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ALL ABOUT SOLVING PROTON-NMR

Whatis1HNMR?
1
HNMRisNMR(NuclearMagneticResonance)spectroscopyinwhichtheprotonnuclearspinis
manipulated.Itrevolvesaroundtheideathattheenergyrequiredtocausenuclearspinflipisa
functionofthemagneticenvironmentofanatomsnucleus.

HowcanwefindstructurefromNMR?
WefindstructurethroughtheinformationNMRrelaystous.Thesepiecesofinformation
include:
Numberofsignals[whichisthenumberofnonequivalentprotonsetsinamolecule]
Positionofsignals[alsoknownaschemicalshift,whichisthemagneticenvironment
inwhichprotonsarein]
Relativeintensityofsignals[alsoknownasintegration,whichistheratioof
equivalentprotontypes]
Splittingofsignals[alsoknownasspinspincoupling,whichistheamountofproton
neighborspresent]

Howtosolvefornumberofsignalspresent
Thenumberofsignalsdependsontheequivalencyofprotons.Protonsareequivalentifthey
havenucleiwiththesamemagneticenvironment.Inotherwords,theyhavetobethesamein
everypossibleway.Itiseasiertofindnonequivalentprotons.

TheprotonslabeledH
aare

equivalentbecausetheyallare

connectedtoacarbonthatis

connectedtotwohydrogen

atoms.Theyarethesamein
everywaypossible.

http://www.chem.ucla.edu/harding/index.html

Withinthemoleculedepictedabove,therearethreedifferentsignalspresent,inthatthereare
threedifferentsetsofprotonswithdifferentequivalencies.Ha,HbandHcareallnonequivalent
tooneanother,thusproducingthreeseparatesignalsontheNMRspectrum.

Howtosolveforthepositionofsignals/chemicalshift
ChemicalshiftisdefinedasthepositionofasignalinanNMRspectrum.Itisdependenton
differentinfluences,suchastheEofthespinstateenergy(whichiscontrolledbythe
magneticfieldatthenucleus),andelectronegativity(aschemicalshiftincreases,
electronegativityofatomsneartheprotonincreases).Thepositionsofsignalswillbegivento
usonatestsoITISNOTMANDATORYTOMEMORIZETHEM!

Thistablewillbegiventousonanexam.
Chemistry14CLectureSupplementPowerPointCD

ChemicalShiftTrend

RCH3<RCH2R<R3CH(becausetheelectronegativityofCinR>electronegativityofH)

Howtosolvefortherelativeintensityofsignals/integration
IntegrationisthemeasurementofpeakareasontheNMRspectrum.Itcorrespondstothe
amountofenergyabsorbedorreleasedbyallnucleiparticipatinginchemicalshiftduringthe
nuclearspinflipprocess.Itisusedtodeterminetheratioofhydrogensthatcorrespondtothe
signal.Itisproportionaltorelativenumberofequivalentprotons.

NOTE:Integralsdonotalwaysrelaytheexactamountofprotonspresentwithinamolecule!

Example:
Inthismolecule,therearethreesignals,A,B,andC.Intheentirestructure,one

canseethatthereare14hydrogenatoms.
B

Acontains9equivalentprotonsinitssignal
A

Bcontains2equivalentprotonsinitssignal
C Ccontains3equivalentprotonsinitssignal

Inordertodeterminewhattheintegralisforthesethreesignals,setthesignal

withtheleastamountofprotonsasanintegralof1.Inthiscase,Bwouldhave

anintegral=1.Theratioisthensetto2:1,inthat2hydrogenatoms
A
A

correspondstoanintegralthatequals1.Thismeansthatyoumultiplythe

numberofhydrogensby.Youcanthenapplythisratiototheothertwo
Chemistry14CThinkbook

signals.

Ahas9hydrogens,soitsintegralwillequal4.5
Chas3hydrogens,soitsintegralwillequal1.5

Howtosolveforthesplittingofsignals
Spinspincouplingisdeterminedbythenumberofmagneticfieldsaffectingthenucleusofa
molecule.ThiscausessplittingoftheNMRsignals.Thegeneralruleforsplittingisthesignal
foraprotonwithnneighborsissplitinton+1lines.

