. Il ,. (;;0 o " Iso Ix; p'UJlloN
b)' bIanohod oa, h<m dea~a llC'}1 <l\I i ng R + and (R _ H I " fnIl unaleJ)', (M Ml '
M J iM - RHj" u.u~ll)' ~T< dom ina'l! lor RR'R-( ' H ",ith ~1rgeI R gm ul'" an d
in' quat.maI)' a lka""..
A li DII'\~ ;"'I""",,,n l P'lll ol' IM - R" ..ndlM - RH )" pe"l> ,sron,,",<nl ,",'iI M
l~ o '\""-" ures R,C H 0' R. e , "" ilh R+ and lR - H)" a, "nimp(lfl~nt T",>d ucls,
T h~ . lhe lone ;mpoflanl (bo lh 4~{; l f"\;' mi. 238 and ! ~ ((',,11, "
,,00
C , .H.. 1 ill an alb "" ' po.>.1 ' um <lomond, (C,H " I,Cfl' fN j,dom",~\ ~I k}'l
'''Uf''', itl J Lcmiu~ the 'tn":l u~ (C,H I' ), C H dc>ri le lhe M+' "b, o"",; in this
' pecl, um lh. (\ H ,,' an d C , H ,., t , pe ak. a", "o 1 impor l,m l. For R ,C H n<>1c
that ,he numbor "I C,,,oon a l.om" ~.' in I....... ""a k .p~ir ion, mu" be an ood
V"hl'; a
C ,. H' J /C " H,, - ' pa ,r l~n
value 01
" uld ind,cQ' e
IC , H , I 4 (;. I h" , lruC!UI'.' R ,C H( ' H > and it , C(C H , )., ~' ;eld a s,ngle 1M ' R)' /
(M _ R H I ~' pair. ' ;ll<.'C ( "1 - C.U . ,_ II n" t. i mp" 't a n ~ 1>0\00'0" " , R, Cn C I{,
u ,ml' ''lIl1d. ll Sl ",lly p",du.:e lOea",mbk 'vi t and ( M _ C H,)' I"a k"
h t<:nJj ll ~ th is, tu,o iml'" rca nl 1M
R)' il M - RII" 1M'" "an arise l'ro m
R, R'CIl . R , R' ,C, R, II'C, R, B C IC H, )~C III~ " alld R .1 qC H , J~C R , (""'" im-p" rlan1 C,H , , dno:! C,ll , : ' p<~k, u>ulJ al<.o . ri", fron, R' and (II: - 1-1)- ;
see al:><" ,,) Wilh " and "' 'q"~mln g thc numh<: r " f c.1r bon a~ in R dlld R',
tc" pocLi.-d)', the nnmhc, , in 1M l "~' 1M - R)' . .'(M RHr pa1I!> 01 R , R'C H
.hould bo 1>1 .,. I . nd" + II' +- I, "f R, R', C 5lw 'u iJ be ~ +-~' + I an d" +
2.'- +- I; of R,R'C . h" uld be In -j. 1 " nd I n ... "' + I; ot R ,H C'I CIl ,)~ C H R ,
, ~,, " k1 be 2" + I and ) ~ ... III F 2: "" d of R ,C(("H, l"CR, Ih Quld Ix; ,In -j. ,
f".
f"""
""" n
".i ...
~ nd S ~, ... , 2. ,\ ~ ~i n, IIR'CHCH" RR'C(C II , l, . ~n d R, R-CC H , ,.-ill ..I",

yo.:ld I.." "", j ,~ <>11!>1 - R' I__IM RHJ' peak. , h ~ t ",(1110.: ~ niza bl e il l"";'
M ' ~ nd.'or 1M C H , l ' peak, can f>c hkn tlf~. UnkllOlOIl S.7"'.-. It, ~"I"".
of 10 ~ nd 1.1; r", II, II'CH_lhdn + I pair would Ii, onl Y", - n, yiclJinp . _ 6;
f" " n " + ~ . + 1 _ 10, ll' _ 3, indicating I( :';H .. l,<' HC, H,. Ihe reneel a"igom" nt (nol( rh.rt
I i , no l iltll">Tla ll' l r Ot tbe RI R'Ie' snuel~",. 5<~ ,'iTI ~
2" ! . ' .. I _ 10 KTI J + 2,,' + I _ U y~ ld. ~ = ~ anJ ,,' - .'1, the "ruclu,"
(C,lI LL ), C(C , H , ), (now C " H,,,I ' i>olOld aka J'1.>J~ these t.... o peak pai" .
but fortun a tely ,he '1'<'1.1 tuln ...., .., C . H , " as mo, e lmpo!l~n t Ihon C, H " - .
.b 'en lhe II, II { : ~t',,<:l".-e ((\I I,hCf'~H" iC lO H,. ) i, eon,i, t ~nl wilh Ih. (\ 0
IlIho" , h no fiI ;. p<...., ible r", II , H C(C H, I~ CIIR, or
" nJ C ol I"'a ~
R ,C(Cn , I~C R , . -\llOlhe' <>.a mrl < {n<) ",, " J show, n, ", lue, r>/ 7 " nd IS
(C, H.," 20/;;; (', H.. I t 2~;; e " II," , 7':-;,; C j, H" " . 22~-;;l' c" H" . (, S~~ la nd
,he n.... t abund.tnl of C. H, . ' to C,. H" ' \ f>u l eLL a.,' i, ""Iy I~;;' r.<l ~,n.b na:
truo' th.. rna ) be ~n It ' ,l it - H f- ' ,,",Lt. R,R'C Il doe, not lit, ,ina; bt.lh " and . '
..., uIJ "'l Dal 7, and R, ~ ' , C fell""0" ~ "es ati,'. ,'alue for ~, For R,qCH, I~( 11: "
K , H,hq ( :H, J,q C, H,l, (e j , II ,,) wou ld )';<I<t [he C . " nd e n iollS. but
.." 1 C" II, " ; its R "qC H , :I~ ' r",J ~" t ", ,, ~ld be C ,,,",,-. H.....ewT. Ihe
R, HqCH, IMCH II, formula, correctly lit /C, H, hCH(CH, J.CHte , II , I,
,e , . H ,,) and now C IIH " - corrc' l'V"' I. " , l( :. H, j, C H(C'lI, I .
h tending this app roach '" ~ I'r~1Oe of ' ht 1M R)"iI M - RH}'
p:" n,
. an an'" from RR'RT H, ", j'h " . 'a l..", 01 " + ~' + n + n' + I,
anJ "' + n" + I; R, R'R"C. n. of :!>r +~ . + I. 2" +"' . I. ,md 11 + N' I . " +
I;' and R R 'CH(C H, I~ CH II R ', ". of " + "' - l. 2~ -t It ' + '" f 2. ~TI<! " + 2n' +
'. ~ 2 ; a ndR ,II ' qC H, 1", C R , R, ,,,of 2 ~ I ~ "
L 4n+ n' - m + 2. , nd 3n j
2~ .n + 2, RR'R"CCH,. which ..I" , " '0:. I h ,~ ~ (M _. RI' i(M - IIH)pair,,- Can be J;"lin!lui<.hed by ito 1M _ CH, t P'l"k. Unh " "'TI .1.6 ,how, ~,
, a luc.. ",C to, Il and IS, fur RR'R T H thIS fi b (~"Tfeu l) l C. H ,C II(CH , l C , ~H " .
but 'h~ le-<~ ,ml"'."~ nl II .,~ R - H]' p.,i, at n, _ 10 could haw been oonlIKins h I! 1t ,It'R' C an d R, Il:K H , J~ C R , R'. tho form"I". "onnot be sol""" to
)<itld "" "1:'lt ";,j~r. for ". H" "' O'OT. fOT RR'Cll(CII , l.CIIRR' the otow.:! u",
C. H~lCH ,lCH ((, H , J..Ct1(C ll , lC.H . i, "1 \-0 WIW,!eDt .. i, b 11K- ma....,. of
llu:oc Ihra ",,~ k P.1lfi.
Unknown 9.1, all ,, ~ y~li<; i, ,,'p non ,,id alh n_ u..Cul 8~ J "ehemi,";!1 1"",;1"
IRnINm anJ 1I" .... l ~n d 1 9~ 6). illustra tes the b e t tha t m...t h ~1 "' ra ,, ~ h ;n8 h.1s htlit: efloe' un the ma., .~ n r llm ill tho pro""""" of . " h,,,i' ulin n Ily la: gcr alt )'1
groups. Does mo . e than oil" ~" m ~i n otion of .ueb , uh<l,1nt;on ~ l '
1 ." w '"Jl o r ~ )' (12 eV) m,,,, ' I"""' f;l .ralh n"" (M........' II 1 ~ ~ 6l ""1) M helrful C
ar
assigning >!r uel,," , " lK'e londary decompa<ir;on, a, e la' EeI)" "'pt(s' ed, and
fragment ,bund' J><:e' ca n be correlated "",,1'1 ion the,mochenlimy.
C.""
('la'''''
"'0""
UnA ",,~~.., T.y the C, ~H ,.
I.
"""''''T ic I. 11knOwn< 5.4 10 5.6 ag,in,
c,
,
,,
,
{1
,., s
,,
,
~L
, I
, ,I
.,
,,
j
~ :
",j:
,..
,,
rr
~_ II
r.
-......... """"'-,,-_.-
., .
,,"
V ,..." I"....' ''t tllip~tlt;c lIy Jr""..,.iHm,-. T he ad ditio" of a double bo nd to an alkane IDefOasn the " t>undaDOe of the C. H .,._, ",ld C. H _,. + - ion """"" a~ . howo
in tho , pcoll um
Idod""," " (I,'igu t\: _u ~ ' ''IC
incr"". ing importa nce of
Ih. C,H " . , J lk~'l iO Il SHI. ' ar 10'. ... ' rna-=. A<ld ing a double bo nd illCr....
[ ~ . '] only for "prnjX>uodl of I,,"-. r mo1e<:\II,. . "' ell>hl. Cis and ITtBIS il;OTJJCTl;
u.u alJ ~ h~ \ " very , i",i1 . r m..., ' I""'lra
Alke". ;('Ill ' . ' hihi! all ~'Ii<: d ,''-',*", (61.....'10"" 4 I ~ a nd '.u~ bu t als o sbo...- a
, Ir" ng l"ndorl "~ Il> ' ''C>nl. riU Illrough m' grnn" n of 11>0 double b<md. I hi, j,
t""
"r
CHR _
C~ H==C 1-lR
rs.
e'!'CC; all}' I' '''' (",
all ",.. "''th ..
1""',~ .m .. ll'C"'ar ""'~llhl
0 often sh_
an d 'll'lligh' och. ;" a lke" ... B, ancl>td
specifIC al1l lic-clel1 oa" or ,""m oog. ment
""""nlpo"n" ,,, a. rc,"""kd h) C"l~';''' a;.b.:li"ll ..ud.... l "1af'l"es d at. 19~4~

' he rna" ""'..... .. ,...l' . nn and ' ''I''" ia ll) roJ,.ene'>. len d 10 be indotpt"nd em
Dr dDubl.bo,od po <lI,Oll u,1lnf ,,," do uble bo nd '5 h ;l'1l1 ~ l utllluh.'t! Dr ~ num be< ' MdOllblc ""nd , act ~,,,,,,,h.'T. ~. in t":',,~lic d<~."t"'. C. H,CH, R , Tn...
~lI t'lic dc......." ' ... r " "j""" ,he C , H. ,,, .. in "11,,.ocilllC ~e il . elarded be"a u""
lbe dea,ed ba M " abo "'Ilyllo;, bIOI i> cnllo,n..,.l 'n rn)TQ;nc. ... .. h .-I1 lhe <"'uved
h..nd " douh l y al l f lic \" <I .... '..n \/.4).
(9.4'
' .o0Y
I
C,H,
Henne"" r" a nd So<ho mbu rg (1968) repOlt that the ' peetr" or hranched uo."tm m e<! . lken... RCH - q C H , )(' H , R' 'llld RCH ,C(CH , ) _ C H R',
a hondanl RI :H, - ," n' ...hien up pear 10 ari,e by initial migration of th. doubl bond
away l",n1 lhe po ,i tio ll D[ br;mc h'ng. Tn hom",,! oalene , d ea oat< a t l he wob!y
an y1i< I""ili"n pm <! " ,"" all a hulldan! (M - 83)- iOlL bu l the cllaracteriMil:
(M - 31,- jon lnvo1\'<5 doubl e-bond migration tD 11>< conj ugated 1'o";ti" .., rt ~
10V1'! by ~lly l ic clca" Ub'C iF'Iua!io .. 9..1). Lev,"n or a ), (T97~) rLl">n th al [.,It!.
.h<,,,
{M _ 57)
ionizatio n m ~.... poectM of alkene, ,110..- allyhc c l",,,- ,,~ c", whlch allo,, " 11<:<1 ";
"" :a l l" c,,I;On or the d<>"hle hoo,nd .
r Ofmalion " r im portant C, H , . ,. fnogrr'ltll l ions by C~ H , ~ d llniJI ~ li <.>n ""n
ocell, try ~ >arl.! y of rnl<:ha n...... (!>lodlO,,- rr al. 1 9 ~J ~ Unbran ched al ~ ~n ~ s
arc cha racl.,ized (h, L" C l S, UOknown 5.10) h;' a SlpI 'l;,;"nl C. Il,: ' O E '
Ion IU les wh",., I"'"-k >lll~n. i"c, ~TC rda li,,-ely j~dcfl"no!~l of douhk -hond
po , iti,m; ,n if" or tllc d" uhl.; bond to inner pt";!.i01\i lA~bltizc M ' -. ill!el'llal
hTa"d, lfl$. a t the """bl. bond jl p al ti ~ ul .f ( ~- eITecti"" 10. '~ d ud ng . p. c;llo di""..
Ci. !iOll b}- lhe l'hyd rogea re"'T. nl!Cnl ~ lIl rEq ni\li.... 9.6. R-- > H ), ,\, di"",,<ed
..
.-
"~
:D,
"
,J
..
in Secl;"n S.2, an electron..u"u l"'3 all)'l iroup al R- .UlliliU! lh. charge;

PA(C'H, C H C H" CH,C1I= CHCH.) '" n c \'. hul p.' r.CH, I:C CH, .
(C H, j,C=CiKH , l = 8.5c,," . Th e C. H, , - abll nd'l>CC'; ;n the ....... lrn "f l aad
2-<1oo ooon. arc ",,,.dy ";"';13" CH e< , uMti tution . 4 C- I .. nol .IIOt:t i,- ~ , The +.
7-, 8-, 9-, a~ J 1l """, 'h,I2-~ nd ."" n e , "I.., , h.... C, U",- - a hundanee. lhat ...
rclali,d)' , imilar Ie> ,110oo:: or 1 and 2-doo.a_ e_pI tllal lbe 6-melhyl l lllll.
a InOA: imponanl{I O':{1C, II IO .- peak, prCII..m ~ hl , l h~ Ch31'g. -m;grali" n
",d C , H ,,<le ll ] j=CH , (II><; 4.ltK.'tl!yl !!i, -.. a baSf C , H. I p<:ak rrom aUylic
(It'ia ''age~ In 5--methyl.2.unJe'" (R' = L'11" hrancb;ng at th. """",.I "'.. no!
d~~ ""d l the C, H i i. "1.,, In",. iml".... tant ( _ IO'\ ~ \>1> 1 ", il l! o lhtr C.H' .., t< , ub"anl;all)' red ut:<:d_ H '~ \fl , J -m. thyi-2"und=1\t' (R' -= CH, I gi,e,
"' lh. mOM "bundo. nt ion C,H , " - , cU t'e, p<lnding ro 7 H lWo"a ~ ~ m.nl ; thi,
fep,e""nl' 80"/~ or ' he lo la! f,,,gmenl C, II .. - "bUD<ian~. T h~ spectru m or
pr,,""
,n
"
"'~_ .-.-e-
1(:. H"l,C-CH, (R" - C ,lJ u ) ,jmilarl~' }'\CJch " ~ i "'I",,'''ml (12"/.,) rrak
tv,mP<' ooma \(I <halge retenlion in Equation 9.6; tunhtr .."h "'"""'...." 00
('~'~"'L"Uli . c r"atrangemw t' , Equation 8.76) of Ib', (,', H "qCH,r-C Hz'
iI''' "" Quid I Lm ilnrJ)' " . co u n l lor Ihe <1"m;n ;1,1[ C . H ' pe a k of
",""IIUm.
li n " ltC!ll. ,t i ,~ tnclh"d for locating one o r m o ~ do" ble l>on.h;h an un...lu_
.~lcd >llail'lIt hyd'a<::aroon eha;" j, to introduce r..nooti" na l
at the double bo nd(, ) thut CUll in<! """ ' f'"'X-i fic hond-clc3 , age 11 ~ ~Jl.... nlallOl11. T h" can b\;
Hchi co'cd h)' eilhe, ~ h . m "'a l dtrin llzauOD t J~1lSftl ,,00 <; " .... 1~x 7 ; Scllml\L and
Kle;n 19~ 6J 01 b)' IOn m"l<:<:uk n;acti,m, a";"jl: CI with isc bu tan e or NO a,
,eacti , e gil"'" IBu<1li' ;~ "';" 1911" ; f .mh om el al. 1985. , h).
In ~e"" ".l. lhc Ir"'llTl< nl~ lk", beha, jot of acetyleui<; (W('l od ~" te 'l " I 1472,
L;[" hiL.c 1 ~i1 I . nd allt olC lWk lOlR rI ~I, 1m) c"mpound, ,"~nL b ltl l h ~ 1 <of
.lkene" (jou r ~Il yn"" "r II ~ I> Ji rr.". ;n ~ ill lh_ po,ition Oflh. tripok bu n,1 <"In
Ix: d''' ingu......-d rrom lh tll m~ss opectra (\f ercer and H ~r"",n l Q ~b~ ( M ' ]
inc... . <es a , the II1p1c bo.moJ """ ,:, in, kJc Iho hydroca rbon chain in keepin; ...ifh
the in<:n:asJng , ,,,bi ~ I ;"'" or ,h e a l ~Ylle OE-' ion, . Inter pretal\o u (l( the ~fIC'.1 r .
j , d ,lI-'c ult 110...''''0. , ,ince . ommo n ulI,y l 10'" c''' ~ ,,' o """,n "<l ror all p"" .
1100.'" iwm.,,, "lt h<.,u~h ;n ditTcf"n L 2 11 " 00."':0'. The spe.:i!ic ctea . aJ:C ol 1be
l'fop;lTgyllic (; - C bond, ob",,,ved onl;- fOI' " ory b , t <k:<:omp... itilm, in rocl.!.
,....i..'io n ' pectr a (I S 10 '" I , ). m ~;- hc .I ....' In tldJ-i nd uced dio;sociah~o ion
iz. n un (W"l1ncr_Rcuckc' cI "I. 19R 1 ~ Dtoompo";I'OfM> II, ro..s '" mcl.~J I, dhy l,
.,,<1 ( :.\H,' DCCUr in lhe ' p"ctn lm " r l,ll n ollMl' ~nc 11I:"t>loir> ",1 1',,,lcT 1 9 R5 ~
leddm g apparent l}' to cydic FE ' l' '''d ....1 i,....
To ,";Icta lc. eo ml' af i,otl of 'pectra of aU a~.IL lb " ,,,-,,,,,,,, i:; nc<:c" aT)' for
f e l ; ~ h le ;dent, fICa tion of alkene:; and al k ~lI""
1""
' ''''''1''
Unk,",,," \-"" ,ho~ld , 1m> be abl< tn dj'l,n~"" h

~'"-''''n'
m<' rc ,,,,,HI belwcC'n lI n_
U lnd S,lo.
"J..mx:",,,,,,,,
Sal......" " .ticJ~"k

Althou~h til< mole cular ion. "I c~d ()llk . """
arc "", rc . bUlld-l lll Ih,m lh"", 01 tlleif acyclic C'()unlerran .. ,h<ir lpect.a arc
ooen mort <h ffICU]1 10 i" ,,:rr "'\. Tne ba" p_ak in tho r.pKIIllm (l( 1......th, 13 - pcnI }'I~I,,"" ......,
to th_ loss'" C , H I I ' . D.."(: }' IC ~ c l " ,," ne , j,njLarl) gi,....,. C. I--! " - Jl t hOl l'lr Ke, ! poak; C ,;H , 0' i, the """"" d li'l-I. fluul at to
Ihe b<ba\ 'J<>J ol lllrs" r . It an", (Lquatio n 9.1l ln ll>e spectr um <.11 u""'u:ykJdo
pent a"" ttoe C . H. ' an J C , H, a re al"" the largest. but dc. n, ~ d"mj>l/l tt lhe
C,H, , ' ""r ic... Cnlli , iolla l aCII~at ion , tudic> (In ' u"'Li, ..",d <)'tl..... lh n" t lklr
che" H ~1. 19771 amI Ion ph " ~ ><l i"'''' ; OIi.... stoo ies nn 1lO .~bsJ il " k d 9 d " al.
kane. IBe", and Dunbar 19'N I Lnd,,:u e- tha t mol:ular i,m, or :0. ,i. -nLtm bered
rin ~, arC "able to ,koletal i'om~nnl',-,n pril " ,,, d;""ocia,i"", bm t h"l lm ~ Uc r
ring, undergo ring_o pening I" r.>rm initially J alb no lO W;, Alkyl. ,ub,I;\uoed
~ }'d " rr " l' an ", ut,.urgo fa" and u .'t "'hIc ring.''fI''Tli n ~ (Zatkin and M,ka y"
l~MJ; cyclopropane SlIuct,,,.. h" . c """" ~"n,i<ief<d a, inte'\Dedi~ te, in I" C
i,omerization of ""'fi n O l'. jo... ILade ,otile aOO Harri, on 1n5),
"",,,,,,,,,00,
'"
' ,1 " ..,,,,,,,,",",
'00_
',f
".'
'00
Fiom.
I .Z,
Mas< spectrum of methykydoho,anc,
Skelelal ring decnmpo,itions must i,,,"olve c1ea,'age of at least two bouds.

which ffi"y eontribule to the inewOled randomi,,,tion observed with lhe,c
compound,. In the 'pecLrum of methylcydohc"nc (l'igute 9.2) IsOIOpic labeling shows tllal the prominent (M - CH,j- peak i, due to 10'" of thc methyl
substitucnt, However. only hlf the eOITc'p'mding peak in methykycl()pcntane
ati,e, in thi, manner (indicating a greater degree of endOC)'dlc cleavage In tbe
CH,,)' ;,m which i,
live-membered rlngj, and eyclohe,ane i!wlf ,how, a (M
n'\', of the b~," peak. The (M - C,H 4 j " peak of mclhykydohexane run he
rationalized on lhe basis of inltiallonizallon at tbe endocydic branched ,igma
bond (Equation 9.7j, labeling indicate, Lhat (;O:;~ of Lhc peak arise, from the
diminaLion of C, H. originaling in thi, po,ition.
(9.7)
However. cmdlll spectral correl,,\ion ~an give valuahlc "'udaml information

nn ,uch comp()und,; thc delailcd 'tudie< of Djeras;,i and his sludents (Tokes et
"I. I 9(,~) on the ,leroid h),dmcar!>on skeleton provide, a classic case. For c,am
pIe. in the mass spectrnffi of 5-~-pregnanc (Figure 9.3~ Lhc (M - CH,l- arises
from the 10"' ufthe angul~r melhyl !,'T'>Up' (mainly C191. Loss ofCoH, by the
noqdic fragmenlation of the 17-20 bond is neg~glble heeau,e of fa"ored 1:;17 dem'age of the D ring produ~-;ng the ,tahle leniary carhenium iotL Radical,ite reaction< of lhi, ,pee;e< ean pmceed e;lher througb rociprocal hydrogen
transfer (Equallon 9,SI and 14 15 ol.,'''"gc to yidd Lhe charactcri'tic OE-' miz
21S ion. or Ihmugh cleClmn donalion to lhe neighhorlng bond. resulting in Ihe
miz 232 reak lhrousb 15-16 eleavage (Equation 9.91. A ,ubstmlial part of the
i - - .,
,-
,,
,
l"
,- ,
, ,
-" j
!
,- -
.,
-~
~
,
,- - a
,-
,,
,-:
--
.,- -
-s
)
\
(9,91
~, .
r, ~
",".<217
base l"'lk II
[ 4~
ion
i.
",i l
2 L1 11 due 10 C L9 llIoth}'1 I"", [[om "I,it nl.
~ ' ; n:tll y .l hc
mi.
comr><>ocJ m" inl)' "r . jn~. /I amI II. b<i.l i, fon ned ;n a romple:<
m~ ha ni ' m
o por. ,i " in coujulIClio ft ...'ltb lri ~ h)<dro j;m Ir",,\kr. Dcop;tc

Ih" uP!'i'. enl d~fft nt " , ~ ,t" ~"",,,,,, , h~ >.lctt<d><".i, u), of
AiD ring. ha s .
Chaf'llCI~risl;~ tjf~t on Ilul pt'<>OOU~ i~
OIa" Spoctru ffi 01 t he 5-P-(~';'''''wmcr.
Ill:
,'l 1 ~91I""': lSI] ;,. "" lC~ In..." . '''',~ i~ ,h., u r the 5-''''''m"" This
"",,,,-1 "" r~I'lli .<:I ) inJ,:",:~J<"1 ,If Ihc ("[1 ' ukl i"",nl (S<oifert ~ ,,/, 1\1121 . nd ;"
r....
t""
t""
Ihe pI~ of ..... w i..,""'.... ,,, ,'c",N! ~c,d. in hir hl y rompkJI

....",1 .'1" 01'011 10 l be ~ me.i. oJ Ihi> J'C,,,,kUJIJ i ,
1"''J''OSCd bcclIu se the b, 1e acid' of man" "" I, ~J C l'I:lI ';I ~;oJJy rel~ led 10 lhe p.1t
lieula.
a~'; d , ;'1.,n,i,",d_
F,a8me lllalion. of lhe D-- rio!, l&jillll ion 98) and Ihe l,w< " r N- a<c d .. ro
"'-'1cri>lic ,,, 17... """i',,loo .",mid.. bul do ... '1 d.~n d o n Ihe PI ~ and
""I.. ... of ' ''.....il_1S io rin gs ,'0 and H l/ ~ . c' .l ;' 1 97f1~ ,..", ample. ch""''''~ Jlc
dcriva"ves '>bow 1l'I"ClIII....... 01C. H , , ' and C " H,,' from lhe molecular io n
.~ ",d l "" rm'" O il ' f'~"'-"TI ' ;.","-
.-oJ I"
c""l~bfub
pel rol e~m mi~ lu"", ~ni ..... ,
".mOd
li _ J .Jicydk ' y4r",,,,,iIoHu.. F or n",oy lYpes oJ ~cl ""l . .....c'" <he po"; .
1100 of the double ",,,,0,1 ~ a & bTl le cffccl OD lhe m.... . pccllUJIL T. o IroIDers
nr C , H . which CO n ha.c nn ring la'llC"1 Iha n q cl" ","fI ~ . ~ ..... >ioni....
t rn. a , do a >an ef'!' of C , H, u l1lu rin ll" + do uble bo ndsl lSOlUCrS and O1h...
com",,""'" "il ~ a hi!!h dq;rn: vi u"""tu'<l.li(>1l.
" d hyd r" ""r .
bo,.. (C,o" ... 1"'0 rmg' - 0,1" .."", hOl,d,) con....inm" a ""-d" h"'..... lin!! a nd
an eueriOl double bond eUti b" spc<TIa ....hleb a rc consis.l.nr -.mh iu,ri., 1
" ",n...r i",,';,m I" a cydoh<....c"11l." >1 ......1" ..... plu' 0'''''' . ClI ...-~ n!!'........I.... ~ ...... a'
rncTb)'l n,igral'ou ,
Cydohc, ene d. "'..." ..... on Ihe orher ha nd. can uDderi<' q uil. 'P"cif,c fMIlmenLo'i" n....... ill""tnuOO by the "f'l'1..1 n<m of ~-y d"he.c"tIC il-\df Wi!!u,", 9 41
T he ba>c peak can be rationalized by a h}d rOfll"\ abstracllo o " '''''ha niwl tun.
lcr nIlll the unpaired el=on to an an~llC rndlCl.l ,,'" I f q.... rlOn 9. IQI fun_ cd
bJ.' me th yl I"",. 'I'be- o.i""ir."",nt odd--ele"'ron ion of m.. .~ 'j.t. ..'hieh at..... through
a rcl ro- [);eh-.'old. r f<'act'Otl (Eq uaUoni ~. ~ 1. 9. 111 is a con nico t ch".>cIcr'ff~
lhe cycl" ho:; ll<"TIC .truc'"",- T h" """',; ,,~ prod ....... a. d ;'_; and a. m,,,,,,,,,,,,
fr"l' mctll, a nd can be h~ hly specif", of the double-boD<! pos ,uon C''''' in OO,n
pic , pol~-.:yc;lic rnoloculcs ,uch .. tnterI'C"'" Or al~alo1d& (Tu rw.~ .tOO Ha nul
""''''0
r.4 ""....,.pc
,.e
'00.,
m'z67
(9. HI)
I ).
19,11)
I % ~ I , T ~ c cyd o nn c"" douWe bond can f>C a par t of an o <1no-<ond<"""cl am.
",, " ie nn ~ such a. ill Iorlral'n " nJ il> hete l'O a ualo~' ~ K ~" ne an d He,,'c 1 9~ 2l.
lu, t a. happen> in ", ,,,,y .iI'n~ -c l oa va g. ami h ldrog~ n rean"n b'l--mcn l ~ . c
~ ; "" .. 1M pnx illch com...." for the po, il;YC d 'larte- Ten " hyJ ",cannab ;nol pro<I""" a ' i$nir"",n l z 246 pe". c"fre'J'X>nd;n~ 10Ihc " .nidd n'onoene lh ro ugh
k", of C , H,; [.q N lion 9.12 i. OM pol 5,b l<; IOlli"'l.ab.ro.t ion o f tnc oloc\ ro n ,hilt.
""i
"'1 3 14
_CHa o
"
",,<:;11
(9 .12)
,n\'o l>'I. NOle Ih 3 t CH, 1051 f' ODI the O f" ",/0 24~ IO u aivo, 11lc M,", pnl k,
o;oo . h l<;nl wi th lhe aromallo ~ t .. h ;I;7.. 1;(>lI aohioved in In i, fi E proJ l><t ioo. Tho
"" N- D,ell-Al"" , rcac t;" n i. olio a CO!l'm o n dcoomp.:o. iu on mode or OVCfl

i,m" " , that a ."bofaut" l plm of the m/z 231 pea. may be ro, mod by
C, H. In", from tho 1M C H , I- io n.
~)""'''' ~
..=
The spectra or ~ - a lld Ifi....."". il )"11" ,,,,1'1 ' 4.12 ..rid 4.1 31illus....d> !t:llrlio"...
[I" ~...,
In k
ArM'4 ti<: ~.,'dr Nao. tK... t 19'J'lJ/- n.. Splra 01 ~"t11e l l!n ~ M" n ", ~~
naphtha lene (Unl ,,,,, S.II. i""",u' no!ine IUnk _'n ~ .l OI- Du"lbend ne (U,,
known 4.1 8~ he~ylbnlltnt (Fit-ar. 3
an '" ' ''1yl ho,,~n<; Il l"l oo u.n 5,7)
cu ml'b. The " "" Hion Q\ a n aloma n.: n"d en. 10 Illl alka ne >uh<.la nti.ally
infl u' il"'" the "f"'ctru m . M ..Ie.........,,'" !'<ah ,,~ hl, l,," Th,' D th OSll of lhe
con",po",hn~ alka ne!, and doublr chll'l-ed "','" a rt .>It'''' ~hu"""',,t (I S~;.).
Arom,lli<;rin~ <:I<
J'f'-""">'M u.ually m.jllue relau vdr ..,gh cnc'lk... a...J
a re accompanied h ~' hi ~ h Jcv;rft or h ~'d r os: e n and tWU d::t1t UI >Cra mMing;
thi, lead, w the dl.o f ac I.fl~ u C ~afflmat ic j" n ..." - (h hlo; A.i> ~ The ion,
C. H n." --{:. H". (.. = 3 10 (.1 Offtn p rtd Olmnalt if t ring COnl ain. chodm
negali". ' ob'til ....nl' ; 11.., "", i"" ( '. H e ... --{'. H , :. t. m o ~ T y p~l of Ih. presencc of cl""tron-d onalill~ su b~ljl UtnU or htt tfocyct;., "''''' I'''un''<- .\ "'" Ihe ri>Ig
po, h i"n " I alk)'1. uh, tiluti,,n 0' 0011) ha. lin lt ....
on lhe ~('>l:rl ru ", (I".
ex.omple. 0 - , ,n- .olld p-x}'le" e h .c ....1 y , jmi. " rna.. ' p"d ra),
A nOlh~, " h~ra,:t"';, li<: l1Un1'~ ~lIo U j ion >ell" of p/len~l "lane< am "" :".. in
Fill",e 3.7 al ma"e~ corrt ' l'0 nJing '" C:. H,tC H , I. emf; n , 91. IO~, 119,. _,):
lh. ~hUll d1lJlc ~ , 01the individual ion. I re llluch nr",,,
k n l o n tI " roolure of lhe nrnl eC ol~ tMl n Ih" "" ,>I the I"""'m. ,, i".. ... ie<, 1I0...,,.,,r, ion lahi_
11zed b) the aromal" '''Id eo. can ho rm""N lIy a .'a OO)' of rratmtlllarion
pa Lh"" Yl, ' 0 tllal the presence 01a la '~ e Pl: a ~ , me ll a, m i ; 9 1, , ;gnir."" onlyt lLd
lhe molecule CO 'llam. " ne (" morc "r ",.'cra1p'",.ibl. m uemr al feato""'.
The mo, t chamc terlstk ion of lhi. ",,;e, in Figar e :\.1 "" n '''t><md, In n ' pmre
r>f II><: bcn,y l" bu nd " r Ihe la'lIe, t alkyl group; tha , I-phenl'lalhne<; ". hiM;t an
abundant C, II, iO'1 (L4uati,m 0.1.1 ). The rc,o"ance-, tabihzed beuz)1 ioll i<
<1:"i~ lI:d n. til<; C. H, prodl1ct, but in pa rlicular eK"', the simibrl y "abihN<l
lrOp);o,n i"" ha' hccn , h" ,,--n '0 be the chief pro duct (for mosl inle!J'reti",
mechnni" n. it is not unpo rta nl lO m ak~ thi, u;,lineLinn). ror ",ample, loluene
m" l 'euL.Ti" ..... II I ~n oegi o. , onicicm 10lose H ' call lllld.cgo i",m"i" llion 10 the
1t >l-It~bIe c~'do~rt~l,ie" e m"l""a lae io", which by H loss forms the trop yliu,"
ion H i~II.... ner ~)' tolu",," ion , h.w " a hi ~h "r tcnJency to 10", H before . uch
N>n"'T" " ti"" .o Imm hcn,~'1 'o" s, bur br Dzyl ions (Mi,- _ 9.:\ eV) of ' uffi ciently
"'~h "'l~roal "'''1\)' can i" ,me, u.c (eriLieal energy 2 eV) ro tho more ; lable
I r"p~li,om iollS I!lU, _ 9,0 eV~ Tho s fron, wloeno or cyclohel'\"tri"ne the
C, H , ' j<t ....~'T, I",mod "n; a crilieal function of tbe iOllizillg electron enorn ; a '
Iltrt>hold "" "'J':.e<. pu'. IWI'~' li um ion< " rc fOtaled. ch"nJl,ing to.o minimum of
I : I LlIo pv)juml 'T benZ)'ll at 15 eV, bUI 2' I at 70 eV (McLalTony anJ Hockhall
1979; "" rli", ....m l .. "-'".......'c,1 bJ Geubh an d Meyerwn 196:\), Such rearran gemtnU ill poI}'alkylaromalics "" n a= ' a n' lor ,mne cun1petinK ~ le av a ge at lhe
ring...lk, . bmul , ,,d . ". 10' lhe "",millenl (M - e ll
p<ak in d tln~l M~I h<-..,.
zene<. O ldin d1m,na lion lTOm Ihe primar y hen, )']
prod uc l can .01' 0 give
l ;'H , tC H, J io.." 01,.;t.nificam abundanct (" 'I ualion 0.14). (Il h,,, been po'lu-
sre
,.'"ll"
noenoe
"q......
,t
'1'''
...
__....
'"
lal cd ~lul In., ",} r 119 ion ,Ic<:nm!,<,"o, I hrou~ h a. pjleny l4lcd C)'d oprop"",,"
il lost in ro""in~
int erm Nli.11f; In I ~< ~_ "C. l~ "'"l~d an Klo~. 6j~" "r \he
C . H, .j
"c
"
.. V
~
(9 13)
(9,14l
W""" \M ..:Ikyl , id, cha,u i, pro l' r1 <IT " .~,r. h>'d ro~on reaTfallE;e.... m ""D
prod""" Iho oharacteris!" 0 ,"' " ion IEq""I,oD 4.36. 9.(5). SubsM oen" in I""
"'l" "; lion tend to ,kc<C>I>OC chis re<ma.ng<mcnl in r. vor of bcn7.J'1ic cleavage
I E 'lu ~ ! i Qll 9. 1J). j,<llOp ic Lobe lll1' 11>",. " lhal 5-, 6-, a n d 7 n,,,,,, h.-red -rinll l l'\ln ll
lion . late, Can be in..., h,-d (We\demJOli, er aJ. 19171
"
(9.1S)
Note !h t Lhc SdHI<' bond il rupture d in l-''1lal li<:>n 'U5 a ~ in , impk ht:n ~y li<
(Eq Udho D 9.l 3~ ...h~h i, nol (",e fOf the .n;ok'lll"" reac ,ion, ol l'Olor
uru"wr .,l<;d rum:1>o>n alilie, (E qllmions 4.33 . nd 4 .14 ~ Soomelimes the rat;" .of
Ih..... ,,"m pct;n~ <cact;"'" C'UI be f a t i<>nali7l.~ l m lc<m. or the re~1.I ,..e ~"" rl!l"
. tahiJiLa" OfI in their initi ating can....icallOnm, Th. re l a l iv~ a nunda""",, of lhe
cones.pon d m ~ r, ;m anb'L'11Ienl ion. C. H, . - , i" the rna, . , ,,,,,cra of .. to!}l- and
/,-wlyl- l-pwpKnc ~r e ~ .~ and o..~~ rtl, ,,,,,,,i,'d )'>tr>mpa, ! co the 8bn OO~ TI C C ' cl
the ion rro m holll }'l;, d<"a"~t"> C , H" ( Eq~ a! i om 9. t 6 ..,.j 9, 1 7 ~ . mb eleo!w n
donating 'ub>t' c.......,. ......" to ,he ~ lkyl- s u bst,tu, n t ..,.. hanci njl: 1I-leu t angcrnc TI (
(Oeenl o",i.. 1 964.~ The R~n~TI g"rnefll j , unfn-o",ble ",hen .'; , hol ,he ~. or tbo
o ,, ~ "~ t ; on, ~ 'C ,,' mrlecel)' snb' titutO<!, "n<1 ' -lr1ually ,,, pp"" ' ,,d ,f th,,,, io.0)." "''''''...... btu!n. ''! In the moleoule I Kin".I.", . , ,II, 19 88), Th o 10""" hyd ro" 1"~,aH.
...
il"D
l~ o; pt ; ' "y
or. t~ric
of ~ n , ,,b,, il" Ie<,! ~ r" m~ li " (...th(>-c~ rl>()n i, d ue [" ""m hOM !i' tn
Md eJeC!loJll;C facm" IK lICk 1989t
(''-11)
l'ol._,1-" I"~"yrli.' .._ I;" , ~>. The t>c h~' IN of ~ i !hct 4" 'malic
hyd roca.rooo> can he ""- .1 ~. ~n C"T~ ('I<>loli"n
1M! ,Il' , Ikylbenzenel de'<:ri1x4 abo. ... The ......l ""ul~f ~n" " " uhly cha'~ inns a,~ 01 hi ~b< , nbu nda\l".
Similar cha~"[ic alLyl >idhai.. d,~vJ~ OX\;lJ r; ~",(>mpuli l i"n ' n LIl .
u.....furatoJ ~ystem 15 ""b]"';1 ' 0 """,TC Io fd w f"" ~,....t .~tlet a l t<:ralU bhag
or
VnLw" n... Try Unln"",n,
4 , 1~
and
5. ~ ,,~a in.
f",
s.._ed Qliplwrir
.I~ olw/,. M a" , poclm haye he"" 8h'~n

