8+/pa

EXPERIMENTAL ORGANIC CHEMISTRY

(CHEM 513)

(8? %) \_-J--l

MIDTERM EXAM

24"' December, 2013

Prol. Dr. Jane Bogdanov

W\**'
'fhe exan contains 15 questioff. Check to nlmbef ofpoinrs rs ffi #.
RULES and INSTRUCTIONS
Molecular models are allowed. Calculalors, laptops and rnobile phones are not allowcd. Cncle the answcr dircclly in the exam. Youcan use the plovided empry blank page for calculations and sh ucture solving. 3) 'lhe answer key and the results ofthis exan will be posted on the Oganic chenistry and biochcnistry departnent's bulletin board. They will also be e-rnailedto you| official e0mail address. 4) You have at your disposal chemical catalogues andhandbooks (Sigrna-Aldrich catalogue, Merck jndex, CRC Handbook ofChernistry and Pbysics etc )
see

ifyou

have cncled and/or ans ered all questions. Ihe maxnnum

.:tOO UY

l)

2)

NAME AND SURNAME

STUDENT ID #

DATE

SIGNATURE

*nt,lTatt')L^

P,r:lo,r:.nti

,Q,'+,,rti

.,.' rtk'iLLNC v \ \"

),
-

re \> \07

'

':*''

YCLgteY't-4r9-EleNF'

pftefil,F eNooe* ) ID PeAei -rctlufteo' tl-u Tfe P|wr*tr-os

DY thsa' $.
r\ -u
\t (.

0
1i

p[-

QlJetl\

b'tJ{QX

[v' 'l\

lJJ;#"

i'?:tJf*#

* %:tu'Hffi#r

| :-,. ^. r^- -l: f.

i'' -- i 3 r; ,. a=r.p[, -. - i : !_y qH cond*',sr.)son

.A- CF:cA- c-cH-

cn

- P/'

(5 pts.) Wlat is the product ofthis reaction? Provide the ILTPAC name lbr the expected prcdlLct!

f 4
tu i|

ccogg - dldol,

J7t<nr.)l d.a)a-?
\ !-/ ./

g {el.-=.'-i-,"(Y/,.;.7u2teoyl .- p-.'ld (-,' I .-\'o,.

2. ,.o -+tc-o_^l --

LH,o

(5 pts.) Draw the structures ofall the possible isomers ofthe product olthe above-mentioneal reaction. During the recrystallization liom ethyL acetate, the iample was accidentally left exposcd to sunlight for severaldays. Instead of the expected product, a product u,as obtained with.mp of o0 "C and the following LIV-Vis propeflies: ),(max)=295 nm (e6ron:20000 L. mol-l.cml). Draw the structure ofihe unexpicted productl'

i _i u'..-,-.,,t
,',s 3.

u ,...". 2e.^r,..a

^"=?i

_*")7^

ol,J!^i_,;='o^i,',,o.

(5 pts.) How would you differentiate cyclohexa-l,4-diene and cyclohexa- 1 .3-diene using UV-Vis spectoscopy? Ilow $'ould you differentiale cyclohexa- 1,4-diene and cyclohexa-1.3-diene using the Diels-Alder reaction? cbiehe\,, - a,l-)ienn qbsqb: uv'- ';t '& 25e.h /l-'^,'9ooo\

,, t!,,, r \d'( - 1L. .i.:" ae,7--;d ,, .a, ;"!-rV ,"^

^lL:,r'i-r"

",

(.);.i"-" \""
4.

^''v '.1r*J;i*r" a "Ji.r.^o t)z.r reeclton ?'::;,':,y (5 pts.) Rank the following conrpounds according to theirieactivity in electophilic
'|-rqc+in
"J,:&

d,ti(oeD ,.t'+

) u

\I

-qct" 4"" q- 1,1-A;.ae o" I,t<

" l-Rt z;

" " "''a':;,''"';"

"'.'

^!'"i"''*'

-6r :O"" ";'' *".lrr,":l"""ril**:." c) )t \/ ; "' (r "' i) a' 2: \' 7, '-r,.,.