Therearesomerulesandrestrictionswemustfollowwhenworkingwithsignalsplitting:
1. Onlynonequivalentprotonscancouple
Ifprotonsareequivalent,thentheydonotcouple
2. Protonsthatareseparatedbythreeormoresinglebondsusuallydonotcouple

Inthisexample,HaandHddonotcouplebecausetheyarefour
bondsapart(seeredbonds).However,H andH cancouple
a
c
becausetheyaretwobondsapart(seegreenbonds).

Chemistry14CLectureSupplementPowerPointCD

Pibondsdonotcounttowardsthebondlimit,butthesplittingconstantJ(whichis
thespacingbetweenlinesinasplittingpattern)maybetoosmalltosee,soitmay
bethere
Forpurposesofcoupling,justpretendthepibondisntthere[ITSAFREE
SPACER]!Tobesafe,adda+1totheamountofbondscountedexcludingthe
pibond.
Benzeneringscountasonebigfreespacer
Allprotonscouplewitheachotherbecauseofresonance
Jmaybesmall
Thinkofbenzeneasagatedcommunityhydrogenatomsbondedtothe
benzeneringcanonlycouplewithotherhydrogensbondedtothebenzene
ring.Theycannotbondwithotherhydrogenspresentinthemolecule

Thehydrogenatomspresentinthemethylattachedtothebenzene

ringcannotcouplewiththehydrogenatomsbondeddirectlytothe

benzenering.Thehydrogenatomsbondeddirectlytotheringcan

onlybondtootherhydrogensattachedtothering.

Chemistry14CLectureSupplementPowerPointCD

3. SignalsforOHandNHareusuallysinglets

Example of how to solve an 1H-NMR Spectroscopy


problem

Wecandeducealotfrom1HNMR,especiallythemolecularstructureofamolecule.Here
isanexampleofatypical1HNMRspectroscopyproblemwhenthemolecularformulais
given,andthestepsyoutakeinordertosolveit.

Formula:C6H14O
HNMR:3.3ppm(triplet;integral=1)

1.6ppm(sextet;integral=1)

0.90ppm(triplet;integral=1.5)

1. ThefirststepistocalculatetheDBE(doublebondequivalency)value,whichwilltellushow
manypibondsarepresentorifthereisapotentialbenzeneringpresentinthestructure.
DBE=#ofcarbons(#ofhydrogens2)+(#ofnitrogens2)+1
=6(14/2)+(0/2)+1
=0(thismeanstherearenopibondswithinthestructure)

2. Knowingthattheintegralisproportionaltotherelativenumberofequivalenthydrogen
atomspresentwithinthestructure,wecanusetheintegralinformationgiveninthe
problemandthenumberofhydrogens,alsogivenintheproblemthroughthemolecular
formula,tofindthefactorinwhichtomultiplytheintegralbysoastodeterminehowmany
hydrogenatomsarepresentwithineachsignal.
Thefirstsignalhadanintegral=1
Thesecondsignalhadanintegral=1
Thethirdsignalhadanintegral=1.5
Ifyoumultiplyeachofthesenumbersbyafactoroffour,thenyouget:
4hydrogenatomsforthefirstsignal
Addingalloftheseup,weget14hydrogenatomspresent,
4hydrogenatomsforthesecondsignal whichisequivalenttotheamountofhydrogensgivenin
theformula,soweknowwefoundtherightfactorto
multiplyby.
6hydrogenatomsforthethirdsignal

3. Nowyoucandeterminetheimplicationsforeachintegralandsplittingpattern.
Beforeyoufindeachimplication,youneedtofindthenumberofneighborseach
signalhas.Thisisrevealedthroughthesplittingpatterngivenintheproblem.

Thefirstsignalisatriplet.Fromthegeneralrulestatedabove,thesignalfora
protonwithnneighborsissplitinton+1lines.Becausethereare3splitsinthe
signal,thismeansthatthereare31neighbors,whichequalstwoneighbors.