methanol (Un2.pwpa m,1(Figure 6.~ ), 3- methyl-3-hexanol (Fjiul~ 4.2), 4-(l<;r ~ ~ , ~
{tJ nLn.... n 4.19). l-d <><l ec.l nol (Figure 3.8), l -h e~~d" ,, " n ol (t; nkM o, n 5.KJ, glye_
ow l (Unkoown ~ .1 1L 2_ami" ", lh"" ,,i (U nknown 4.2), and ~ - l am j1Lonlt t h)1 1 _
..1 t>yli-t,,"' zyl ~ "'" llC l (Figure 4.5).
AJdil'nn nf ~ h}'droxyl group to an alkane low. " the ioni7;ll;on cnec!,)' , but
tbe molecular ion " t> u n d~ n cc dccr"~"c, I~nd "f" n i. nol oMer-a ble. U lU the
,... ,ar~m nr Fig~rc 9.5) M,pite thl, Slabilllation becam e of tlle illcreaoed u "" of
de.;ompo . JUon through roaction, initiated at the ioni""l hy<lm ' j'l group {)/fsell lllQth" I"". of M ' ,,,k nhn!, <In undcr go ion -molecule " actio" s {o ti.., ..
r"" .. ~n...,jepend e 1\1 M H + peak which is useful for d educi n~ molccul.... lOe;gh'
(Section 6.1). T hermo! and cata!ylic (kh ydTO<->C1\atk>n an d. d.cllydratiot, of ' be
~" m plc . . .... e i~lI y in melal
"}" tem CIIJl gi,'e .puriau. peaL> "",h ...
(M - 21- ', t\1 - 18)- '. a nd (M - 20)', alt hou gh tho.. c~n oJ.... It<;'''' IbrooJgh
~ DOVI'n 1.3~
""""oi,
,,
"~
..
"'"
,
..
,
,.
~
. h Ii
, ..
,
.
'.
:'r
7
~
,-
dcct.......im"""'_md .....,J fJ;ogm<.... I ~l u m; the I'R"""'<:<: ,ofthe a " l'I:>J" mJrns C Al>
o r mcl~ 'table ion prod llC1 {Se<-1 'otl 6.41pro. ide<. a OOII....,it.. ' proof of ,he Iau~r_
1\ . u......... 1i.l1 pca\ III ...... I ~ ....... b ilk D ";,, n iD~ bg;:;auso: H,O con ""';1, Ix
J'I"><"1" hoc:o "", of ......... "l'ti< m in the- inlL"! ~Y 'l<: m '" .... a n ;"'1'''' ;11.
Both ,be radtcal W and tbe cha rll" ";Ie m Ille bl d ro. yl voup a ~ ,nk rmM I'
ale in [heir ClI ralHli1y lor """" i, m ini tiati on. w tha I mu , ......"<'l fa
OlI",, ,h,,t.
exhibit manl' " r IIIe IlP" H" rea~li""" n... linM in C hafllef'l " an d ~ I e" ;" ry
alc<>hols roDtam the lar~ . and (II",.... ry aioollols the m1 ~ nesl. to ral a Mlnd.' 1I
or o ' tl,. ;n -eo nl.ail1mll ~ m . m <1" ,;. '1'C<:ITll . In all told the "1"'<'1'" or ' ....lh .." I..
-clea,. ~ (IlqllallOfl " .171 i! , he mo., lIllCful cha raa ....... ic rea ct ion. In t he opec!rum of J.met hyl-l-hcptan<:>l. lI',;u. r 9.Sl lh.. p,,>d~ ,he ,m p<:'ftaOl ~ k . al
or
--,.
- ,, ~
c.Hol~ ~
~.
,t"
'"
H,
C,t1,.--.Kd
"", 1o,
-% .
~
~.
- C.....
,.
"" -"...
..-f , _
H
-'"
C~
J:.d
mIz
I I~
CHp<=O.<
1 \l . I ~ 1
""...s
CtH.CK=OO
--
,. ~,""'"
--,'"
"". 31
1 M. . . . . ." ... of Co.,," on 0""," " " 0'. ....
mi. 73, !f)l. and II ~ r[qu,llion 9.18), whose a bundance reflect< the ,i ze o f tke
~lkyl ~"" p!j 10,;1.
d i.p1 a ,, ~ n ...ltt
l'h",~ ~r~
Fo rmation of , u,," C. H,.., 0 I ion, thm ugh the eyd i"" tioll-
rearrangen.. ltl ([quation 8.1031 ' ho nld bt of little importan "".
several possIble paths for f" rt her de"ompo,itiol1 of thcoc F~: ' i.m,
(n.. onl)' , inlpk ~l<;a~a8" wl,i"h "" uld yield . n" lnOr t.:C ion. Equation 4.21>,
..c, onl)' H ' .l ~ "arran~.rnem of hydro~n to the carbon atom oft~ e oxonium
do uble oond to elitninate C. H,. (Fu ll.ti on Y,9 S1 .;,n ~<-"' lUn l (oc the mi .l l , 4S.
,,~
~ntl W pca" ; ~he m", ~ abund. nt ,>I tne", ;' Ih.llt I'f""<l~ (or lhe I""" of the
la rge' t C.ll, . mol'cIlle from the most abundanr ptimu y- rrot!u.;t km. '-unl"".
, il-membered-ring r~ " l r"n ~c rn ~ nl . l 4 11. ' i<)n Y. ~J e...... ld til"'" ~ ic'ld mlz S<;l a" d 7J
10m .
rhe main oollll"' titin ~m))O'i llon of the EE' C.H .... 0 ' "" " '" dcb}cba_
tion, which "ontrib u\c, to lhc (."""'t j" n elf I....' .....: ~~. ~l, and <n ,," aL~(Eq"3
tion 4.4~J. '(1", ~bu l\danl m/: 29 a nd ' 3 ~a kJ a n,." In pdf1 h om ('HO ' """
C , IJ , O - , which may . 1", . ri... ho m "-'rTlp.";,j,,n "f ,Ito; C,H , , O ' i" ,..:
ob,'iousJ}', "ore , n" "l d be e ,.,d...1 in ""ing ",,,tI,,,,, of son da, y- U:' ion
, cad ;on, . ' udl a,
a nd th~ of EIl". I;on 9. IK a.> e"iII ~nn of
T he ~lher lD.1;o[ d ecompOlmion flit lh\.. ~ p'...nhlc f", .k~ ,"',l m,""'--vlar """,
le~(h to Ihc It"", ,or H , O ..nd .>ftH , O + C. II ..1 ( ~ <!: 2\ EqI' mK>n 4.-'l!. A, ..",
bt ",en from lite ab~utla= 01 II... p, e<lio;tQIi "'." 112 a nd 42 rca' ''' Ih", ' "acli" n
i' 1.., CQ(1ll"' tit" e in blanched ~k"h"l .. In "" nl...." . m(lli.l ,11 lhe "('<'Ctra of
"' rai,bl.wa in ""-",h,,k, .""h as 1-do.lltCan.)J (f , ~ ~ ,e 18 ~ sho w product! which
..." uId result fro '" suc~ a primary dohyrl... lkm "f the m ,,1 ~ ~ ~14r km. T he
C. ll , . ..O - ions which wo" ld
fmm ";mpl" ,..: Iol\> a~o (m/, 31) and dis
" Iaccmcnl fEq uation 8.103) a .. lnlnur, T ht 1-.1 of the '!"letl urn c!"",ly ",,,,m
bleli. that oI l~c oorr~,pond alkol><. a ' c~n he """n b)' ""mp4rill~ Ihe ~po>Ctrs
of I-hnatkcooo.>l ~ ...I J _"", ~ Jctt "" (lJ nl "" wn. ~. 9 ~nd ~ , 1 0J , T he promiocm
c ,H,. ,~. C. II ",,' ,and C) l ' ._j, ion ,. rie, of l , ,,lk,,,,ol. (wnieb "" uld ari,c in
p.l n di...-JI) from \t ' I C.IIl S;,'C c"idcncc tor h'~"eh i,,~ 01 Olhel structu ral roah' R.. ,0( ,IJC e. ' '''m , k .icto ,~ this ImgnJtnl J tion boh" " ior g.n.n~l} rol1o", ~ ~ha t
""tlined ro, Ih. co, rnpondiog hldroc" rbo n,.
t""'"
1fT""',,,".
",i""
t~h m. ~,~
J' M , e,-Jew "g ain II}' Unknown' 4,19,
5.~ ,
5,9, 8,) . an<l8 (I ,
( 'ydiC Qlip~ati,' ;</e" lw !,. Th c ' pt<Otrum of 2-methykydo hel aool i' ,n " ....n in
r ' g" , " ~.~. Alpha d t 2yagc (Equalion 4,14) is fa" orcd 01 the more , u\litat..'\l
ling bond (Equati ons 9,19 "" 9,20i, Further , """tion thmugh C. H,," .Innlnalioa
IEyu4tion ~ .\.1 ) 8i""' d tara Cl" i.q ic OE " iOll< at ,~/= 44, 58, 72, and M. H" ...
"""r, ~hi. rca "tioll i. " " t as favorabl. a, hydrogon OJ:";lraet;,,n, ",hidl mo,~ {he
radica l lifOto "n " llyh" ",,,i lion (Fy ua lion 8.54). Eli'ninalion of an a1kti radlCll l
gi,,". the , tahle C , tt , o' or C.U, O' (Eq uatio n, 9.1 9 and \U t l) i"... A minor
p, ocesl tEquation 9.21) i n dic ~t<;d by 1a"",ling "utli"" ;n, ol,,,, a bstract ion of Ihe
h).lwlj'1 h ydro g c~ (~ fa-o red type of hydrogen lOr .., ,,,r an ~emcnt l by the init", 1
, aJica l produCt to gi". t~ e ht pla""l moloo;;ulal ",m; ("<th",, Jocompo;.ilioll of
.., ..""'''''..
,c
'00
"
"
"
fig",. 0.1.
&
,J~
" ......
M ""poctrumof"_ rndhylcyclO"
00
100 Hcxanol.
120
7'i&
,:
--"--
~"
I
C,H,
ml! 57
~
,
m;z 72
)"
m'z 44
{9.191
--'--
~
II>'z
CJH,.
71
(9.20)
..
I I
Of _ ,
Co_""" C
..
.r,
,
lh;;; and the aualogou,ly r"",,oo 2."'''th lheunal ",oil al$.o. conl rihul c 1" ...... \0
' nell as mi: 44 and 58,
II, in th" m" " 'f'C'..1n o f = ydi<: "le...I." I.. I,,,,, <or H ,e l l l:q u~l;'>Il 4 .) 1\) ('to,-ide, the ollt" major pIIt h way for M ' - d.lco m pos il lOR, Thi~ lllr,ely ;o\-oh"n Ihc
hy dr ogen atom, att " "l>ed to
.1. 4, and 5; Ir."''''' ,,( 4 H lI'q ual;.m K ~I\)
in,'ol vo" ,-i. -<t... """bem iSll)" C'f tloe ~ ~m l n.o l Ct1 &'tO O~ 1ft " It boa lfon u llJ",i
lion Slale, The .pect( um', hydrocarbon-type ioll$ a rt w n' '''~ nl " itl> I ~ ' ''''' ~ .
po;ted lro... f~l1 hcr dc<;"m"""i !i<m . of .uch triC)c1ic """~dT~ (;"" rMd~l" It.:
""/' M and ~ 0 (' + io n' would "1'''''''nt t lim inal>un of a brid j Ulj ~rO\l p Il the
!liable C , II. or C ,H. lno le that die - ruk- 011"". of l h. br~..,'" alk "oJi"~ 1 d"",
nO( OWly I" thc <ii,mna!,on of m" l""ul= in lhk-.ca'" lho e ., H. ;oll should be
mO'e <I~hlc Ind u.... more a buodanll han the alt c rn ati~ . C.H . -- iom,
""rboo.'
,I
~.
n.c Ol'Q,vum nf ,>-m<lh ~ lp hc ~ ,~ Wi" utt ~ . I) illa'lrale.
<e"e ral fra ~

" "' n II U",,S chl ra cl....ISlIC 0111>0 h)'d"'X)'1 gwu p on an "",mal ie r;n\l, T he .....ld
"I...o n (M - CO," pe ak, wh ich i, u, ually "cco~lpa ni"d hy 1M - C HOj- , i.
npe<.;~l~ Il ...: ful in ,,,,,,,!!~ i.<in~ [hi, funclionality. Th~ apparent mOCbanllnl
( Eq u ~l i ~" 9,221Involves .limin alion of o,ygco with itl adjacel1t ri~ g car h,,~ .
demefllllflbbohnl l1\' ''' ''' ind i c~Tc Iha[ CHO I"" i, accompa~ icJ hy ' ah.. an_
, ;.,1 hj'd",lIC'tl ..,ra n \ ~ i n s.
1 1>0 chlmeter istie OF" i o ~ at 1M .. lX) ' io lhi, <pcclf am ;, "-n cump'" n(
lhe "ofth(l C!1,:I;\" lF~ uu d "n, 9.23 and 4.4 1): lb' ahundanc.. 0( til<' (M _ l 8"
,.
I
.
.'
_..
"0
" 1 .,
,~'
,I
;r
I
."
. ..
'
M .....p"'VU... I ... _ ~ y l pl>mol .
..
p"" k i n the corr<S!"Jrtdinl.l ""'a and pam i!i.omers a ~ onlr 3 al'kl 2';~; . ~' pe c
' i"" l, The lar~ , 1M - It ptnk arise> from the 10M , ,( tho: bel1zyli<: hy d T(I~ "n
a l010
~ ~
1.9.H J
A I~"h"I., <'Iintuilfin. "'..... r_lH1i<>tw1
1:''''',.... /l lipha dc hyd ra,}'] group' tend to

"a'"
ad i"al e til. ~-hydto~ m, t<Of "a".rc-r t tl nth., fu nctiOll~1 aroups; I,,"' ....
from diols or mc''''''''' r,,'m methyl e' ler, 01 hydro ,~' ,,"id. (Cquatio n 1l82) an
pTomolo J hy the p<'fi<'n.:e (Of the hydTm yl. Th e ph enolic hyd ro. yl ") d H'~'"
"' nibil' a I,i~h tntdcn~ 1M ,, ~n, i"r lo a rad ical , it. (F<j ",,'i" n, o.ll ' .24)
~a " ... 1"'= " aill"'- ) a' D~ l'~n C~n b. dd ""alizoo ' ''..... ,M . ""q,,11ic r in!!_In a
p!><"o l tho: hyd ro') ! hy J f() ~ n alllm ~an Ihu. ~ et a. a re.ody donol for ,,, ''' lho-
-'"
'"
dJect "", rr~I'''"_ Th~ b..., peak " f m<"thrl ",lic}i.lle i$ d ue ' " , ~ Ion of
mel ... .." L ""II ' he ""rre"""" d '" 1 ~ l>o'ndll.nee. fo r , he ......" MOO /'<V,' ;\(1,,,. .... a ",
'" l ~_~ h " m en<: onfl.;W. ... " ther ' '''' 0 t!>oK ,h_n a re I">l.il>k fur 'he I""wl.
net ion or l q wth, m. " .23 000 ., 24 C~ n ~ "" olillle these ('o)~ 13t ;"'" for t !nko"",.. '1.2?
_ _
. 0
..""
m"
" "
" """
m
m
n. "
"
,n
,"
'"
,"
....
..
'"
'"
'"
".
'"
..
'"'
,.,., ""
,n
'"
"
,ro
""
'"'" """
n,
"
m
""
""
""
""
""
on
"
'. .
'-
~"
'"'
"n ""

",
"" .,
" "
" ,"".
,."" "
," ,
" ,.
" as
M
M
"
".
'OO ~
".
,, ,,
"
"
"
,,
"I .
..jh~
"
J"
, , , ' , r -''"
' 00
"
,.
,.
'" '"
,m
,m
9.3 Aldehydes and keton es
AliphQtic IIld, hpJ, _. Illtd Ii f l oM .' . The m"" , O. UII at !Qlln, ,]dehyde, 3-1>0010oon. , 3-methyl-2-!>u lano"". 4-melllyl-2-pcnlan()nC, ~.m "l h y l .2 .pc n l"n """, lind
2.3-hut'lllcdinnc bu,'. b. en ~i\'.n '" Un known' 1.9. 4,9,4.10, 4.16, 4.1 7, and ~,2;
those of 2- and ~-d odecanone a,.. Figuro> .uc an d .1. I I, lh,"'" "r 2 .., [h y l h ~ . ~n ~l,
6-mcthyl-2-heptanone. and 6 -met h)'1~ - b eplene 2 o ne ore . hown ;n fi gu~ 9.R
to 9.111
.oo
<ft.
'"
~-
c
.......l~
e,K, I
i
I
,
,.,
I
I
\CH,j,CH<; H,CH..fH,ficH,
sc
00
.oo
'"
.. ..
.,
,~
(CH,),C"""""C"]
H'vCH,
A,Ma in" "f II "" tt><,n)'l ~rn"I' to an "Jh~~ I,,,. ,c.,,e t~" ;<m;7"-!io n ~n "'ln' ' allIlI" ",,1 .,. luei iTable A.1I of 9 .l 10 9 R eV a rc !>elm., dw ", of I""
' r1l:>po ooi nll ollpb;u" akoho li, Th. lnQ!e. u!ar ;<)11 of ''',<,,, lorO'''r kcto n"" wjth
... ,1nC ....'t" " I d ' nin bt ." ,:" ing " .. "",II~' " f " " ",,,,'ablc ah<Jnd. ""'. M ,,\<:<:uliU
llanl ially~
,u
s. ..... .. e. ..",.. e......o. CI. , ..,
I ... ..
jon.; oI l.1 'llcr alip/lal ir ald.hy..... aro oflen , malt bul "lin "" iJ.:n lir...'y Ihe
plOL-nao"rd ..r.u,1Cf,,,;'; IM H,Oj'" and 1M - (' , H . l' - fm ~ m. utl (Eqllfltion
S'IOl- T he LaUef ' ''''. ' ,",Cyt! I>y I (I m~" un il. ...t~ "'1J'."'iaUy pro m i""nl in Ihe
12-<:V mas, 'pcc1ra of slr aildlH:hain alk" n al. l M acroJl a nd M ru<.e~ I Q86).
The cfut.noo;lcn 5Ue po;~ h in Ihe """clra <>f calOO nyl compounds ploYide euu,pie; o r ......"y or ' he m~j", ' Yl"'> of I'ra l""... "'",ri,,n I"'lh",.." d,-.:",~d ill Chup_
tc[';
4 and 8. The<;<' are u t,hu d ID Eq u all onl '.U S GOld ').26
,oJ
ralionali, . lh e
[''''malio.. o f It\<: < """'.t<1 ~ .j' l ", !"'a l _ ,n 2'C lh ) 1 "" Ul~ 1 IFllla ,. ~ .~ J " lid (,.
me thyl-2-heI'MlIO"'" ,f ifU'" 9.9~ The G-clefl", . ......I'''n .. ~"n"r"lIy m uch b.
importa.nl for aldeh)"OO than fo r let."'..
C HO ' 'm/: 2~) ptBk ;, pm",i.
ne,,1 onl;< lor "".11<,. "I"" hy<l.::. ~ OO those ..-it" lIi ~ hl y elecllolW"lto'11\' . funotjonal;I ;~"lC " o<'h lL' e ,l ',( 110 "",or,
ith 1~ ','T ~II ~ I "" :l1,J,; h)d e, il i,
alwayupe rpose<! ",d h (, II, ' ; MJ n< d; a~ tj c ' 1lvc i. l(,.. , Ille allt' Ma tl,"
~-<:l,",,' agc }iddjn~ (M - Hr apl)<:a r>o I" b< ;,ppr.. ble ollly ,.,toto t ile RCO '
iOll Whi<11 j, formN II ' ''Mlanl i>llly . ta !>ili,...,"". "" ro. a r"",atic ahkh) dL.... Alpha
d." ..... i. mUd l morc pronunwr ,n a~phal" btOl'~ )'ieldln. I J"'il or aq lillin
Ll)m 1m"": 11.1 an d 41 in h gu,c ~ ~ , a n ,1 ~ pa i, all yl iv j ; 85 an d 1 5~ Th e
me r. ab undam ")II,,n, i" n II u. ""II) [,,11I,<1 tly 1100 I
or the L . ge, ally l
1!T""p. wt>< rc", the ,,'on lIl:>1md "m ;"~ yl '''0 IS usualll" 1'" more ~lable.
n..
v,
O,H,-
"(".'
)1
,j ,
C, H,
" '" - --'--
m'z l~ a
"'-(1.
..
'
<;
m'z l OO
"
~
","zn
C,f-IoIC,H"ICH'
m'z99
'"
C,H o'
m' z ~ 7
(9.25j
c~.co
"'H3
,~ ,
II
", o
A
m'zS8
c,H'i '
rrlz70
"'0
A
(9.26)
Ald. h}'d. , ilnd keton., . how the , h" ra,t. ri, \ic ion ",rie, t .~. :N, 4 .\ 57... d LL"
10 both C. H, .., CO ' and (: . H, .. , I ions. Allh ou gh lhes. ore besl di'lingnished
b~ hith-l'. ,olulion dam, lhe ab. ence of a part i, ular C. H.,.,, ' ion ca n ,,,me
limel be dem OllS1t"tood by tow U" 1- n' J.-l'" J i" 'lopi e. hu ndance "a lu"
\S':<.1i"n 2.1).
t n il i ~ l rear'M~em.. ut of a y-hydrogen ,n om follo",ed by fidca" agc can gi I' "
II" ~" <>I h,n Ii'll: 72 an d 1l ~1 in ~ 'i lU'" ~. 8 and m/ z 58 in F i ~ u r e 9,9) and ito
compl. m. ntJl'Y alk..lIe ion. E.q u"liom 4.:13 a nd 4.34. 11>c n;la ti,'c a bundance, 01
th. 1.e c<l ", petl\ i"C prod uct> ;m: rdkclcd by , heir i" nizali" n polt1ttiol, (Ta ble
.\.,1); .1><: "' ~et i"Tl i, m u, 1l b, 'p<:c; fk for aJdeh}'<ie., F urt her ,.-d . " .. ,, ~c of
enher OE - . 1IOi jon tro m 2 -<!tl1 y l l><:~a ll at will p...xtu,-" lne cc"manc. -' la hHilrd
<.\ H, O I ;'-,n. C"m rati" m l>f.he r md uc\' " r lhe ~d"a'..age and the {Jd...." g.
cca<.1 i" n. In u, I""",'id"" ovid"""", of ,ubs!Ltue nt< at the ~-pos itioll('~ If " ketone
collta;m ;- h yd ro ~<'fI atoml lll both ch";lI" both b)ltT\lg<.-n ~l "m, can t-c rcarronged
"' ; Ib h...., :.. <lr I'>.,t b olen" molc<: ub (""""=u[i,. re~rrongement..- Equ at;on
~ . 76 1 .
Dcc<lm\'O";t,o n. ot l o " -c,,,:r ~ ). I' ~ rti~,. "' rl y mc(a,ta ble. x.:ta,," ia", foUow
d,ft.",n[ flalbway. lhan I ll""" OMHd in the DOrm"1 . lect ro l1 _im pact-ma
S{'tra ( M ~A d o o 1 ~ 1l-81, F<>t C' ;lm r te. at 711 c ~' Lhc 2!leu n" .... io n I" .." pr<<1<,m ; nan~)' In.: C . ! m<:lb~I I" g". til.- .t~ble ~c)1 io n C.H,CO +, bo ",'..-.
met a.table io n1 uDd. r!" ~ muU"t.p aff " " llemCm b<-f"", r.nJing t he lo
{-
""
, M . ..
s,_
. .. Common Com,"",. CI.....
energy pathway for methyl loss which eventually produces protollaled penlenone
(Equalion 9.27; Ho"chou.' et 01. I~g]). Th.lo," olthe C-1 methyl from mota'labl. 2-hexanone ions acrounb for < 3~-; orlh. (M-CH ,I" product>.
~,
,
, ,
CH, +
'0
--
'0
,"
II
, '
,.
n H~ I'
,~ '
~
_ CH,.
19.271
/JR.,aluraleli keto""."
I r (he ?_hyurogcn is vin yl;", (hi, can Jm<lically reduce (he
formation of ions from hydrogen l'earrangemem and >ubsequent jJ-clea\'age.

Thus Ihc,,, OF' peak, ,"e of ,'cry low abundaJlce in 4-mothyl-6-hopten-3-one
and 4-methyl-4-penten-2-one IEqualion 9.28). How,,''', in 6-methyl-5-hcpten2-on. (Figure 9.10). isomerization of the double bond to a more favotable posilion i, po"iblc (Equaliun ~_2g). and lhc C,H.;O" ,md C,H,' rearrangement
ions a1" ob..rved in fai" abundance, although [C,",O-] i, Ie" lhan lhat in lhe
salllrated derivative. Paralleling th. behavior of alkene> (Equation 9.5). doubl.bond i,omerizalion "pparently h,,, not occurred in "11 M' ; the mi. 69 ion.
whlch would be the pmduel of allylie dea,'age, i, more abundant than lhe
.,-cleavage miz 83 ion (Dia, eI aJ. 1972). The rearrangem.nt 10'" of the .i-alkyl
<-'TOUp (E4ualinn H.9) i, ~haracl~ri,licor ~.fl_umaturaled aldehyde, and kclonc,
(Sheikh et oJ. t972).
Sometime, di,plaocmenl rc"el.ioilS (Section 8.11) "PPCar to be po"ibk at the
ca"bonyl gl'Oup: 'uch a reaclion (Equallon 9.291 accounts fo" the ba", peak
eorr.sponding 10 (M CH,)' in the spectrum of /I-jonone (Unknown 4.13).
.... ""'-' -
'"
."
.o,
- ~- .A
"--0
11l.1N)
",
..
Alicyd ic k n OM. T he rna.. 'peetmm of 3,3.S.11lP>C l h~I ')do ho; UIl Oll< (F i~\l l~
illu, l..-alL" major tildilianal rru rmcnlal ~>n I'"" h",,"\ , ~ '\lnd ' <If cydi"
~.5)
ketone. (Equa tion UO~

,md in So:;u i" .. N-" .
a rc similar 10 lh ~ dl""" ...~ 101 Clchc nlcohols
A"",,,,1k
<OMrltys MJ Uf""*". F, al:mc"la li",,, rn the"" 'p.H a (""" . al;"'yl.

akk:hldc. l. nkno..n 8 5: p-nitroocet ophe norw:. U nlr.na""'l 8.1; 5-pbfnyl2-peutanone, f"~ ..re 4.9, benzo phcnnM, l :..llno w" 5..1, ;".. ,1 J.6-di"h l<l""nu"T1.'Tl""".
;/
<
- co
-~
i -'- r - ~
~
mlzl l ~
"
"",~6
.~
'"
O _C
~_
. ,
_ ' C>o ...
fuJI",..
'L' oknown ~ Hj;" 1"""""'1

,xre ~"d p'Hhw~ l' ''' rot ~~~mrle, benz" ldchydo,
sho w ch a rl <:( tr isl ~ (M - HI and (M - ('HO l" ions. I.. ... " f CO can = 1
IT a ble ~ ,4, o,[1Uo.-\.,lly if l be carbon yl ~w"p .. cndocl'ClLC. suc h as in ao tl" ,. ~ ~ ; n(l n " (fiqUll IJOO' 8.1 21), I,u" of "" "')'c lk CO i. <h ar~ct. ri. t ;~ "f ""ruin
lural lyp.., c . ~. , l -a"OLl llhla<ob (Po~r 1985). T il< ahu ndallOl" of RCO- ,.trom VC "H.C(JR- - ha~e booen ShOWIl lo ..he) linea r free rD.'JY l ~pl ......",lal~ m .. ~1l!lO lLgh a ",,~,bo; r of . ub, \;ILLt nl ntT<lctN ["01,,,.. <" ",,,,1 [R CO ']
.true_
IMclalfeny" al. 1 ~ 7(l,

V" kM"',," " . a ..... )' 01 """" "<lmpoul" h """ ~~ given ;\, unkn ",. n. 1.9,
a v. 4.10, 4.12. 4,13, 4.16, 4.17. 5.2, s a, e.s. 8.1. and !t IC.
. ,. Eale ..
A""""n:,- mel' y l eHr rl, The d~,," c Mud;'s of S\cn h a ~. " .,?n l ami hi, c,,.
,.." r Ke]", in tho 1 ~~ un lht mass 'pretr" uf r:<ll y acid ....en ...... pn,oob l}' the
dear <l<n10" " "" 00.>11 or 1M , 'alac
ma SI .pectr~tT} r" , deducing the
m \l~ IU'" of OORlple, n ~l ~r ~1 pmd LLc, m ~ ~ I" . Th ~ m ~". spectr um of melh;'1
. " n <lt<:allOO le i. , ho" n in fi~u j'e 3,1J. ~ ig.. ,~ 9 II i, meth}'l 1.1,1(,I S-teaa -
fi,.,
"r
'llI'fh ~ .h ~ ,~ d "" a ll oat~
~""" ~ '" "bs.:r"abl~
(110m
hu tlc rUu ~
M""".. lar i,m. " r apprN;i. bk
~h unod .
... ~hphalic
I>'l' I>cr mo!cc ular we' ll"" ( > C~ ~ ,11 bo\l~h it
",'en f" r melhy! ...reI, of
big ".mG "'"ul",-w.j ~hl
",:i.l " [ 1>1'" ,,<t u ally in ore o<n ~l

d ""r~,,,~ , ",ilh chain b(lnch in g
RNh ~ h e o.l rlJoo n ~'1 o .~ F'" and the l a lu n Hc<1 ,, ~ y g.n itom of ""len; C~n :lo;1 as
, it", fo, re""ti" n inilLalion 10 ~ ' V C r" ~ "l i a n p.,!b> <>1'<,11:<1 fmn, Ihe seP., , " I"
beh. " io' " r thew r.. ...-Tiun.alilie. , "ld , in Mdition. nt:\Oi ..... ctio ns apparcn lly d ue
\" lhei, OOmhulcoJ d rcCl.
Meth~1 eslCN \~ ~l do nal OOI'!a' n an add itiooal fua:;tionalilY ~ho .. (he e. p.x:tcd
re..1;, _ of Ihe carb<>h yl gnlu p-- x-clr"~ 1< (Equation 9J lJ ~.Il<. 1!.., 1"" ."g~
..i, I> ,..byd IOgCn fe~"'"~.nlffil t .q.. ~li, ,,, 9.321. F0' m~lh yl ....~.h n~l ... ,uch
a, F I;urc :1 .1:1, ~-cle."3l1C ; i""" ct..af~clemfic (M - J I)' a nd ~9 - i<m . who se
~ h u nd a n c ~ . <!:rca...- ,. i' h incfe<lsing molccular weipll. Th e l~ - ~~ r a l ~ )'l ion
an d th e C H ,0 ' i..... ani ' '''1' smal l exccpl for Jowm<>kl..ul",.weigh t el len. Fur
tho, " ''''_ position of the a lkyl moiet)' pr<><l......... the dl.'fa CleIi, li" C,H , . ,
~nd C. Il .. _, ltm ",ri ""
- -----
IC, >Hu') _
C-nHon " , C, H, , .,
~ =
(9 31)
ij .
ui
F'
,
,
-!
,
,
~
,i
-.
,~
<-+ e
-. ,,,
,-
,t
;
>
.-
--; !
i
.,
"
,
,
,
r;;
r '' ~
--.
".
(93 21
( ~,n "'aoch Ln8 (F igure 9, t I) p" ><l"",,. ch "l<:l~riolic changes in 1M
('II ,O('OICH , I. ' ia n seTic, . mi;;; 59, (73\ g' .lO l. ... . lllloullh in<T"" ,..,j dca . _
ago,: ~ l ~h" tertia ry car bon. How ever, Ihe . t..ir11l-eha in 8ILanos ... sllow an
unu,ual pcflodlClty in the CH, (X :O(CH ,l.- ion stfleS lqnne dlller.nt from the
regular "!lund,,....: ,I".rca", ,",'ith i""rea.in~ mo lec"w "'~llh l [" und fm tho
C.H ' "" ' ,e ric. ~a lh llC>l t', 'ing unu"",,") hig h 3 b~ndan <le' fo' m/;;; 87, 143,
199, 255" ,(II '- 1, S. ~. l :l. . . , ...., a..... I'igure 8 8). T hoe '~ iz 8 7 ari.., through
inihal mi,,' nli,," ,>l ' M 6- Iv ~ hJd l'<>l!en IE'l''''' ''''' ~ . 7~) f"t1 "",lXi hy 1.4- (or
1,5-}-hydrog. n slllft .,1<1 ~ k ~ ... ~'I; o f the bo",d "'LW""" til" p- and 1-alrbons. The
fragment . ' 0l' ",,,, oting ,,lhcr p:.ok nta~ Lma in th. '''ie' '"P" I~teJ by fpu, <:l'ta;n
" to m , I...."" 14l in F ig u re 3_1 3~ I ()I, 11 1, 24 1 and 311 in F;l.'urc 9 I I, "";n(orced
Ill' I h~ cha in branclnnW Il,,,holl>l y '''' oil from displa cement , e~ . ti ~ ns lSc<1ion
g,l l l (IT fu o...-tl . :irrou l I,4-h)'droeu migration, ,",'nion "OU";dC lhc 8"'ja<'ftI1
C- C
fm d ca , age_
AnOlhet lLnusual w"ran~.mcn l yielding C.H,. _,CO+ ions iden lif'N by
~I~nh~~en alld hi' "''''''Nkc" in" llve-. the loss of !be " -, p., and Y..... . ' ... 'O'
it ' ( \ H,- (MoUo,'n and Lon#" 'inlk l \l'llll Cnam clca ' ~l'" )'''lJin5 the
J Jkyl ion <;all b<; ,igniri"anl al fully ~u bslnule.l ...roons; 1M """C!Tum "r . "
C "H J,qC H , J, - CH ,O:XX:U , sho.., . <: " H., ' p',ak of ift'~ ~hu" J.."ce
(mi. ) IS, 100'\ ; miz 74, 75~,;J
i' .....' .......c 1~-nJc"TICJ rOT ~ do ubie hyd,ogen rearmnernent in "",thyl ~...
of l" n@e'<ham ocid.. in Figuro 9,11 yicldin\:
,./. 1,1 (""" ~,,: Ii " fl S.l Q Tlucc bolids dt :,,'ed ~ "aD II. g'oup i, ethyl or larger.
!iC""nd.r~' /I-h>nd cl<'avage can gi" a c~'njug~\<XI EE+ ion (Equations 9,~ ~.
8,79 1,
or
1><,,,,"
'M,.
"'n.
'"
., two
'~EFt-
"
t~
....
I, '0'. ,
", , ""
" " ' M ,,"'
1.2. M ... ' l"'<I"UO\ ......
""tOte. The M " pea k or m,.', t I(; h.. ."
"
"oo""a.... cI 0.1:'.
~I
~ "' J.,
Ir I"" . m: olTM alcoho/i(: .Ik~'l group K i, indi,,,te<l by The (M - OR)- and

