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1HNMRspectra
chemicalshiftandintegrationsummary
Twodifferentsignalsof
equalintensity
Twodifferentsignalsof
in1:3ratio
Thesignalintegration
isshownasa
curve,ora
value underthe
TMS
baselinelikeinthis
spectrum.
TMS
104
1HNMRspectra
2.SignalIntegrals
20.5
Thesignalintegration
valueissometimes
shownunderthe
baselinelikeinthis
spectrum.
Hereweseethreedifferentenvironments.Roundingoftheintegration
valuessuggestsa5:2:1ratio.Why?
Quickinspectionofthestructuresuggests5differentsetsofequivalent
protons;OH(1),CH2 (2)andtheoArH (2),mArH (2)andpArH (1).
However,thearomaticprotons(oArH,mArH andpArH)allhavevery 105
similarchemicalshiftsandoverlap toappearsasonepeak at 7.5.
20.5
RealWorldExample5
MagneticResonanceImaging(MRI)isessentiallya
specialNMRtechnique.Looks atwaterintissueby
measuringandquantifyingvariationinrelaxationtime
thesocalledT2 ofthenuclearspins.Thisvalueis
heavilydependentontheenvironment pathological
tissues(e.g.tumours)givedifferentT2 fromnormal(e.g.
brain)tissue.
Brain
tumour
106
20.5
Example11
Whichistheorderinincreasingchemicalshiftvaluesin
the1HNMR spectrumfortheindicatedhydrogenatoms
(lowestfirst)?
a.IV,II,III,I
b.I,III,II,IV
c.IV,III,I,II
d.II,IV,I,III
Iisaround2.02.3,IIaround4.14.7,IIIaround1.21.4
andIVaround0.81.0.Hencetheorderis:
IV,III,IandII(c)
107
TutorialQ#8
3.Multiplicity:
Signalsarentalwayssimple
CloseinspectionofsomeNMRpeaksrevealsthattheyaresplit
intotwo,threeormorepeaks
Thissignalsplittingisdueto
spinsontheadjacentsetof
equivalentprotons (e.g.the
neighbouringCH2 group)
108
3.Multiplicity:
Signalsarentalwayssimple
20.5
Asignalmaybesplitintotwopeaks(calledadoublet,d),
threepeaks(atriplet,t),fourpeaks(aquartet,q),etc.
SignalsthatareNOTsplitarecalledsinglets (s)and
complexsplittingpatternsarecalledmultiplets (m).
quartet
triplet
doublet
109
3.Multiplicity:
Signalsplitting the(n+1)rule
20.5
Thesplittingisoftenreferredtoasthemultiplicityofa
signal(atriplethasamultiplicityof3)andis
determinedbythenumberofadjacentprotons.
multiplicity=numberofadjacentspins+1,ie:(n+1)
Threeadjacentspins
Multiplicity=4
quartet
CH2 signal
Twoadjacentspins
Multiplicity=3
triplet
CH3 signal
3.Multiplicity:
Signalsplitting the(n+1)rule
20.5
Thepartsofamultipletarenotthesameintensity they
followasystematicpattern.
111
3.Multiplicity:
Commonspinsystems
20.5
112
3.Multiplicity:
Commonspinsystems
20.5
113
WorkedExample20.14
Example12
20.5
Predictthesplittingpatternforthefollowingcompound
a.I =singlet,II =quartet,III =triplet
b.I =singlet,II =septet,III =doublet
c.I =quartet,II =doublet,III =septet
d.I =quartet,II =quartet,III =doublet
Answer:
I hasNOadjacentproton(s)=singlet(thisgroupistoofar
otherprotons).
II hassixprotonsonneighbouringCH3 groups=septet.
III hasoneproton(CH)onneighbouringgroup=doublet.
HenceI =singlet,II =septet,III =doublet(b)
114
TutorialQ#9
WorkedExample20.14
Example13
20.5
Letsconsidertwomoreexamples.
1) Howmanydifferentenvironments?
2) Fromchemicalshifts,whattypeofenvironmentsarethey?
3) Fromintegration,whataretheirratios?
4) Frommultiplicity,howmanyneighboursdotheyhave?
Molecularformula:
C3H8O
1.00
6.05
Molecularformula:
C4H8O2
1.00
TutorialQ#9
1.48
1.54
115
WorkedExample20.14
Example13
Letsconsidertwomoreexamples.
1) Howmanydifferentenvironments?
2) Fromchemicalshifts,whattypeofenvironmentsarethey?
3) Fromintegration,whataretheirratios?
4) Frommultiplicity,howmanyneighboursdotheyhave?
20.5
HCR
1)2differentenvironments
2)1aliphatic,onedeshieldedbyO?
3)Integralratio:1:6
4)Septet(6neighbours),doublet(1neighbour)
Molecularformula:
C3H8O
HCO
1.00
6.05
Molecularformula:
C4H8O2
1.00
TutorialQ#9
1.48
1.54
116
WorkedExample20.14
Example13
Example13
20.5
Letsconsidertwomoreexamples.
