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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
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]