ROa r ~m .. \he ma"" of lho reJrrangem' nl ion CR.R;qOH)OR I thu, det; n~ l h ~ SIze cI tilt 'N uMtilaentr.. The reciprocal l1ydrogen rearr ang.mcnt
c1e. .inl.',he 6 7 00lld (qll'l>un 8.78) lhrn ,hmo"~ the /l,ubstituent' by differ~1_ l n f llll", "".l l ll," Mi: j 'h nd 295 ious iudical~ R-COOCH,; mi=74 (aod
7 ~ 1 indi<.. ~ R' CII, _ COOCH, >. oo mi' 101 then indicat", R"- CIICH, -
CH , -(:( IOCH, .
b., ~ .q iii! :"", , """. T h ~ m,*,-'Ut" T ion peak of Re O OR' g~u ~ rall y bocom.,
lban blllyl (<1' 9 1 ""'laIc> Fi ~uT<; 3.14). Tho
rt latiwly -.mall .. ben R' j,; 1....
' PCCI" '1I\ of _ b.Il}1 ."""" ~ ("lUTe 9. 11) inc"Irat", lb. a<l<l iliolUlJ ctio",
tha t ....c 1I'. .. iblc ,.itb such ""en. R"",.,.~nl'--mc"J)1 "r
If",!""t ion 4.33) aDd
IE'lU-Rli.>n .4. M) hydm [!l.. ...lom , is hi,JIJy ""'" acle",l;,, (E<! aali<ln 9.3-1).
'eT
"n"
'''''0
m'z 1l6
-,"
M
I
. ""
~~
-"-
""
A
l"'- z 6Ol
)
:
~, y
';;,...
f )l
...-,'; 1
(B t l
".
1M...
'po_
of
Commo, eo ...., .. C"....
For the formor reaction, aiken. iOIl formation prodominates for propyl and
high", ester<, cnn<i"cnl with the i()ni~ali()n energies of ac,d, and alkene'_ A
slereoselecti,'ityof _ 3 kJ mor' is obs erved for the ",coudal)' hydrogon transfer
in Equation 9.34 (Green et 01. 1982). Although tho double hydrogen re ar ra ngomenl prc>dure, an e..en_e1ectron ion or only mooerale ahund.nce. you ,hould k
able 10 recognize it from its low rings-pills-doubl.-bonds ,'alue and beelus. it
occurs in" rathe, unu,u"l ion ,ori.., 147. ~1, 75, _" I.
Alpha deHage (Equalion 9.35) at the carbonyl group yield, the large m"",
43 ion, the altemati.elM - CHJ)~ pook at mi;: 101 is smalL This lattor poak
,,-{C=O)
CH,CO.,~
tc=O)
?H,
-r
CH.-----C-OC H-C,H,
{O-CDC,H,I
---'-----
",/zI01
(Oc,H,)
mI.73
o
ct(C-O)
,,>'z116
".
CH,CO=HCH,
miz87
o
~(C-O)
~ ~
".
ICH,CO=CHC,H,j
mizlOl
c,Hi
miz57
(~,35)
actually ""n also he pnx!"ce<J by an a<l<Jilional ~-"lca\'age reaCl;nn ;nitiale<J

by the ,alurale<J oxygen alom: a similar ciea,age with Joss of the largost group
producos lho significant m,/e 87 peal, providing a moans to distinguish this spoctrum from that of "-butyl acetat<;, in which lhis ~c1c~'age "i\'C, a peak at m/z 73_
"Ole lhallhe ion serie' m/z 59. 73_ 87"
. can he due to eithor C.H _jO or
C.JJ' jCOO+, A largo pe.l k in formate ostor, is formod by ~-clc,,,'agc foJlowed by CO loss IHCOOCHR, , HCOO-- CHR; HOCHR' + CO):
ROCOH' al,u '-~vc Iar"er RO' lhan Jo KOCOK'
Charge-site initiation at tho salllrated oxygon, RCaO-R'- .... RCaO, +
R', can give important peaks when R i, ,mall a11d R'- is 'table. Thu, for
lhe "., ,<I,,:., anJ 'er,.bulyi acelale' the ,alue, or [(M - CH,CaO)-J,/Lx.c, are
L 3, and i7~,;, respecti,'oly, A reaction like Equation 4,38 predicts that
C.H,.,CH,CH,OCOR' shoul<l yield C.H,." as ""ell a, C._,H",.+' ion"
(Figure .1.141
A rather \lnu,ual 01" ion can ,,,isc [rom the elimination ,,[ the o.'ygen and
..
........ r"'''' "r I" " ak.~) hn] mniot}' a, an ald enyd" "",1,,<:,* ( rtti. meehani.... i. nol
in the spectru m in Figur e 9.11.) Thi"""te~ R ( ', H,S CO R, ... n
g;"" a ",s n;r. "" nl tM - C , H. S)' ion (hble K.4~
If !><lth the ester an d ,he scid cha ins a re of ouflici<:or IonSlb t~hl-I bUIJOOale
or lal ger). the hycl roi cn reUra Oi!<'mOUI. of Eq.... lio... '>13 ;: and "'.~4 \>4n ,,",UT
m nsccuti,c1}'; ~hc"" Ch ' '''"ICri. ~ic ion. ,.iOa ppt'8Tal mil 60 a rid 61 jf the acids
~-c a l' bo n alo m i, not lubilltulod. n-H
yl alld homoIot:ou. h ;~be r c a , b<,. }' l ~ t<:,
cha raoteristically )"icld . 1<,,,, .I>u
" j,m oo'"""'l"mding 10 ,he ~ tyl eSIOr
(M,y, ,,on " , a), 1993l
E'Ier> of du rro' li ic a.:i<h tb<>l h melb)"1 mod ethyl) usnally i1ive >ny low
molecular ion" t/>,:;c ""n "" . ....~ oyri "' d h, ~ h u nda n l douhlel' of (M _ OR)O
~nd ( '-4 - HO RI' , anJ f"'sment_ du e 10 , ub<"'l uent , Iimina lion of the
o t~r . Jcohol molecu le tM _ OR
H ORT . Dimcrhyl alh,," di o a ~.. . h....
Ch...-llClc<;. lic fNlgmcn" 1M _ C H, COOClJ,.lo .nd COOCII , 0; t~
CII , =C(O IlJOCH " - ion i, ~bu D<l .nt. but I..s promioeJIt tha o io tho '1'Ct-1f~
or m.-Ih ~i .oJkaooo tn
imp.,>tO~nl
bl", c_fli";~g Mile_ ft,~<tin~QI X"'~l'' (lan" hn~ ... <II 198Jl As .. 3. ....n. i.oncd ~ "' , v" . ,he ,a turated c.' ygen atom of rhr K lt!'! " ouP .. 100 ""n a<1 ~ . a ,"Ie
.0 ..hLeh a hydr ogen atom can be tmm.rcrrc.l In h l"".i"n . ... 1 of beflzoote rolters,
III<; pcCKn "c of an ~" hldrog"n on all oft ho lubs lit uen. Hi- a m ara <l"rl:;{i"
"",dud i,m <orr espo ndlng to (he 10.. of an ..lcohcl n',*n.lc; lb. addition
of a 9. IOdonble bo nd to m" thyl ,~ ~ " h . ......", @i' <'f- (M - O I, OH )-' a, the
largo'l peak in i ~, ,pectr um. A labile bl'd ro tl"D allad lOd I" , ho; Ch p",ition of a
rTlt{hi'] a lh nonte ofteo Ei,'cs d ...... et" riol>c t M - J2)" ' ~n d (M - 16)" peak,
(Eq\lall" n ~ ,~ 1 ). n ~ I...... "f RO H from M - ' app.t r . nt ~ is Iavc red " nil if tho
radica l , it<: i< ; t ~ blli 2ied ; . h' , O E- ' i<>D <>fln>'Mn I...., CO tf"T ~ ..",ple. ort oo. ub<lillll. d brnro .U I"n l (>I ( "H , Co. 11>< TC4uin."1'tIOnt of radlcalsile sla l>ih
,.,,{i,," ;, aIM, ""'I in U , and wme O E" jrnflment jo", ~f lIt f. " " '~'" Iha l
cont . i" a Iabilt hydro""., 8,om, F'l w,tion ~ Xl. a, di, cu, ,,, d in S<!ctlOll 8,IO.
lbc """" 'P"'-1r~ ~Ik ~" "'~l ~ e,te" aa relatively independenl c( t~ dt.~blc
I-.md f't",iLi" n. "'hid> 8pp"'U ll)- mIgrates ,.adil)', for " , ample. ",.,hyl alkenoa.es usually sho w lhe >It,.'; 74 4fld ~ 7 i,m, chara d c ri, {lc of "" Ihyl al k3D<>a1n,
ah hoogh in k", c-r ~ hu nd~ """ Alk.noate; gell'r. U)' gi,'. ",.ak ""'kt:..... r ~ m ..;
, h. 'pe<:1ra con lain ab undU ll' C..H l . _10 fr~ b"n"nl ' " f lite all
"'~ no
I'yrr ch did. d.ri>ali\n (Aoden on ~r " I. I ~Ul and ion <>ltenle re.>c"
linn. IFerrer-Correia '" al. I ~7S ; lJ <JtlLi~
19115; EiuIlo rn Iff trL 19115.>.b) ar"
clkc1.i", ,,~y' to diff, umiat. ber...c. n ~o ll bl e bo nd 1" '''0"... (..,..;c w.
and
ern" 1987), .k~-Allenoat.. ,ho .. t .... ' I'pia l ........ "r tl-- alkyl groop" similar to
lhitt in cnnnc, (E<[ ual;" n ~ . 9) . U",..lllra. ed methyl a nd el h, l ""Icr", . hihit I"'ah
rmtn the . llmlnatlon of CO , I1ld HCO, (Tabk K)~ f.rn') a,-"C ~at"' and olh..
'Insmurated " cetat., gi, '. ;01\> n ' n Olp.,ndinll ... ~ hc I"", n( ~e "n" . Polyacetoxy
c"m p<> und, <an ' Om,' clun.ct",i, ric (lU kl soch ~s (CH, CO), O ' (f.4uat; nn
~ 120) who", [orm llion m~,{ invol.., a<>rlyl nu ; ra" on
"r
...,eel'. '"
'.,,'kJ;
J.""""
.~ ,umuri<' ~ .,t< r., . T n., cnmTl' uQ ~ , r.r rOJ , tion! , iled above are fou Dd for a mmat ", e,tero; (..e lhe maS' specm'm of beLt)1 bc n ~ " a ," . lJnK"" ...n 4.21. be_),l
b"nzoate. ~' i >, u", ~. I ~; l'1"<1pyl p-hydrCllybem:N to, Figuro 10,1; phenybJanine
met b~' l e'ter, UnKllo wn 8.2; and d ~ll l l' l r htha latc. Figu", .~ .4) . N ot ,urpri,ingly.
cllarge , o,om ;"'n On \he .r~ k"n l"i n i nll fr,,~mellt i' slrongly favored. If the
aromallc ,in~ com .inl alkyl grou!". \h~"" und ergo the typic al fragmen tat ions
"f ,L.l. .......... d.,..,,,bood ~bo 'e . "O rtho drect' (Equation 4,41) ar~ u." 'ful in
Il
nfying ruch ring ;~""ri.m.
" ' <ln ery of ne..- ru clion ~ th"iaYI ar c mado I" " , if>lc hy the "bility of the
~n"" . li c ring to ~ce bonddi'SOeialion " , ,,~ i ",, (Equatiom 4.41 and 8,811
m bib.. lhc i" n . nd . aJ ....1';lc,- ~nd provide an un saturaled sito fo r "'arra nge_
....1Il, dlSplacemenl. aud . Lmination ' ... <lio.... (EG""li",,", 4.>ti, 8,110, 8,122.
lU l31 " . llII e. ~ m plc of Fq uauon 4.:16,
CH , CO)- ' " a po,.k eh,.,,,,,.
in the ' pectrum of
tefi. lic of ar yl aceta' . ~"""l'~ IC.H. ( , " i , the """.,
M
'M _
po,, '
C~H,OCOC H, ~
The l phUnl o f diolhyl
ph ' haJa'" was given ... ~' ; gmc 5.4, In .ddilion to lite
eA!'""l<<l f!l'Il ~ n t;oli "ru, I'hdl..la l~ &I"" ~y chlll1lCl"",lic peaK. al "'/Z 1 4 ~
an d 167 " II ,,,,,, ~l>und;onu: . at.i<. Jcpeodo, on lhe leulllh '" 1he al~yl cll. ta, 1lle ir
f,,' m""o n is rafWnal!,U<l in Equ. tion 9.J.6 1m- rn..e-ct h,1he~y llph l1\ "1_ 1<
(DEH ? ) ",hieh i , _ rn mmon . nd omni p"""nt co at . min. at from p laSl;cio:ed
polylm" (Dnde and Sl' itd loc l'l gl l The ....... ions . '" produced npoo con,, ;" n_1)) ,,,ti" alcd di" ociuio n of plO(ona led Db" " (H un l... III l'IlltIl
-.,.,
0::
1
'>.
\..
,{
(9.36)
1 . 5 _,
...
...- .
Acid' ,...,,,,,..11) "',"" ,,,. 11,,,1 ,,. m(>/ula r ious whICh i n ,, ~a-e in ~ I ath'c abun.
d..""" ...-111> ,ncrea.ing "" okc.-..l..r "'d gh, for .... lk~noio: acids above C, . ln poly_
ca mu. yh<: .....d. M O' i> ......k 0' I bsem, bul in 1!Ie.., II>< m" tc<;\l\ar ...oi;ht can
onen bt ded....,d from 11>0: M H ' i.... fo rm 1 by In ion ~,u~ reaction,
pt,.
.4/ipMt~ <Kid n..: m.....

of ... 'phl lic aCId, , ~mble d"",t ~ th""" " f
"",fh}1 e"e"" and pri mary .mid~.. ,~>m,..'c ' he . pe.:;tra "r d<>deean eic acid
It'~ure J ill an d or'lCIadcca noic . ,-id jFi, uN 8 9) ...ith Th(Xll oft lle Ul<"thyl ester
( t'i"...,c 3,131 aod ....mde (rlJ ure H 9) The Ill1l$$ "r lhe p,...." in. nl ;-. h}dw llen
rurn"""mcnl f'<"..l . ( :RR-q O H), ' iodl"l' n , be ,:r-branehi"i (mi' 60 fo' R _
R' _ H: iff Section 9 01 ind ~ <l ul lion U OH The ('Ji... C OO H ~ ' cries i'
eh.,o""''-;'''e "j . hl lll bf ill>ChinR ,\ lid al<o a ri... s ' h, o ugll ma::-hani, m, . n"J,,_
ROO' ,oJ r q ul lion '1,.13. I he (M - OH, o. is SOffit ".,,", 1 less Jb\lnddnT tban TlIe
(M - OC H, lo of me' hyl Hie, hul io; dialln'W.....U) ....luI fur hil lier and un"" lu'Ol<:.J ac'.J.. T h. ' l'fCl,," n of 3- bro n><>-J.-pht1l} I ~ ropi "" ioc acid e~ n . t>ow,
a hydrol yl , roup rnrr 'lftgnncnl in lhe oJecom posilion of lhe (M _ Br)~ ion
p;. , . lId i"~ Ihf mrl ltoX)-l rea rra"te"""" of R""cli.... Il. ll 4. Fmm~l">n ,>f
(M - H, O)O' in acid 'I"Xtr ~ ~pea ... ' 0 be impon ant <till} DJldet ' he specia l
t.... (""""ti"n of t~ CH,O H)' pc.>h In mrt hyl
cond llio m oolti..,.j
c'lo",. Tho I"" ". en , i. otI en round to . 1It spect ra of diearl><nylio ami .ub.l;
lilted acidl; ho w.Hr, , hi, ""n "-'>I, af ;"" froID thermal drearbol )....lioo, Aliphahe dic.il,t><;Il ) tie acid' son\<'time< ' M "" o ~ar",, ""-;" ti e I"..,... of 3ft jH. o,J and 46
(C H, O, l.
w'
add." Arom atic acids gi,,,, opr.:tra oho...ing pmminl:Ill O H I,,..

followed by CO 10"' . A Iahilc h~'dro~en on an ortoo "" bsiit ut1lf CSUSC'> a dominant (M _ H, O r peak by the ' onho" olI<d . ",'hieh "' .......in followed by CO
10"',
A Y~m Q lio
A",y drid. J, Thf rna" 'pectru m of succi" ie anhydride i~ s~"".-n in t illure IU 3.

The anhydriM, of aliphatic a<-"id. ' ho w ooly a small or negligible mo",:,,"'r;on
peaL but again the useful MH+ ion ca n he f"nned at hlJlilef ""m..... pm"'....
rM ''] i' usually .ignificant;n un",t\lrat ed anhydride,. FQr miu<l. an hyJrI<Je..
RCO _O _COR', the aeylium iens RCO ' and R'CO ' are gener..lly tbt Iar~ '
peak.. an d these lose CO as e~pectc d . A ch.racle"'li" peak in ' he rna .,...-tra
of cyclic anhydrides ef diearbo~}'lic a ,ids i. (M - CO, )" , ...hieh , )(1 frat!ment, fur ther by the ejection of C,H , . or CO. The 1M - CO ) ~' peJt II mIlCh
10<;, mmmon.
. ' _ _ .. c _ e...... ,. clo_
~J
ooJ
-.i
,,
~.
,.
...
"..
...
"
,,
Q
~.
i I
i i i
I '
'00
- ....
,.
..
" ..
,...'"" ..
.."
~,
" '"
"
'.
".
' OO
"
"
"
"
" "
ec
"""
- ,t<
U,,"_
"
""
""
rs
"
"
"
-n
',.'"'". ".
'" ",.
'"
''". .
,oo
isc
' OO
,oo
'00.
"
"
ee.
'.
' OO
,.
,,
.. . '
,"
..'"
' OO
.. ,.
1-4t'f....., n.. rna" spectra or laet~ 1 I ~<>'" lC~ l un:o ""1M' similar to thOM: <f
an hy<lrides, t,;";to nc, "r ",.~ y J",, ~ ....->.1, , ' W I) pi <al OE rm llmcn\, <I"" lO
.. p"hi,,,, nl CO,. C H, O + CO, or C H ,CH l 1' CO, L"<Olnnes fro m nonle!"_
minJIl h)'<l r01) acid. , uch ~, ,~" ""'''~''''1 ''''. 01 r -c.l pro lactollC .aoilt I"..,
th~ danithnll lLlkyl ~m "p" je>.ptriallt . et hyl o r lar g..,) ,'ia ~ -cIe ~v ~ !.'C . Mllt, p;x lrom"\ri" ~T.. I;''';< of a nhydrides and Iilct"ncs i, m~de ", me""MI diffICUlt
by lh el, e~tr.nI<J~' ,ma ll io nilll llOn ",.",,, ""di<>n' . WhIch de<;re.... l he <CIl5iti'~ly
of the Im " "" ~ \""Il I ,, ll'uruXk <1 at. 199Oc),
1.6 Ethers
A/ipIuItU' elkn, T ile lDll<' spectru m ,If dii. n hulyl et"'" is 5i\'~ll in Unkno wn
4. 11 and Ihose or i,,,pro pyl p<--nlyl eT her and be:ryl ether in ri ~UI"' Q 14 . nd 3.9.
i.
j
,,,
..
,m
,.,.... ',14. Ms" spectrum <of l""f'I"pyi rentyl rtb<J. fTb<

""-Te-. ,,' i .~ hoc"'AAi"g ' ao,plo r ... mrc,.
",.
,.
, ~I "i_ o "~ ~ n d~_ of
"'i' 1J !
r ho mole<;ular ion peal I, om ~n ~ 'ir/l alic . Ihe, teu ds '0 boa ",,"c .hu ndalll
thau thaI from "llructlU~lly "'nil,a , alrohol or oom par"blc ma l<o<:ular "el~bt.
but .he M ' f"" k i. mu ....-ak 10 1lC~'lPttlC, A ~ain, ;<>n-m al..,ule fonn'llit'll "r
lh. M II' pe~k caD be U'!ef..) lOT m"le..:u la"'.~ ij!.hl infor maiiOflTlw l.. gmo.... lali,>n <>/ el he", r..embl... th . t nf am;n= 001 wllh a . maller
p, o pc n .il ~ (n, . de~_ate and a mu ch I ~T !I'" I cnd ~ncy for ch.ar1l"-";te . ka_ail".
a' t l.fl<-"ll fla m th. billhcr indutti . e IIo'illsdn wlf of elo<1",,,, hy a .ygen , T he
imp<>JI.... I pp m" " dc a_ages of isol' l'Opyl pentyl cl het IUjen s,,; and F e",ela u
l%.'i) arc J ue la l hcSl: two types or clca~ "t'" (.,;q ",, ' iOll 9.j 7 ~ F or th e com peling
. -clo.n ail"'. tile [<)!o j nl nrclh~1 from lbe leMiouy Qolrb<m ,iclding ItOi' liS ;"
almo" t " , fa-ora b'- u tho lQfS of the la' l\'T hutyl va .!]> from l be """ " ",Jile'Y
carbon, s..cond Jly p' od\i<.1 it.n. in 1M ...me C. H ' . _IO ian ""ric. (m.. '< J t, 45,
S9.. ,J "an be k,rm . d tly rea r m ngem cmt 10"" or " " " I. nll mC>loctJIr from tltnc
'"
1 M. . . " ......
..
~y
of """"""'" " _"" " ..... .
,I
0..
.(
m,~
>...
C,H,
~,
o>'Z 71
(9.37)
31. In "Onlta,t to lhe spectra of amiD"" lhe mo,t nbundam jons. C, H,' Jnd C, H LI '. " ~ Dwduced by "h "r~._,i t,,_i niti at<xhc,,"tion,_
fX;ut"T ium.b hd in ~ indical ", lha.l ~ ; or til' ba," C ,H , - peak aris e, from
furlh er de<oom po. ;l;o n of C, II 11 +; forma tion of the latter ion through both
pathway l prob"b1j' ;o>,,)v", ~ ",,,rra n~ ,, mc n ( to avoid th<: c nc r~c[i"ally unf a_
H>t"hk primary "nh",,_ lion ""<"lure (Sec!io", 8.2, 8.6, 8.10).
I mp"'tt am o<kl-<,lc. tron ion< urc no[ aM}' ladi ng in Ihi, ' rcclrum. Highet
>l,"i~hl c hain elM" do , how abllndam C. H- - ions; mechanism 4.38 can aeroum for abundant ions of this type ill pa rt icular c~'c" For c, ~mplc. ethyl hc'yl
c[" cr and he, yl elM' (rig",.., ~.9) edtib;t prominent mi. 56 and 84 peak> in
their ' I"'ctr. , (Char~e rete utiou in Eq uation 4,38 would ~i,'e C,Hl._10R " ,
"" hose " bundam;c , ho uld b< low b}' ~ na l" H t<> thai ordlC "" nC'Sr<mJ ing ~ I ka _
nol molecular jon.) Another <ource of C. l! " _. iom is 10" of H ,O. which )'ield'
..... l (M - 11,0 ), ' pe. h in lu~ h.r "-.J ~)l "'hers. Hex}'1 Jnd hiher unbranche d
~ l he " lInd ~ rg (1 f\:a Tt;mg"mcn t "r 1""(1 hyJ mgc n . tom,. yielding RO H, ion, (rOT
~.a m r i e , ",i t liB fro m h" 11 ~I he r~ which on drcompos ilion provide . nNher
l-Ou roe of R ions,
i ,, ~, (t: ~ualj" n, ~ _ l l l - K _1
.....
A/iqrlk a_d _~ "" ' IWt1l,. tJ .,~

An i l l u, t r~ t i., " cump1c " r , u~b u lmp<J umh
! i, en by S-eibl (19 70, p, 126) is 2,6,6-trin~hyl-l-" iuyltetfJ h)'d rol'l'Tan (Fi~ure
9. ISl A r. tlOlla le Q{ lhe form .lIoll o f the pri oop:,l poa" ;, ~;" Cfl in ~<! u"tion
~ ~ ~; ~JJ; li"o ~1 !,",lh"ay. arc l",,,,;!lk. 'tich a. through eha rge-. ite in;t",ti" n
( = See!i"" 8 ,9~ Teuahydropl'<an)1 et h,,~ are u>ed in organ ic s)'JItlle"Sis to pro-
0,1 . " . ..
'"
(9 . 3~ )
tat ",h 1" c!) II.e hydrox}' gr oup; J < lu..!" It, the lcln'~ l dl<'pYf"nyl oxygen
i, . n ,mp,," ' ant f'T<"-"'" in thoir fllll.S9 ' f'eetra, This gi'e< ri .e 10 a ~~I: at rn./~ 8,
whicll Itn do mi""l.. ll.e ' I"'ctrum (Equation ~3~~
('l.3!l)
\bcrOC)'clio po ly<'lhen I"crown elhe "'"l l n<l pol ~ b., I&clonc:, gi" e nc:ghgi
I>k M " . w1>c,,:,.. 1\1 - H J I a nd , ovm .t n" .rn.1 ""mpl< J'T<>Su"" . 1\1 H 0 ions
art re~dily deu.cll Me. The main fragmenla lion p1th""'Y" " , eydic 1",I, Cln ~ l<."T\O
glycol, 1E<J "",ion 9.401 iIl. ol, e ,e quential n pul' lOD of C , H. O uoi" M <l ring
d ea ,.a~e "..ith h~<l">g<n Ira""". h' yio, kJ ~ hunl!an t C.H.O, ."'/. tl~1 ~I>d
c.n ,0, - (m,'" 81) io..... Ind uctive , *.. ,a.~ in the latter give< ri ~ 1<> an inlr:Il'<t:
C ,H,O' re nt , pombly pro t<'OO tod o~ if" ... IPodda eI ai, 1987),
- C,H. O,
"" yell.: un, atum tel! ethel'> M,e li kd~ inlermt<liate' in deC"m1"" ;lio n.. " f <tI;o
(Bouchou~ 01 " I. t ~7. 1 'l8~ n..: ~"")o; ~ " 4~e in cyclic un.. t~
' <l tN clhe, ,, q ;,. dihydIOpyr.'Il~, competes ..i , h ' he r<: 1" ,. Diel,.,'11dcr (RD A)
fr"ll""-'ft'a lio.>n of Ihe lini\ ( Eq~al i o n 8,6(1: Mon .w' " " , 1981). The compotilion
is conlrolkd by the k",i , a li,, ~ en e r~i e s of the one r,ag rnt llts lb ~ 1 d<lnm ;n< the
' hcnn' >cl1em,Sl' }" <>l lhe RDA re~cl ion . Fnr alkll.y , ub..;we m, (Eq'~11l0 n 9,411
RDA i' cOlt,pcli,;"", .. """ 11>0 villyl other ions formed arc o'e1)' ..uhlc (.... So: ~ eV}
For <l cyl ,u b~tilue<llS RD A req " i"", hi ~l.er ~tit;eal ener gy, e,g" IE lC II , =
CHC O C H , ) '" ~ , ~ . V , and , he rom pe1 ; n~ ~. d"a ugc prevail"
pha'ic cf'Oxid<,
1.' -
0~ -
-. ~
_RCO ,
Q,
*
(+
(~
A~k ~Iko l .
(94 1)
~oa
n.,; m~... 'pc<lrum ofmelhyl phenyl ether ,how,
~ ~ ..-... ldix.
llC pu .h I", . ", - CH, )+, (M _ CII , _ COl , (M C H, O )", ( M - OCH, )"
and (M - CHOt (minor but impo rl ant in "'"n" d e<i~au, ~ Iypic.ll of Ihe
m ~ ~ '~ I (;I 1
beh . im of mClho, ya ryl w ml"'un ds. Et h ~1

d hig"'" aryl
<:Ih." l'ivc a highly cha racteri' tic OE ' i<JCI II"'" Ih" d imm.. li"" of C.I I,.,
C . II, DC. I{ ",., _..... C" H"O H ' {Harn;, h and H" Ift>ei, 1991; look a",in at lhc
'p"CltUm of 1.ph"n" , y.2,ch lotoe lhane , Unu.own 5.1 4). 8<",,)1"Ihe.. , imilatly'
gi.c a <ijl:lli n~ant (". II ,C H, OR !",ak "" ..ill a' a C..H,CH I peak .
Kna& and a, ,,,I1., f Un kn" wn R.4 is. metb y1al, CH ., OCH , CX:H, .J Th e preseJlce
of two alko, yl ~fOU p& o n 11>0:' ... me Ci>rho.>n I"'",'ide" a powerful reae honiniliating si," . Tbe ", ilic,,1 e....-. gy r.". ~-.deavage, R-- CHIOR'), .... R'O C H OR ' .... IIO-= C II - O R. iU llbot;lfltiotlly lowcr",l hy the re' ona nce m bilt""-lioll of lilt prod"'" ioo. Unf<)tlunalely, lhi' also cause, tbe molewlur iI.a I" r
.i mplc .au:ll<J. a nd l elal' \0 be neglijl.ible, Some reac tio n' an; o ~ r-'~ " h,.It
an:: due I" Iht secon d IUlKllO Daiity, ,ueh a, the elimination o f II ,CO from
fOmIdkkbydc ac<lal, ITa !>1..: ~ .41 H owe,er, in general lhe ion d.:c<....po... io' n
p&t b w~ } , ,mlfutc't! abo ve for elhers are applicable,
-lin interesting example i' Ihe ' lr i ~ in~ in n""nre " f l he et hylmc ktldl moi!; lY
On .t< T(~ d rna" ' pcelra, a, ,ho" n in lilt .la"ic 1.-oft of Fcw. m ~ nd l)j eta Sli
dOO l!>cir e,,w m h o<. T he ' peelra 01 SH ln dro.'aD J-one aoo it. clhykM keta l
~re ' hown in Figure 9.16, Mocham, ml for \ 1><; ~ .rm ali"" oI lM Iwo major p"" k_
art i n'ell in FGuali" n ~.42; inlo""linp.ly, l1>c>e are dUeclly anaJ"gou, to l h~
lrugmcnt" li" n "r the oorres.p<>nd,nl j a minOlfero,d Call you "","ounl for lbe
mi. 112 peak?
V"""''''''I 9.( A ""mpo"""
i; eJlbe,., 12 Of 17."tu,tcroid ('"'C Equ atio"

ne ( , 11,0, pe"k in Ihe rna.. , p"'c lr utn ,If itl ethyleoo kelal i' lar ge:.
Which oom pouod i. if !
~ .4 2) .
'J<
f -
,,
,
- , -a
,
,
, ,
,,
, , .,,
2
e
'i l
"
,,
, ,.
.....-
i"---!
-....,
, , ,, , , ,;1:
,
- -
~
'a
,i
, ;
- , I
~
.. .......
."
, ,,_ _
9.T Th iol l
" c.non.o. e
and...-.
Tho mas< 'pcct r~ of (hi"l , and sul6des is,,mple ~ nd DJera"" 19M. 'a~ de
Oru f ~J)d M cL~rrert y 1977: OJU n ~I. 1979) resembk lhoooc "r lhe cu,re' roDd10M~ 1", "' () 1 , and elhu " T he "f""''lrum of iso pro p)'1 rcn' yl sulfide (Figun: 9,I71
U n lie compar.d W lh.l' or ~ pr oPll p. nt)'!clllN lFl!Ul< ~, 14), FillUrC.1.21 and
; ,12 un: the ,peer", of dod",,~ n o l hi ol. and d llle> ylsulfJ dc, 800m. of lhe ",,""
'~ll i li<;a1\l diff.,." """ ~ r .... fro m tho I" ", ioniLalioJ) ~""'"Tlli ~l of 'U
m'f ~~,m
""ullds, whi. " ~,~ ap protima ..,ly I eV ~l o ' Ih" "" of t ho corrc ,ponding o'x u"n
compo\lnd . I hI' ma kes po ",,; bJ. t h ~ fa" " ; (>f moro 10",of"",,,,,rg)l molonl!;>T
i"n<, ,ul>sl~ull. lly ino,~a,iug
[ M ' J-
C1e~ " "b'"
. .. 1'" C '- S ,,-bond ca n OCCUT ,",'ith ch~ 1ge rclcnli"n ill lho ' !IUur"","'inin& ', ~ gmc n ( (Soct;" " 8.6 ) ~ n d product-ion it~"' Ii.t.aIJ OIl lhrough i,o.....-ri<~t ion to ~n RC"II=S H ' _" ""lure (Eq"ali".. X,77~ 10m ' ''oh a< lIS-,
H , S. H ,S I. anJ CH~ ' ""c ,," uffi<:i<'lll " ,,\>i lity 10 gi~ ~n ion ""' ie' \l' d ol r...r
ch4 r~.krL,at ion; p,~" Ih.ll few OthCT lyl'O'" of rompoo~ J gi, e pe" k, ~t "';. n
.1 ~ , and ~5,
TJrNoI F'IIPl .1 ,2 1 i, tbe SpodlUm ,,f
<!(l<l~c all.thi<>~ ~ -1.-k.... ~ ge
yields tho
l3.'F" C. H,.. , S- pe~k (ion ..."TiI.... 47, 61, 7S, " . ~ b" l ,*", age ~l olher . h in
r"5il'''~ ' to )'i.1d thes<: i,..., i' m uch more prC" olc~ 1 l h~n io tho COITC' I"-,nd;ng
alcohols, 11l 111 " i ~r,1 duUn n",rc"p'~m ( R9+ ] ~ rr5 ] Or l lOr ], indiw ' iull a
r~ ,,,,,~ hle d ; ~ l n;a, linn I E qu ~ l; O ll lU 03 ) I",. \be rorm at;on ol C. H. !>II,
1b. h)'droc.l I hon i" n ...ries 27, 41, 55, ... , an d 1'1, 29, 43, ' , . ~<. d ... ra ,;t ~o. h
...__ ... ..
"
<.",...
t:8l1y larp:, ", j' h C." , " ;>

+ fv' ~ ;> 1 1M - 5H I+ ;. .ignifi~~nl in
=<>ndary Ihid ", in ,o nl r~'l 10 tho lack of (M - OU )~ fTom alooJwl\ , In primar y thiol> the (M . (,ft)' 1'' '' ;, , upen.cJed bl (t.4 - SH , I '. this , nOJ l he
p'r u k nl peak.
(M - S" , - C.u,. J" "'he:<: ~ 2: 2 appea r irJ 11>< C. H,. +
11ll. . 2, 56, ... ) ion ""r~ ll::qua, io~ 4.38 ),
Ar"mat ic \hloi' undergo lra j1TTl<:nlation, . imilar kI those . x!X'ted (Of ;>)0,:" ,,1,
the main n orpti"n, ~ lnll t he a d ~ iti""" l (omw i" .. 01 (M - 5 .- ', 1M - SH" ,
an <J l\( - C , H, l" ' ...~ k..
r".
Su/JIJ~. Altl" ugh th.; ma.. ,"rtcum of C H, SC H , C H.C HO ltl>< *ooiOJDY.