D,-';>,.a- " ;.";:. 'b,; ,::;:i;;::
a me*yf,reny,
,-V-.
,,1

r;.7: .lLd- A,,a .," (o( ..,"u. .., -/1.j,^ "r'-i l-..,a.,. G0 :1 clr.rr'^ L- h. h. a) bromobettzencnitrobe.rzene btbenzoicacid cr o,-.,r^,.

a-romatic nitation (from least reactive to most reactive). Draw the structures ofthe expecled dominanlRroducts fiom A| b<"ee,"<

mononitration!

Ttr:i!,:r*r,:

5.

(5 pts.) Draw the str-uctrireS ofthe expected products from the follou.ing reaction sequence. Provide their IIIPAC names. Propslr plocedrqfor isolation ofpure 2-nitroaniline.
!ct+5

t)J.

.'-,'

a"S8-

., !,, , ;;:,;;:t:,"q*, -v,\.,i-r::. ,\'

.m )12

C.o
1. HNO3 / H2SO4

,At t{ )l '\2'

"'

-.

.,,-\,tnp 4Z'C.

tul
.nJtz

mp 1(

)'L

''t't :t

:r r C.L .n<)L LG1)^- +4rt^ J( I iscr^us " '-r'cl ;s.l,r"l-. p i,r-.: (-)-t1 ;dr!\^, ti/a "to,tci br, h3 , './'ri,r\L r \.F,ut,1 r.) y]-*r/ .,../ pp. p..rA.-t 1 /^.2 +) it1" -a hF.c .,<^pto.rql _{. cl"ek iG ,iA?,^ ,.. ,/j ,.,t/1" -F:'t''c l*FtC ta'-,o k :-,1vet^ l.

't'

r., -)

*r

'

bP 281'L

bp tbc'C

.+a-* kvd*Yt

+" l lq

lr@'aad^1

Jrc*$,iU 'r\st- taoe deao '

t.

ig

l",t yoaLtte

a'o'rXil

bq
F _ (^ \--l

et+fack4

t\

v-c
\l
i

*'t't 'l
-

/?\' \J,

4..
\\\
L1

,,Vh
tl

1\. o*c, .,

\ll
No lnw"4

$-c-H
f

ct\..
I

li
+
k -n^

P"*'.

/?\
\ nu,

f(-C

- C-O'
cltr
I

a,
,o

6.

(5 pts.) $/hal products would form under the following reaction conditions? Provide their IUPAC namesl

C:'.

o
hv

IJ
cH3cooH
A

btn+oph<no

n.

H.c-/\cH.

'l

bt

r-'

go

p;oc.

W.ftd,pr^c,ca \c..L

7.

pts.) Do you expect the photodimedzation ofbenzophenone would take place using 2_-+ethyl-propan-2-ol as a sole solvent? Provide reasonable explanation?
(5
e

\ -f.'. \ o ,",.^ " ' , :

PN
o.lc"h

a^d jl..g ) "i L1^5f rc; Jic, ?* car r^tvq.rhrk>s parJrc;paJe -u,-,-" ssli' l\ 6'4o ft"-i.-" - d&,t '1 *tAa,.. 8. (5 pts.) After the acid-catlyzed benzopinacol rcarangement, and the appropriate \ ,ork-up a
product was obtained wilh mp 184'C. FT-IR spectrum was recorded ofthe isolated product and is given bellow. Propose a stucture ofthis product and explain what happenedl

^."i1., "

4u'' 'uaq ' , e4 c,.utd l-L-e p la c4 ', )h"'' " '9<s 'qi.o.b" i*r:*n a A2)'"-'/ 1l .7,."p t cq^ .raih a p,dk, a'1d f'"-p ,r _-- p{.\, ..-a-:, A' o-A: .ifrz ' p o-

(-J)

:>

1;r

o\_, ---*"t-,li;i'

elrAqnrt, I 61

/ /at

ro!qe

Gnh ;b . -L^ d".,Erj.

n" .:^la)'
n,err+.u 5i-u c+,,1 ,

,iii"fl.-

a-c
Y:-+r'r,tr zd,.!r.F.