Thesecondsignalisasextet.Thismeansthatthereare61neighbors,which
equalsfiveneighbors.

Thethirdsignalisatriplet.Thismeansthatthereare31neighbors,which
equalstwoneighbors.

Nowyoucanfindtheimplications,whichdealwiththeCHskeletonofamolecule
(orNH/OHiftheyarepresentintheIRspectrum/molecularformula)

FirstSignal:hastwoneighborsmeansthattheunderlinedCHpartofthe
skeletonthatwearelookingathastwoprotonsasneighbors

2x:CH2CH2
2x:CHCH2CH
**The2xand4xbeforetheCH

skeletonrefertothefactorinwhich
Twoneighboring
Twototalneighboring
youmultiplythenumberof

protons
protons
hydrogenatomsunderlinedby.This

willgiveyouthetotalnumberof
4x:CHCH2
4x:CHCHCH
equivalenthydrogensyoucalculated

beforeinStep2.
Twoneighboring
Twototalneighboring

protons
protons

SecondSignal:hasfiveneighbors

2x:CH3CH2CH2
4x:CH3CHCH2
4x:CH3CH(CH)2

ThirdSignal:hastwoneighbors

2x:CH3CH2
3x:CH2CH2

3x:CHCH2CH
6x:CHCH2
6x:CHCHCH

4. Afterfindingtheimplications,youthenlookatallofthemandfindthemostlikely
implicationthatwouldmakeupamolecularstructure[MOSTLIKELYSTRUCTURE=LEAST
NUMBEROFATOMS].Alwayslookforthesimplestimplications!Additionally,lookfor
implicationsthatcanbeeliminatedbasedonvalidity(YOUCANNOTHAVEACARBONWITH
MORETHANFOURBONDS!).

Bothofthese
implicationshave
CH3CH2inthem,so
wecanassume
theyarepartofthe
molecular
structure.

FirstSignal:
2x:CH2CH2

SecondSignal
2x:CH3CH2CH2

2x:CHCH2CH

4x:CH3CHCH2

3x:CH2CH2

6x:CHCH2

BecausetheimplicationscircledgreenbothhaveCH3CH2in
themandcanthereforebeconfirmedaspartofthestructure,
wenowneedtofindafinalimplicationthatwillcoincidewith
them.Becausethisimplicationisverysimilartotheoneswe
havealreadypickedout,andbecauseitcontainsaCH2CH2,just
liketheimplicationfromthesecondsignal,wecantherefore
concludethatthisisthefinalimplicationthatwillmakeupour
molecularstructure.

4x:CH3CH(CH)2

ThirdSignal:
2x:CH3CH2

3x:CHCH2CH

Thesecannotbepossibleimplications
becausetheyaretheonlyimplicationsthat
aremultipliedbyafactorof3.They
thereforecanbediscarded.

6x:CHCHCH

Thesecannotbepossibleimplicationsbecausetheyform
hexavalentcarbons,andcarbonscanonlyformfourbonds.

5. Nowweknowthatourmolecularstructureiscomposedofthreeimplicationsthatmakeup
2CH3CH2CH2structures.ButifyoulookatthecircledimplicationfromtheFirstSignal,there
isanattachmentonthefirstCH2(CH2CH2).Thismeansthatsomethingattachestothis
carbon.

Ifwelookattheoriginalformulagiventous,weseethatwehaveaccountedforeverything
excepttheoxygen[thereare7hydrogenatomsx2=14hydrogenatomstotal;thereare3
carbonatomsx2=6carbonstotalthisishowmanycarbonsandhydrogenswereinthe
givenmolecularformula].Nowwehavetoaccountfortheoxygenatom.Becausethereis
anattachmenttotheCH2,wecanattachtheoxygentothiscarbon.Ourstructurewill
thereforelooklikethis:

CH3CH2CH2OCH2CH2CH3
Andtheresyourmolecularstructureforthemolecule!