""'l ly" od>>r rlQfll p.-,U01Oft.: WAllt r ' 972, p. 716) n hllmub:! tu li. 1 M l3 ~~;)
~Dll .",l e<I'~~" ICH .S ' ~CH" 2 ~~.1 poeah. the ha '" peak ,,,r re> po~ <i, 10
CH , SU ' ptoouoed hy a h~'d o g rn rcan ange.-.;n l I,mil" r I.e> Eq""li" ni 4 .31
an~ 4 oW 00 " -dea~. 1l" r.,r n" C H ,50' ... lhe ~nd 1' 'l'''''1 p". k. SJml!. ,ly. JB
lIdoJj lK>n to ....:Ie.o vagc J'l'odu<:l'O, C, H,SfI con,p"unoJs I~'pi call ) lor m C, II ,S '
and C , H , SH " p'''ik,.
" . can be """n iu th, .poctr um "r isoprop, 1f" m .1 ' ulfode IFigure 9.17). (ClIks
in the C." ,.' , S ' i"n oef j... ""n uow ... u..: from c1<11 "li e or lhe C - S ,,-bo~ J;
lillS ....."'unh flO' II>< pt'c""n.. 01 C , H Lj 5' 1"1./' 1031 and, in N It. C,H , S ' 1m,:'!
75 ). "'o, tog"." 10 the b<h . ..;,,. <If i. n" c"!,,,1 ponlyl el he-r I r..ul<' <J I 00
EQllatioo 9 l ~ ).
~ ieldi IC H , ), C HS . -oCH 1 l."j. 119) ~Ild C II ,C H ~
S'C , H "
Ill) W" .. .. he,,,, " ,,",omp'''' il'cn' h) hyd ro~cn ' earr angement
~:'1 u allO n ~. 9~ should plod uce H 5' - CH , ("',i, 47) and C H, CU - :> -H 1/11,:'=
6 1t ~c,mp,",;~inn of CH , C II-S - C , H " 1:>1 Equ.o ti"n 119l i> ;on ahern;Olive
.",ode
r" nn al;oo of lhe /IIi z 1~ ptak.
In ro",ras.t 10 ' ''' ]>f0M l p<.:n ~l' 1 ",h"" 1h,. , uU" k '. m4 , peCINfn . howo oh r.
act~fi. lic OE ' illn, at mi. 76. (C H, 1,C HS H " 00 01-1 70. C..H '0 " (pi ... "",'z
41, C
'j Wf lbp"nJ illjl ru lhe romp.-:ri" 3 po-odu<:1S of ~4<l1l rioWl 4 31 aDd
4 l~ (("nnaf...o "rIb.. ch. 'se--,eu ill<:d ion i' '\ dmniuanl pa lhw' l" (I f d;sulflJ es),
r"n. l~,"ltin~ from the Tu rr""gcmr nt of l"' n h}'dr0l'"l .!om. , iUch a' ..J z 11
lprohabty C ,H . SH , ' ), call ;,,'" 11$ formed in Iw,,11<:< ' boonda roor. On I'" N hc'"
hand. lhe daarl:"~le pwJIlC1 C,H " " (Eq...
4.22). .. hich r.; Ilgnln, am In llle
""""Inlm .>fthe rtltn , " .'ery ' ma li (po " ibiy o",m~ ' 0 the comJl"lllion of Eq u"liou 4.37), altho u~h lh. l;om poni01\ prod uI'l C, H , ' is ~llil . 11. ba'" reak
P h~ n )1 ~I.y l iu ll"Jd.. ..!\derto n:.,.;lions l~ pi<llli of Ihcir ronlll<'1""rl <thers ~ u t
",,", w Ilddili<nal ok elcl~ 1 re~rr" n b", rnr m, lhllt ' " mplica.. , t, u",ure elucidation.
Uioni'Ulli'm or SH ;, co",,,, ,-,,, in oon, .,,,,,,,,i . ""h" ", u.ual d",,~ .l[C pu h.....".
~r< Ie" r~,ile. A",mat ;c di", i'icleo . ,flc.. wuk l l" additlllnal ~, of S, ~nd.'or
I""',
,-dca.,.1'1
rot
,11.'
,i,...
HS,
Unh ",. n 9.S ;.. known 10 cont",n " h y d l ~ , yl groul' , Co uld ~ o u ha' " Jeduccd this ftel I'tom th<: mas. ,pc't'ttu m'! l ry Un.no.... w 4 .' . li S. a lh1 8.10
a ~ i ...
".
" _ _
_ _ 1.5
,.
....
"
.."""
-- - ---- "" s.e
"
u
"ee '"
""
"
""
"rr
.
,.
.
'''... '....
'" ""
,.
'" "
'"
"
'"
' OO
'" "
'
tl
-- '...
.,. ..
',w
tl
"
'.
-..
t
.. .....-
" e.- ~
""
"
"
'.
""
,w
'.
i
j
9,1 Ami....
i\ l i p~ . tic " m;ne. " . hi b,( "" ry [0",,' ionization ~r ~ ~ deipl!. this, tn" a mine
gro up I'm . ideo . udl JI', ,,,,,n ul <lri.-inK lor "" for
i.llltialio ll , , ]fI>O!.f
al",.)" the b.", peal "",ult. from ., ..;:;lea- a ge (I ' " ""*,"",,,,," pi ", ol.f,ll-[O," ~
arr an.." "". nt , Eqll3.!ioll 4.44) !bat mo kwlar ion. are of 10 ... ," nq,1 il ibl<: ahll/l_
d. oce, F o rtu na t el~ , o wing ' 0 their hip, pmton o!tilllti<. ( h Me A,~j . mlnco
can be sd:<:i\'ely prolona tcJ at mod cnw,:ly hi~ h .,mpl. pre . .. ,..... or ""Ih
"IH . ' in ammonia C I to yield . 'or)' , table MH +
thl rom_;"'- m<)I';u,larweight infonut;" n ( K <Xlu~h ,uKl [)CSt"bac 1'181; ""oMmore and Alau d din
1'186),
S:l.l l' o f amine ba,.;" ....,0 not vap o rize III the rna" . poct ro meter: tI"", " lh. )'
oft en d<co m pose o n llealing in the ;n. lru "..." t to relea.>e th e Ir.. am iD< nn d the
".iJ, Th<; p~sen.e of abu nd an t pe ah corre< pon<!;ng to HO (",,/~ 3l\ a",l )lj) 0'
liB!' (m,/' 00 aod ~ 2) 't'nngly imlica tc:> . uch . . .n, sin "" t he.. ;0 '" a ", no t
for med in abundance a. pr oduo t. uf elc c1.n m_;rnpa.I_;rK!uced rea"tiollL
,.octi""
i"",
Stndi., on indole , ~ k" loid d.ri"Hi ve' indi. ~le 'hl ~ualernary niuogen comp<>und' (K .. H) d<eomp<Jsc thw nally on heatinll in the rna", ,poctrometer by
IwO prlDCipa l p;,th, lead;ulllO dilfenont leni ",y am ;n<' ( He.~ and Leminger
19M ~ F"r h, ,,mid. 0' iodide . all" d<alky'lation with formation of the amine
and the alkY'1 ha lide is rJ' or<'d (Equat ion 9,43~ For the " um ide ' alt, a thermal
Hofmanu de ~ ro d " llou involving ah. l' aclion or a hydrogen alo m {J to Ihe qualern ary' ni,rugcn i. ra""rod (EquatioJl 9.44t
r: -L.
~'
:)-R,
t)2,
" ",
"
~- ,
R,
','
(9.43)
i I'
j,--N-.,
. "'
(9.44)
H,6-!K,
",I-I",
i~
i I'
R,--N:
-L.
HC= H,
A/iplUlti" IUnilfe.. The rna.. ' P'"ctro of I-om;uododecanc (Fillurc 3.16) und a
numlter of C.H 11 :'i i'''meri. amine, (Ll nknow n, 4.4 10 4.8; Figures 4,3 and 4,4)
hove hc<.--n given and realure, or their 'peelro discussed in Section 4.0, The mass
' fll"<-'\ ra of dieth ylprop ylamine, dihexylam;nc, triblltylamine, and cphedri"" were
~ h o ....n in Unkno''''' 0.2 and Fi~un.:s .l l 7, 3.18. and 4,5. The mass .pectra of 11'methy'I."'. i,,'pH)py-I.N.buI}'lamiue (Un known 4.20, see Chap ter II; Djera"i
and Fensclau 1961) and ,",,(3-me thylblltyl)amine are given in Fillur., 9.18 amI
9.1 9.
Alpha ""'..age i. a dominant reaction of amine. , generally PW<!""; llg Ihe
ba.. peak in ~-a l kyt am i llC ' ;md ~,um. tilu(ed primary amine" with I"" of the
larlln t alkyl grUllp fOYl)[cd (liq""-lio" 4 17). Thi' eleavage aocount5 for the "'/.
Xl ba'" peak in F igure 3.16, the ""i: t 6 ha.. peak and Ttl,i. 114 ill Figll'" 9.1R,
an d- Ihe ..i : 100 in Figure ~.I~. Peal. in Ini. C. H,., N+ ion 'eries can he
formed by other pa tnwaYI al, o. ho......er. In primary ~-alky1:lmiues di,pl"",,
8,I I) acoonnt for relatively- ,mall peaks.
" ",nl ....actiom (Equa lion 9.4"
....;th t1H: mo, t fum ed al "'i: 80. F",- h i ~ h e r p<imol)' ~ . alk~l amine. the peaks. t
Sect,,,,,
~
V
(9.45)
, M... . ..... of C....... C_ _ C1o..-
""t<..,..'"'li'
b '
',~
,_.
'
' lO
' ...
~ ..... . .11, M . .. 'P'<" u.n 01 "' ....th.1. ..-_rrop1~ "' l>ul ~I.",jn . I"'claln ,
, OOnd.nee of tN ..i, ' 30 p< .~ i ~"... ..'nh """ ..wo ... "'rIo p'rssu, .,)
,-
, .,
"
"
"
....- ., ,. , "b .. . '1""" Jlnn of
"
,.
W M' ,
,,,
'"
,Rd. Live . b un<l . """ or ,I><

"';' ' S3 "".k imu,."" " i lh incr<a,i ng , a,nl'l. P' '''ur<.)
b;"3 - mcthy l b Ll t ~ U . m j nc,
lc,,,,,
",if 44 ll""' ud,>--cl. avag. Equ ation 8,91). and t o "

",tent ""i: ~ 8 and 72
()' and 5-ck.1Vag.~ htco mc i"'-'Toa, ing ly important ("'.. . ~ 44 ~ 40'\ , in ,he "f"Xl rM'" of hc ' a d<>::ylam ine), ~'o r higher-molecula r-weight "mine . thl: hydro"., .
l>t>TH H'" rc", k, ",I" , inc~a,e: in the spectrum of LC , H" C H(C H, ll , N H , the
al~yJ ion re."lli u~ fro m a-cleavage (mi. ~5) ,how< 34~~ abu oo . na. bu.1 the
lmmo nlllm ion from ~_dcavagc (m,/. 156) has au abllndallCl of only I ~-;;'
" n ~m hcr ,,( ,oe c ndaI)' roarr ang. mcnl dcm mpo<iticn, of the prim a I}' irnmomum iou c'" u produce otocr C. H,., , N' ion. (Boweu 1991 " 1. Th e ",," l oomn'o n . uch ..," Ii,,,, (Equat ions 9,46 and ~. 94) )'icl<h [he importa nt .../, 44 and 511
10nl 111 f igure 9. 1 ~. a",l lhe Ie", import ant 'tli' 3lJ pca ' in Figu"" <,I 19 (=
';o~t\l>n X.lO), AnOlh., possible r' ''''''tn!P''cnl (1:4""lion, 9,47 ...00 8,9 3) "f'I'C'U"
to Account til; lh~
pea k at "'it 44 in the "f'O"lru m of b"t l--olfi b.y1bul} l)-
I>a,.
OJ A"," ..
,.,,/:'-'\
ICrlV,Crl~-CH,-C,rl7
C~,
-"
-'C,rI,
1>}':44
(9.401
m'z100
amine (note that the hydrogen is transferred from a tertiary carbon atom).
I." bcling studic, (Djerassi and Feoselau 1965)iodic"te that 65/;; ofthe miz 72 in
Figure 9.1R ari;e, through such a mechanism. Thc remaining FE' rearrant:_
ment', Equatioos 8,92 and 8,9~, do not appear to be important in the al;phmic
aminc <peelra that haw been e'amine,l, ahhough mcchni'm 8,92 may inerc,,-,e
in importance for large alkyl groups. The loss of1'<l1, or a neutral amine mol,culo (Fqu"tion 4.38) i, not important except in the spectra of certa;n pol}'functional compound' (for example, I"" or N H" in ~_amino acid, and diamine,);
(M -, NH,Rr c"n be imPOrlaUl from (RNHCH,h(CH,) ',
C)'el(}{llk)'krmin.. (see S'Clioll 8.9). A thoronghly 'llldied "ample of ,uch 'pec-
tn, i, that or N-eth}'lC}'c!openty!amin e. Figure 8.fj, Alph"-c!."vage in the i1kyl

group lead, to the (M - CH,F peak 01 modcrale intensity, HowC\'cr. ~_
c!.,,,'"ge at the second a!)' ""rbon in the r;ng ,hould b, favo"d; this leads to an
i,olated radical ,ilc wh",e IUTtheT rcaotion (Equation< ~.4~, Kfj.l) account>; ro,
the miz 84 b"," p,ak, 110mologous e"en-,l'ctron ions at m,/. 70 and 56 can b,
rormcd by a ,'"nely of pathw"y" as W"S discussed for aliphmic ,~cohol spectm.
Thu', although the miz 50, 711. X4. and 9H ion 'eric, i, indicative of thi, geneml
type of ,tructure, the individual p,aks, e.,pecially tho," of lower mass, "" less
charaderi,ti" 01,pecific 'lTuclUTat fcaturc,. The ,matt m/o X5 pcak appears tn be
I",m,-.,] mainly by C, H. loss from the eth}'l group (se, Equatio", 4.37 and 4..,9).
III the 'pectrum of de.,_N -meth}'h_obscurin" a similar mechanism (Equation
9.49) c.ln expb ;n the loss of tbe -CH z ---CH(CH,)" CH,- bridge plus a h}'drogen atom \n I"rm (hc(M 51)' ion. The (M C.H.r' i, of much lowcr
abundance than th, (M - C.11 o tThe mass spectra of nicotine, indole alkatoid" and ,tryehnine are ,howo ill Figure 5,1. Unknown fj.3, ,md Figure 3.2X.l
Other type.,. 01 reaction, that are p""ihle fot cyclic amine, are discnssed in
Section 8,9, A fiv,-m,mbel'd r;ng containing nitrogen ejects two r;ng carbons
and the;r ,ubstituent, "s an "lkene (Equ"tion 8,571. For larger ring compound"
t.
'"
1M... S _ of Commo, Co..
po,'" el.....
'~c:
-C,H.
CH'---l-"'/~'
HNV
CH,
H!0
n1z70
;/
-,
't
or
C,H5
-,'r.I
NH
)
'~'
I
,,-,:i/
"
II
t:
- C,H 6
CH,-LCH,NK
"
.,
r-c
.
m'z56
W:V ",
-"!.-
CH,=NH
-CH,"
.'2' I
r'
GH,
"
-s-s-
('
.i~
m'z84
- C,J-I.
-c~
r~,H
-'-
)"',
t,j
-"!.-
C,K;'
"
m'zB5
m'z56
"'~o
-"!.-
CH,~H,
m'z30
(9.48)
./
""
C,H.
,
(9.49)
'"
.....mid..
such a, 1.2-dimelh l'lpip<:rid inc ( t'igll~
~ .4 ~
Ill"
~J '1io n
i. of low impon a"""
(m/, 71. 1~~;J. Th e EE ' iOIl fonned by ~ ..d "" 11l" (";J Yll. 1 lXl:':;) ~~ uDderllOa
relroDi.I,Ald.r reaclion t" l i ~ld ",II 7ll ill l r:~ ab und,\ n", ' Eq ual""" R.6 1~
Unkn"",n., . T" t l Oyr kllo wledl'" w,ll! t.:"llk nown.
1;,1;_4 8. 1;, 20.
S. II. e.z,
~ ,2.
8,3,8 ,9, and 8,10,
9.t ""'Ide s
rnc m ~ ",," .pc"II~1 bch~v ior 01 pl imal')' amide.uch a, d r>d. ca n Ollmi(\e (f>;~ urc
3. 19), ci" ""ly ,..,,,,,m l>lo;,:, thilt ,,{ the ~on l'p('fldJni <lci<l and m.lhyl e<l.r (Fi gur..
3.n an d },13;, Th. bclul~ior of seconda ry (' ueh a, ..,'.bulyl a""lamide, Figure
1J,20 an d t<fOOI Y amide, ~"',N "dlp<'nlylaeelamide, Figu re 3.20) pa rallel, lhal " r
..len 01 highe, Ik..., "'~ ... ah h" U<lh heTO. in lh o", rea"lion. initiated by lh. , alU,,"u:d " ClOTo:Ilom , the roo", po"erful direct ing fore. or nllrogen I, "learl y evi"
J<nl. ,\ mMl",, !po,; mol:ulM-lcn p'ldh IIMr are s .nerally more distlncrh-. than
coult1.r pan. and h.a'e a ' lro nl.! !L'TI,lon"y 10 form MR' ions bl
lbeir ..
i"".......k'cule r~.C1 ionf.
11k resc,nblanCl' ott .... "1""Cl r~ ,>1 ,J,>Jc<:an" i. a";d and ils amide (Figure, 3,12
~ n d l 19) i , '" "ll kin,ll hal lil1'" ~ <! d i lJon al m""hani<llc Inlerpr"talion i, n".", sa ry, The nilnls en.., mlaininl pea .. ~ re o.hilled 10 [o",or rna, ,,, , b}' one onl t; the
/-I-de;on ,e h, d, ,,*en u~ ,ra nt" rne1l1 ......l ,",i ll fan in tl><; ",rios rill: 59, 73, 87, . , . .
,~ Il rl f,...""" PIW ","", rl>o ion -.en .. 44, ( 5&~ 72, 86, .. . ; ,"'Ilh klngcr a liiyl .h~im
nU l ima 8pt>ear a i i" ~.a b. " " 1'O>f'<moJinI/ IO '(~H,). - m,/: 72, 12S, 184, and
!ol(l n l l ~(><l ~ b the <!fl' 1 is .... prononnctd The nume.,." " , lty<lr(lC;lrbon peak s
. ,.".., a. C. H.." a nd ( "," .. _,' ""' ...... abundJInt "" C> f""-1 ed, t .... n in the
' ptn III ' !Ie an'"'-'!!'.... ",,--i<b..
T it<; 'Jlect 18 o f =olkiary and "'It "n)' ;<mi<ks ........ lhe ad dilJoo.l1 "xpn;led
reactio,,,. w;lt a. p...-tca""ll"' at rile N -R bond ..; lh relITT~nl.!.-"rr",n' .>1 0...
c'pe>i. U}', Iwo ltydro~n at""" (mf r bO in r ' I:]OI. 9.1U Eq..."on 4,46~ 1n
,.r
"T.
. I 1~
r l I
00
I I
"'t"O
' I
' 00
i '
"'"
00'
""
~C'" 'I'
'n'. . ,
-------
IlO
iL'
""
I'
..a
'H
n
H
"'~
~O
9't
'u,
""'
OO!
L"
00
'lB
"t
00
- ..
"
-----
"
~,
,.
"
.. ----
Ol "'"
-001
0'"
I',
"
6'0
flO
(/OJ
to
(tV
n..
<I'
...
tt>
0',
"L
LO
01:
. -"
""
'"
z/w
09
'"
zjW
'"1
zfW
'luI
,~
'"
2'0
.'9
.-0
0-'
(I"
0'
UC
~l
0'
9'
.'. "MO"'!Un
J" ,",\lJ.U. U(lll~zm('l' P"Jnp.' All~"'~
'~l )0 ",n~""'I ""lS~ U1 u~ql '''lU'''~ 'pmu " UOTlU"l.' ,';l1uqJ 'OJ AOU'pU.)
'~.L -Ir"w, ~"" ,linm" II "41 pUP, P.~'!I!qP.]" '\II"!lUp.l'yn, '! -_UI H N(J:)ll - 1'\1)
001 ~U1nn'~J oql JI "IUO SIn"", (Sl't JO 1''1' SUOlIP.nb:l) !ll1]p.1I0ll'Unj
~P!Ulg ~q] lUO'J A~,"~ UOIWJ\!!W "~J1"qo 4)!'" lU'W~j!U~.l.l~~J l1'30JP"H ""P'U'~
-1"""lA1V..,\')0 "'1:>00, '~1 11) '{R,d "1'U01,r.JV.4" hlOA "<oplhoJd 0'1" Sl~l ''')''1
.",," p'lmnIUSUn)O J01_,~q.q .ql S"~~nBJud '(6['1' uOllunb,1l SSOj ~U~I"'llJ'lJIP
o~.,pun (~P!W~lOJ~[A~P!PN,\' ~Idw~,~ "oJ) '~Pfw~ ~woS "IUJ!W'4" J!'Q1 01
",n,odx ~ 1101.<'10](0) oUlln 01 puno]:m lj'llj!'\ 'HOOJl'HJOJHNJHJ'HJS<I
"P!"~ 'lJuldg",~w ,g lj~u, "~P!W~l'~~ fgUOIPuuJflluW uf .'R<'I4100 UO<l
""dw"oop lUlrjJodwf U~ 'lU",'J(!ol ,jJ~"",p.~ -'l"UlI..Ld -'4 pOWJoJ ,u"f
+,13: mOlJ ,"O[ ~O~l')l '!l[~hlP,d,,," '18, ,lUI) 'H'.lHJ-,N'H pm, itt ,lUi!
'IDIl:J=.N'H ,ppl,{ 'U'lOl )0 uOTjUl11rnll" Aq '00< 'SOljl JO uOTjTsod
-w"""J' ]u~w"liuTI"J= u~jJOJP'4 lO4P~) ~Ill'o o,mliH JO ,unf ,('H:) - I'll)
~lj1 ',(n""'" 'PO" .{'H'J
WI Oljj S~A[~ 1''4 p""npo, o~"''''~l"''~dIV 'o,"ollm
JO hOU'P""1 \lupsIllnl-1lOm~'J \lnOJ1' "]1 IO~U'J o'is "P!WP. "TI!lJOI pu"
""pu",",]O 'UOllf'''dw''oop ~q.L '(,"p,'lllXKkll '09 pUP. 'L~ 'SR " II ZlUi) +{'H'J
- 'H':J - H'J - Wi PO" ',.I'H'.l - 'H'~) - W) ',I'll'') - 'Ii'J - 1'1)
'.('Ii',) - I'll 'OJ ,~~,d lU'UfUIOJd 'l!q!~'~ 'P!WP.()UTI'O~I'qP'P-N<."" 'nq'
'-'PfoW
~~l W01] '" no_" ilollw uo sum~~ ljlO<[ mO'J ~]qT"od
:lJ~ 6C8 pu~ 9t.-t SUOlmub:I ~~n SIU'UI'~lISJJS'" "'!I~O"'U"" '~PfU-'~ AJ~f1,"1
)0
S~pTlU~I"J~
'ss~pql'''A~U ~'PllU~
p""
..... ,~ P"no.wo~ "" ""~ 10 "".d...." I
.u
----
. " _......-.'
rn
more compl<~ ......lcrulc.. " ...' h u ne",id, or mercapturic cid .. u'UOn) e . hibil
ch""..lcrislic (hi _ CU,CONH lr ' pe~ks (Vcrrncu k n ,I ..,. l <ml ~ ~R CO
SK U , ), 'pec! '~ e, hiM a!>u nda nl mit 87, 4~, an d 100 ion.. Pf_ m.h1y (, ,,,,,
lhe m... h~n i;.m., nr Equall on. 8,70, 4,39, . nd ~. 78.
l-1. ;ovago of l~ C N bon d to Iti .,c tile a1huuyl i.... (CH ,CO - in f lgUle!
l20 an 9.20) is greatly redu ced '''C' lha l in cs.I.... (C H, CO ' is lh. 1>;0... l'C" k in
....butyl ,,,cta~ Figure 9,12), The no rma lly unb oro bk C -N bnnd ita,'age
" ilh char~e retention on N, ,ueh .,;n lh. _..-md" 'Y am ide !Figure 9,2(1. " ,i: 72\.
I' mcreased suh' tanlially in tlte ter tiary alolde ( Fill",e 3,20. mi' l 5til
The IlOla ,i"n en<:tp.:.. ," aliphat;",nitrile. and OItroalbnes ure uou, ually ~ ; :h .
an"- ,hi>. ii relkded inlhe nnusual degree to which Ih ~l! "omI'OUoo, undergo
..Leltla l "'.>II" n,o"",ol on . k . lron i mp~et (Sectio n 8 6). T ho basic rules or roo
d....mp.-.,;Ii"n iOPJ>COlr 10 ~ I." applicable 10 nilr ik. than 10 . IIY1I1hef oimpk
""""",,und fInss. fo r the Ionization eoerl1io, ol YCH , 'r _ eN hu the hit besl
value of lhe .o mmon ru n" tio n~l it i", li, led in T:>hi<' A.3. eve n h l~ "" lhall lhal
' m Y = H 1,l\ccli" n ~ 2) Furlher, the principal nilroICn'COllla llllnl "'II ocrio<.,.
' ''und for nmi)", . C, H 2. _oN ' and C" H,, _, N ' . .... ..., ba ric .. i. h l ~ rum moll
lIydroc.l rbon sorie. C, H ,._, ' (21, (I . SS. ._.) and C) ' .. ,- 126. 40. ~, . " ~
M olccular_ion po:ah . .. weak Qr lM'glqrJbIo in ah plwl1Cnilrik . ~llh~ ugh they
are ",ually slr ong in aronlOll,( w mpu ulId<. "'",t" lIKtd }', aU phati( nitrile. hm'e
a ' u b'taot;~l tendc nC) to. (" nn a n M H ' pu k by ioo-moleculo rea.tione.
T l>c m ~" Sf'I'drum of dod~1 cy.nid~ i. givon in Fi~urc 125. I.. nv.ra ll
appearall"" j . u.........l by ma "" ' ~ la l ,t ~nd a rd , ; il rc",m bico an ~ a) k . "" Qr
.:Ik.....pectrurn tFiK" rQ ,\.2 and ). ~, in h. lact 01 specillcity, bu t it II"" al>ul' w nl
f'l':'h a, higlM'r .... ~ and ....i" or .illD lfi e ~o t peak> ",pa<a1M l>~ onl)' 0...
mao. uni!. Th ~ 1Cl-l, i.C-'; <eric, (41J), 54, 68, ~ 2, __ . , dominat.. It>< uppe r
pollio-'Il vi lh. "!,",-1 run,, the hyd, ogen ' Nlalrangen", nt .. rio, oomi....l1 y ""Itt
'f" ,nd;n~ 10 C. II , . _jN" (41, 55, 69, ~ 3, , .. ) i, uf ..,.,m!"l'"abk imponaoq lor
,, _ 3 to 6. Th. ~lrgest pc;!\;o in ll>c r" rmer " M are (CII, l, CN' aod \("H,laC N '
r""" lh. displac<meot reacrion Equ ati on 3.103. Cbain I>nonchinJl does incru ,,",
the ab"nd,ln. os oh he appropri" te i ~n. in , r.i. ...."Ii.... bill .uch data mu.r he u",d
wIth cautloo fOl , truelUr< ,lcl eTmin ~litln . T1>e C.H " , N' od<I~ledron ..ric, ;,
..nalOIl" u, to lho C. H , : ' series from 1-alh oea.l llIIl alw '" ~nd Ihiol, (Figures
), ~. H . and 3.4), replacing - C H-C H, by
C = l'O I're .um.ot>ly lhese ions ",e
for med by h~dr o~cn .e"'T~"gcm"" . ..llh oIc1ln loti: RoJ ( 1 96~ ) hil' ,hown I",
4-mcl~ylrmt ~non"riJe that lhe abundam C, H. N " i,'n arise. from ~-h}'drogell
migr" tion (0110 1 t>y ]'-("l...... gc.
,\ furt!oeT u
ual ""'tllre 01' 1"" spectra of ,~kyl cYiOni,j",; . lhat [(M - It] >
[ M- l LouolJ ICN ' a n o<rul if .. I..hile h)'dn,gen i. uaiiab le in the m ~.
%.(]c,avalle ;" unf...unbl.:. req uiring ro,malion ora quadruple bond.. e -N ' > to
, I .._
. .......
Co""".' c.... . ,.. c" ....
soa bil= !he <:hargt on nilrogen. I' m <h , lq ~ nidc. fl~l c " ' ,,~e with h y d,~ ,.o
m,n a lQ;cmmt IEqualioo 4,331 10 8;" 'C Il.C= N' H, i, in.ilni r",~nt; hilh.
reoolUUOD m..asur..... nl . ........ Ihal ~ ~~~ ,,( ' ~ e '"it 41 peak 11 C , II ,~ (th,.
<cllmul!!<lDOnl I"O<:nS i. rna", in,pona nl fro , malic . m"lc<:ulc,)
This bad-dcmaticm Bf ....." '1r "". by ' he Ollrik group mi Y al", i cco",nt [M
tl1e a lHcnce o il M - CNl' forma l)on. .. h..... ~"n"~' I' wlIh the behavior of
cl<x:tmn ."ithoJ.-a "';Dll lI.ro " "" lJCh as chlo",.. and Momi,," U.4uatkm 4 2.1~ th<
beho vior or CN acr uaUy ..........,,1<> 1""1 " r n" ,-",... much more cl~ly in Ih. ...
",!,Itnt< (S",..uon 8 .6~ Only 1100 10.._mass
in.... " 1'1; tormed ;0
abunda......... ",mini"",nt of Ih.. 'pocu a of alb "..,. lhe ('. H, . _. ' killoul d a, i...
t hrotL~h I",. or C. H to,.' r"I." -.1 "t 1<", of H~ { EqU.lt.O ~ <I<ln ai:ail\ a naln.
II"'"to tho to,ha ' lo , of ha logo....
Un"" , ratcJ . nd " . "ma tic nitnln I\; ..-t much m o~ .bundant m" lecula. ion",
, tid thooe with 00 ~ h !'d""S"o . h.... 0" ,i,n;roc"nt ("I . HI' . AJ.01n. ""ilny ( ilK '
witn tath<, unu. u. 1br ~<Io ...n pII t"... ay. ,n thei. 'p1'" h" , . hc~." ~~l.-d
"yd"""" """
link"""'''l 5.1 2 ~ 0<1 8.6 ~ a ,",orlh Iryi.., '$l in.

N;troa l. I ,.. "' h. ~ lot ' I ilium . tN II)' ,he rn. .... tl",cu~m o{ .. i' mprn",,,,. "
:r-H fO<l uanllem..III cau luiT i~ lr doco!>'P"S"ion. Ira<l m, 1o d imina.ions of Oil
" r cl ~ yl "Tl<: ( ~.~ .... t;"n ~. ~ H;n<l" ..., ('I nl, l'l lWll Ah.h"''llh l~ ".::un0ll',menlh
compel. poorly with 1M 10$0 " f NO, {rom (M moltatlat ion. they ""aiD somt
ll llllificance lor SII l>CtUlr n liann.. nt; (he plneuoo iD the <pt<:ttum of an ion
m.iz ~ 1 clear ly
\hat ,he !",Ilo at '"I; 12 (1I1e hi"*",,, """" <It-to.1roJ ca"",>1
be due to the molKnlar jon, N itro aromaoo <tIDW dl.a ~risl ic 1o<&"S of NO
'n"""
1~"Cfl( ~=o
"".6 ' ; 0. "'.
"'i! 12, 0.4%
(9.30)
, , - _.
\~lion
8,11) ;In" NO, ; w,ll1 ~<kl i \i (l na l a ro matic ",Wilulion, N O, 1o", can ~

min imized by ~'OUIpetmye 1" ,-e1 of ~ O, CO. ' C lI zO, CJ H~, 'IT H,O tYin""
I'N21. Oxyge,,.,om I"", can also

o-i,om e< }icl.l. (M -
~ "t;
ror n;un lo!um and nitroanilinc>l, tile
om' . b u\ th~ .... ~ n d r-i.o mc!~ lield (M
- 0 )" .
T h< followi,,, rn,,'" o.roear a 01 hlogona tN U>D1l",und, are IU,,>lnliw:: 11et,
CHIllr, 2,2,: 00. , a e. CO F" 2,S ; l.~-(-, ll ,O], H,

e, HU " z 1.\: c , el F" 35 ; C ~ ,CN. s.u, I bm m"hexane, ~ .l > l-(~hl"'''''''''lh y l}
Unln"'.. a 2 1.C"-,F.
l. ~:
""rca"., ~.I ): aD<l J -r h eno x y2~ hl <>T""lh a ne , ~ , 14 fi~ wres .lI D, 3.23, ,124, 9.21 ,
an d 9.n ,ho,,"' the mass ' pe<:l r~ ..f I, l- aDd l, 3-J;,,:hlorobulan<, l-ehlorododc':" 0". r.heomodod.,c.",,,_ k hlo,ooecan., an d J-b fOl~an<: .
Mea,ur able m"r.:.:ula. iom ;In; "bl ain. hIe tnm> ~I k yl halide, (e. <q>l DuoIldel) 01 mod<.Tald} luSh m oleculal " ,.., 1110 (>J with "'me 'hin hlandun~ M "
,
'"
..,
~.
""
.. . ,J,
~+
O/JO
' C l ' OO
' '''
fll"'. UI , \ 1... >1""1' "' " ,>I ; ohlo.-od<=ne. SruU (0, 1j and n, O .~-J ....... ""'bJ ion
peak<ar< Pf"><tJl ;n
116 , lid l ll.
"'i'
"
..
,."
.~.!-r'-'"C~\. ~'n'l',..,,,~ ~'T'

. J
' ...... I n
p<n<nl "
fd ."
, '~ '
~
,i
'
, ,,
~
<f'OClr"m of J-bro tnt>deeant , sman (n. t X ) m <>l",,,I:.. ioa poOh a rc
"'i' no .r><! 222.
, I M...
"PO<!<. of eo..",", Com,..... C......
i, "ften ncglib~blc ror pc,h"logcnatcd compound, unl"" they aro unsaturated,

The presence and number of chlorine or bromine alom, in an inn j, u,ually
rccogni'''bk lrnm it, charaoteristic <'isotopic dust,," (S.ctiou 2,2 and Table
A.2).
The halogens have a relati"ely smaU inOllence on ma,,-speclral reaction,_
Iodine is the mo,t influential because of the unusu"Uy low dissoc~ltiOD onergy
or the carbon-iodine bond. Also affecting carbon.hal()gcn hond cleavage, hut in
the opposite order IF "" Cl > Br > I), is th e inductive withdrawal of electro ns
by the h"logen alom, However, lh. tendency for back-donation of electrons,
which 'trengthen, thi, bond, shows the ,am. order (Uuorine great est), sub<tantially compensating for lhis erree!
There are two main sources of C.Hz.X- ions in the spectra of alkyl halides,
One souro" i, ~-ek",'"j,.''' t" form the R,C X ,. ion, which fon""" the expecte,l
order of electron-donating ability F > Cl > Dr > L For bromine and iodine
thi, reaction is negligible for an but low-molecular-weight componnd" and for
~hlorine thi, "aeli"n i., of imp<>Ttan~e mainly for IC'Ttiary chl"ride,. Alpha_
cleavage does give unusually abundam (M - nt ions for lower-molecularweight fluorides. p"mJleliug the I:>eha"ior of alkyl cymlides (Sectiou g.6), The
weak C.H,.X- ion 'erie' found fDr many alkyl halidc' i' '-luile chancteri'tic
aud thus useful for general identillcmion,
The second ,,,,,,ce of C. H ,.X ions i, tbe di,placement re"ction (Section ~.I I:
Equalion 4.42). TlIi, lead, to an unu,ual1~ abundant C 4H. C1 or C 4H, Br ion
in the speetra of !I-alkyl chlorides or bromides eontaiuing more than Ii"e carbon
alom' (Figure, 3.B and .1.24 and lJnk nown ~.I). The ahundance, of ,he,e ion'
are greatl}' lowered by chain branching and are negligible for flnorides and
iodides.
I'he" are ,ull'lantial dilTerentt' in alkyl balide 'pectra in regard to tbe pro_
portions of (M - nXj" and (M - Xl" ions formed b}' C-X cleavage; the former is accompanied by seeondary ions ch'm'etcri,tic "f an olefin. while the
(M ions characteristieolly decompose further by losses of C.lI ' .' A promineut DE' ion from the loss "fHX i' observod for fluorides and primary (lower
ror n_alk )'1) ,md secondary ~hlori,lc, (Figur", 3.23 and Y.1l ,.
Bond-dissociatioll energie, (Table '>",3) account for snch behavior: lhe RF- - II
anJ Rei
H bonJ, (fiDE ~ 5,6 and 4,6 eV!) "re ,tronger than the C-H
bonds 14,3 e'v") in alkanes. making the hydrogen transfer H-CRX ....
CRX H energelically fa"orable, The formation of 1M - nxj" can be
'lmn gly innuence,l by (he prese"ce of olher fnnctionalities that "nect the C- H
DDE's 01' introduce labile hydrogen alom, (see Hydrogen labiHly-, Seclion 8.10).
1,2-Remraugement of fluorine has also been identified (Morton e, "" 1989,
19901.
For tertiary and aetivated (for example, allylic) chloride' and for bromide'
IFigure 9.22) and iodide" the formalion "f(M - X)' and In","cT C.H, ,' IOn<
generally is dominant. Electron bombardment can abo produce R- ions of
unu,u"lly low "ppear:mce energy by "ion pair"' processes: R X -, R + X-.
xt
.. 00-_.. . .
'"
!\!thoug b C) I..._, - ,p n, .~ 01, ign ifical1 t a flundance for lo wmo'"" ln ....,. hl

of thi, tyl"'. ' M y cvmmoaty Jme by 10'" ofHX from C. H,.X I"n. ([qua
Ii"" 4.45l
Perhalo",naled aomp<)und . , e.emble hydrocarbom in the., m ....' f'C'.1 'a l
""hio. Including a high tendcm;y fot "'''Tr8nll'''''''''t. T he sm.lkSl per h.<.loJ I ~ yl ions are usuaily the mo, t ' Ial>le; Ill, . <am ple. C F, Im/z 691 ;. the mo. t
"tt\l nd.mt km in pcrnuoroalh ne spectra
K>Il.
~ ,.i<......
gi"" .aln able .ittail:< on the flaimea tatlon beha . i, ,.. tor
Ol Mt d l \$C~ Ilf compound. ;",d appliaation, in partic ular ~," a rch a rcH . Sjna
Ihe fhi'" I ii'"'' of 1m. "' ~ , x tbe,. has been tt emendon, prollfeSS in the m.....
' JICI.' roD' c lJ1 ,of D" ..."lal ile compo und s (Section 6.2). "' !'f'li",, ~ (m, ,If l hese
led utiqu., III idenlifi"'li<Jn. datcation . and ' l' oeture elUCIdation of compk~
com"""n<h. e" ,.,..,.ny tho", of interest In biocl>e nti m~ 800 blolo). """ he r"..n d
m m" n<>l!' . r h l of M Ot lil (198 1), MaNcal ( 198~l Fa<-d>eni .19115~ Burlingame
aoo C. " . llnol! (l Y8Sl. (ia, kd l (1986), MoE..." , " nd Larsen l l99Ol, Sueltcr and
Watwo ( 1990). and M ~ Cl o , k ey (1990\. F n glDeflf:lliun m",h" ni"", of , ped rlC
cia,,", of compo llndl ure al"" ",o'k''''''''' ,n !he ~cn 01 5ILOI" 1.9, ~ , 1 2 .
and belnw; nnl}' lh" ", lin the thi rd edmon oft"" hook will be 11' 0<0 here , ~' or
earlier work chacx Lhc r ,e. io", ednw "" '" I.... 1>0<;, Sc<1i",,, 1.9 and 6.8, and
thc com pilation, of DudlU:lt wlO 11'lll3 19\12),
A number of
Co rtlfJou_d ClP .
Alka loid" Bud.zjl"' u 1 98 2. 1"8 ~