-lk

Utlt.t?Pia culane hJ>

/})p = 444 -ci h";;*;o?i"i:?Xtl 4\. oc.Jt a.I ttfiwcArrl :

,4
mo ( tr"-ro 1 r:- rbonri yr+,p >d--+e.\ t5 :;-<" n q+ 4e e t,4144?^'1

a1 a54<

r1* - +*" ,-^h..,. -;+e,,,.-"

n.a

/r",.t, f-- -r+ "

-iAis ,x.u"rns ho .^Ai

cv,\5
t-t-'
p

pa,!

5t(n-47:<-Sie ae-\,.r a+,kr be-\tap'^.1La i

9) -c- )."-"d:
O^

.ly

r- !a- .a2oecr, t phc:tz cor+a 1^3 "LlL 4t-t < izr,n.en; c ac;d I0-a a^ l^tu h,, b.1 ,,nr,^,ta, 'A pE) ,-t e. <j-a.,A JA< .121'e.\.5 lagza +" . s-p^." +- Jt* .h,i,e . Lbe JAcm c,.ed #z-L J4 nlt Vno',t la 2z-- a. r !r{ j\1 -li- !<aea;g .:.ci d *-^ r.l> 9 u i1, -Ih.^ g drq. sL- i^- qz,a@s sd1,. ar oh +a E^4"7',']4.,* <,,,

\r f

.,, J cls.els p..d p, +al-c, 1 15,teJ= la"- th.** -cld,-,j-i.h, 5 L 34.," J-/; 4a eprt tu> >...u+i ?^ 1* t,^o"<2* 'h'k.,"1 rt ,,r1., Ju a^1 *.-;*; I ',"t--".,1-"^" p-;atoJLLol ta d U. ;J. h 6l ;+ ,_*i. ,_.p4 t ho,,z ")-a-" ^"t L4a5><d d\,^( +.-- th< otSan-c, b 4: "2,-.-i ,.1,"u. '?n ; 4. e4h<^oL uilL e-" pc'r'o L -$.e-1, , s-, g )"4.a;+ ra'.&- b",t-,to.,,- ?l"sL t^' h*. *A< &'3t> /1.'A'.-, J<--p.-a.h,rt e
h<'"+

t
R

"*

{
3'

,-,'*xo l\.'\
\-lr*/

s +t'q (,* z-.q;r-r -la.;h i] A.-+'t b"+ ^"+ k+ i+ .< -.A gg-.ao, t fir- .+a^"wl 4a* r crv',a tnJ pn -lne C {1, t:f , lo g<,r *+1-t lr L-r" ,i ''' he s<-p^ra*.d v.ia f-^d;a. r ^ [ cLrge\ lleh^, but .hrs o5''n'<' CUz Ciz r*i/,( e-- oora}<, -11,-51, sa e,*V aaarl ,.;tl b- *y'- lr2,-rl .rA.1t, k{t (^ *hz brn-4.-^a f iasL a,, )"ik .".< c'*. +:.-"/t, hocg <n4 o -4t-c" 1e d-!A O, )7. "^ f'r.4;hJai'! -tAL f.r.4;h_iax a-t < -a,9"C 4<:^p-e-.-c1.itr< tt.l 4-rALe-.,a.D"<
i<-ocA
e

e'Lt "{:--s '/"-f * (t" tZ ' wt< '';4t\'a J '.',n oaa *a,4.) and >,''' 1' -4to1@tL1 ) iJ:< t+ i, tJ&, "5','':' 4 L*.r,^ o" d ta,p* \ d^-/aea4 -f;,.?t )^_+" t*ct * t^i j ,, at, +""nr,. n.,*-"u,1 I '' q da-r ,\. ><-V.l,,el-t'"- L4rJ ,i oti'o':v'" i'l +t- azt/< zt';s ltfz <^J +r-- .ii,-ta',-^{) -. /a)z-s,
(,- n.mJ, b,.ro;,
mp 4O'C
t>? 2+5 "c

(+ ., ne,*, s;rak t< w,;>h

\.-\./

,.:c( '"
-+

-".^\,r^ rdap'*^-:,!t*r/l tni;"W \*''''

no p i^lhq

b'*

\-/ .. r_\'glb . ,\

la)

(p-+"i"ic d.,'J ,

o,;i

,P

(j

+tc^'l-,-\')