Note:Makesuretocheckyourwork!Checktheformula,integrals,numberofsignals,
splitting,etc.andmakesuretheyareallcorrect.Alwaysperformanatomcheckand
compareittotheformulagiven.Additionally,checktoseeifyourstructureagreeswiththe
DBEforthemolecule.

Nowletsdoanotherexampleinvolvingmassspectroscopyandinfraredspectroscopy.

Massspectrum:m/z=154(M;100%),m/z=155(11.23%),andm/z=156(0.26%)

IRspectrum:

HNMR:2.1ppm(singlet;integral=2),1.9ppm(singlet;integral=1),and1.1ppm(singlet,
integral=6)

1. Wefirstneedanalyzewhattheinformationthemassspectroscopyistellingus.Thefirst
m/zvalueistheMpeak,whichtellsushowmanynitrogenatomsarepresentinthe
molecularformula.Ifthem/zvalueiseven,thentherearezerooranevenamountof
nitrogenatoms.Ifthem/zvalueisodd,thenthereareanoddamountofnitrogenatoms.

Inthisexample,theMpeakhasanintensityof154.Thisisanevennumber,sothere
are0oranevenamountofnitrogensinthestructure.

ThesecondvalueistheM+1peak,whichtellsushowmanycarbonsarepresentinthe
structure.HowyoufindthisisbydividingtherelativeabundanceoftheM+1peakby1.1%.
MAKESUREYOUDONOTDIVIDEBY1%;THISWILLNOTGIVEYOUTHERIGHTANSWER.

Inthisexample,theM+1peakrelativeabundanceis11.23%.Youdividethisby1.1%
andyouget10.209%.Thismeansthatthestructurehaseither10or11carbons.

ThethirdvalueistheM+2peak,whichtellsushowmany(ifany)bromine,chlorine,or
sulfuratomsarepresentwithinthestructure.Iftherelativeabundanceisapproximately
4%,thensulfurispresent.Iftherelativeabundanceisapproximately33%,thenchlorineis
present.Iftherelativeabundanceisapproximately100%,thenbromineispresent.

Inthisexample,theM+2peakrelativeabundanceis0.26%.Thisdoesnotcorrespondto
anyoftheabovestatedelements,andistoosmalltobesulfur,sothereisnochlorine,
bromineorsulfuratomspresentinthismolecule.

Wecannowusethisinformationtofindamolecularformulaforthisstructure.

C10Possibility
154(12amuperCx10C)=34amuleftforhydrogen,nitrogenandoxygen

O
N
H
Formula
Doesitwork?

0
0
34
C10H34
No,violatesHRule

1
0
18
C10H180
Acceptable

2
0
2
C10H202
Acceptable

0
2
6
C10H6N2
Acceptable

Inthiscase,wecanruleoutC10H6N2becausetheIRspectrumshowsthatthereisacarbonyl
inZone4,thusrevealinganoxygenintheformula.C10H6N2lacksanoxygen.Youcanalso
ruleoutC10H202becauseitdoesnotcorrespondwiththeintegralsgiveninthe1HNMR.
Theintegralequals9(2+1+6),andH2isnotaproportionateratio.Thatleavesuswith
C10H180asourformula.

C11Possibility
154(12amuperCx11C)=22amuleftforhydrogen,nitrogenandoxygen

O
N
H
Formula
Doesitwork?

0
1
0

0
0
1

22
6
8

C11H22
C11H60
C11H8N

Acceptable
Acceptable
Acceptable

C11H22andC11H8Ncanberuledoutbecausetheylackanoxygen.C11H60canalsoberuled
outbecauseitdoesnotcorrespondtotheintegralgiventousonthe1HNMR.

Therefore,ourfinalformulaisC10H18O.

ThelaststepistocalculatetheDBE:10(18/2)+(0/2)+1=2(possiblytworingsor2pi
bondsoraringandapibond)

2. NowwehavetoanalyzetheIRspectrum.Wedothisbylookingateachzoneandseeingif
therearepeaksthatcorrespondtodifferentfunctionalgroups.