Ammonium 4IId im inium "" h'l: Vieth 19SJ.
" n l; f,i , ~ n 8<" ...... <I W, 19S5.
B,1e aCIds: Elli", 1980,
C; ,rm~N ...,;,. h H."q 1 9 ~ 7,
C.., Ik,hy<l, ates: Reinhold and C " l" 1983, llu dli H:...,ic" 1'M x:; Rembokl l9U,
C'fOl. " <lld" Budzik;cw;Cl 1983h,
p' " ", ~~ , m !" , un J<: Lel>edev 1991,
~ n tty add" Jen " l\ and Gro>. 1987; ( La: ) . 1939; I.d )ue.... 
H ~t e toc y<:l c " P,,' lct 19R5,
I ridnld" PoJ'>O\' l nd Haooji=l 19S3.
ls opr~n o id " (klfWot" " D I'I' xl u<:" ": [ 1ll1:1J duQ Ryhaao 198 4; Enzdl and.
Wahll'' ' , g 19 R6.
Lipid<: l ankcllllil t'f <lL 1983,
Nucbc aCId.. nuc!f<>f;"I1.,< an d n u cl~o tid e" Lins chrld 1983:. Jl.ud, ixic wic, 1<l85;
McCl<.. l cy 1\lll6: G ' 01j abn 1986; Crain 1WO.
.,M
...'........_C_
0Ii lt"~j yc osj d es: K o m o r; ~ ,
al. 1 9 ~ 5
com!", und " Iluw;k b "'i", I ~~J; M iller 1 9~ 1.
P,:pti<!'" ~nd prorem! , Bi<mann and M ar nu 1987: W ~ d . ~ I "I, 1989; C. rr,-", ul.
IWI , H un! d ul. 1'1'1 1.
I'hosplloli llld ~ Jense n and 0 '00<1988
Small.ri"s I>ii><>r",,,io: m<;>k<;ulu' 7;" kin and Mlk'y, 1984.
S.cfO,d, a rid h"';o.I" ..hem... .1;" n" ' (;'''' Lin and ~m ;lh 1984,
Org" """",~jjic
" ppM<JII,_
B,,""...,..,....'" RurJ;n ~"me . "d ( .'\.~noJ; 1 9~5; Ga'ke11 1986; Odh'lll or aJ,
1984; r &<:<.' h.eni 1% 5; M ~ N 'iJ 19116; MOlTi, 19HI; Carr et aJ. 1991 . Smith 01
aI. 1992.
C.... ,. m;n.n.'"
~ ,n<k
('osnlochemi~, ry'
a nd "pi le II,.,.
1 9 ~ ;::
Calm , N ai, 1989.
Dd . ee'er 199G.
<'
I"n, i" ",,,,cu1.lol Budllkic...ia 1'i8t>a; HJlco 1'185; K~r~",k

ai, 1985; Clement
,nd l ....iM\di... j .... 1 9 ~ 1l.
Enl )""'" M illtuj!..on 1986; Caproli 1987; M cn". k e ~ 1990
"' pl, ~ ",", y i...... 1982.
F"',Of eo,np"" "' o' $: Sha'" a nd M""ho)J\' , I 'I!!.~ .
,,.cnl'" Ylllen N Il7, 1991.
Oeoc hcmi>try' Philp d u ~ I ~.
G lycoooojup 'e<: DdI and Pallioo 191\6; " U" and POlor_K. l.li" ," 19 ~ 7 .
Mcmbra M lipid" <.'o llcllo 1932.
M ' l ~b< ~; "", : H ..-n j n~ ~ f aI. 191<'1
Polym cr add;!""" [..an",,,, . aoo lIarris 1935.
P, ~ym<: .-..: t.iiJ.,.-"'ald 19HZ, 'ichultcn and La ttimer 1'184; Snlilh n ~J . 1985,
Pyrolytjc ""'d lOd" M o ~.daar n al 19M9; ""n. . oo AI"'" N lIl ; f1all;"lrcr; rl uJ.
1991.
X. " obK)!;",. to"ic m ml'(lund\.: R",bngamc f'I " L 193.l
10
Computer Identification of
Unknown Mass Spectra
\>oth 1'" "/" "''<1 . nJ ~ inf" ..... tino "aincd

in IJ1lnpret inll unk nown rn"'" '!"i'etr i . Thi. il eol""cially
for KJ:!obllJ"
..n1..."" " ,, llw,. on which vel)' hllk other Iuuct u 1 'nf",,,,. ti,,,, ill . ,'. ilable,
,~cll as spectra produced by " utom"ted ~ .J"" m. ' o rnophilllSl. o;-, pectr"me{.r
l) . ,,,m, tn IMc an"I}', ;, of complex " , ganic rn;u" res (e.i Kpo t hn ~ nl '" body nu;d"
in"". !
drng metal>olltos, .lld pc l r olcu m ~ I n U"",aJ such , )'stems
a,t ald. to the ;nf" prncr. "oo ", ill I-.: much .... ,~ ~i l ua~ 10 you J1 you ha,-."
good \> ;0 und er' l.nding of tbe imcrprdahon p' ''"'''' ~ri l>< <! in lite pre,-jous
chap'e,. Ho",.'-ct , Illch """'pul\:' a1~"m, " 'C""...... fa.<\ ( _ 2 .j and ,caddy
C""'r~ln l<c~nique, "an increa, .
ph."""","" ,
avnilah lt Ill;,! it i, 'ol ' u" gly nnnnll><'flded lh81 3nl' unkno" D5peclr" m b<: ",am
incJ h) o",il an I lll<'riliun M ore y<>II rtm ' }our own ;n' e' p' "I.a'i,m etTorl1,
ROOMI e' leusiH R ' iewJ 01 sud . ~..,rn r u lCr a lgo rit hln ' (Mcu flert y and
Sta ulfe' 1Q3S; M,la"'en y n al. 19'i'cr, , hould be ' llldied for Ibe pnl>l;ipk.-. or
.)"tcm, a .... f<>r , pec , r~ , uform ~l "' n on tit<; va';cly of a lgorit hln l lhftt ha ,-e hcelI
pro poK<l. II i, ~>cr~l ,,, <h. i"" 1"', .,ible approache, into Iwo lyl"'f, ~l"'em, r""
..,,,;.,L<J "Ad 'ho~ 10: '~ltrpr"'~ ljon of unknown rna.. ' I'U-..... I ll'uy... and
McLaIIc-rty 1 ')7~ ~ TI1 . mool widely u,,'<! ' ys' em, whid> b.o.. a!so been (\en,on.
Lr" ted 10 b< ' he mO'1 efficient , il Probabili l)' BallCd M" ......ing ",8"l ) (Pt'J'11a
N ai, 1976; Mel ,atT., Iy .. nd Sta uffe' J ~ ~ 5; Loh and Md..aflert ) 19'91 ; :-1. Lt rk n y
rI ~ I_ 19'1la,bl. T"" only lllle,p, ell'" a l ~o ti ' h lD wlticb i. t;eneJally n ailahl' (.me
01 the first u,"f"l "artI ficial ' n'cllig,....." " p"'IIram. , i!. Ihe "Self-n , irunl ln'orpre l;vc and Relrie ,-al Sy' tem" (STIRSj lKwo t n " I. 1973; Mun '" ~1. l ~ xl ;
Hara ki d al. 1981: McLafl"f t)' Ind SW.ll"cl 1 9 ~ 5~ P H\t, or PBM and STIRS,
,n e a\'ailable now on ma' .... pccLr. """' er "'II'u.... OI ' yOlen" fro m mo,t manu.
rac lu rcn, [,om lbe p~~s.a<lt Co'p<>r~ lion (l 99 I ~ a~ d mr L"mpu lcr nelworking
lystem"
.,..'il
..
10 .1 The 1llaU.1>.o. . 01 "le r ...,. EI masa .pectta
The capabi lit;'. of a "'lrie>al algorithm depend dllrob . ... lbe q ual'ly aud
",,,,, p:rchen<i. tneO\ of 11l~ lff. ",noe file "m p~"yc<.l II)' far , he b~ d al ~ boI ""
" the Regi, t, y 01 M. .. Srcclra l Oa18 (McLafferty a od S....ul" , l "~", 199 1:
~ d . affcI ty d ai. 1991a,bl. in 1992 ronta iniOjl 1lO,llflli dillttUI !f'\'la of
190,000 different com po und. (t"" I'N 2 NIST da ta"""', 1M "" ' I t. rg.... 1 <Illlel:
lion, represcnL, 62,000 ~nmJ'<) unda) . T IK Co n ...u colk<tim, ~ a , resulted from
111<0 ",,,,pc<alio n o f Iit " ra U ~ Ihoul.;lIld>. " I rna.. "/'fi1Wll>tI,im wo rldwide. anI!
there are no , igni"ca nl L~'I ""~ i<>ns of ooe plOpllc la ry 'P'-",i ra no l included III
In;', da lab . "". u..c..u ,", rhew m=II .......enl. "" !lttn made using a wide " aricl)
of instr ument, ,,00 e ~pcrimL"JlI.1 ", ", di lion ~ the abundance valuc ' can ,'u y by
m o r ~ th n an nNn- or ..... ~n ;l udc. To aId "'-;th thi, pm bltnt, all availa ble 'Jl"lCll a
"r lh. .. me oon ,pouod ale ' ncl",kJ ; ~ lhe data ba,e; thi, has bcc~ hmd 10
rfilooe Ihe mil'a! .. n mg
,,~ 42~~ (Mcl.<lfIorty er al. (9II la). A funher
""...n,ap' j . Ihal co mpa rison of the,. a,W;\;" nol lpectra provioo. an e . cd len'
cheo:k ror etron ; m w the I. , t decade arrroxinl.ll ely 6<l,OClJ COT" '" h .., bow
""r ~t in the ..1"~nce f,k Reflecting this,' n m" tt;";"! 371 rando mly seJecled
unh .....n Ipret ra of com pound, pro",nl in f>N h flle-l llSio, en l...,. yicJdmg ~-~
lna ,chmtt relbhili t.y {",me compound "" " ol..f<'OiSOOlerl. 14% of ' he po"ib/e
corr~t lIO>Wel1< w" ~ reca lled wit h lhe N [:" d. ,.. ba..e '..... us 36/~ ",ilh the
Regisl ry, despne t be f.<;t that the tatk.. h . > 2., lioles u mny p<J""ihle wrong
aoswer. iMcLuflcrty f' "I. IW I h~
""".u,
Sati,,[:>ctor y ntJO.d"nl of all " " k n """ n and a .clen"""e 'J'>'t 'urn co ns Tit ut es the
fin ll1 proof of moJecuLo. ........ (;l ~ (Section 5.5). Howeve r, eva ln.'ll ion of l!lc Ic loobl~ ly (It such a n ioc.. ' i[ou'i oo mUst also con sid er th e Jimi(ati" n.
rna.. <poe
romeuy, p"ak-abtln<lance .~rm <nt ",ilhin a "or,' ,m all CXpeflt'Oelllal , ,,o r \$
often ot>.e. ved oc t",'''''n , !'Cctta oJf ~Te"'O ~nd geometric
nd i' l""'~ hle
1><1.."", , pectta of o,her d O' ell wm ilar com pou '''''- Tl", """I ...,~ abl e ..wll eh
i, obta ined by r"nnin~ the un knl>...n and rcoference lila .. spccIra undfl clo>eJ)
,......' ie,,1 experimental condition, Oil the same instru" ."nl H.....e"". llIe
iJO"ible , tructures for the unknl>...n rnul' be roc" ,ad 1o a , ebli>ol) , m;oll num.
ber I>f ~ ,'ai la b l e refe, ence comiJOurnk t.el<.>rc lhrir c" ",,,,,rioon i, feas ible
"r
i"""".-.. ..
o~pertment a lly ,
raMin"I>rp"ra ,os ' he unique fe8 1 ~ m <IS d) la ~ .....i~~ !in8, " pn,.-on iMvaluabl.
rnr d ocument retrie.,.1 from b tmu in [SoIIMl l <n 5 ~ and "reverse ,eareh," The
we' llbt lllll in>'o l...,. l hc \..1> princiro&l lyJ'"'$ of da la in Jow-resolution m ~ " "P"".
t, ~: m. """" an d a bullda ........ Tho pfot" bility lh'l! ..ort icular abundaoces w,U
"""u, folio.., a IOIl-nu,mal di>lribulion, 1M probability of <><currollCC of moot
m. .. ~ .. "". ...lso . a ries in a p<edicta ble ma n ne l , ... di",u.ood unde< roles ror
10.'
"' ~ ' . _ "
"""_ _ . _ .... .. _~
pca k ill'r..m.,oce~ (Ch apl" h T loe la,!"" qlOl. cu!a, fmll"'<'" '' I. nd 10 <lccom
, ,,,. lIe, frag mcnf>; "" the p"obability o( higher 01,': ' aru", deer. a
by fa"I'" o( I...~ appro. i.... ' t1y n ory 13U rna", U W ~ Tni. .......i\lhti ng sy,tem i.
u",d for indoxin~ ,t.: ~Imp<>nanl Pea k 1"d 01 0( I"" Registry 01 :\<l alS$ Spoctral
Dat Q (Mel.affi:n y and Sla uff'" I ~ 9 1 ), Tbo ......,. .nd un'q"" fealu' e ..( P DM. ""r
v' Tlle ""a,duJljI. n ~.l \l aM" for the i<kI',ifical",n 01 ~ om T'0 nen ts in .... ,u ..,.C'I. In
lhi<, PBM .......... tain. wholher the (lNIh oI lhe Icfe' ",lC' Ipcctn lln a~ p"..enl in
the unl q" wn ' pectrn m, ~ , ~ whether the \lnl nowll's pu h ~TC.' in lh. reft'fOocc.
Tnu ; l!>e ,..,v"" o ,,-, ar~ h in dlect ;s nOTci ..." h in rho unl nown tha i are " t'( in
lhe ,deTe""" ' pec!,um, ";nco the se could be due to oll>.;T com ponent> <or lhe
",i , luTe
PBM paf,,""a,,,,,, ha s a1" , !>eM e.'.a!u:>I<J n alisticall)' tt> find out lhe ,..1u a l
lel'a\JIlity 01 til<' prodiclion<, "ased on the d'glee of rnatd. foulld helween the
unknowns 'llld tho roferonco 'fIC~"a , T hu, a r. p" rtl.'d 9Il'/o.. Ji~bi lill value ind;C~' "' Ihal in ~O'>; of 'II<' Cl'a luation c ~ , . , in whictl P8M , clri e... d a refefUlCC
' I""lru'" with Ihis df ll' ~" ,,( ; im ib rt t ~. Il>c u........ . .. . ~ "" e ct (thi. mo; u"" or
, diab ,lit), abo a... ~ ''''' thMt a , pcct lunl of the Iln ~ no ..n CODlPOUnJ. is flRSC nl in
tilt.' ,.k...,,,.,. nit se1lrchcd). Itoiia bilily ~"''''" a ,e repCIrte<l for t..o d<ll'~'" or
" ""'ttUMl l ,miiaf ity, Cia. .... , I a lod I" : . 0 1 a Class l mak'h. 111<' ans,,"e' i. cons idered cone" ,mly if the ' e1 I"" W ' peet, um ;" uf tn. same CQtt\l'o und Of a we' _
eoJ'OrncL FI.' I CLoss I V rn ~ " h Ihi, ,lcfinition is br o.. .Jo.-nt\i to ind U<1c also
, inS_p",iliomI'," ' ><T"- homo/0Il' ...OO oompoull<l. which can be ",.J. lhe sam<;
by moving ~ " "" ,,", bond ;;;2S~~ of the ch~m length 0' ",,,, i,,~ One ..,... bon
;lInn' (Lo h and M ~I.,lfTc' ty 199 1 ~
~ ~.rar f<" Iu, e. bay. boon ino." ''"f'Omled in u' th. PBM sy>.I"", 10 minimi,",
suth m~""4 " "cie" >l>\I . 1", lh"'" of ...mpl. and rdo;'~"D"" imp ur ihc", Spood
i"'T'''".",eut, ltlilitin ll .. fer.nce-fi le onkrwg _
n'la k~ it p'-'" ihk tu .,,,, ,cb
Ih. 220.uuo ..re...,.."., in _ 3 . (Pa fj , ~ 1 9l' 1 ~ "'" enoullh to kccp Ifp with Ihe
ch" "U, olll<l phie ",,,,,,ation on m<" 1 G CiMS runs. Thu~ II is ",.;orn "",~ded
Illal PB M I>/'
Oil each w"k _ ..
" "y ex gmin",i<m It" ".. ;. '''I'' eler,
... rurlh. r Improvcmcot i"''Olp<''"le, "f",ward ,,-,",,:lllnll~ capa bilities, ~i .i n g
. <Jdlt ion,,1 "" Ild,ing credil I"J In. a bseooe of nt>nnJII lchiuil
b peciaU y
ul. jlll fo' unltlO'Wn e'I" '""'I. each of tilt.' in;ti., Uy relli..,. d b,...t.m.lehiog rd\..,._
enco , pe<:tc.a ill ' U"" 1OO 110m tM "n'_n ~liu"' . rna tc h iu~ e. t;t. ~ " a l
>1" ":(' '' ''' in I" , ,, ".,,;,,'1 Iho ulhet ",",_"..,tching spoctn (Sta " lkt ... gr, 19 ~ 5~
F"nllet . 8n ", ,' ad ma. S PBM" (I'.l-'IIM) h.a' beon d",o~'f'ed fm hlllh."" olu' ion
>fIC'CI '" ' 0 ulilize the un" , ~....~ ..t;on dllluh ",. rem iclint I..... ma lch. , aCCOfding
I" the . lemonl"l Ollmpo4ilio n {lj the ",reren (Lob ~ nd MoL" f1eny I <1\1 1~ Glth
{If th c PI! \ f improv"",,-, nt, reduced the "''''''8 an,w." r' Iricvoo " y Iulf.
I'a b~ 10,1 in",I,. t"" tbe P HM n~ulT. l<>r an unknown spectr um ' "!''P i'''''
bl Dr. H"nClc""rg (1 980) as p.." or a rompo"'li" e ' tad}' or Pfop'..., d ide nt ifi ~ " .
lio n ~ I S''' ll h , nl , !-D odoccne was lhe COTTeet ans"..." .nd .. UIi,,, lflCcIra of this
compound in Iho ~.Ia """" ,.n e fo und by P8 M '"-' Ihe besl m" l<:he. Spect ,a of
I I a (!) " , her i, omer lC (', , H 2O compound, ..... abo In tl>< da taba' e; 01'lC of I""'"
" ... . 10
gl".
"'Ii
"'1"'"
pc"" .
,e I
'"
""'-' _
C"H,.
,_ .
C,/<..
1-<j"""" "
...,",1.
CI. .. 1
Cl. .. .
"ro
' ,,H,.
ec
"
"
sa
c......0
e.,I<,.
eo
""
"
--_.
. ,"- .
,_
ss
se
"
"
"
""k,,,, ~"
"".,.,,""
"
"
.'"
C,,..,.e),
C I1,.o,
C
".
e.....c'.
'"
,.
=
~
)t ~ ,
C" H "
' "H,.
C ,,..,,
C .Jl ~
o' ",yO1OIl ~ ",.
'.2-0'.
"''''''''''',)'< )'<' ' ',,,,,,,,,''''''.
1~"""""Y' '''''''",*,""..-2,
p.p ",-<kIII""",..
"d"',"
.....,.I<I.._"" ""II1)-leoe
_...
2-'".'""...."'...
l_.'ly"" '""'''''''
'u,"..'".
,o'.-n
~ " ,;...,.
II
C ..... .,t ,N,O
"'''''''''_
0-._""" '''0
""opo, " .
_ .. ........-..."""""'O<l""".'"
C"""p,
=
m
'"'-"
(: .,Il..
.ro
til" '''''' ,&CO"""""
""""'",a<oRW>t
....
""
IV m,.'ch,,~ .. ,
C" H ~
u"""""
--. -
_."
,-000 _
il-_~y l ' :>-""<l O< .".
_ ~ I" """"" _ ,-
c.....,c,.. .
~ {1
C ...., .
C,,H ,Cl ,
".
t"H"
., ....""" ooc......""....
C,,H..
0"".
2-d"".,.n.
'_u"""'.,.
' ,,HoCl ,
dO
. 00
'd""e, . n,"
0'/0100 _
F",,"ol.
<.
, -do..""" .
c .....
."
-"'
.
=
.""-" =
un ' no... n
"
""
...
~~-
c. ......
,.... PBItI and EPB'" ~""Kt Clu.
Wo. ' poon
..... .. _
0;: ,,11..0,
C"H,,o,
C..,.H "
C. H , ~
c..., ~
C. ,>l,. ~ O
C. ... ,.t<O
m_
,do
l -heude<"..".,
-,-
~_.
'-m..,h)'1pym,,,,,
" oli ino
oct.ace. _7_10.... """" 0"""'' ''
""t.- ." ,1Td ;O 1\01' """ ". 1'" ""
. .-. - ... ".'.''' ''''"'""_" ...
_-
'"
'pc<._
11'1 "" .......rI, as r<li"bIc. tnalch '" 11>01 m" . l poorly M:l lctom~ l-dodecene
lrum. Ob,j ou, ly "",t.
I rc, uh, rOl a tme unk...." .. " 'ould lea\'c , ul.olllltial
doubt. Khoul lhe identi/l..l Ilim\ (COOSi.rCllt ...ilh the 1>milarity ..flen fotlnd lor
,pcclra of iso,lK'Iic hydrocarbons, Sccliom
although lh. oolo<:t,on .J II..
",me co,np.. und for llie beat fl,,, matehes p!\1>'i<Jc, useful iUI:nI. .. li ~ 11 M . If .
lnO <C tt:liable ldemifi"" li" n is .....,.......-y. lhe reference , pcctr"'" of l-dod<c<:nc
. hauld be: oblKined under 1M ""m" cxperlm<nl"l ~M Jiti on.IOI ~ ""' pa r i ,o n ,
~;'i.""ly "".......-1" I"IIM rrI .....QI Wilh lnese ,mprC1>cmcnl' lhe molo "",,,, ..
1M I I' BM doc' ""I ' <1 rit\' e a cn"oCl .n.",, is th~l l h. corr e, pond, "! ~
sp'~ ~r u m i. "'lim I. ~ l" , or Ihal ltl ,I;m, .,.., ' "b<I.nhully dilk",nl jrom Ih"",
..I I.... ullkoown I><..;a ,,,. of diffc<on, ",po-nmom ,d conditi "n , Q f ",ron.. I In lhe
pooilivo, ') r<trl~' ed " ilh high predicted
" lbol ""I'H,t Ih, wro o~ M.'"',"'"
n:Juhilily goncrally rep t'tS<'nt c ..,. in '"'Mich rna" Spc<.:t........ lry is ins. mil; to
,h . mu "h lra.1differ<n=. Th. (, La" IV match <Jclioiliom Me 4ft itrat)' o, il""l.)
tM t d a " i r~i the majonly ..1 I...... ins. noiti' ;l," (I'e>yna n "i. 1976; l.<Ib ;,.>d
:\.l cLifIerty 19\1t); Ih",. follow t he 'f"dCa1 ill'ClpTCla lion prilltlpk:>. al",&dy
l>oook. Tbo," Ihal do not t.ill di. ....;l]y in lhe Cia .. IV CfI1u la aro
oovered ,n
,]]u. tra tnl in T JI:>k 10.2 (Lon aod ~k l. a. lTcrty 199\). T lx""" repr-t'S<'1l1 lhe incOTrffi reference ' , el". ,ed ~ l rhe I H% "",all lev. l in r.. nni n ~ P BM a,,,i 1'. f> BM on
Ihe J~? random ly w-Iedcd "" knoWn! u, od l" trol PDM pcr rorm anoe. At Ihe
> Y 4~;' reliability bel. tho numbor ofincor roct m ri<'a.l.. 12 for PB M, ~;o. .......
red u ~ to 1 rOT l. P DM. Tho C' aclmau d~1a arc d r""tlve ill d i. ,;ri minali ug
agaiu'll "'te.e ....., ;;poclra It.. """'0l! el" "";' >lal oompo";:l' ''''. ",-i1 a~ Ih. COlm
h<o,," ~ f. m "", for 1M' !'f e1n. ,1edi<mc uukn"wn ,md 1M<- dHO . ",, ~ t (lT di a ," p .
".ide ' '''''leU"" rOT lhe chlc. ....""""'. ide unl ~,,"' n: Qf lbe mnain;ng f~l-.e
posit;\'C relr 't" als, ""''''l IL~DI ~bli nd 'I"'t.~ of ma>os ' t><-"Cl'QnleU)', . ~, 1M
'''' la de o a d i< M yll'~rmlidiM ' P""" a aTe \"..""tj-e \<> ,he doubl. -b<' nd ('<)<ilion
hc<::. Il the fH--J~~ repr o" lllinll 1M. py, ro l!dio" end of lh. mol :ulc d"",mmle
' l""'lrum. T o r"'"al, il j, s.tfOllrl ~ !=)m....lld.d thai POM be 1'\111 " n any
" n,nowo brio", j'''U allompl' it. inl" ' 1"otatlolL , ince c ymi oinl , uch "nearly
ro"K\" "'lr KoVal, \l sm ~ ~"u ( knowlotdll" or Inc weal _.... "00 .llrenQlhs, of
rna.. "l"' <:tromel.ry ", a h,gbly d1i"icnl "'3Y to rul, ro '"' Ih" ' \luctural p,,,,, ibili,,..
for 0 l'l ob al ll~l n.....o. A liM I "aulion: ~ W~ to i..d \lde olj Ihe u ~ ln o ...o fIO'dh
of m/= :" ~6 ,n the I'RM '<Ca t'(;h,
cu.",
')n
r-ra....
,hi.
(,r
t""
If PBM C<l nnol i....." 'lIry ' ho uOKn"wt\, whd! it "",uld not if therc i, " II ><re-spolming "--(err"",, If''I'1r um ill lhe d ~/.io ha><; an inlc' I'U t;vc algOlilhm ca n be
u""d 1.<1 f,nd al I<" M p~rt\al ' lrn ctural i.. f"rm' IJOn, T hi, . h"u ld aid in rnlc'1"rota llot> of Ihe o:pccl, um and ;n ,1r....1 ur. 1 idCllt;f1 eal.ion of 11>< un ~n o wn . STI RS
oomhOn"" fi kllowlodgc "I maS5-sponr" t f" lIm. m .tion m "" with ao em pirical
>ta",h for CNfd"um" of '""len",,, ' l"'ctrn, T o 1lI,., ,,,, plioJl lhe fonner, 26 ""'Slot<
of mas. -, pcc t' al d;i, ~ ha'~ bttn ",,-lcd cd whi_h are indi "" ~,,, 0( p;tCticu.la. I ~!""
of ,truetu, al fea t" ' "" fur
m" I. , Iowm ~,. ;00' "" 0 be dlac&.to,. I" of
. l.dmndonal;u, I~S . ,...fl 1.hc ~mino SN u~ and aromatic rints, 01
$
1M ilia. "" <1f n"ulr ~l, 1""1 from Ihe m. ~",,~lar ion can indica le d oclro"" , al'w
f""olion. htl<ls (Char lor 5). HQWC..." . Ihen: a r<: no predesignated .!"t'll. !
struCl.,," , ,,",clatio,,,; instead. S r1 ~ S io ~~lt' 11a i ~ in~" identifying p a rt i,.,. lac
....,Ieal~'r fOlltn, e, hy matehi Oi the nnh" ' lo n'. 'J'CCl.a1 d~t a in "=h of lh ~ 26
d ........,. a;.oin' l the cor, e, p"ndinK<l eola ,;,{ a U rcle.c",," IiJe spect,a to find th" oc
lla l are 11M: m'''''1 ";milar. If a parl;'~I ~r mMtr1JC(Ure i>. f.." nd In a Ilisnificant
p' Op<>r lion ill Ih..., "Om l"'Ulld . ill p,"~ """ in the u n kUO_ ll 11 pt'<l f>abk.
Ab-c-nor <If a sulmrucl nrc io noll p",diet. d, since lhe m~ _rI 'al loalU= of
one s"Mtm ct"re ca n Ix ....de ....1!ligibl. by Ihe pre""""" of a RIOre ....' ''''',ful
f,a gmcnlation-dm:ctinll amup. H e d " taba~ fo, Ill<: oy.terTI [[d ud"" inforIlIalion from 175.000 diIT~..,n' I>rg,m;'; eom po~ nd . ~o nla i ni n g the common
_Iement ' . II, C, N. 0 , ~ ,S,. r. s. Cl, Dr, and,im I, ~nd no ot h~rs.
1'" u'"' the infor mallon pm~iJcd b} lhe STl Rl> iy.lc-m. "ne . xamines lhe
compo~"d, or the hc. t-malcll!ut """"""" . pn 1l;1 Ic uud for each dal" ~la ..
.....J idcmif... tMir cOmmon . IT!J<1 " ral fealUre<.. T o a i<l ,he inte rpreter in Ihis.
~ , hi: c..mp Ule I examine, ! l>c (I ~I . [" 1 the Prf<oCnu o( (,()(1 _omOlOn , nb
,1(l,,;1.. ,~ ( Mc La il<"y eI ai, 1980bj, T ile ",Ii. bilily 01 aoy J'<.dk'li" n Ihl a
, ubo.l . ..d ... . " pf~"" n l in the ~ nk now n ;1 also <:atculalCt1 from lhe , ta ,il lici
obtai" N by STIRS 011 9(X) ,andom ly ,~l.et.d nnk,,,,,,,,, Of"OelTa. STilt S alec
l' ",d' cI' lhe mo ""'..... wright of the unkno", n C<1mpo\lOO producing t he rna"
'P'Olf~m; f", ' ~D<lomly ",,1IN ~n k "" "'n. the fim-choiu: ~al"", .." , eont in
9 1 ~~ of lhe case,. a nd the ~ I sl 01 seceod il, 9 5~{, of the _aseo (McLaIT. " y rI ,,1
I Q~\IbI . Th. program Ilbc> prC<Jk1. 1M , ing, -p1us-douhlc t><,w s v.l... o f 11M:
u ~ kno "' " (Dayrinl,'Cf and McLaflttl y 1977), ,md the Dumbe, r>f chlo. ;ue and
hromm. atom, in pcak o!lUter'S o f 1M ~n.k .....wn , pc _Imm, by matching "-J!,,;nsl
. ... !"""",ti_al i, otopic a b ~ndancc ..I..... t\'l~" <1.J 1 Y17~
The b.asio inr" rm" tiOll n~aila ble (rom l>"T IRS i. ill""" altd in Fi ~\l" 10.1 by
t ile ~ mal.hing compo~n J . fo ~nd fo, Ih= of I h ~ !oo'Tl RS da t" ela, ,,,,, ~,in J!:
th~ Unl:fIO"' " "Jl"l.'1I~m shown. nat~ cla.. 2-' .""'" t he f..... m ",t "b-undant
even-ilia" and (our m<><.\ ~h\lnd allt odd-rna,. I""'k. in lhe IIlI1f';C m/z ~ .- ~~ , Tho
12 rc1'.;",,,,,,, <;ompotl,ld. ", hr""" dam in tbi, Cla ll m) ' ,'" hcool 11M: OOrre:ijXJnd ;nll
dar" of tho " nl ...."" n aU roBta m a ph_nyl KIOUp 101 wbJ<h g a", di!.umh luted).
m ongly md le. \;n1 1ha[ lho ~ nk ...mo e om po ~n d . 1", "" nla;n. a p!>myl voup,
n au ela, . 311 U>oL-. ~ n ti rel) difJere-n1 ' I"'<lr..l d.l ta, tbe se"en m" .t ~ "'u nd~ D I
p<:ak . in !h~ ra ng. IIl.iz IW - l ~ ~ . J\pm ) Imost all tho host-ma t _h ing Trl<-11<%
com(lOunJ' <"n t~in phen~'~ bUl in adol ili",n most have both a hydr.... y aDd a
~ rbo Dyl 1ro up '~ b.'li t ~ Lcd 0" lbe aro malic riot!- H",,,cve,, oot. thaI lh. ,-"" t><"ly l
1'....uP it. o;ontained in a va riely- ,,( (unctionalilies: .,.!et' , amid. , k~ooe, 1lCld, and
ald ~b }-d<;. The ""I~rc of thi, fnn ~ tioll. I ;' t, i. m..... b.n er ind;"aloJ hy th. " .~
lr"is loft (rom tM molecula' i"n (Chaple, S ~ da la do... ~ D oses tM fiv~ mo,t
ab unolanl """h Ilvin~ ma " -!o," ".IU\-'S (If 34 75, H~", mO.l " f the \lOot mateh-
...
,
.'> ,
,
zz:
z
<.
.... . . . . . . ; 0h
.... 0
I-
U UU U;S Ur.
oO
![! Y
I I ; I '!::
i rI ~I b~
u u u S "' ' 0,
S""
, 1' ..
. .. .
.. .. "' :J:
---~l- g
",
:II:
"
JS
,
;;
...
'"
o
I-
..
"t.
.,
::; ii ;;\
I
o
1i
" "
I-
"'
,.
... ,'"' o1.or.' .... : .,'
z..
"
:i" 8 8' ~l 3t 8l ,il51 8"

.r
1
'"
::< :: :: " " :1: >: %. :1: _
... ... u ... ... ... u u ... ..

I I
I
11 11 =
"
.. ......
. .. ..... ....
. ......... ..
e r .. ......
" u
;;;N
0<1
" ' ...