"t/-phz'^'7| ut+,|- s-L-L,.1,1., < .laa /, ii 4ooh.l

i**^-, * ace-tn mi dz

Eaa-t'v+e

^',

,,),yo,, -f -"

65 J ot:o^',t",o
-7(rz X I
:/ o''
\1

?i!hl.""I* I

^rrr,ll)1,
hLv ,ej t'1-o1 (ortfou\J' Y"To'

,o=,,Jr6,^.
tn'
I

b'-o-'^^

P: t r)/ft(

r
G'A PoLtu

aa '<* s-a o. t 5 V k, ' -4 a- loac, f,t ,, ar ZZC

e1'c ^o-

t 04

i;(

gt'"da 1$9t P.?,r'^

9. a,\..." r ' ./ r

lstt'l-."noul

'o:

(5 pts.) How wduld you separate a mixture of ethanol and benzoic acid? frow would you purify a sample olnaphthalene contaminated with sodium chloride. Draw their sliructures and provide r: reasonable and practical .raa

/f \-u *i
ifl

*X'!fY

rr."',!,11[,
-,i 1,, a

procedure! -,.-l: ,,..,r,n,-,. | , t.J . or)t) ) .-L f* rar",T, bp

,-;, I*.-.\i*^t..."t ,.f^..*", i

or;!-l,it
np ' 1'C

]s,'a ,^p '')t ] C

ta ,,4 ,y ,.r r< ;., /, ,- tl

.^e. J - oj u"u...-,t.

*'"[:

::lt;f:;:'

'^?o.t",f**,""urrAhasgivenyouamixtureor4-methyrb"Jij";fl*l;j

,3d organic.olrcnr. I tplet}e tr' ,$lq 11' t.hi9 i5 c b'><, s,q m a qo :...d. bo><, ..,j ,l .,.tid, *t ,/,.. cl n , i'r.^^7.a, r.t ,"-.r..^J. i,d'ua.t n"jr-iv ,rr+ 6t: ' i,.. ",L.1 -i.,-') ^w,-. ,rl1 ).-3c^rr "nJ '-ie i{ lo r"
l*t'tt

acetanilide. Describe how would you separate the individuai components of this mixture (It is desirable that you show the scherne ofthe separation process). Draw the structue of tle products, provide all the relevant rcactiolls and provide the solubiLities ofall chemical species irvolred. in uarerard d.e r3ror!

ftfi|;i"!;::;:;'
Y"

d";,,,I,.ra;a.4-r,-.tu.,}^i(tit, I.e.1d sub:1-nc,s, f,'.i^L lAe aatr .,th< a2eo-,e 1c'tl ]Aen e<,:Jrat| Ihz l",y-, ,f. y -.+;",5 e-,ircc!; t>, 3,h.-.1. a '"qr+JU1. ?l<& 4" q2,<.'' pheL i. q,1 t(L b<-tA 4;11 t,-p 6o-c) ^ft -r1'-,',..i. -G q.r.r.4 isala.k lAe aJ,l ..1-t"\a+(ar) enL e- d-.', c,t .taq . i.i",, e !"f , '-r.+,U 4<. 'To
Lr1*"1>ln"p .|ga.c1 <,'< ]a.^,,,!, khi.,t, ao,]-n-^ tx.i"J.,1 letct.L^,.'-.- + l,iq6aa. j+1 c) ! s;^plj t-'x'-o* 4 I c6hpz'nd (bp .rs. laJe uu+o^;1,A", +'t,. n,n,..*u , nib( .,,,.-? 1t I rt )> t ) tr, ,.-t .n. lr-+ L2-^ ..-t.,,ntJ to vx ;) t't,, ", ',t kap+-'.t-n h". A -, "', ';"t''.L,t Le, "-P.,1'4 rb, ", i.1't4'c) a61q,.;iidr soriJ 1rp (!e9u a-l al,l co-r, kQ,

11.

(10 pts.) Draw the shuctues ofthe following b)

compounds:

v[r*"
\e

pi\

XZ.

^ -CHz-c4- cH?-c l9r ir. D.

a) l-bromopenlale

a\ , \-<,

benzene

(;',""

c) hexanenitril?