Zone1:
Zone2:

Zone3:
Zone4:
Zone5:

AlcoholOH:absent;nopeakpresent
Amine/AmideNH:absent;nopeak,nonitrogeninformula
TerminalAlkyneCH:absent;nopeakinzone3
Aryl/Vinylsp2CH:absent;nopeak>3000cm1
Alkylsp3CH:present;peaks<3000cm1
AldehydeCH:absent,nopeakatapprox.2700cm1
CarboxylicAcidCH:absent;nobroadpeak
AlkyneCC:absent;nopeak
NitrileCN:absent;nopeak,nonitrogenintheformula
CarbonylC=O:present,peakat1716cm1ketone
BenzeneC=C:absent;nopeak,notenoughDBE

AlkeneC=C:absent;nopeak

FromtheIRspectrum,weseethatthereisaketoneandalkylsp3CHbondswithinthe
structure.

3. Nowwehavetoanalyzethe1HNMRgiventous.First,putallgiveninformationintoa
table:
ppm
Neighbors
Integration
#H
Implications
2.1ppm
Singlet
Integration=2

1.9ppm
Singlet
Integration=1

1.1ppm
Singlet
Integration=6

Nowwehavetocalculatehowmanyhydrogenatomsarepresentforeachsignal.When
youaddupeachintegralvalue,yougetatotalof9.Thereare18hydrogenatoms(asseen
inthemolecularformula),soitisa1:2ratio.Thismeansthatyoumultiplyeachintegralby
2togetthenumberofhydrogens:

ppm
Neighbors
Integration
#H
Implications
2.1ppm
Singlet
Integration=2
2x2=4

1.9ppm
Singlet
Integration=1
1x2=2

1.1ppm
Singlet
Integration=6
6x2=12

Nowwehavetofillintheimplications:

ppm
Neighbors
Integration
#H
Implications
2.1ppm
Singlet
Integration=2
2x2=4
2x:CH24x:CH
1.9ppm
Singlet
Integration=1
1x2=2
CH22x:CH
1.1ppm
Singlet
Integration=6
6x2=12
12x:CH 4x:CH3
6x:CH2

Thecircledpiecesaretheskeletonsthatwecanseearepartofthestructure.Theywere
eachchosenbecausetheywerethemorelikelyoftheimplicationsassignedfortheir
specificsignal.

4. Nowwehavetoputthepiecesalltogether.
WeseefromtheDBEthatwecouldhavetwopibonds,tworings,orapibondanda
ring.TheketoneusesoneDBE,sowehaveoneleft(eitheraringorapibond).
WeseefromtheIRspectrumthatwehaveaketoneandalkylsp3CHbonds.
Weseefromthe1HNMRthatwehave4x:CH3,2x:CH2andaCH2.The2xCH2will
bemoredeshielded,whichisevidentbytheirhigherppmvalue.Thismeansthat
theywillbeclosertoanelectronegativeatom,suchtheoxygenintheketone.

TheblueCH2groupsare
closesttotheketonebecause
theyaredeshielded,asseenin
theirppm,thussuggesting
thattheyareclosetoan
electronegativeatom,like
oxygen.

Andheresourmolecularstructure!

Note:Makesuretocheckyourwork!Checktheformula,integrals,numberofsignals,
splitting,etc.andmakesuretheyareallcorrect.Alwaysperformanatomcheckand
compareittotheformulagiven.Additionally,checktoseeifyourstructureagreeswiththe
DBEforthemolecule.

TrialanderrorishugeinsolvingprotonNMRproblems.Themorepracticeyoudo,thebetter
youwillbe.PRACTICE,PRACTICE,PRACTICE!

Goodluck,andIhopethishelped!

WorksCited

Dr.HardingersChemistry14CLectureSupplement
Dr.HardingersChemistry14CLectureSupplementPowerPointCD
Dr.HardingersChemistry14CThinkbook
http://www.chem.ucla.edu/harding/index.html[IllustratedGlossary]