"' -
-
C
__,
" 'C_.~_,.
,_
11.1. sr/RS
. u b . lr uclu r~
p _ iGb""S lrotrtlll1>
-,rum of p.>fO_ C,H, _ CO_ O_r>-C ,H ,
,~,.
Su ........M .
..0 -e"H,-eo-~-~
.,.. . 00 _
. .... ' -00-0---00 0 C ,.. .
."
R.""",
(p. " " " '" ",,)
se
""
"
,se
m~
oonlp" und , are prop}'1 0"010. "d dl ~ i tlle U>U ~ of ...."t:..!il..tod ~ ny l

lIyJro.)1 ( 1 7~ carbon}'l (28), and p", p.... ) t~l gi"" a psodidw m"lec uls r
"-.",,hl of 1&0 tor lhe", ,ub,tt\lctur.J UDlt.. ro<""'I'<'nJing 1<:> t/u; bigh..1 m U S
peak in 1M unh own speclrum. inu;cKI;nll lhdt lhe rnoioruk i' a propy l ""l~"" ~
hyd ..." ,ylK:n.,.,ic ~<;'l. Th" int .rpN'l ~r JnJg.hl ~I ",-, n" l;~ th at l,M 291' IS moch
larger tha.. 1M - 15)- , ~ . a nnll indic.Hlion Ihat thi' i. ~ct u ~lI y I~ c ..prop,l
"''''r (lin %-d:a.~ Scc1i" n 4, 6~ i lt l"' ''ah STI RS h", nol made lhi' dJfJ<renlia
tion, Tloc besl mal.iling ~~' ''' I'C' ~nd $ 0( dJla cla, ses 2A and .' 8 ,h<.". lI" oo<.i ~.
teJlC)' for 0-, 11<-, or p-rinll l'O"il',m .. llIe jDlerpreter would recosni'" lhat m ~ ..
'pectmme l<l ;. ",~( r,dl y poo r ilt mal mg ' ''''h ~ differentiation, (To rllnera' e.
STIRS j, an ~k1 1o . ~. ~ a ", pl,,"'''''''l 1m, the I ra i ~e d i ~ lerp"'lcr .) Tile compu ter
will also , ea",b these I"'tl ol lle.t. ma l,:hinli' co m p<J ~ nd, for the p t'elle"ce " i ~J
sub'lrU ~"l ur c , ~ , unJ I" be f'( odicled t"" mo,1reli" bl, I>y !IT1RS: lbese re,u U. are
' hown in Table 10 ~
116~
l'rofICieIlCY;1I tbe in te'1''''I~li "n of rna" s!",ctra as tSe:'Cri"" d i~ (lfc,;O\lS cha pI..... <If I..... bo<>k roquire. practice: ,0 d(le; dTie~n l u.. of PBM AndSTIRS lor
~~ l unlflOwIb. 1''''' d<..
....... ription of these algoruhm. w~ , 1'.,,1"..... y Idt uoh! the
.'n4 of IhlS book, <i. - a rea l un(k"'l~ndil1l1 cttheir utilily dMun.h a goo.od
,ene-rai l no...laIgc of "JlI'I'lra1intnpretalJon, M . ~y )C~" "t U>lC in tho~ ... ntls of
' " bI>l ~l or ,eo; otI A "ide vAriety of un kn() w~. h , dcmo n" mted cooou<iv-ely, i~
(>1)1 <>pinion, tha t lhc<e progra m. <:"40 " " ~ reoJ ald to the interprel er, rapidly
nitrro",ing the f>eid of p,,,..bl< rom po>~ nd,. and " ,mclime. providin ~ structural
tnformation which rould nol "" di_I_ 1 " 'eu by experienced ;nl" rpr e l~ "',
Becau,", P8M i, now avaiLtble on mOSl oomm.....:...1""'''''' pectrometer , yneUli.
i nd bcc. u>c it> time requirom"'llI u e only ,.,.:c,n"" il 'h<.luld be run fin t 101
. , 'ery unknown . peclr um. II wrw r ~ inlerl'felali.... plu, lhest da ta then d"
nol produeo " 'ati 'factorl . ..." er, me $T1I1 S "",w I>. .h"uld M O be obta med
and examined. It ha' ""on the ~ 'P"I' .nce of IIlO.ny iulerprtlen 1""-1 lhe "-eli.
'"
STIR S al." "~ " be v. l"" hle in i<k nl if1I n~
no;"" >I"',;1Urc:~fO."1 n1 corr c1ali"", evco lOT "' re rie<><:<:d m~", ~pec1J om ,i , (,.
(raining"
~' pec l ~
10.5 Oe ne ral
ot ho lh P BM
~nd
r~e . &...,n
Ash I Y ~ S: C1upman IonS: Gra~ 19~ ~, Hile, 19S5, McLalJeny aDd SliOuJIe, 1989,
lWI: Mc"ai..... 1987, 1 ~) : Royal Soci<;ll .1l Cbe m'OIJ) J')S3; Sh,,,,,r \986:
Smil h 1\1n.
11
Solutions to Unknowns
A:> ha. been empha,ized in ot h ~f part, or this tx.lok. the m,,' t importan t way 10
loa,n how til lnl . rp ~l rna,S ' I'l'ctra j. by actually working out , tructur.. from
unkuown l pe ~ tf a . Whe ther Ihi, bo ok i , u,od in a formal co~"c or I'm <elf.
instrucrivn , ;1 i, 'm pu rt anl \<1 "" r. through a ,arioty of unknow n ,,,,, etra, In
" n empting to solve I pIlrtlcula r uok nowlL use the , elut ion her. only w'hen you
(Illut )'OU ' !lOw tilt an. """, o r when }'OU C,m Do l ~" fur th er. Wn..'1] }'OU ncc'ln~ to arr ive nr your OWll answer. Rcfere.n"" . pectra , hould nor be
" Mod to .oh c 1 ~ . 9C unknowns. T he... unhowm "TO dc.ignc<1 to illu.,ITaIC principle. ~.l frJrlIl In the leU. M ost ore Co mmon molc.cul..; so litt le will be learned in
lClCl\t1ll!t the'D In a mot"noc file of speelra that i. properl, ' iOOo,.d,
f " II"" " II Ih" oppl k'ohk: ' l"l'" " r Ihe -S landard illlorpretat'o n procedure"
OJl .ide the back CQ~ e r) co vered in Ihe toXl. Th e , olutions will foUow thi,
Nder, " l!hOUa.h ' l' _ limiloti" n, l'Whihit 0 <li",,,,,,i,,n nl e>er) point (or oach
"0,"0"'0
The 1>,",lra h~" o been taken from the files of Ih i, labo ralOf) or from the
bM oture. Th dala ho,'c bco;n ~~, m;<,: u;d rn" ",, ~ I.- i h u li ,,", rrom ;ml"'n li<-" , ion_
mnle.:ule rcacl,o ni, and h a c~ s rou n d _ whore moh oo" ed,,,,,. appeared to be
" " :"'>al)', Th e .bt\nd . ~ of a peal; du o rc the wnttilJulion of n.t uro! isoto pe,
II uo;wr ~ t~ ";t h;lI lhc l , , ~cr <f lho foll o "i D ~ limit>.; 1. t.-.r::~ "'lali .... to l he ohun _
dan.,,, or I"" I'..k, ... O_2?_~ rt!ath'e 10 lhe a""" d.""" of tho la rgest pea k ill tl>e
~pooct Nm. Pea kl or Imoll a bullda noc tb . t "' ere tbou i bt to be inoollscqumtial
I" l he ""lul;' .n ,,( ,II<: ' p<;<.1 . ..m ~ " ,,: !K>:n om ;l lC.J '11>i. includ "" unimport ant
pU b belo,", 1% I reIa,, ~ 10 t~e m""t abuooant pea k) a t rt... lo..
end 01 ~
v .... r ,,( ""~ ~ . or uni, In . . . ,. " ",. . I;'.n, ' " ,,' I~. I" ..'_m" " end or
"f'OClrum
I I Tn;, Ihe mil .. opectru" , of "'ater, If any re' " in Ihe sptcrru m W rTe,po,xh lO the man of ,be IIWJ"'UIe (thlt i:s. ,ool...ul,,, ....
tim pal< murt be
'--ma.,
t""
;,,,'1-
".
the ODe of b ighL"' l m,o " . T illi sp:tr um, \110'10<<:, ind"'alco \"~l lite <amp le has
In , ,,",,,,,..,, ,..eig ht 01 18. T h i. m ol<",,1o:; m ""l .'Oola n. . le"",o CI of a to mic we ight
I.., , remer than lhal ,,[ 0' ygrn. MKh a< hJ d..".... . ,,,b<Jn, nitr,,!I''Tl, or ",ygen,
.. h i ~h ha ,-. atom ic weigh ts " f I . 12. 14.,,00 16, ""'1"'<:1i,-.ly. An ob~jo u s combin.Il llon is H , O. This i , "" " fi.med h~ the I"'a ks at rna" .. 17 aDd 16 ...h"-il
Icpn:>enl the ow k cular
fragmtn l ~
HO and O. re'p", li,'CIy_( WI U'I]

J.2. r o r tlli' . pect ru m a molecuL., ""eight of 16 i' ind icated. which Q<.uld
co rru pcod l<><:H . 11 , ~ h <"T "",,1..1 in ue SP.CllU1U suppo rt thi.. <:acll <If I""",,
corn:. po noj IDJ ,,, a
rl><>n atom to ", hleh i, . ([oched r.malkr n()m~ of
hy dr o;en a((lmo. LIoklh. ",, ]
/ 3. A .... ,~ Ula t ...igh! of 32 cor re, po nd,
1<.0 """ ' If to'S .... ygen alOm,. OJ i.
ru loNl OUl, as ill only po'l.ib!. fragme n t ",'0,,1d h l .-e a ma.. of 1" The element al
"""'''''''';Ii"" C H.U i> indicated. The only posubl. n ' i1n!l'--rrlenl for the' e i.
C H, O Jl, 'Illd the other ('C ah in \he . pa.1r""" Clio ~11 be Ju,\ified 'IS picee, nf
su ch a SlnlCturo, [ ).1 ct h ~n "l J
1,4, The howlodgo that I~ main i""OOu, components or ~ ir ar e nitro!!"",
, ,, y~n , and ar gon idcnt; [... ,he J. ,J.'C 2K ]2, arod 40 pOllk. " ' 1'1 . , 0 . Ilnd Ar.
re, pee\i, 'oly. M"'''''. :!OJ ~nS"'" a nd ,,~)'
lI<n . The , igniflca<= oI . ueh n.' Wmlly "" curring i,otope. wID be dlloCl.......J Iat"" ,
Po,' L, at m ~ ""," 14, I f>. an d 20 ~ pr e se n t mon,," \om;" ~nJ .... u l>ly e ha , god
'l'\lL'k.." If" r c u mrJe. miz
"' !iJ = 20), The r-:~h ~\ m/~ 11 u d 18 Me due
t o} 'u ' " (Un k""wn I .I ~ m~" 44 i' di' cu, ,,,,d in Unk""", " 1.5, [l'l'" oll,;n, '''la, n. ~ r",n, ""'11:' ]
1 5 If lho ;solopie peah of rn a' .... 4.~ and % a. c iJlflorod, Ihe ba,e (1.\l aI)
I"'~L in tM "ll"lrum indicates a molerolar ..~'th1 '" 44, The major r-:al l 31 12
a nd II> in<l i~ale lhal Ihe COm]Xl<l OO co ntain. ca lM And oxygen. and "'/1 ?II
c<" re, po ,idl t hen 10 CO , Note
th<n! lire ~ 1"'11\;1 at masses 13, 14. ~ nJ J5
,,'hieh ",ere in d;c~ LI .e of C II. groups in 1M 1pe<;\IU of C H. ~nJ CH , OIl , Tl>t
for m ula " r "arb o n d,o>;"" dQCS iii Ihe oboc,,"J p.:ak,. with lhe m.. .' 22 oo" c
<ponding to CO, ' , [( :"'I:... n .b<" j<k}
1,6, Ignoring .../z 21 bf ,np u, 1" ' ''' inJi cate,1 m'.....;.. lar .. <ei~ht of 26. TOO
only a ppal'''' IopitllJ OOml:'m;ol;On of atoms i ' C, H. a fact "lIlCb caD k dednoed from tloc
I"' ak~ III
12(C ,1. Dd ~4 K' . ~ Pl:>tl . a l m,l. IJ
I n<! !S """"",pond 10 C H and C, H, rc.pet-'1i.ely. and tltt ~ m .' iDl n ",,,ll r-:ab
h....) j ..""I"". [ AC<\lylenel
1.7. {Hydro gen oyan ide]
/.8. fFlu ow olt th. ne]
I," , L M ~l h ~ nal ]
1.1, This i pectrum could i!>diu ", ~ m" ",.." le or rna" 38 which oould fOI1n an
dbunJan\ It a~men\ ion hy "'" 10M 01 '....0 hydrogcu ato m, (.../z 36. ( M - 2)" ).
TI>c hi" .. In In. le~t .hou ld lnd 10 lhoc " hocrn tion in T~hle 2.1 01 1M J!J
ahu ndan", 11.1'0 ,of Ih ~ nalt" " l obk>n ... ' IOt OjX'!l, rna".. 35 and. 37, n..... lht
spectrum i. ~ ",i"." ,, 01 H" O 811d H '''C~ in proportions CI). m.pood.ing I" the
i",\o pic abunride 1
A,"
,11,.,
1"""''''''' ....
>o'.,n
rna,,,,,
Ia,,.
2.2. lhe
pc;\b a' m ~ ",<" ~4 and % ,hould .ro u~ ~ ""'T , u, picion"
b'Olumc ...... ;...m" "" or ma" 79 and 81 an d of llClI rI, C<jual a~undam;es, Be
""u'"" ....."""" \14 and % rop..... nl th<> lno le<:wa r iom., by dl lfe r~ n " e th<> mo lecule
,,,maIO' I ~ rna" \lnit' in addi li" n h' 1M bro mw alom: the JTk ..1 lugical assii.n~tll for I ~ i , i, CH". Pea h at ma _
9~ aoo 97 2re du~ to
io.ol, 'f"'lo
l "k lh) l bromidel
2.3, Look flf' ! for tho - 1\ +2" elemenl$. In thi, ea"" [mi. 6611",1: 64J
cqu al, ~.Il'/,: 1M iso(opic--.a bl,oda""" 1. 1>10.' , n" w. oni~' !wo elemenl' ,ot . ""h
[(A + 2)-lf A l uhono, S; (3 4 ~iJ an d S (4.4')1.), T he for mer i" "uloidt Illt al
low ed maim..", ",tali.., er ro r ~ lIY>~, Tbul , ulJur j , ;ndic:Jud, wilh lhe >IS
"b uml."", .to X.gl'ft m ~ ,,' i !~ riA.. 1)+J- Allh<1 ugh S , would hau the cor= l
rna... rD' thi<. llot m l ~ m.il y 01 the mi~ M peal would be &. ~~ Ji""" 11m ,' ",a uld
be lwice Ih ~ proM~; li ly lhal one ~ tho t,,o S a lOm. ,.," uld .... "'S.) With S,
r-""",I in ",/, 1>4. the l'elidua i 3:1 ma,.. un; l' mu,l "" auigned; 0 , i' on obvi "u,
I""'"l bil ily. E~ch of th~oo wou hJ ",' ntri !>ute O.Z"/, 10 lh~ proh bili(y 01an i'otopic
"'it 66 pc" k. or wil h ~, a tOlal of 4. g~~ ap"~eiBl: ",011 "'i lll the o b'erved 5.00::';'
Th< ma,, :n dilTe"nc. between M a nd " !> mig ht al' o be al silrned (0 CH . O .
~u t las wiDbe di""", ,,,,d in ~, ion ~) , llu . wouid c,m"" a 1.1 %
oon lributioo
I<> ~,/ . 6~ . whicn woo ld .... k~ Il ~ p1edictcd ~b u nd a n" . much too lu ",. ['Sulfur
"c
Ji ,, ~l de]
f'C'l k ",.~ due 10 C, H ,O" til<; " , pccted ..... 4 ) mln.ll y

~ !Om . p-rc...." L Thus II>< <>b\oe r\'fll ' ali"
ratio would he ~-;. h om Ill. two \
"""....(.o..(b nlor~ cl~ly I" lhat l"mdk led for tim'" ",,-[ boo atom" ' uch U in
the iOll fo""ula ( ""H, ' How.v"" one should " lw"Y" he a", art 01 l h~ po6$ible
oon lri .... ci"n rtom "b a "ky o u n d~ in the ;n' lr umenl" wbieh is much mo,e lild)'
10
a hiGh ("0' low; whi l) indicatio n Dr the Dumk l cl caTbo n alomo, O n tbe
other hand, ;f an ' ''l~ en alom i' p"""nl in , he "l; .H i" n. the.. ,hould br a
o.2~,~ ~"ntTi t>uti atl to Ihe mi z 45 pea k due In C , H, " 0, unfort una tely. thi, i. j U'1
" " th" iimit of the ,,""',lule ~rro, a<.sUmN po",hIe ill Ih~ ;n ten, ily dala or IhtK
unknown ,pce lra
To c~icubte tbr nwnhcr . o1' .."' "'On at " m, in the latir ~l/: 5 ~ f'<:lI l . nill" I.... .
til~ in tensity .I io of ma~' $'l:~G is 4.4~,;. From Ihi" 'h l'llo 2.2 i,odJcaln fo~ r
Cl<' \><,11 ~ h..m; a <mallu n umber w",,,ld nnl be p<,,'; b;" .. " Ie'M Ift.'! YJ conloined
a ~ impu rity or e.<1r"",'<.>u, Fragment_,,,,,, canrribmion. Thu....:: SMc.",<:sponds
'0 C.H,o (bul a""). The rn" of 1S to !live the loa"" """~ ~I ....' z 4 J is most
~ 'Ili,,,,lly a tntlhyl Group. confirm inll Ih<: I'm:l iction of the for m" ,", C, H; I ror
Ihis rrnllm<ot ion. [ Ilulane]
2.S. The ["' it 79]./[mi' 781 nl"e oC (> .3"'~ ..~ or""""nd, niceiy to IllWt rn.ln
ah.n', " rr3'ok 2.2). By dillenm ce thac . ho'uld al'" be six hydro~.n ~l"m, in ,"--"
78, lo r n probable . lomenla l rompo:<il' Oll ~ C . H . The aromatic molralle k n
, ene i. 2 posol'ok , lmCl:urt """""" mo b ...I.., i" n oh",uJd h"v~ tb~ indi<"" ctJ high
~, 4 .
If the
m ~..-4 3
'c
gi,..,
't~bi1ity, rBrnz~llC]
2.6. The "4"'<1 ral rt8ion ...,/= 71 74 indiCK\<" thOi "" ~A ... r oltm<"t.
other t ...." 0 0)' #0 ,l ie POUi'*; " Iher"'i'" [ m,.'z 74l -r"'i ! 72] > )*4 f rom t ile
tt l _ _ .. O"_
'"
l 7J1T72] ,'. I~, T~ bk 2.2 j",lic,d c, three ca rbon Qtom. in tt.e hw.I: J'<'Ik II rna"
72; howe"".. " " Ihi.. lhe mi;; 74/72 ratio Iho~l d "" O_04~,~ ill comparison 10 IlK:
O.5~,~ r" and Chtek tilt COmmon i,o(o!",< nl Tab le 2.1 for ~n " pI;ln . lio~ . The C,
I CCOIIIIl. for only 30 ~mu Gf the molecul", ..~i~ht or n. &lh thi. dlfl~l en~"
a nd 1'" ",i= 74,.'72 ra tio Can be aCCO<lnled r,,, by a",uming the pre, "nc" "t
Iw" ,u Wt n atom,. F o r lheoc 11>0;;", ..-ill be ."',cel hoe p robabilit y lh al 0""' o f lbe
<>llSens of the mo lecule .. u " '0. Thus. 'wm T abk 2.2 the mi, 7{'?2 ral;O
_!KIllld be 004~.'; + ~ I,noes Q.2U:',.. ", l).44~_~ eh, eklng the O, j ~,~ fotlnJ The
moJ~ c"J u r fOlmuh. <:,11,0. ;s tbul in dic<l.tcd. Simil. , ~. k" l .ti " ns iud,,,,,..,
C,H,O " In' ....f . 55 doss 01 O H~ In (.,b once, pr. vrnl w<l. cal~", "'l; "," on
otMr pe . ~ t (",'! 46i4 5 inJicl te. a maximum of C, ~ In inlc:fpre1lng the 'pectrunl, I"" 1'I. .... mcnl m/z 27 mm! be C, H ,(il isl~r too iIlltoM \0 be m""" 54- '1.
<':,," ,0, _ C, Il. _ CO , H . uM<..... ting (although IID1 , equtrmgl a carboxy'l
group a$.n . ....illnmtnt for the ...i : 4S. Tlle onl, acid molecule oI'thi. compo";
Ii, m i\ O l ,= CIICOOH. (Acrj'\i<; acioJ]
1.7. The . tr tkmli ~alurc 01'
ir.oh)POC Imios Ihat you ,h"uld nofe in tbt.
' pectrum i. lhe I" "" {M + l - 1/fMol , al;'. and , imilar ion-abunda ~ ....1.....
( "' i ~ 72 i. not t. bula t..... <ioce it . i nlen,i t ~ is < O,Zj , Bec.use ol' ,""'" ral ios
lhe element, car btm. ,uygen. , iliron, . ulfur, and ~h l",i ne "'" aU dimiDated
from C(,nMderatio Q. NOI. th at there arC in t e n ~ ~h al [ Jot - 19]' and
j M - 2 x 19t as ...n 01 "liz 19 indicating the prne""", of fluorine- [ "ill'O ~en
t""
l,inuo,i<lcJ
l lt 'IM presence of the "1\.,. 2" ~krncnl chI0Tul"-' l hould be obvi nu. from
both 1M "liZ l04iIO~ and ~ Sia, ,nw ..ny Iali"", TIl<: "l i Z Mi 10 intensity ratio
""Ii. a\<:, the p,",sence of O<>e' c:lt bon al"m . which II consilient "..ith bt,th "If:
a~i8~ nnd 50/51. The <om.ininJ rna.. 01each of the. e ionl m ~" he: p<0 .'jM,j by
an "A" olem,..nl , and n n1~ O""M t .ppca,.. to be app ropriate; a n ;lIlcnse OIX'
car oon ../. 69 peal< is tJp;e; .1 ,~ ,he C F, poup. rChio ro tfl!l u<>t(lm<1 h.......]
] ,9, The {OOL-': l.l4lilmi ' 1J2] ranc (sr. Table 11.1) ek.-... I ~ , howo lMt no
,ilicon. ulr~ r. ch lo , ine. or bro mine a.tom, .re p.-= nl. 11>< ["'i: H3 }/[",i. U2]
.'Illae ind icates C.l l>ow<'C,.. if lhe ", I "i,~ <'fro, hoot . hu.J ba;" _Iightl}' larger,
botb C , and C" "' ''uld have to '" "",,<idc,ed \. Tlrio ac...... "n l< for only O.~4 of
lhe: l m/ , 1341 ,aJu e 010,1; "0 llW Y"""" un to fonlle differ. " ,,", Tho , ema.in&<
T_
''-1. Dat.
,.
,"
'"
'"
'"
"" Unkno wn 2.P.
0'
""" t I O
'00
~ .1
t III
0""
<'.
'w
"o a
,.
C.
'w
0."
is
0,
'",.
... .... _--
,,, ,
'_ ,1.1. OtIU /cf
-,
"
"
""
""
"ee
n
<"
U/1'I;I>Ow n
; . 10
,ro
,.
"".
~
""
"ee
"
"
I ~"
,ro
."
Do r~ I<>' Un kn o ",n 2. 1 1 .
" t.
""ee
"
""' .0 :t U.l
, .~
J. o.z
0 .0
t o!
._ _ .._
"
0.
,ro,
U =O'"
< 013
'_ '1.1
,.
'.
No""..".
~ ' J. O ~ 7
""
""
.......
&,
~-~
,ro
I,O i O ~
""'
1.lj:O '
o.o J: M
""'
..,12
C,
'ro
< , .,
. .. ,----
I''' ''''_ 1'"'''''''' _
_ -_ ._ """ ~ . ,
"
" f the mi. IllaU u h... ",!rich rnu,t be duo to ~ A~ elemen l", i. 8.oUnted for by
H. fCoH. O. ' .. JI> _ 6)
1.11/ .n.. a"" nd.""" of rbc mi. 78 l"' ak (itt Tabla II .l l , Ito.... immediate!)'
lllat no ~A -.j. 2- element. can be present , Fo. Iho ~ + l~ element' , Table 2.2
le1k uStha t thc ",... j b iht l~ l are C, and C ,~ . For
,onl dlOC"," cd in Chprer
3. Il>c '"i. 76 molecu l ~1 IOn c"""". <:<mlam an odd o" mhe, of oitrogen .tom,.., th.t C , is "o, re",L A po osible romb,na h,m "f ~ A" e lem~nts il H, P. (C , H , l'.
>\11<1 no ' fragmem to yield "'-" H. j [ C , H. P, r + db '" 0]
2.11. If m,h 86 . Dd 8 7 '"'" on ly lso1ope peak> of miz 85, then llIe p~""
01 One sJli",m atom e lplaIn< l Mtr rel" ';,e a hundance' , 1llc: ;oh. .... .ce of "'!: 84
"" ,u ~ lly i. e.idencc t hai ,h ,.,.., .n: no hydrogen . tom , in "'!z 85. A k1I.......1
co mpo~ tlQfl rot- lhe ~A elr n..nll 11 F j . l SiF" T + db _ 01
W
1' 1. The moM101m"" pc~ k , miz 182 ( I~~ Table 1I.4)can conlain n,'~'" .. 2
rl"""",,,I, ' ~ pI " ' Jl:"n; the indie" t"d ~I:>un d .""", " f Ihe WA ... 1 ~ clementi i,
...1f...."... J, I!'~...I tha ' these must be "l'P't".im. te:d hefore a calculatIOn for o. yI!"" "" n be made, T ile [mi. 1~ :\lI mi: 181J val of I ~. e ; indica,es C !J to C"
(Ihe . ta red ""or limi' of 11:1;,; lneI> ' ha l 1
tile fan ge D,6 to 1 6 . 6~",
m" ot be co lllid"t~d ), T he intcm ily 1.... p<ediclN fot mil 1H4 fOT C ,, ---c ..
:>.Ie 0.8, 0.9, 1. 1. and 1.3, respect;, ,,I, . if no " X),V"" i. pre.em , Experimmtally,
' hc ..I"" of [mit 184]'l P1!lr 1 ~ !] """ be (1.1) to \. 45, ;' lJo",i " g Inc fo rmulas
C 12 0 "_" C" o,, _1. ( ',. 0.. ".nd C". How",,,,, (' ,,0, (ma.. 1 ~2~ c oo,
{rna" 1SS), and C ..O lll1an 18<l) . fe ;mp" " ible, and e ll ,", ould be """,'iblc <>Ill)'
"
Tol>Ie lU CbU 1m 1JO.... _
..,.
~,
"
"
"
". J.
'"
,.
0,6
T. ... 11.
n.S)
O,l
2 .2
"'''''._,e
15,1 1 1.'
1.( .. 0. )6
, . ...". .. . . .100_
.'" ,.
'"
..'". . ,." . ,
ree
0"
1'-'
' ..l
o.r. IOf'~2. 13.
., '.
'"
,....
0'
se
...'".,
m
0,1
' 76
malize
,.
..
"
"',
M.i OJ
''''. ~' 0
e.t
r u-
('.1
0.2
"c,
..
"
o.
.,
,.
.'.
I'CL' )
''''
l' ~.)
(0.21
fDr mi~ lSI witl> The uullkdy m" lccu.:" for mula C " II, (182 - 15 x 12 = 2).
A,>ignill~ ~ ... " ckmcn", lhe remaining po,sibilitic, ~r" c.:" H, oN" C "B,. ,
C , .IH , f'. e n H ,~O. a nd C.. H ". Improved "'I',,,i",,-"1ll~1 acc" rAC)' or compmi--lion informa tion born <>11.;, ' f'\:..1.I.1 pea h would be U""",.;u y 10 l .:tIt""l th;.
ltn rurtocL LC" H,oN., C" II ,., C,.H, F. C, ., H '00. C,. H..]
2.11. InlenK p,,,h fcllmc" b~ lhe 1o" of H , a re UUl\ ""'~ the " bM-1K'C or ~ n
1\1 - 3.1+ .."ul<l . 1..., h< ~n~ '~ aJ if m,i: 172 were thdM - 21' rn~ , ,,~ Vlould
' c'-''P'v c ,hI (wo peaks of neal ly = 'l \l~1 inlcn . il) .., paraled by IWO mJ" ~m t .
(ill be d ~. to Br , (Table ( 1.51. (hi, II true or m/z 173: 17~ a. ..<11 n 112, 174
U,i na mi' 172 as lhe A pea l Tht n ind " a l" Rr, al>d c.,. ","",. Ihal lhe latter cnn
al,., be du ived fwrn L175 ' 1'[ 174 +]. SI~ almo.l all inrn ...1 '" , mi" 174 rcak
ha,', the "" mpo sit;on .. 'C." Br. Tb l$ ~I:JO) ""'~ ... Ih~1 Ih. [ 176- ].'1l74- } ratio
~an Illd,c"uc III< "A ( 2" clemen..... 11", Ihall Br" '" lhm at lea ' i on, o'},II'"1l
nm.t be pr......nl. ({'-.;H ,8.o, r -j. db _ 41
1.14. In I llempoll1tt 10 <kdu"" ....mcn ' al ,," mf'O'itions in thi, group at prall!,
"'-art
the mnn 'nll;n>c J'C'l1< . .,."" ,,~>ence Ilf on. or mOle ,.'" .. r clemen..
t..,ul<I t,... immN;,uely obv;"" . , Altho~K" 1m: l ",I~ 132}'[miz DO] value of O.9~
,{ronll,. SUIlICSI. llr" lh i, i, rulc<l (J U( by the bj ~he ! rn"" rali"". Not<: lh..r 110<
" n ios of I""
[1291'1 !J I ] i [ lJ3liTl l 51 arc -.ry "m ;!. , {n lh"", of 1M
'I<:rif:.<, [1 J()1'[ !J21'[ 1}.Il [ B o j , and (ha l (nc"" rot~po nd t to.ely " 1m lbt '":i....
lopic cl~ mrM lor Cl, in Tabl., 2.., and A.2. The n lall>'e Jbund.-.oc<:l> al " li. 131,
\I ""
,..,j",
... ..- ..... _--_
'"
I ll, and 13' . ,. Unpo6$lbly h i ~b to b< fitted by an y "'A +- I" ekmenll; IhlS ..
ca
b) ""c, lap"; n; t lll ~ ITI...nt' <ill< l" 10'''''' or hydw p fro<n ll>e ion, of the
..... in ...-i<:. (m,l. 112, 114, Slid 136). The n um be r of A +- 1 dcm.:n... i. indi o:e lN
" Illy ind irccl ly by the [mil 1, 7Ji Lm,' z 1.\ 1>] vol"" of0 0 Q.2 ind ical t$
lflu
llraph, ;ndi<;~ (i n" the"" i,,' \ol' ic co"trl Nl!io~. a ~ , ho"' o in SI,on 2,7,) Tile
maoo dilTeren ce du e to "A ... r" , 00 A~ """"o l. of 25 11 'ltl ~ , '" l!! _ 2 ~) can
ooI}' be d ue to C 1 H. with "" n<j""'a, i<)n "h alma: rrn riclions; l hi6 a..il:Jlmo.'Tll
;, ~l , ,, "on, i, lenl with the ~ b.., llU of ~ 1l1 M - 11- pt4t , [(~ , HCT" r +- d b _ 1]
3.1. C,H. ", "'/= 28; C , H ,O ' .l>I/r)Y', r . H.N, .../z 7 1: C." . NO" m/: 86;
C, H,Clflr ' . m"", ltlJ; C. H.OS , "'.'z 124; C" r ,. ", ", it 1469; H,O I m/: 19;
and C, H.S;O , rn,/' &9.
3.2, C 'QH" O is an C1o'<:D-cl"" ITOn ion. al\d !I) Connot h. the molecu lar ion.
,l.l ( : , ~ H .. u. an " dd-elecl' on >On. The other ion. rop",,,,nl I",,,,,. of H,
C , H" CH , . C , lI s C ,H ._ ~nd C, H , . re, ,,,,cti,dy. ",II "I' which are l'O'SlIlle
10<._ 81'l) Ib<:1lZnI<' " ..... k! n hibil ' uch ~ ' peetlUIO
J .4, Thc p...-.cnce "r tb< large mit. 96 and 98 pul. """,,. dout>l un tile a"'llJI mt1l1 01 "" : 100 a. th. molecular io n. N"" o or the COmmon isorol'"" COIfespoo"., 10 ,h" IYfM: "r i' Gl" pic du.rer , however, The iom or
m8... gill<'
hdpful hinl' lor el<Kcida ling this. No!e palticul...-ly lhe ItO! : 1>3,'6 1 'i<>. lhe
ch lor m" <l30poOl. Form ation u r m,h 61 from "'i: % i"yol," l M I"", ,,[ 35
daltons, " hinl ror .. """,ond chlorl"" atom itorile rnokalk. Thi, i , ",,,,firmed by
checking tho i, oto pic abuoo ance. of lOa""'"' 96;'Jll! IO'h gain.1 Tal>kl 2.1 or A.l .
To c~lculate the Ci<. oo n <~, n l" nl of M " fro m .../2 'J1/96 , do nOT fOf ~~ \ lh l tho
-"'CI" ( :I i"ot"pic ;01\ of (M - I)' .. ill CODlnbu' . 64~~ 0/ the ",i. 9S to the 9 7
p"ak, (2.4 ~~ - 0.1>4 ~ I.S/~ ~6 1% = 2. 1 /~ OJ _ C, . T hl. caleulalJou i. suporlluOUS, ho",.,'cr. ";no:; the tt.olan~ of m o lo<:olar for mula of 26 am u (M +, - C I, _
% - 7'0) i, """'t lop:-aUy dlle 10 C , H, . II i. diffIC ult to di,lingu i, h !'Jtlwe.'D lbe
possible I""mer.; 01 C.",(.1 , with.....t ....andar d '>. [ lrans- l ,2-Dichlo roa th)'k neJ
1.5. r ite is.<ltop;<: dll.<lu . 1 ...,'l 11S 137 indieale, ODe chlorinc ,,10m . ~nOJ ItO,!.
U S cotIlaius a maximwn 0/ 1" '0 <;Dlron ~t~rn", ll.~i24 _ 2. 1 ~~. Similllr $5$i$fl romh <:dJl toe rna"" ror the l" \lie.. ma~ LOnl~ mi. 119, C ,eI,,; 111/%gS, c ,a ,; ...;,
/'1<). C ,C1o: a od m,i, 31, C', Cl o' The aboenlle of ~" i dcoo<; r"r hyJ 'l!"" a1011\$ al><l
lhe di!lerenees 01 19 mnn bct"ccn , <; ' <;, al pair. of io no containiJlg The me
n um ll<...-. " I' ~"'lori "., alom . implicar. /Illorme II rbe m ll ';.." .... menl. Th
I""
fo, m U ~lS C F -. CF, ' . CF, '. CClF, ' . C , F. ' . <:, ~ . C,CI ~. - ",ill oor, ..polld io
mill' 1<' \he " r",ninenl p"ab in tM <pc(rum. You st.<>uld hall<' alrudy ootcd
Ihat the "'/, I3S and 137 peaks failed o.e.e~ WI"" /I'f.l un """", ,, ror a mo lecula r
ion. Bocallse there I. 00 indi.cu ;on . '" ~ , n. ",' nl ~ i ninF. more than Two carbon
alom, or ( m~ chlorine atom. tM rn<JS( prob.oble llrocl nre to " ccoun! for thi,
' pectr Ulll II Celf, e r, . (CItl<Jropeotaf)u"" ,,'ho ncJ
C,.,.
w-'
',
...6. l Cllrt>on
~1 '~c hl","dc J
4.1 l'Joe /Irsl ru le cm ptla. ~ . l he im po r t;Utce of pn,J u.t.io n " ability. The
highl)' < tl b,~Md "'l m in obcn> ~ 1 i,m (Ii'l uatio n 1),) ) p. o du c ~1 by far the rn""t
. bu nJ 'D t puk in Ih;,..pc..1 ,.ntl .
" ,--
.(l 1.1)
4.2. I\lphu cle''''~ae ~ ~n be Iniliated by ,~c ' lUJ.... I ,;\<: on ";l hcr the " ' ygcn
the nitr" gon al<>m (Cquu ion. II 2, II 3~ The Me.:l ron-<l""a ling altility of
........
,.- ~
~~
H,.NCI1t
CI1,=6H
111.2)
"".31
"~-"' A
H,N
~
--'--
.....=-.
. CH. OH
ru.n
M'~
nitro>gon i, "'p"rio r 10 ' hoi or o. y~ n; w-niza, io n mould OCC1l' mOle lead;I)' al