"' ,1,1 v "

d) dimethylsulfoxi de^

ettta

ti' i
cu'."'/+" "v

e) ammonium

chloride

1)

tetrabutylammonium chlo de

g),{N-dimethylformamide

!"V

''^""

,.)e (t!'+Lf !(t1' t u,, u.,u.ff.91y n..',,, u,

cl+L(

C+s ,t
Crl
j)

X/., pa

2'

"11

Lt+? c4 3

h) benzyltriethylammoniurn clioride

i; t s-".o*''-e -."/"t

hexamethylphosphoramide

/:? \:_2'tt-U - C L+.clJ. t' ch,ct!-

''.-.,''.'' l-'-n'-J

t9.,
./t),

/-t \)
LC\

b --1

(.itt

Ci.. \___//^
/

)"-f=ol
ci,,
'
H)

, c u, r'J-/ |

:*at
V\z 12.

(.oa

iu

trs$

S*,',r^9 ,, \r_co,.sa

VT cr?,

pv

tte

o+d

r:,

0i$\t0&l

CcH1.
t
+

(10 pts.) Draw the product(s) of the following reaction. Classify this reaction. What kinds of solvents would dissolve KCN, and whal kind of solvents would dissolve l-bromopentane. Will this reaction take place in methanol or ethanol? Provide explanatioD! This reaction can be perforned in dimethylsulfoxide in presence of heat (a). Also, this reaction can be carried out in mixtrue ofwater and benzene. with addition of tetabutylammonium chloride (b). What is the role of tetabutylammonium chloride in the reaction (b)? Could tetabutylammonium chloride be replaced by 18-crown-6-ether? Which of the three option would you choose to calay out the transfomation shown bellow and why? a) LIrr '+

-\-/-.\--.-.'.Br

KCN

b)

>

.y^'r-.

=AJ l.'Br

'"'' ; bfii(6j"4'" "'' b16.o".n, Hro, ffilcurcHrcHrcn,yu cP a" .u?ai" 1 , JJ "' r .tr-ir< sra,', )h<,, -tt .! e ph.x _.+\^,k.:,c,.-i.-t"t,+t/ ii\!."2.t::^"",.h 'tt',."/. rt'' ' nl.! c ,),;, F-.+
r'/r

i^.-

'

itl)".-',[' *:.;i I l_ - L .;,..-' f.;;,1;1 '".i 1-''r'' 'I la-aqn,t

13.

:,' -"".',:^?,;,."1;, il: :;)^';;:i":"" .",i p..r"-,,- ^:9".: n--k.eA,I,. *;(,;"a^.

'"n

/1".

"l "

' '"

p,',s

,....

j/-.*

,I
I

:zwlt

L''

[, pi'^'i ry";

L,|

"+,..

..t+o,"t

(10 pts.) The compound A, CsHs, bp 744146 "C is insoluble in water, but soluble in HzSO,r The compourd discolors the solution of Brz in CII:C1:. Witb aqueous diluted KMnOa, it reacts at ambient temperatue giving brown precipitate. When treated with hot concentrated I(MIO+, followed by acidification it gives compound B, CrHoOz, lvhich is white pecipitate (mp I2O-I22"C). The IR and mass specta ofA and B are given bellow

a. draw the structues of A and B b. what is the structue of the product obtained by reaction of A

with

Br2?

(n

n'' '.lr.r,ez> c+ rir )

1",
"",

Ptz

e7.a.l--m: ,r., l-,^i. rl ..lL>n-" a=a-r

2z.oa

-.--" =) :),.*i;I;-e{ir.,-qr,.a.r th"tt

.j- .)so

-.2r.:,,.-.
^'t

tt.- teetrlt.,.