ni tlll ~ o n rrabk AJ l iODd ~h of f " "" Iw-n ' 1.2 . ~t>ukll>c
,\a bl~
Ihm ~ , " bt...ali.... Il. l ,\.;1 1, [ Itl/l )0] _ l 7% '" M al ioniu.tiun. he, ea,
311 "- 2. 'l/~ '(bir,;" also
, " Itb Ste_
n'l Rule: IE(H.NCH, 'l =
r"'il
li. 1 c'l .and
I I<~H tlC H , ' J
_ 7 .1> . '1.
O . Tbe rallo [mh W I![ m'; 97] i$ m lJ<h ' 0() b ,~c lor m... . 98 10 be the (A -+ I)
;",Iop" real< ol an A pt,>l of Mi; '; ' hus "" ~ 9lI,h<>uld be con. ldoreling '; ",1 fur "" -+ 2" d em enl>, Ih. ' a l",. [m/%
IOOllfm]z 981 ~ 4.3 is co......ent "' i1b S t . II miz 98 .ir; the moloeu!.u ion, mil 97
m..... mo co nwn tUrn; ;" "s L, ,,,,ri!>u,i,,n ' 0 mi. <XI m",.1 he: . ",buleted
before o no:: c.alcol.ales the "A -+ , - dc_ lit.. The .,. idml1 al>undalUlO (1 3.6 0 ,8 - 1!J = 4,9) lS ron5lSlen. with <lthe , C. o. C " from whIch only the alomcn_
t.o.l <vm"""';l;' m C , H...'" (. -+ ,II> - J) i, klg;"al (C. H t , S 8 i~ "" , -+ dh _ - 4). The
...... abunda nces of other peaks ma ke equi,,-nca lthe delermination of their elemenial com poon ;o"" r, om iWlO pi. abu ndan. ... alth ough C HS' ;, a l" g;"11
a",ignme-nl rt>r m,i, 45.
Tbc mi; 98 """ ~ l"'''"'' " U tesls ror the mol..",l,,[ ion, "nd as . ueh . ho uld
~ l a , . Jati ly .t abl. ' l""' K::s. T he io.. 01 H i. the dominant """han;<liG
lealu", of the 'f'C<'lrum; it, 10"" .ould origio"le from a radi.al , ite on eitht-'T
,_
'"
n ,I. Dltf1l lor Urllm" wn 4.3
,.
,.se
,..
"
aa
' ''" m o ll. .
'"
OW
13.' - 1.<
4,3..l. 0,<
"
,.
"
eo
(",I
I"~)
lUI
lUI
"
,.
""
- ... _......... -
.....
, ullur or u " .y, t,,,, (r + db = .1. <1T bOlh. Pos, ibk: , ,, ucr ~ ,.., , con '; .I,n l with
In.. arc 2_ "r )-mtllofllbi<>phcnc or th in-2,5-<;}'do""lIdoc nc, l 2 MClhf llhioplomc]
4 4 ,hrou.qh 4.S Ao ll hough the", Mr<:. .. sta ted, iil<wneric C. -amincx, ca ktl mtion oJ The elcnm lal ,xnn po, iti<'> n <A M - wou1<1 f>< lOll hli h in 'C>tral ' U e,
iI Oil<' ...u e using the >IIi t 74.. 73 n lln, mainl)' bee. uoc , .( lhe pr od ucti on of
(M 1)' ~J' un ion -mole<:ulc , caCl;C>1\ (lite Secti"" 6:1). Note lhe 'ub,lunlial
d;rrCT~l'Ce5 in ba",-pe"" . hunda nces ", th o p<f..,nl~ 0110' . 1 ion>; lhi, i, useful
in ev" lu nt i n ~ lhe ",!ali' e icn po (l ~ n cc of J"C-'lb in dilkn."fI 1 spoctr:a fG ril!"h ~
19TIJ.
Iu ' n' ''' C' 10 lhe qucstion in lhe 'c~l, 1011O ,,' :n ~ met b)'l gWlll' i. in cocnpctiri"" ",ilh Ibe lots., of "Ih.. ~ ,u ~hr u<-n!>. The prol>arnlil}' 01 ~ -CH ., I" " i,
m<1C b gre"ter I ~ an Ihat for x-b)d"'@I'll lo.., but Ie.. ' Nln th.J1 [(II ~_C ,H , 10".
Thi, 11<11'" 10 ideunl y U,,' nO"" 4.8 . , C , H, C H{C H, )N H. Of rhe Ih 'c ~ .(' H ,
. mines listed lsee lc~l~ onl y ~ CH.d ,C HNHCH, and C H,CII,N (CH , ,, ..... llIn
unidrmifJed; W Iinl $bollld huve ~ 1" "'1 f '" -CH, nM ' n lk, . and <Q i>
Unl no..-n U .. The a"is nmenl of l he lilll e.,. "'N cture to l;nk no ..n 4.7 is bo rne
out Il ~ the ",,'r 44 or lhlS speCfru m. il i. for med by Ihc d imil,. tion of C, H. f, om
the ( M - l j ' ;o,, 'hwu~~ . f c.. m"'tomenl , imil.. 10 the lo" n.:ll i,,,, 01 miz >0 in
C, H,NH C', H, (,c c ~ tio"". I (l~
Tk rcm~i~;n8 po<siblc ....."""" Jr, C H ,C H , ( :H. CII , NH " (CH, I,CHCH,"' H, . and CH,C H,CH, NHCH" Thc li..... 10010 lho uld yiel<1 aburnl.llll '.....
,,{ ",.i z JQ and ar<: Ih" , Unknown. 4,4 u d .. , ~. The.. . pccl r~ IlU . U'l'r";"8 1y
simllar, ll:flc<:tirl8 ' he dornina~l d r"' l of tbe omiM fU1lct ion <>II the clc' ''' 8e;
h"""'fl", lbe sm oll ...h "" i" le dlBe1cn"" in l~ abundafl<lC'l "f lhe alkyl ion, . re
"",rod ucible an<1 .i gnl!\canl. The a lsundance, of the C , H , ' aud C. H, ion. iD
linkn.. "'n 4.5 Jre ~ a l l i """ lhe corr" r on<1ing a bw>dan l;ft i ~ Unknown 4.4
lonl y . maOcootril>at k,n. \.hollid he prc",-"fI! f.om C, H , N' . "d C , H , N - ~ ",,,,,.
pmible ....ith ~_ a nd ;"ooulyl..mi"" ",,,ignmeol' " ... 4 4 und 4.S, U l......ti.-dy. Nn
, peot",m i. ai'~n for c-,H," n CH" it . hould " ve a base pc.a.I. al MI: 44, bUl
. n insigni f",",nl !'t. k at (M ( :H , l' . [4,4, BUlyl' m;",, ; " ..1, iwbtll y'ami",,: 4.6,
OOp.- "", l mcl hy l ~ m lllr; 4 ,1. d hy l di mct b yl ~minc: and 4 .8, s-buI ) lamioeJ
41;1, 4.10. For l~ " ",'mmetric 3pcn loo..,,,,e, ~- . nd 1",,1""'a8" oan gin only !he
C , H,<.'O ' and C , Il , - io,,", mi' ~7 and 29, OD I h~ Olher hand, 3_ ~)'l2
b uL,."onc , Ilould ,icld CH, CO" (CH , J,C Hro., CH ,.. and C , H , Ion>
al ..i: 43, 1 1, .t 5., anJ 43, rc'fK'oti>dy. [4,'9. }-P e nt ~no ne ; " .10, :Hnclhyl2bU lane M )
4.11. hu il it. ol"",enlal W m/J""ilion ha <1 not bec1I gh -c... IOOSl 130 appea r<
to be- a g<k Jd p.lssibi\it)' fo r the molecular ion; tl", ,on <eries (Secli"" ~ . 2 ) 31, 4S,
W, n 81, 101, and ll ~ Olroni (Y lU1l8eM, C. nnO. T aMe A.4 .!lows thal l~
ah\lndanoc of "" i. indiculiv. of ,," elncr. 1\01 _n ~kohol . F _oil" cle. ... ll" nf
C.-C~ hood hOlJId yield the mol' ~ l>undanl C. H , , O I ion. ; u.. IM 41)'
is Tbe m<xt . lrund_nt 01 th eoc bl Ill" a nd l hn. indica" , ooc o r . ...... !'fopyl
i'oup" _u",",lluted On 0"" '" balh """r b" n alom.. The abt.ndao cc. of
l~ - m ,l and (M - C , H, )" arc ,1 and 9:;;. ' '''pcClj, dy, 01 tll..l '"
",
1M _ C, H. ) ', m.\m, ' h~
pi... ...,.;
,,4 melh.,.1 '" d hyl . "lJo.lit"""lI oa all
:0-
carb<on ar..." llnhk ~I~ , ~ 0Iht;. common ,I..~ "" of ethen "'~ cleu a",
he C (Il>ofld 10 )10:1<.1 I'" 11\ )1" ... .. ron Sl,. ;lM!icltcs a h l,1 ", he, ("l ' t }1;.
uf
C. II ,.O ",..'I \~. n t>o: " d,b..., 1 01,,"" IC.H . I i ill"" Icrmco1 by
ind,,,,ti .~ dl~lIj"" of (;H, -oC. H.1 The 1o,,,,,,1lI C,H-C H,OC.H. "
""l"ifed The abund"""" of fM CH, )" lad 1\11 - C, M. ) _ Icc C, H.( 11,OC H( ~H . IC',H , bo PfONI:>k.
Ibnol.
pernurwo ..hoorl O ~~~.~ ~.;.
ruponn ely, l:>uJ I'" Sf*.'t1'..... of d'".1, 1d ha
o.r~
~ D-+Utrl
co",,,,,
r.,..
-'
tlher]
C....
111.
4. /1. 4 /J TIw ro:tn>-[)od-. AkIcr ~ "' ~ lor . - - *"'I'C'''' " Tt
T1Ic 10. 11l"lbl..-.'t "'ir 16-1 , lot 1l'Co>noi ' pecTnlIn .. <Ill. ' Olhe
_ p. N .....
of ClI. by " .hpI' ''''''14"'tio,ll 9 2'1).
a, :1>1011- . 4 1). ,.I.-.nc]
-",,,'0. btR
ru
or,be ....
or
1'Qt'I "'" ("'"
II
( lI j )
(11 61
"" '60\
,.._ ... -
..
_-
'"'
4 ./ 1, See f q,, ~ tjon, 1U and 11.8,
Oil!i<l. :;o"J,
:j .
O=C><z
(l l.7 )
....r 28.IOO'll.
.:"\
+ Ct~"
OCHz=
,,",r
28, '0&\>
4 . 1 ~ , See E Cl u a l ion. I I,~ l ,,1 1 13
v'~
'"
-'--
''''
c ,~
~~~. "'
~
""
..
'"
,
m'z 87
.....!!!- ......!L-
II ,
'1
r--',
"'"'
trI:z
---!tt..-
II
UI.91
'0'
):
'("'~
\I 1.10)
"
'"
"
~"
'd
"
II
.~'"
00
1I1.1I)
"'0
'"
--'-
A... "
"
']
"
II
"t)
..
( 11 12)
' d
, ,,
tcA",o ,"
--'-
II
::l"
"
4.16, 0 7. Sa: ( q ...lI ion 11,14. L4. J 6.

2pcnla n,me]
Jtl
~
"'I>
~,
~".
. . ""... ..
-"'-
00
4Mel tl ~J- 2- pen l a ~ (Jne :
(ll.13)
4, J7, '-methyl.-
' '0
.J.-.-
. ,N
-"'-
II
{I I. H l
.,n
4./11. Tht " Wl'.."l moleculnr ion a t ...,'~ Dol (omaw. no "/I + r den'lt nl.
(e"""p. ol~,. n h nJ I() or 11 c:lIl:>on . Il"",. wnml.lll witM C IoH ,.. Tilt W I ~
' I"'ndlng r + dl> , al u. 014 i' Ihal e,pooled ror p/I. n~" : [hi. .. . uPf'<>l'ted I>y Ihe
C, H, and C,H, m,illnment' for mi: 91 and 92.altd by 1M a ro ma lic ion saiesw
(So"' i,,,, .S.2), ,,,,,,,"Sling lh l Ih" mol<>:;,,\c i> a t :. H. C"H. ... omer_ v .... should
lIa" e marked "'it 92, C,H" ... an important odd -de<:tro ll io n; ~ lhal iT is OD
lhe h ;~h -m aSl sid. of the ba&c 1'",,1< (cuI< iii ScctI<>1l ) ,41. Dot h lho formation of
C, H, by n::.rran ~ltI<:n l and C, H, 1 ' .,;;Iea",!!" ind l<=l le Ihe """""';Ii"" i.
u" snbstl!,,!ed (sre . lso T al>I< A.61 C. H,CH. - C , R, . "The low .. b uDdance .alio
" r ",/ : 4V2'l il'Kli "" tel \hi<\ the nil )'1" ha in .. not b"",,"hed [Rul}Jh",-nn;J>C]
(11.1 5)
4./ 9 MaSin 4 ~. 13, and 87 prob.,b1y M \'r 1-..0. fo al l?l, . 00 five .arbo n
..tom , ",,,,I>, "lid \h" , <.'(In''''n " "" " ' Yl:"n al"''' "a, h. T ho: ri-Ap-plu. -do"ble, . 1"" "r eh or,~ and <If l he ", f , IN ;Onl sho uld Ihuo equal !,
so Ih l 1I",}' a ~ IUralN EE" ions. C.H, ,0' ~ nOl bo I1M' moltc ul..r i<>n: i\ i!
an e>en-dccrron ion. T he "" , .l l l ~ m i. a" ,><Id...' k"'I" '" i,m M.... l )(l mig hl be
\ 1" , hul it< al>unobnu 1$ Wl I"'n e.penme nlal enol ol lhm n pccl.d for Ibe
h... vy....,lope eOnl n hul,Oll '1(>Ill ";1 In . "The '00 lC lon lSo" ;on S,2j ",i. -'1, 4 S,
59. n , 117 ... ~ l l a hk A f'I1 I h~1 an ~"'"<)J,ol '" elher III""I;on II . domillnn!
btu'" of lhe mo lt<:ulo: Ihe L, ck of tot md ic<l los rIable A.41 I ~ ' ll th>! i, nOt It
r.traidlt-clw.' D d hn . A . "".... n~"k h~p' ~ h", .... \ .... , mi. 1:Ill ;, lhe mokc" lar
KMl, a nd lhat mf: 11 2 .. lhe \ tot _ 1&1 formed ~l lo S! <>I' H. O from an . k oho!.
"The IDr llLll1011 of UOpor!3Dt DE" ' ion. from elhelh R 0 ' R', hy Ihe t".. or
ROH i> un<:<.mmnn. F"'l h~..,., lhe 1,_ " r H, 0 from prim" ,y akoholl, RCIl , OH,
.. so f~ tha i C.lI, . _, O iom. are t """mtty of lower abundance. The "hundaDl 1M _. 43) and 1M 57)' i"", intl;"a' . Ih" id':Tl (il)' "f lhe ,..,yl alco ho l as
C~ H~- CH OH---C>H , ; lilt lad 01 1M _ l ~l Rnd 1M - 29t ion! iodle" l""
Iha l 1lteIe IS no cha in hranch mg, (A o extra cllK ;. the l"et~'I ..bl" io n or mi. ~h.S ;
.... Section 6.4. Fo' II.e lJam'; li" n "'/. I:\()_ I I 2 a metan ab k! would be exf"'CIed 31 mi" %.4; "..,", 129 ---0 112 -..oukl appear at mi; 97.0, bot would in"",I" e
Ihe uDllkriy 1_ of 17 am ll,) [4-OctanolJ
4,20. AJpha-<:lean gl: reaction. can r",ult in the I" " (b qualio" 1I.J6) of three
difk " ,nl g ' ~: (: .,H , ', (:H , '. an d II. The, e reactlom w;U pr oduce peakl ~t
"'/ : J!ti, 114 , and 12 8, wllh abund ances decr.a,in~ in Ihi' ordcr a, prcdletcd by
Ihe flOI< I", !IM' I<:J'" of the larb""l a;kyl gro up. Each of lhe"e lon' call underfo
~)'" of an olefin b)' cleavage <>I' aD N-C bond with hy d ro ~eD re..rn. ng. me" l
\[.qllal;on 4,44~ See Fi~ \lf e 9,18 and Seclion 9.X f"r a m",. thorough discu ian
"r lh< ' ~ I ru m of Ihi' com pound. [Methylisopropylblllylam ine ]
4.1/ . Ma'" 1 7 ~ <an be po<lulal.d a, lh. mo;.c u;ar Ion. ",'Ilh ro ughly lwol.....
Cl1rbon atom,. Ik>lh mi: 105 and 123 appear 10 contain , eyeD carbon atom. ,
"",nd>.
..
" , ....
_. -
"
""'-CI'~,---i.i-l-eM'
6H, ,
rrl z
+'"
y C-J<"
CHt=N-----<:l1(CHsJ.
~,
.:ISI
, ,,,,,,,,- i.=cHCH
61-1:.
ee
r>.J- CoM"
CH'4 -
'"'
(l L1 ~J
C~TCH,),
"" II.
"" l l Z!!
,..I-c....
'H!C.H
,
l+-t
CHCI1
H----7'=ClC">lt
'"
rri z sa
~, ~
Tbc Mi : 122 i , ,,[
~.
~n
que, ti ~na.bI<'
f'Knific.rn:c ~ ~ an ood-el. "tr on ion hcc,u<e of

the " b andan! l1I/z- 1 Z~ i<>tl, h"...~",". lh. lWl.. -~ 6 pe~k . \M - J n t ', s.hould be
IIOted , A wea k alkyl. io ll ""t lfS IhrOllIl" C. is pTe""l , as is a u oromanc-ioo ""';n:
(\ S<cl;" " 5_2~ The,e ore ""Ilk . Ikyl-Ie", ions
<It
(M . , .\ 1' , (M - 29)'. an d
( M _ 4:1) ' , b ut instc:1J or 1M - 51)+ Ill.r< are th e m:lj. >t l<'N al (M - sst "",I
/M
~ l . ~' r om TaM. A.S U COm m on [,, " o f SS is 100J of C, H o from csu,-,;
(d ~" bIo; .h ~ d ,, ~ rem ranKem<nl) and the 10", d 56
' upport,
0<Id..,,,-,,.,,,,, i,,"
this; Tablt ,1,.6 imlica los a C<) ", s poll d in~ C. H. _ RV 1tn lclu,e. Two othcr
ahundllnl Ions pro" j"" lhe final d "~ mi: n aod 105 ,"o" ld ~ phen}'l ",ld
bon royl, lu g ~ ting t hat th e ooln )J<'llnd i, ~ bonyl ocn.<ClIlte . T bll is pro b a bly not
,",,'- or .. " . buLyl~ fo r exam ple. 1M - I S)" Ind (M - 29)" arc h . llbu1'>llonl t ba n
(M _ 4W, [But yl bl",""" tt:]
5.1. Altb o ul:h t n~ (lO"Slble m olecul;lr ' un I I mi t 128 prob~bly has tk wm~
, ilion C"H C. rOfmul~ ""nn" t he rllled Oul On tl>c h , i. of "",l"pi~ . bur>T he p w t...I>lc """",,ula, jou i, of hi\:h ' Iohilily: th. ", "'" Ic-w II'lIlP"<'hl
fh bk A .6k The
p"a k, of imporl ance , l lld t h c," rC"-'T1\ble the . ,oroa t oc
lo.r,e
also ly~, ".1 o r ~tomalic" The (o, mu/;o C , nH. JUl" ire, ,"ven m'lJ'
p ial d o uble t<,n,J,. (10 - t + 1), Aga in , ,"",e" co: op<'<:l rn ,u lOId be occc " " r y In
dootin lui, h he l ,",'Un the . ovorll1 i""""-.... pn'iiSi b!c. [N l pb'l!,"'rn:J
da""",.
M" "
"",N;,;
--_..._---
.1.1. M~" 86 appur . 10 hm'. the .l.m.llt~\ ,ml""'i l~'n C. H. O, Ie belte,

dlk .. ith iootupi. ~h Ulld u n ,, " , ( h~ n C , H , .O~ Ind for ""-'! 4 3 th. fOfmula
C, H,C j, definitely prefera ble. Moss I S should be C H ' . The "1'P<~Tano. 01
th. ' p'<':llum (tha t i. domin"!l hy rna.. 43
Ul ,u"e$l~ e . H,O and CH ,
KroUP \hUL ~l'C readily 10.1. If th. ell , ,. f'Il ft ill
('l B, O. lh. bal" """ i. c o.
TM ab~!\<lIl of other peaks " 'i'i">t. a S)'IIlfIlOWic "" toeIU",- ( :H ,(:O - ('O CII ,
(CH .,C O -C H- N'" H . , n, ,,, ld r rod""" addJli<>na l lrng.menl ionl), M0,1 other
0 , woul d be .~pcct.d t<l vi'" . " me other
compound. <>f 1M formulll
fragm ent<. lbe i \l _. CH , I' iI. mu. h .... al.",. than C H, ' "'cau of ilS rc. d)'
furl hel dii<S<><.iali" " by ""'" Co. When 1 ~ CII, _CO bo nd i1.4 .~d, the
charge j, p<.te, ab!)" ft'la.ned b) the C II, i ro n!'. [ 2,3- lIutancdiunt:]
.1.3. Note th.1 1 d" a buooa l"X' of ",i, I ~ I 10 184 are identic.'ll to rbcee <lI'
lInk""..... n :U !- O f tht four poulble elemenlal com position, 10 the,", Jata, only
C,,",oO is collSlstenl at, ~ mo:>lc<:uJar io n t hat e ~n pwd uce the N ,i ; lOS fu g.
mm t C, H,O ' ;0>. .. ell a. mi. 77 C.H , ' . T he abundance 0{ mi: I ~2
a
>lahle molttular ion, in keeping with r + db '" 9, NoI iee th t the", ill a defuoi'$
m:emblance bet"" u n the . po.lra or u ~ ~ n"",o, ~. I and 5.l; the pe.al a l 39, SI,
/)). ~o " n "'~I,'I.." t arn ma tle character. From The simpllcit y or Ihc "I'C'-'lJ"....... t he
mulecu le ,h ould be generally nable, wil h o n~ 'If a fc,," h<>nds of mllch !li ~ h e r
b bllit". T he "ompo,iti" m " f lhe majM fragment" C." , and C, H,O ' , ... lKon
"..mbinI
ra. DZ<>p heno ocJ

S .~. ""th the mi'" JJ9 and the III,'Z 1.'>6 re-k, COllu in """ n lind ""en C
atoms. consi, teo! wit h the f{lfm ""'" C, H.UO and C, H,ClO" (r + db = 5,5
an_I S ~ KO<l "'i: I I I >hould rorrespond 10 C. H.O (r , dh '" 4. ~J. The miz 156
rulfi ll. tho rt:quirt:fIlMU fo r C\( +', Dl.ltl118 1he o the r t .. " t'"~k , (M - OHr and
('M _ CHO, l A cartx>~ rlI!f'l UP ...oold produce the<e and tho ", i : 45 peal< by
~. ~nJ i..."'le.I .a p
The hi[th r + db n lu.. and lhe nq :lis ibk: ( :110, ' . uggeot thaI
C. H. C1 is d llorOJ'lk nyl (ADlh= ,i ng i,o"","" ha,'" ncaTI ~ idmtk al m" SS spr<;tr",f [ ....<:h..' '''hcn''''''' acid]
' J,
T he C.H ,_ . inn ,or." i, strougly indi cated, "nJ ;t. ... i. tribuli.....
ho uld __ ' 1 Ihc .... Mi nched a lKane C I"H,. '" the wmpo.><.ln,J yieloli spec.
trum ~.~ . IComp""$ t bL! &pccrrum to Figure, 3.2 and 5.2 )Of tbt C. "
,' ion.
of Uol ..",.n 5.h. "'/ ' 2 11, lb9, nnd 85 are more ~hu~ <Lmr ,h~ .. ,he "" I lowe r
('- .", , - ion aDd th u! mdl ""tOchai n b",~ "hing. L"rres pondillg 10 C,-C" .
C. C ll , aDd C,, -C , . 'r he gro ur in g C. H. - C HICH.) .. iO u pl. ;.. ,h t<e
tla' a. The ~'"Ompou nd il actually CH,(CH , 1,CH(C H, l{e H, ).,CH allh ou llh rhe
com pound C.H,CH(CH , l IC H , I. C HIC H , j(:. H. aka s bou ld gin " milar pro.
m;n<nt alk yl io..,. For Un knowa S.7 rh. lolli of ",,1: 18.\ 141, and ( ~ bi y ) 8~
.I n: ab undant in comp u iso n (0 Uo' no wn ~ . S, in Ji"' l; n~ bta llCh.. co rrespond.
ins to C, -C j " C ,
C , ~ -C . , A li...1 poslulate to fit these data
mlilht b" 11>< C,H , - C HlC,ll. ,-, roltp. bu l lbLS '" rrnJu" im pro bable by th.
low ah~ndan"e oi lM _ C, H. t ; lhat n . tile II<"g<Irl... in form ation thaI th'le is
'.6.'.7.
C,., .oo
",_"_no llf'll"""iable I,," of C" C J ' C" or C., i, ver y ,, ~Iuable. T M <lala """ be fi' bj
rc"H,,),CH C>H? and by IC ,H,j, CC 611 " (F or a ckt..lcd di" u"";I>n 'lee SecIio.m 9 I) [ Heu <J<,cl l\/:, ~ m et h }' lp ell l ad cc ~"", and , . prt'p}'llriJ e.:a ne]
5.8, lon-"" i.o int"rma li"n l Toatly tacil ita tes the ""Iulio n of ,"" un Ln" ..u,
lle<:auS<' Ihen: i, M o~)g.<-n p"'''n!, II>c poal<s a t mJr 13. ~ , 4), 51, and 71
ind icate lho ,orie, C.H , , for" '" ! - S. Thc is,'toj>Jc a blu>dallces of ",...-: 105.
92, and 91 indioale C. H. ' , C , H. ", and C , II . +, "" pect '~I) . , hi. and the P"'"
euoe of Iho al kyl.;" " _iei ;tldic. '6 IT. !>" A.I 11 1 tho ",n ..'ieo 11, 9 1, 105,
119, 133, 147, >nd 16 1 ' Cf'..-:n'. <:. H ,(CH, l. ",II<I'<' ~ = 0 _ ~ T he . imilo,
, pedTUm of lJn kno", n 4.18
IMII"" impm' anl O U" ion
ca u ) Ii ..
by ;--11 , oarro"!",,,,,,nl to a ph"" yl C H, -moid }', and the oompound i, Ih el
p""nyl (" H, ( ;"H .. ActuaUy. Ihe ~ Iky l . h"i n i, unbranched: lhi, il CODS;S'
\<..., l ",ith lru.a botndance reb h"'llhip> of tl><: C. H, . , , ' ion , orie. , The ~,y
mJ ximum of "'iz 133 in tllo,: t' . H, ICIl , I, ""ri o, i, not due lu eh~in hranch,ng:
LtCI" ,...d in fun<:lionalia:d unt>ran , hed
lox'" ...ao ;"", 'ICJ"',ated t>y - (0 1, 1,
~ Ik .",", ouch a. Im ty acid , (Fi~uIe ~.YJ. [Oclyl""n,one]
'.9. $.10. ~ im por lanl ou - ,o rio, C.H , , in Ih, \lllf"-T flMI 01 bolh ' p"111 W\l.IlC' h (T a hle , 5.1, A.6) thai the UnkOO....ni " Ie C.:'H ,. , .. C. H boll Y m o1t_
....1.... ""Le lhe.. ,or io, in FiguIe, 3,5. ~. K, .1 14. . nd 3.21. 'I1>c: OIoJ): real di rkI.n""
is !he prese nce OJ';1 .. -t 4 in dox" """. in Unkoo",n 5.9 wm.,rn.;nll'" jz ~ L 45, 59,
73. aD<! ~ 7, " hieh i, indicative of a salu,.led ili.hul or ,'111.'1. [5.~, Houdecanol;
5 Io.1 -heud...ene'
j, )), ne ~','l 12'> i, , he lugical candida t. 10 bot lhe "",lco,,!:" ion. which
mean, lhal Ihe mol ecule conlaiDl> II odd nllm""" ..! n it , o~en atom,. The ab undam ion. of nell ....... . w:b ~. 102 9!l, and 78 co uld In Ihll ",.. y be "'en_cleotr",,
ion o, T he ~ il!h ."" ndl noe of th,. postubled mo leeul", ;ll n ,"" \lId 01", be
lelll ",il h lhe J rOO" UICIn:>c ltm ....-ric. Agoin, ,ovora l j, onte n a~ po."bk: of doc
formu la C. H .N I" " " ph.. d "u ~1c ~ , nd, 7), and roforell ~ lpoctra w<>"Jd " " ,
~ mure """,Ii ,. idtllllrlc,llLCIl. [1s oq " i n o~n e ]
j .l 1. lbe-r, un: ",w T..1 . ign, tha I this com po und i. q"ile .NT" renl r",m lhe
p,>:d i,,!! 1m.,.,. .\1a, ,,",, 76, 69, 50, 3I, a ud 26 lmvc a "", <imum ' ''' I''''' .me. .,n e.
em... and " lit ca rbon ntoOI~, reo"""li,. ly. Ma" 95 i, "lher ""{ lile o>oleao i<m,
OJ el"" l>as an odd nu m"",
nil1'O!!en a l""' .. Simita d y, pr o... ,......" i" l,f M,/:
16, 50, and 26 are oitller od de lO1;\ru n i<~~m""l iu n.. OJ COJIlain an odd fium bl=r
of ni lIO~en alom. T h,," are fe.... or no 1l)<l lU\;Cll lLl\.Olllol JlT"",n, In.> ' ''OUpl of
pea... in unit-rna" ,equenon, bke (l6.. t>1, M . I>'I~ l he pracl1cod nyn tn~y h...c
fou nd u ,'u luable due in I h ~ io n .. toe< or ma'<$O\ J l , 50, AIld W ('I<;e T a~k A 61
T he I ~ ok of hydrogen, 0'''''' lDal ... IM 1o"....... . J'C'lh of 12, 14, and 19 01,, tn
Iho OIom, ptOsellt. A.",mil>ll ....'I"~ 10 II< Ihe mo lecula, ion give, eorre, pon
d. nee b<:lw<."I:n w h. a l rna.""" l') . nd M - I ~, and al 26 and M - 26, , uW< tin~
,he PIItl r - eF, eN. {T. iRue.......'C h .nillik)
5./ 5. Yo ur sn<pi"-;"". Ct'I<rYninB 1M Mi: 11 9- 121 doublet can bI= oon ro l"ttlCd
01 ""'~'it'> 10';(- 107), 91- 91. n - 79, nnd 63 6~ ; lh i, i, Ih" ehk"".l k)'1",n ..,ron.
I..,tn pic abundon= indi<o.te th. C. H , . _\ km ~, .. nnotheI impo rtanl
stlo....,
c,n,
""""i,-
"r
--__...... __.....
'"
fc~I ~~ ,.( TM .pectru....
romi n"DI wilM lh. dcm<:nl~1 Ct>Itll">Sll io,)n C . R 100 lor

m ..... 14ll "" Ih" moJ""" la, iOD, AbLlnJanl pt~h oo r"",pondlDS I" (101 - C,H , l'
I. "d 1M - CH ,t-1r . uU e' l Ill' , u b S lrt"~tu rc (; , H. -C_CII , O , fOl which a
I<>v;i""l ", ,,k'.;~ ,,, would be (C , H , ), C{~ H , Cl . H" " ,,ver, tile fOIDl<l tion fr" m Ihi;
,,, C. H. lIS 3 ba.e p"ak ,ee n1' '\lfl' , U.in8, .uUC"trn~ C . H,,(C , H., )e HeH ,Cl a,
an alt" ,n,lIi' . The I" " "Ilh<: 1ar~ alk yl ~wr. (:.." ., is actually g,,,-1Ir r tha n
!he
of clh~ l if Ill. cbar~C-<Illl:la li"n ~. _ II a, charge-ret. nlion p<,>d UCl <
a r. con3idm ,d, (rM (', H. I - ] + [ C. II.."D> Ir(M C , H, )' ] + [C,H, ' l~
St.'. llSOn', Ruk O(>prJo ri incon, isl"nl with Iho "h, "r..o:d a bundances, sinu Ihe
i"n i ,~ti"n
or an alk yl radi. al , h"\lld be lo
d by U ........it.. ' ioD.
1I0w",'. r, bot h C.H. ' " "d C, H, ean be Ionn. d at 1:>1 """"ndary docompo. i
tio n.. aod t"c i""" ' ( H(C',II, lCH , CI "nd ' C HIC. H.\C.ll,C'l can un derS"
I,....a. ill HC I and C', H , CI (' e<; ~"" li" n ~.6 ). [J-(Chkl romC1hy l)""pt~"" J
j,/ 4. Yo u , h,;>Ulol ha>. made The f~ IJowiag ~ "N h le auignmems: mi; 1.\ 1'\
M ' , (. H. O CI: 107, (' ,11, 0 , and!l4. C~H60 ' . 0 [ " . A phenyl ring i, ind i
Cl iO<! I>y the aromali~i"n .erie. . Ih<: h igh abundanc. of tho "'i: 77 i. a b irly
,. haN. ;n,(;~~li "n or ffi(>n""" b"""' lon ~
C, ".0' p"at indic,'.' th.u " , ) Il"n i , " l( a ~h o d to th. M g.1bo 1....1 Ihlt (M - ClIoCW i, m lll;" \.o, !",," IM O
(M _ C11' is indi "",i ""
Iobil< m . C'I il' 0u p; d C<ivage alpha 10 (lie C. H,.O -would " __"1"" (" , lhis. ""U"', ' rns C. H , ( IC H, C H, C1 , A stro ns pc~k ra.~lrjng
from hyol"'ten rea rra n""""",1 wilh i" ,,, "f C , I1 ,CI ",,'ouk! be e. ~nt<l b r thl'
e.,m pouod, _ oun" " ! rm I h. bas<: O E " ion ~ l "liz '14. [2ChlOfO<'Ihytphenyl
eth.rl
J. n. 'fl>t mi: 146 148 " pp"an ntt .hould SUl'lI"! ~IJ i""IOpic du ster, The
IIIOSt proba bk ' U' I"'" " ul T d >k 2.1 ..... ..Iic< >n ~ nd ... lfu,. One atom "r . u\fur
fit. thc rna' " 1 4~.' ' 1 46 Iatio belter, """ ,hi' l'OlulalLOU Ieav., ~ re,iolual at "".-':
147 (cor recling r~r the "s ",'nlrihu rion from mi; U S), indicating . ight or Din<:
carbon al"m, (c"T",...,.,ndm~y, SI, " '",,kl inolic~," approXimately C, ~ 5ulfu.r
(or , ili. " n) I, al>o ind icalw in mit ~<;, t>ul '>ol iDma' ... . l l ~, <;~ , " r R4. A....m'''i
tha i mit 146 i , 11><: m" ~~l a, ,a ll and ~~ nt ,, ; n , n" Itill'llgrn alom.. a "";.,., of
abun.t. nt " J d...k.:1TUriI ion$ ;. .pp~ ron l ; ma.,,", 42, ~, Xl, 34, 'l ~ . ~ OO 112. Table
A .~ ' USi"l'IS ao oItfut-ron ",rieo; the abu ndanl (M - M)<' aJld lM - ~Zl " indiu te a IhloL Th. i> , uJ1!"Ort.d by tho " U. yli on ".,ric<
by 1M ",i l 4'). hI, 75,
S~, I O ~ i, on ...it. M ass 8~, more l<hunda nl ' han " it
",;; 7 ~ or 103, oor r.,poJI<I. 10 t ~ e cyeli< ion fomt ed by di"J'laco;ment ,-nrra>lg. "",m in u nbr~n chr:d
nllyl Ih,ok (fqU li" n 4.42), For a dram~tic """fu mation of Ih" e~iole- ..... .. oom pm. Ihi, . peo;lr um rc Iho.. of
, H.,,511 aDd ~-C,, " " O H, Figur"" J ~ I Knd
3.8. [OctanethtolJ
6.1. T he m.i: % .S lDef3OU1blc j><ak <.,r..spoll<!, to "' i ~ 130 .... 11 2. hen
though 00 M io,)"" 01
n o a ,. discern ible Kb<W" background, eno" gh do
001 di, iiOci"'. " o,il aflo' leavinll the iolt so nrce to S'Y' , hi> "id'ol """' .mal;On
or tht mo lt<ula. ~ ill hl.
~.], The i..1It>]'oll: a bl",d. ace, of Ih.l ~r ge pco.ks indiQtc lhe ekmcnlaJ "am
""';1;' _ CI-I. N, C,H,!'!, C: , H" N, altd C. H ..N . Th_ .re consi' tent "..ith
i"""
"""'fry
n.c
<"..
...c,
..vI
'"
,h. s.ol Uraled am Ine-ion serion, aDd a molec\ll~ l ~omp<>!Ili<m of C, H 10 N. The
lartnl and _vnd l" rp
pcah mrrL-."on<! (n lho: 1".'0> "t C,". and CH"
~ 'JlO'.~ i> . I)~ 11>e1. -.b,mld be ethyl and m elhy~ but 110 la'llet alkyl, aroup' on the
ca rbon alOJIJl ' ) alph a 1<> tho:; nil ro ~.n " lorn, H,,", c'-cr , m any ; '''mcTj~ C, H 1, N
.min... til Ih... de""riplion .
Th. lh,.. metastable ion peaks co, er, pon d to the decompo.iri un. 5 ~ I _ 3lJ'
100' . S ~ . and H6 ' --. 5H' _The m o.t "omm nn palh ",. )
C.H,. Io u from
_ "h h un.. l !ro n ions is l h. charge-sile rea,rang"mou! leOm On 4.44 in\'C)l~lll&
c l .n~n 8 . ufth< C
N b on d. Thu, the (M - C H , l' _ 4M_ C H ._ C , H.l'
tn e!;on indi cate, lh. ,lnlclure CH , --C_ N __C , H" oIIxl 1M valh"", )'
r",
(1'.1
C, H, )' _ (M
C, H" -C , H.l ' in<!icalL.. thc l'" ",.:n,:c nr ( ', H.-C-
N- C , H'" T he o nly C, H L , N i, o rner roDl llining bo th of Iht$e sII MINe"'.... ;.

1,NCII, CH,CH,. [ DiethyIprO(lyiantiDo]
tc.n,
6.1. (AI R, - K, - H, Y - II , ; (111 R, _ CH ,O. R, '" ca ; \' = HJ ; IC)

R, _ CII ,O, R, _ CH" Y = 0; see Ilinnann 1% 2, p. .'OY, Th ~ peal< al
(M
~ ~J ' ;n A _nd H. a n'" 1M - 421' in C
",
v
"
"''""
r:
J/
I,
-v
"
can t>r ~'rJ aintd "" 11 17.
_ rn H,~~V
11 1.17l
8.1. A , da li.d) abulldam (M _ 2)+ io n i, uu us ual iu moo, spoelra., SO lhe

164 /1 66 sho uld be cheeked 0111 a, Mp<,,,ibk: iMJ IOrHc dll","-, One hm min,: .hlm
i, indi~alcd bl ,,-,"u'al . uch Ion [>I.;" T he ioo .....ies In,/z I ~, 29, 4lo H . H , and
85 indicate, aikyllo C. ' or !'O'lll>l y enboo)'l lo C " 1b< bro miru:-.:onlaill'PIl