(:( oa',., pr';l " lt a ttd ^ r,,L

o,

i!r',^-" [i'?t:::
J2-ql..r,J-(

tii_;;:rt
!4-) -

' ,.1 '

")c

tlr"''\ A

/"ln,.-:i..,

(
a,;.171

<i>o " p="L o1 5 -. )t-.L[

Ca
t16

i'

.t ^. "
- b.
1",

. lle

rz < s...1-a

C7

r,: i;),. b",,t*,

r(t t. -. - >&-)

o.;,1

rt-t

P: ,P. 6.-..,:,,.:\*". Jt \l h;\ ,.^ b.' )tttc"' -

.:)u -r,.d "^' ,nJ ".''1 , c'+eJ-,t*q e^ ' , 'f " <_

,".,.- ljofl,.SiF,X-.

l?ocr.--

i.e+. tl'-! {ih i^ 1

tn

iP

q}

,ti1r

t-

o
D

T l
-t.

f"

P
+ \
t)

FT-lR spectrum of unknown A (liquid lilm, NaCl plates).

Electron impact (EI) mass spectrum of unknown A (70 e\.).

FT-IR spectrum of unknown B (KBr pellet).

J
y.

.*.
-o

Electron Lrccrr ur rulpa(t impacl {t[) m:t\\ \pccf spectrum rum of oT uDKnoyli\lt unLno$AB (70 | /u e\ e v ). I Lt t mass r.

2,L

d;^rt-"h g J,.+zi

Ae-t, c

l,:e:

(J7--1i Lr4t'1?-

,.t-r'),c'., - iJ\cH3

11.

(10 pts.) The compound C, CrHr+O. bp 150-152';iz, density 0.811 g/cm3 is insoluble in water, but soluble in H2SOa When compound C is added to basic KI/I2, a yellow precipitate with mp 122-124"C is fonned. Witb the 2,4-dinitophenylhidrazin it gives reddish-yellow precipitate (mp 88-90 "C), but it does not react with'follens reagent. The compound C fonns senicarbazone derivative (mp 126-128 oC). ,--r,.-nA

)inc. J!."

A*;

,tht .,. ;+ b.Identifythe yellow precipitate with mp 122-l24oc 2 '\t"he ,i+t5 h'i br P1u'r L'+"' c. Draw the structrue of2,4'-dinitohydryzone derivative " -+hQ+ -nr.'tt"t C+rof -4n > p,<L;p;leJ< -rm > *,. +r+ ij L.j{J np = 4zZ'c , ,i e.r^ i^r' i x._p,." d 42,+..1 p,.);,h-reb 'l+ b?.a! a "-,4t42 lp

a. whar is the structure orcompound

c?

ir": T":*.""'"f& l;"lli"'":'tt"" '

7-s4rt 1,t'^

ck-iva.)-. rs !,,.,,-- i L, b,,t1 t.+{'+- a-d ',,l.L, hJ *;/ eo,^p,r,,'] d 6., CU1-Cl-la- cr f+"- C-Nz -C-t+,-cl'- ap3, 2 h.p+"^"ngl b, 'tol'C 15. ( 0 pts.) Severa] physical prcperties of an ulknown ester were experimentally determined: boiling
1

d-^. Lrt 7r.11ta;L." i+ 't'? Pft''p +..+ )A< *" h'awe ."n qr"ao'lc E++)hr, 'i.A "+ p.t c;p;4a-< i, rn.../-t ,uztt -L/",1"+,.. r. e!rpAeJ--c. J,<rv;c".L"+*." ",-,sA

,1 ,7r,,. ";'

la a.A)'

'-.'.-,L,

z.

a
H - /tJHf<

point, refiactive index and density. Using these data and catalogues and handbooks indentify the 1H NMR and i3C NMR unkno\an ester! (In order to confi1m your choice you are provided with spectra recorded at 90 MHz and 25 MHz accordingly in CDC13.)

e -C -O rn

B oiling poitrt

Refractive index
1,.37'.13.."

"., >zdzt .+

0.8718

r/-1,-d_^
LUe

,", /

i:.t'
O..l?

3, e5>

.1ft ro-.r.,4,

LA<t L ih -r11

'<

J D ,-l
t)
$,
D

N
tr -t o s

>

11

109
rH

5
ppm

3Z

NMR spectrum of unknown ester (90 MIIZ, CDCI3)

lrC NMR spectrum ofuuknown ester (25 MIIZ, CDCL)

tl 2AO 1aO 160 140 120 100 80 . w"t

60

40

zo

=:::_==-:::
End of exam