;oll,e[ie, ,,,/;:; 79 ijl , 9 ~ ~ 5 , 107 IO'J, Ill-I n ""d I H- I J 7 gi ..,. .1rotI ~ ......
po rt 10 lhe pre""n"" Ol ,he I lkyl ~lIai n, . nd I., the IOnnula C.,H"Bt IOJ lhe
"',/;:; 164 166 iOllS. The I"". or the: ...... U tll' yl , . dK>ol "h" old nm he f" "'f ed
0" ..- C. H, .Br ' k",< fro m the "me ca rbon; a I"" ,cal np" U1alion 101 1M l.r~t
"'Iz 1J5 - 1J7 iotI< iJ; lhilt they u ~ I h r oo ~" Ihe d;' pl. ",m"," ,C,",-'1lt'n 4.42
11-Rromuhc. anc1
/1.1. The pr=uU'-Jepe"dtnl "";:; 180 pu t i> ploo. bly Ihu (M + I) ' ion
(McLa fferty 1957b) and .. a pl'lo. imalcly ( ' , ,, flo{ ,. (In,." 1791 ,ncn co nlain, an
odd nwn ba .>fni " ....g L"Tl .. ,om.. T h ...iz 12(1 aoo 88 peab lon e ,'alues of 8 and
1, ""'l""'livdy. for lhei. mlU imulll number of c,u lxm atom,. Lo w-m"", peah
ind ,cate 1M pl_n~ 01 ato mMOc ;,. ",I';llur ~..., J am ine (mi z 30) and oxygenaled
r"l" 3 1.45) funOllt, nahtici. ... met hyl estel, - CO- OCH" i, a proba ble ~au ",
tT . ble A,5) 01 the pea.. H;p,c'l(;nl;n s (M - 3 1)', (M - 321' , and (M - 59)',
-... _. ...._-_.
.....
'"
mi.
I .... of , he IIl,,*"SI pe.Jb in lh. , peclrum.
~~
"nd 9l . cctlld arioe Ifom

ctu""fe 01 ,he ""me "' ,nd (~ 8 + 91 _ 179); Iho mi: QI <IO uld t><: ('6 H .rn ,~ .
The t"c~'c' c hal~ , etemiou by Ih. mi~ 88 , u"""to ...." bili...lior' by lhe a mi...
moiely, - C}{( - /'I ' H , )(X I OC H .1 appears to be tbe onl y l"O"ibk Io?"up ron
I~m;ng ,Ioc =rM~ ymc lhyl func liolla lity; lhi' .liIo ;,. "" ""....en' with the hlllh
~ ooruia """ or m/: 120. Th. , n i~ 13 1 pea\; I"o ballly "rise$ from lbe <:omhin.d
1""0' of CH , O and NH. [ I' i>cnylalanine met hyl CSIer]
S.3. T h. ion or m,i: (0) should toe C" Ixt..... Oil the C. l:OmpoaillOD of mi: 88.
Th< abundant 30, , 51l, 72 lion .,... iI.. .... indiuall vc of a ...tllra l.d "min<:; lhe m/:
103 eompo,i(icm Ihu. ,hou!d be C , I I , . :S-O, and il pa""'-", the M " lem , Alph a
clca , ag'" init ialed by lhe am me ' ho llkl Ix dominanl reaction, ; IhelM eH,)'
a nd (M - CH ,O f' pea l . ,h... indicale lhe nwi.tie, /'I C .-(: H. and N C CH , O H. "",p<rti'-cly. ~ven rl>M " hyd ro. " l i, pre"nt, Th. l'," ' jble mole,"'b are M HOCli, CH 'CH"INH( :. H, . (h) HOC H, CH(CH , JN(CH , lr , (.1
11OC H,CK H. h NHCH , . (II) HOCH. CH,N HCH(CH,), . and (d IIOCH :(:H ,N ICH,lC,Il , ; no N ilo' a lo",
(M - H )" i' po, siN e fro'" ~ ..y ,,(
,hose. Th e 1>;0", m/z-]ll pc ~' ,hould ~ril e by the fllrth.r <ic<xlml""il it>D 01 DJle
oJ I I>< a .c1< . ,~ "" p,od UcTS {OIl' 88 '" 12) t h",..g h hyd ro l!'"D ""alfao",m" D'
I( q ualion 4.44t thi' would not "" l'O" ible wllb tM I"rtlary amino>; " and e.
h .><:I '(In ",; ~ uc n ... ro, the rem ainder ' hoold be.
".""pI
HOCH,cH{CH,lN'H=<:H"
,"
......--- >oICQ1P;~ ~
""
:
""
,
""
~""~
-,"
........ =CHo
(m'z J(lI
~ H=WH.;,
1m', tilIl
CH,CH=N'''''
Im-'~ ""I
(11.18)
HClCH,C(ct<~~ ",C>i, ~
CI UIJ,I
,CtW~ ><C""
HOCH.;, G H .~ '
* -,"
--
H==(; HCH,
H >G~ ' HC H I G H , 1,
,"
+-Y>"===CHGl6. (""" "' )
(1l,20J
1".-, 301
I h~, " ' honid giw weal< tIIi ; .lOand pc. h . The ",/<. 88 ion 01 a , hould ar tIe
mainly b,.- I"", , ,( C H . rm m 1M more hL$ hly bm nchod ~--<:"rbon. ' 0 l h \ l",-.. "
. ho uld be li~nif,,:am ",-,. 60 ipD. S" .....1 'l1'I' d cnr rcclly predict' Ih bulI
da nt "'.-'Z )0 and 44 pca1 0; no,e 1""-' ,he significant m/,-70 ion i' oon , i't\:DI
wi,h Ih" >-Iahle . 1ruc1u l'e CI T, = CH- J'I'-- H - C HCH " l N-(2h )dro. )'Clh)'I)- ,"I .
tto propyl. ", i...]
"
,--.
--..
8.4 H~ " e you ""i~ncd the f"'m ula. C, H ,O, 1(> ",," H n d C, H, O 10 m,'z
If ..." . " " ""Tk th" problem assuming th. ... dlluo " . Ill JuWl;ro try. hig....
rno! u'i on mUI spectrometry.
T h . ' >""trum ;. dim cu h beea .."" of t he ., "'Iy of ISONne ronnula. which
"an I>c "I'l'ljc,d l!) each major ;OIL and been '" of rhe .bs< no;c oj a m,>Ic<:ullH ion.
Y.l m Jny ~tud enl> a~ a\>le \Q 0'"'" at the "t>rrn.1. <I1'ut\u~ in I telalivoly ' hort
tim e, m"-in ly bo." au ,"" the data fll [hi, ttructu u "" well. Wil lll)U! te te= c< 'pee_
Ira it i. dlfficull to . limmal. ""'Dy <IIh... po soihk >I t''''lu'''O un"qulvocaUy.
How n er, ouch . "I><" gueu- u n ...r,m be >cry' ~.lu " bl .
F or , 11<-'11 \0\0" n!Ole.."lu"";l(h1 co mpou nd s, th. liICk of M .' .uggcm !.alurated , tructu r. (Ta hk ,'.4\ CH , O ' , C ,H ., O , and C,H ,O, are lbr moot In4 ~~
>arab lc I'O"luLtl<'> lo r , h b undll nl >It/t 31, 45. Jnd 75 io ns, re,pc"ti ...~ y, T il....
m.l, 75 m""t ronl"'-D (" '0 fulKllon.:J ~ roup" ; tll. i, no odd_eleot"'.. (M - IS)"
ion w ind icale lha l ei1 l>cr" a "l'dr~ ,} sroup, The abundant CH , " . ,,"""" a
C H,O moic1 y; ,d ali, " i,,,, 'lahiblies predict a low abundallCe ro. C H . " u..less
il i. auached 10 an de c1 ron-J l traCl1n ~ ~w u p. Tho C H,O gro up ;'; prob:>b!j
au"elled 10
CH , in"" il OaMol be par! 0( a C H , (X:HICH , l- VI
C H , OCl C H., ), ..- gro up. If tm"e groupo \li . ~ r< . ~m.. tile aIIunJ,o....", OF lhe "'/:
~ 01 13 ioos, respectivd y, would he m..,-fI 8..... ler til. .. ;,; obsn" cd. J h. few
,,""" danl ;0", in lhe spectrum suU".;t . simpk mol<alla.r OUw,;l mc;.o 0"" of
\h<: hoo n,}'g"'l_conta ining fuoc\ion.;l aroul" in Ihe "';: 1 ~ ion may well be the
1l<1m. as the one in the ",/: -45 illn. I( tIIe,e ;. no "yd r o~ yl group, lhe most logical
. W,K; lu r~ Fm lhe ",/'~_75 ion i. (C II,O),C H- . an d 1m the molo"ule it i'
CH, OCH, OCII ,. It 'h""ld be . cempha>il<J lha' ,lob " as nm " rigorous proof
ot " ruolur. by rn"" ' ped m metry. bUI "" ' h", a .. ay 10 bypothe,i"" a pTOba ~
, trud ..1'e ...-bk" can lhe n be cbcclcd I;.,i ",\ rd cro""" ' ]'\I.",lt " 0' olhe, techniqun . [ Met b~ la IJ
(lUll
'\/
/ .;-"
~
CH,O -
"
CHl'J.
'OCI',
8,' , The rnass-12l ;'-"" "Pf'Ur1 1(> ha , e se,,,,, carboo atom, afid two ,"Yt""
ato m,. '0 it eould be C~ II.O : , T1fipp1Il6d.....l:>lc-txm d' .alue _ 5, The ../: . )04
i,m J'O"i bly ha' ""von calOOo a\orn.. u J 1\ .<hould be no ted a, an oddd c"t",,,
ion .I ong ,",'im lUll' ''''' \I4 .. ...l 76. MU I III _ mI lO be " primo ea-ndidate fnr
_ . "' _00 __-
'"
t loc "",1<:<-1.11... i"n, .md it> at.u~d., JKX: indicate>. hi~ld ~ >lab'" mol . '" In lhe
low-m.. ..s "'t'On the ('!'Nomina nl ion "' " ... ;n<l ICJI.. a.n a ro ma1ic b~'d l'<Xa rl>oo;
.'a)""
the rings-pluHI<Juble-1)ond,
of S OJIlQJ'<.tIJ. 10 " '*""' J I ring 1'1". an
ad ditional rin~ Or do.. blo be nd. l b e "' ril ing (M - W "... l indica!... 1h. pres
on"" of a lab ile bl'dro1:<'" atom, and 4M - 181' indi<:.' ln a rudy """ o f H ,0
(T"" " A5 "Im;",l' Inal thi, i. d oc I" a h},dr.... yl gm " r~ the (1.4 an d
1M - 29)- ion. are prob a bly C. IT. O " a nd C. II,O ", 1"l'5f'OdJ ~ly, <I lK' to 10Sl0 of
CO, and COH , a. lo,... of C. H. an d <\H , ...auld yield unu,uoll y un,. tu'1I l. d
" ruel u,"",. The . ...l - 29)' ' uggOi l' tha i til<: - (. HO group is present, ~hl~h
....o uld aL'"OO unl for tho oXlra do oble bond prt<lJctcd by lhe rWB.. pio.o ooble
bond. CllkuM ion abo,,,,"", !'rorn the"" indi tiom of u I" bi'" h}'dr"gen, rhen ~ l.
---O H, and --C HO an "!,,io u' ,tcud " ,"" pO' lulalion i. HO- C.H.- CHO. a
,tructu re which also i. consi'lent ~itll the ",it -7&[on, C, H ', The oddd .clro n
ion "'.i r 1(14 indicates lha l lhis is lhe orth " isomer; an (M - COr !", a k is l iso
commonl l' found in the speetr. of phonol,. [S. licylaldehyde]
zat
~
0-c: : ~
-
o=c
,./H
o~
;Y
';;c..
--L.
,-
H, O C,.l-<.O
CO C,HoO
(11.22)
~A The mi. \I'Ii9~ c~lio i, t<", l~rllC ror "'it 9~ to be Il>c ," o,"""l"r ion; t~e
miz 84 mak e' "',i~ 99 a mllCb mo re like])' candida te. T his ouue>ts tha llh. mole,uk con t~im an ndd numbtI " f nitroi en atoms. conli , ten! WIth th. C. H. N
a,,;gurnenl of m,i: 54 (EE- . r + db _ 2~ Bt:cau.. "'iz 59 . <mla;n. ox)'g.n (c E ' ,
r + db = OJ.lhe moM lolli, a] as"1I1lffiem lor m,i: 84 is C. H.NO (EE' , ' + db ..
2~ and lh"" C , H, N O 10' M " ' rhe , ignifi, ant rna". 31 , 4.\ ,,00 j9 ;'1nl , uU ,,.,1
( h ble A.N an ak" b"l m elt", lunc\lonM>ly, For "'i: 54 Table: A.6 lu,~lt l
C,H.CN. an d the pre..""" of a nimle grou p would . 1", e' rlain the unu. uaJ
(M - J)' anJ [M - 17)' ;0_ n.c "'i: -59 i"" il most likel, H OC(CH sl. - ,
CH ,OClI (C1I, )---. or C, H,OCH , - , in ~gl" " r (1.1 - I ~ l ' .. (M - 2'W . The
""IJ
of 11J<.,.., """p"!lbl. "'ith lhe ba.. ptak at ma.. 31 i\ C JH, OCH J - '
{ /l-C ya nO<1 h)'1cl h) l d h...-]
<m.
'"
r-... ,.
Gl-l,c..,ocH,CH.c'i
Il
-_. -
CH, .
+ CH, = OCH, CH,c N
( li B )
m,M
(11 .24)
'1~ --.L!!..-
C,H. " HO= CH l

( ( !.H j
M.7. The mh -l50 ion appun to hJ" e C, and 0., co m p<l"'-'1l l<; [hi, i. """sis-
tent ..,ifb C. a nd 0 . rom poncn l' ;~ nl,!: 165. Th. ma..-l04 peak !I... .. IOU 'm Um "I' ..,,,,,.... "" rbom a tom, . T ilt ",/. - 4~ 1011 i! OIOpo r ~\ ;(" p<J;n\ to u.., wrnl")<iIi,," c: , H, 0 . No ... or t il< t" m . Imu n" t. ' ~ . .I. 1~5 a. Ihe m. ........larimo; il ... Utl
then con lJin an odd ll\lmbcr or nitm getl lt ~m l. M ~-. l(lol an d 71> ""'." tIC
.. gnifi""~1 ,'<i<.!""kClw n ions. n l< moleoul~ MPN "" t tl tc !P"-"fahy '01.~bl~ gi\-_
;.,~ a rt", .i b ~ ndant ions . The low . ro m ;ol ; ~ >en.:.. . ugp.'01" decl ron~ al i".. , ul>Slitu.ntl, Th e ubundant 1M - J ~t indical" ra.:1Ie 1_ of CH , . and lhc m/= 43
1M 4~J I m. k" the a"'tyl group, -COCH ... ~ p<)Wl tok "''''''''' " r thi, 1o...
I[ the """t, '1 gr~\\p il Kttactml to I"" ph,:ny l. lben 12'l ~aI L"" 11.26 otfers an
oxplaoatlon fur .ho a ~ ~ nJ" nl -..'z 104. Tbi<. """"mJl'O\lllOQ of an " ,'en _electro n
inn to yield an I l>u nd om odd -<:lc<lron ion ;, an a, aal, and "' 'l ui,.. Y to b<
,t rongly tAtctlon . llr 1Inl- ,\ddilio" aJ ",'iM""" <o,,'os from mi: 76; lhi, "
dl.u bslimlcd a,omatic compean,l, (T.Ok A.61. If "'.
<ommonll r..'rm.:d f"
tnj, ,",,-'Ond r"n<h <>n greup coma;", 16.\ - (76 + 4)) _ 4 ~ amu. and is probabl)' NO , . C, II. NO, I"'.. .: I SH) - C , H. O (mi, 1(4), L<>.. <>I NO i. Iyri",,-l of
",t'.....""'... IT.~I" " .s~ mi' 120 may b. ()vi C H, - NOr , a nd",;z ~~
....y be 1M - C H., CO - :-': 0) " , l l, Nitm ac. tophelloDtl
",,pic 0bundan"", Tllli oorr~"". 1'-' Ihe ' epla<L"t'JI",'1 <>f the elem.O' l uf C H ,0 , in D O E by a n <>' Yl en awm. and an incroa", in the rin~,.pla
,h ,a C>le. bo nds \'alae r...... 'J I.. 10 . ')'1le m,'. 248 I"'ak po" ,,, ti><: le'" fOl' !II<'
moleculor '''''. Ib= are n<> <>Ih", Pl''' l . ' I)m ~inin8 more than t..,o chlorino;
;u< """ SII'QfI@add nional C\'i,!<;nc-crot lhep,ese""" or OXY ~. ll i. p"OvXlM by the
abaad.1nt OE ' i.... ~I mi' 22(; lhi, , houM repre:>\Onl tho [0 "" r,(CO, IliIlCt C, H.
""', '"'''akl .... a nlikely Irom a h' llhly ar"m alic molecale. No te , hI I~. p'''''''....
ckfnt'l\. l rom """ t", n of tbe O E - ' j"n or m,i. I SO is e , ." . II can conlain n<>
--... _........
.....,.....
~.
cM<m "" (W "" /11<"'. 60 it mu,", be (M _ Cl, - CO)" , Thi, i. also evidenoe '''''1
2211 " (M _ C O ) ' . not (M - C, H. ) . f\ L,,~ ( XI I"...
the o t - ' ion of
pe~'
a pheuol os endO<)'clic "" . oo o}'l group; ,he lauer would Mron,is.
ten t ...il ~ t"" ,'~"m;"'U1 Iori",,1 molecule. [3,6-Dic hlorolllloreoonel
'UUC'"
m".
(11.27)
,he
S P.
mi;; 303 peak eorr.""po nd, In _ " ...... i.... opOc a buod ances to the
M" of eoc.,ine, a Dd th e relati, e a bundall(:e ." thO. ~ i. """,,<tcot with the
. t .hi ~ty
of thi, cyclic molecule, There is aD a' oma.!c-ioo ....-ies.: the I"omi""nt
(611~ &2. and % inn, arc c,,",i,t.cnt with IIJl
EE l;>" ydo alkylaminc _ lOS and"'-",

a.n (IE " cyd "" lkyl serie, (Table A.61: , hese are a l,..-, . 1.If'...." lal. by the ~1nm
<tan........... ml;; 41. 55. g3, and 97, T be intense higb-ma.. peah a t 1M - 31t .
1M - 1OS)' , and 1M - 12 11- ~ i .e ' tT""1l cv;<!e"ce for the p=nce (II tbe me'lhyl
"'tff. betuoyL and ".,," vyl<.... ) ~ r ou p". respecti"ely. The corr",ponJi ng i"n.
at m,i: 5'.1. 105, and 122 10 1''' ', ~.~ u~tio n 4.33) provide additional evidenoe ror
the m .m o~ yarbonyl, benzoyl. and b<,,~()y l ()X y b""UP ' . rc , peo;;ti, 'ely. Hiah
re,oluti"" inr....mal i" n un d ...",cntlOi COlIlpo,itions would make all thil e~idence
mor e f'O'itl"". ho...,wr. ro.. ua mpJe. the Ia, ge mi. 122 peak may abo be du e
to the I" "" nr t.;n""rlo~)' a nd ac.e1 ic acid 10 f,i the <labl. m::- inn. C , H, , N . .
The mit 94 co uld e<>t"",,l'o "" to ,he k"" .... C tH. from th i, ion tEquation
4,311. rC<><:amel
-.-
--
1l1 .2l!)
ll.lO, TIle p<nf D<e 01 al "'"t 'wn " ' l'Men at oma and on e nitrogen ,,10m ill
' 1Xl";, cd b}'lhe fuCllhatl bi. ;. the elhyl c' ler oran "m; M ilcid. 1lIe mi. 1771179
ratio <Uf#<l< a n ;""4 "';0 ..-luol""I. a nd the abundance. a" con';'tent with .....;
<alr" r and aro und . "hl ""rbon aloro> f(>t m!: 177. There i . pro bably a , ulfur
atom in the rcab at ",,'; 143, l .l I . 104. ,lid 61. To ca k ulate the ckmcnll C, H" . Nnnc of th. tom
".
""",ma l mi. 177 a, the molulu i<m, C , H, , NO, S. O ther odd ~ I" U ions
au diffICult to idfmif)' \><:can"", . ... ' h. 1"" "'0"" of the n;tro!!,:;" a' '''''
The la[~. n uml!<'r " f fuOC!io '>aJ gr<>nps presco t "",k"" it ""'u <lJllIcnll to
judge lhe .ign' fKa nee of t t>;, low-rna" ion "'"'" In lIoe all yl amine III:li<"Io M,/:
J.O ap pears to be l ~. <Jnly ion of lmportaGCC; Th.. In''l pin. an aw'e.:lcilbk
(M
11) I indi""tc a ru e amine gro up. or I ~. ;,m ",,,i.e, 01 T abk A.6 ront;u ni",
""If" . the altyrltiol or , lI!fide """ic. "'iz 41, ~ I , 75 offer " Itro"t...-e ,,-,,"gn mem
lor lbe . nU" r atnm in ll>c ......!ecu.., The rM _ 151' . (M _ N j". aDd (M _ 261 '
a TO r u ,, ~ lL I J a, e.<p:fN lOr ~ n <lilyl ter. hum Table A.S 1"" (M - 4~) I'
ion could \>0; due to a _ _by] , ulfide. nod ' hi, "'''''''' ''' lilt u , ignment o!
CH, SCH . n 1M >lruclUre " f lhe base peal 41",/, 1\1 arod for the aroul' k>" in
m""I 11 6 T he 1M _. 731' i, expcelN (Eq u t,OI' 11 . 2~J far K_ CO OC , II , ....hen
-,.
l r*l,
R--c~ ,
1l.. .:t H:::.-cOClCA
R ' i,. hili.red, " och .. ,"'cu,,,
(Dr
.. . ~
11 U ~)
" "I ,mno m;i ,h (Tab le A.S), The ,,~hle
It - al$O . """ uuh for Ibe lack of the e.p.",lc'\l (M - C,H . t Mnd (M - C ,II ,,- ,
,Ii,
mu'JI h. w: a ma"$ of 177 102 _ 75. 3nd mu,1 "DOl "i n

R_ CHi'; H,CO OC
CH.,SCH, - , <0 tha t the m"k,cula, >trlleture CH )SCH,Cil>CH ~H ,cooe ,H,
is illdic. ted. "The lionnalioo of ~i: ~ " ratinnoliud w Equal..... II.W [ Methioni""
<Ihyl eM","]
X. II . 1be QlaJ;mu!D ,'alll"' fOI ~kmen ....1 ",""polilw m " " nnt particularly
me~niBglul T I>< "I.it 75 p". k l;~n"'01 he ~ + ' , "'i: 61 wD ulJ then be l M - 14)' .
TI>< """,ci ty " I " "t D-rna" pc.ah ind ICates Ih" t Ihe leu. M " i. at aB ~ ""n mil"'
" ~ m be , , A, amHe...! '''H''" r""cT i ona ~ t y i, ind icated by ,he 3 L 4~. (59, 13] i" n
u ric,; " , ec,,!O d D'U' h m ,J;e ~' cd b)' mi. 7 ~ and 61 (C , H , 0 , '; C,H.O ' , hn uld
n,,1 occu, in th;, " bunola" e, wit h"ut ;('>/l"",,,I,,,,uk "'''''hOC!" "1' 0, lbo "liz 62
ednno, t>e C, H , .O' , TI1, mcla. l" b!<' io" pea k at 10.. : 111.4 indie. !.. Ih. l
10/1 M c~ ... 10'" 11 , 0 (30.4- _ 43'.. .6 1~ lht ...."'1 logic~1 ' tr ucture_ fo r it Il ~
-C1l1OC H,O H an d - ( :-I llO H1C H , O H, Th, ,. aro _ i~ 1f",. n , 0" ' - ;00$.'
".,iz 74. ~ 2, and 44 (and- 1! ' UMl YOG m",,~ 1""",'.0. The "'.,.. hhl ~ fTJ' lU-" " fo,
m.i~ 74 [otm" lion" lito 1M' of H, 0 (or R OJt ~ 10 ",it n (74 + 1gj, C , H , O.\ , () f
" higher h.....>olo/t- ;,. a ",,..,i l'> lt candidat, I'm , he M " . Compou~,l, , uel1 a,
HOCII , C H, O<1--I , O H 3J1d CtI,a CH ,()(: H , O fl llh labl<) ,ho ul<l gi, . , igoilic"nt "',i~ 4~ 4nd (M - 17\' , RC H,O "'=C1I 2. GI) ,. r" l, HOC II , C H IOH j("H , O H. i>. a 101l",nl.l!rorn ativc; bydrO*"lI lt dllanllorncnt can expla in the ....z 62 and
44 pea ls IEquali"n 11 .3O\. f G lyttrolJ
~ / 2. Th " mit 141
he M O' if' l ~ " n ta i n< an odd nllmhL.. of nittOIi,n
" I,m,, ; it ~pp"ars lo' ,~"'I~j" C.NO (n, C ,"', OI. and m f ; 126 corre ,poBd, ,<>
C,NO. Tile P""'"""'~ of - 1\n ck'1l\O "!S F , ooi<lt P aPl"""'" 10 be (eguin"L C~k" .
Ialo<l llu.. i",a fu. lhc <~rh"tl numb 0( n,ho.~ io.... 2"" "'.. . 1 11 4, 97, and ' Il. (".;
" ".Id
... ....
y~
_.._._-_.
r Ho a
00
Il..
'"
('
~'Q
: .1<00
!.
~, ~
a nd mi. T!, C ,. The latt>:. l M .. 691' pea k lUll thus l<m ollly C , ; a I~ l
a ""gn"",nl is (M - C F, IT, wh",h "I",. lI.""nunl, lo r the inloM ",}: 69~. C F, ' ,
Th". M" ' . I>ould beC ~ H . NOF " r ... db _ I. The unlll ua ltM - 211' ~' n mu. t
be d ue III , he 1, .... of C , H, . nnt HCN , '" .. <:y,"" de "" ould lfll.ui.. r + d b >- I;
Table A.5 ru U "'lO tllat an eth yl amide ,,,'uld """'...." I" , (~ - <-. H , I' , . or ..
IIWlecuL'lr ,truct:u re CF,CO NIIC,J t" Th ibould . 1>0,.- In inl.........(M - CH, ,"
:mot! ... i. n by el"''''ah'''' ~lph~ to tl><: nit ru ll"" l" ocll('>O, . 00 at "'/ : '11 . 0<1
12 (a t a i,,! by ck,a , agcs alr ba to l b. carn.' n j'l rU" eli" " . N<.>le t""t Il><: h j'<l,u
get> rear r. n,..,mellt de<:<>mpositio n of ..i. 12 by ~ eaCtlOl' 4.44 yield, "'if
44: H C H, CH , ",-H -C - o _ C , H ~ + H ,N ' ---C - o, [ Ihyl ln lh!oro"
:Kctami<k]
~ .1, T he , xtensi"e C. Il , ,' iotl >erie< i' consistellt with an .Ih ne, and Ibe
DE ' i E ' pe" k pa in ,ne o\wiou,l~' tl1 o"" al "'/: l 10i21I, B ~i239, aoo 2Nii261,
cor res.ponding to " . ,alue. of 15, 17. n<! 19. I'or RR'R"CH a lkane. thll ~i .......
the form" l" ' n I ~ ' I 1 = 15. n I ~ e f 1 " 17, aod ,,' + + 1 _ 19; solving
Ihe"" ., im ullan """. cqual i,,", ~ i, c.,. 11 ~ h, .' _ ~ , aml n" _ 10, nr ~. l>....}'lM"'.
,,,",c'D< , C"H" (tt>. R ' an d (R - lIj- ' pe.h ol'e not important). For the
f()fm ur a R , R ' R T , l ,, ~ n ' + I -<o! 5 , 2 ,, + ,, ' + I "1 7, lUId " I ", 1 . " 1 =
19, or n _ 4, n' _ ~, and n" _ ~ , "-' l'l"\" fKmdin l" 7, 7 . di h u l y ll"' n ta d" " a n ~ ,
C" H ., (using ". ~ 17, 19, and 15 }'ieJ<l, non-i me~er . \'JJu el). F UMlly, for the
f"'m ula, RWCH(C H, lKCH RR' "n cr R,R 'q C H, J.,C R, R', sulution! I" tn ~ ..v rresponding . quJ tiom }" ield negoli,'e m " alae. T he com pound il actua lly an
i'oprcnoid. but tho meth yl branohe' would be di'ceruible Qui}" by oo m par i n ~
spectra of ck"dy rd ated "ompound,. [ 2A I0, J 4.Tclramcloy l. 7,\~ .mclhy l p"n tyll
penwdecanel
~ " trick" que,tion; th e com pollod i' not ph. n o~", whi~ h you
9.1. Thi ,
mighl have assumed if yOll i" cQ r ~ ctl }" identi fied lh. rna" \ i2 or - ' peok .,
1M COj. It, elemental compo ,i tio" i' C, H,O Bl', and lhat (>f tho probable
M -' Lon al m,/> :"1:11) i, C,H oOllr. Don'l , kip lhe ' lcl" in the Standard Inl"tpt "la.
lion Pl'Ooedlll"! T h. rean angem. nt 10" of C, II. eonnot Cur if the C , II .
moidy i, dir""II } attaeh<XI to the riog; tho 10" i' likel}, however. ift h. moiety i9
atlached to a nother olom (, uch os OX}'gcnJ ",Ili"h ;, a ltac hed 10 lb" ring . [po
flromophenyl cth yl " ther]
,,3. Calculati on' (}n i, ol',pic ollundance, , ugge", ",,,m,,nlal e" ml" ",it i" n, " f
C .H oO. and C . H,0, for Ihe peaks at mi. 166. a nd r49. re,pectively ( ring ~plu~
dou hle_hond. ,'aluc ror e""h cqu" ls 6j, T he OF " m/: 166 ion i9 " 10ii~" l "'lJId i -
w",
'"
J a le r", In. n", lc. ula, ion. T h. ,..,au cllarac ler i'li" low-rna" arom ali. ion<, 'm d
the ;meow pea.. a, m.; 1 4~ [( '>1 - 17)' :1 ",iz 12 1 [ (M - 17 - 28)' ) , an d mi;
45 (C HU, ' ~ I"ov;,;,k ' ln1n~ cyi<k nce 10' a ca rboxyl t 'mlp. The.. C.H,
'md
- c oon mo;"lJes l..lYC a n ly C O, lmaccounlcd for in (he molecular form ula,
, <1 11' " \ ,, bl;n/C",-.,Ji"athm } Ii<o ,,""-Kl i' " l"tiCllII'O' l LLlalo. Alt hou g h tli< in ten sit y
" r LIN: pc"k at mit 121 i. , lightly great., tha D thm expected from tho i'''\opi"
cODu ibu{IOO'. in lhi' " ".e "on llO dre. I>" ~i y ", mi, I22 and J 4h pcak , of much
hi!.'". , .nandan,," (4~ ~'; and 5 '~,~). ( r. ~phlha ljc acid]
~,1, _
"'lpha de"." ~. of th. ll-;, omer k ad s to two r<'" il:>le radical ,pecic"~
\
(lUI)
(lUll
",'r 99
".
""i[h~r
of which " In abstract II byd",!!,," t tl give "',/: Y'I (C , H_O, ' ) l>y m"' i.._
Equ~l; "n Y.42. f or 1M I?h lo d.ri" l flve. bo..." ',,r, .>-d ..... '. .
or loc ","ake"l "" nd It ad' 10 lIIi: 99.
9,5, The i' N " p!C alm nJ ano;e, "I ll.e "', Z 1 ~ 4 ",d ICa l.. Ihe wmp<",;!i<m
(\H coOS. , + db _ 4: [hi, pea k P ~ ISU lhe "' . 'es" .I "" ll>c '" i. an aro malicion , er ie,. and tho pea k, "I 6Q. 82, 9~ 7. un" ((~ ........ " "idc noe fur sulfur al1iKhod
to an "rom " I;" rin~ (Tahle A.61, "lIh" u. h a Ib,opb.n.. ,,,t>.t,,ul~d ";I~ an un""l
urated or cyclic group is 31.., possib l ~. Th. "'/J 47 a nd /'II """k> indi ca, .. thal ;rn
alkyl mo iet y i' al"" a\\,:I...' tor'\> forma li"" md ude Equa
(ion 4.].6 wjt h a. and E<! "" UO" 4_ ~1 .. I' ll b, 1M pst"..:>e of ,1 h ~ dlt" y l
gr oup, JXl"ib!y in an ",lJ>" pt.iu""- is indiQl~ l>~ Ihe p;~l ~l ",i. 121,
ni,m, , imlla. to
(M - C H , - 11, 0 1- . The mfz 98 ,,1M!. pJ ."ti m~I:>I) , '17 l""ak lltjU,onlaill . ul!ur,
and Ihus appd r~otlJ ...-c(M - (', H. - CO)" and (M C , R, C H()j' , con
-';, 1<... \ ...-iln ~ r nenolic-l)'p" hy<1rox)'1 ~"-'Ul', l Un) ! ,,.h~'d"-'>.Yrh"nyl ~u1fid~J
"'./I. Ir rna.. 101 is rh~ mok cuT3T in" . il m uM cont. in ao odd numhcr 01
nil rof"'O ~ Iom .. Thc 1M ~ CIl , )' ion ~ppears to nay" JIi) mor" Iha n fou r car
00 11 "1" ...,, JMl "'i: 59 10 h.. ... 1-"'0 ""loon ~I "m-, an J no mort Ihan 000 o. y;cn
i I,,,,, , A llY ~""o--elCOlr(>n i~~ ",rica " r Tshle A,6 Ih~l jnclude, m/: 59 i, r uled (lUI
t>, r~ M it""" "huoo~n=, In ract the jdenlit y of Ini, ion fragm"nl is a major
h ') In It.< id",n iry ofUnkno-..'n 9.~. Wilh a max im um of C, and 0 " and " 'ilh
t he rndJC81N vr<'" ,n.. ol' ~ i \TOgen_ lhe for m ula C,H"NO i, a logical JXlstu.
LlIe 101 "'i: ,~Il. ,,00 i' all ndd-dectron 10". 1M - 42)-', T able A.7 sug~"'I'
H , NC(X ' H , - Z -11 01 HO:-; -CHCH, - Z - H; for Z, 42 am u, T;<hle "-.5
wu estl C, H. " , C H,CO, Cor rtsponding to these. thc prominent 1M _ 15)'
a",t ",i . 4J I"'al uggen either CH ICH ,) , or - C OC " , a. ter minal ~ roul"
D,tl'",emj .t '~ D \'It'lw o \1>< ,,""ihle an, Ide and m:j me str uclure' al"" requ ire>
" " dy " f ' ....-crenee l l"'Clra of similJ r com pound" LJ- MOlh}'IMl lyrami<le1
,"
(11.34)

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INURPRETAfION

T.~" 1' , N~'ur~llsQrop;e

.... _ ,. ."" , ... .- 1

1-1, ~ conIr iblJtiOM; 1M u rbtJn . M1 nw~ It _ _

, ,~ " 1 .. . 0, " ' ''"', H " 0.70

... I ~ + ' 1'C.. , 0 Ol;

" , ,., '"

" " "

. '~ men '

P""'" (unil rumubonJ In>Jn

Uni"""ily Scirn "" 8 00b

Producti<m m.n'i<r: I ", ,,,, l oif~ ~

I'rin '" and bjnJ o" .-I-l "rI '

",iI II<K,o. .\ / " "J ;~ 'wi"" G..,

CoplTight il': 19'1 l I,y II "'''''''nys.:.."", I" " ' "

<of C "" ~ , ... C.,.l o~

~ U l.ber: n-~ ::~ j ~

Prin ted in [be L:" j,O<1 Sr.' " <It ,h"'n<:8

,,_. '" ....

,,,,i~n ,,,,,n{ .. poo."; ~

' lruefur'.... ~nd ,.<m utated m..:r,a

~'( m ru ~n ..nt. " ,

Gl olI...Yend Abb.eyi . Uonl

"'P P""OU1oC<I' oI,"e _~ , .....

St. M a,d Inl. 'prel ' ''Cln P'OO@d Uf'

Sta b- . l.o!cI>e. Clus,fi" ICl n "'coo,aing tCl Na'", ,1 " O</flda" .

C O" I"'"'IO(" ... .. A1I ~ _ a ... _

J , Tile MolecUlar Ion

11""""."'''''10 '0< (h. _

M"""",II"" "~_ '"1C" \fVSU' SI.>en,,,,

4 , a.&ic Mech .niwns 01 Io n Fragmentat ion

LJ.'''OIeeu'a r loti D"""",po. ;(,ono

Ba. ,c Fac t"'" lha t Influ. "". 11m Aoondo ",,~ 52

OI""eli"" lo" ,a lion '" A""" a l or Cha rg. Si..,. 501

5 I POSlulililion 01 Molecular StTud u res

o.. "" ra l Appe "". ol th. SpeWLJm II';

Soft lonizaho o Me\hod . 103

7 , Theory 01 Uni~u l e.r Ion Dec omposillon,

F"",9'o' De po;iliM a M Rille F.-.cn"" " 11~

O<! , ivat, on <II 1'( 8 Fu flC1 ,on.

C" l c " la ~ ..... ol ~ I E I

8 I ()@lailed Mechanisl'Itt a nd Ion Fragmentation

u.. "' '''eeu'a , "", D. c omwsilio....

RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e.

8'llmt-Bo 'l<1 Di,"oc iali on ( ~ l

[)e{:_ ~ . ' ti O ""

C ~ " ' ~ . S ' l'e

Initi.tioo (~ -e l uv.go ) 111

9 / M. .s Spectr a 01 C om m on Compound Cle nes

Hy<lroca, boo . 226

ACid., ~.- , eno l A<' ''''' U

Th'D1e . "" "'W'de '

.'I' ivh aticH.li<lfl.

10 I Computer klenlltW;"t lon 01 Unknown M . .. Spectra

The O."'bftSe DI Aa'.renee ~I Mass SpoocIfe 2601

,",pplic otlO n 01 P1l ~ ;III d STI llS

10,5 Go"" ' o l "'. ~~

RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e.

8'llmt-Bo 'l<1 Di,"oc iali on ( ~ l

[)e{:_ ~ . ' ti O ""

C ~ " ' ~ . S ' l'e

Initi.tioo (~ -e l uv.go ) 111

9 / M. .s Spectr a 01 C om m on Compound Cle nes

Hy<lroca, boo . 226