1) Howmanydifferentenvironments?
2) Fromchemicalshifts,whattypeofenvironmentsarethey?
3) Fromintegration,whataretheirratios?
4) Frommultiplicity,howmanyneighboursdotheyhave?
Molecularformula:
C3H8O
1.00
1)3differentenvironments
2)1aliphatic,1adjacenttoO,oneadjacenttoC=O
3)Integralratio:1:1.5:1.5=2:3:3
4)Quartet(3neighbours),singlet(noneigbour),
triplet(2neighbours)
6.05
HCC=O
HCR
HCO
1.00
TutorialQ#9
1.48
Molecularformula:
C4H8O2
1.54
117
InterpretingNMRspectra
Differentfunctionalgroups
20.6
119
20.6
Q:Whatwouldthespectrumlooklike
iftheCH3 groupwasreplacewithH?
120
20.6
121
20.6
InterpretingNMRspectra esters
Protonsonthecarbonadjacenttothecarbonylgroup(C=O)areslightly
deshielded atd2.12.5whiletheprotonsonthecarbonatomboundtothe
esteroxygenaremore stronglydeshieldedatd3.74.7.
Thismakesitpossibletodistinguishethylacetatefromitsstructuralisomer
methylpropanoate.sowhichiswhich?
Example14
OCH :4.7to3.7ppm
TMS
TMS
122
Examples.
Example15
Whatwouldthe1HNMRofthismoleculelooklike?
Step2:Numberofsignals(symmetry?) 3
Step3:Chemicalshifts(typesofenvironments?) 1xaliphatic
2xHCO
Step4:Integration(no.ofprotons?) 1:3:6
Step5:Splittingpattern(spinsystems?) septet,singlet,doublet
20.6
Aplanforinterpretingspectra
Step1:MolecularformulaandIHD
Step2:Numberofsignals(symmetry?)
Step3:Chemicalshifts(typesofenvironments?)
Step4:Integration(no.ofprotons?)
Step5:Splittingpattern(spinsystems?)
Together:Structuralformula!
Letsdemonstratethiswithsomeexamples
Molecularformula
C5H10O
125
125
Molecularformula:C9H12
1)IHD:(9x2+2 12)/2=4
Example16
Therefore,4doublebondsorrings.
2)Numberofdifferentchemicalenvironmentsin1HNMR?
Therefore,5differentchemicalenvironmentsforH
Comparenumberofenvironmentswithmolecularformula.12H
butonly5differentenvironments.
Themoleculemusthaveseveralgroupswhichareequivalent.
126
Example16
Molecularformula:C9H12
3)Lookatthechemicalshiftsofthesignalstoseewhattypes
ofchemicalenvironmentstheycorrespondto.
2xaromaticsignals,1xaliphaticCH3R,2xCHC=Oor
CHAr
CH2C=O
CH2Ar
Aliphatic(CH3R)
Aromatic(ArH)
127
Molecularformula:C9H12
Example16
4)Lookattheintegrations tofindtheratioofprotonsineach
environment.
A:B:C:D:EA:B:C:D:E
1:1:1:1.5:1.5=2:2:2:3:3=12H(togettothemolecularformula)
128
Example16
Molecularformula:C9H12
5)Lookatthemultiplicity ofeachsignalstofindhowmanyneighbours(n+1)?
Zoomofsignals:
s=singlet,
d=doublet,
t=triplet,
q=quartet
129
Example16
Molecularformula:C9H12
Nowputitalltogether:7.50(d,2H),7.17(d,2H),2.60(q,2H),2.36(s,3H),0.8(t,3H)
2xaromaticsignals,eachwith1Hontheadjacentcarbons.Whichoneisit?
Typicalforparasubstitutedbenzene.
1xCH3with2Honadjacentcarbon,
1xCH2 with3HonadjacentcarbonANDattachedtoeitheracarbonylgroup,oran
aromaticring.
Molecularformulahasnooxygen,somustbearomatic.Wealsoknowtherearearomaticsignals,soitseems
reasonable.
1remainingsignal,asinglet,sononeighbouringprotons.
FromchemicalshiftwecanguessCH3Ar
ArCH2CH3
130
Aromatic(ArH)
CH2C=O
CH2Ar
Aliphatic(CH3R)
Example16
Molecularformula:C9H12
Nowputitalltogether:
7.50(d,2H),7.17(d,2H),2.60(q,2H),2.36(s,3H),0.8(t,3H)
CH3Ar
CH3CH2Ar
131
Example17 20.6
Aplanforinterpretingspectra
Step1: MolecularformulaandIHD:
C5H10O:ReferencecompoundC5H12,Oxygen=no
correctionneeded.HenceIHD=1210/2=1.
Outcome onedoublebondorring
Molecularformula
C5H10O
132
132
Example17 20.6
Aplanforinterpretingspectra
Step2: Number ofsignals:
Twosignals.
Outcome twosetsofequivalentprotons.
Molecularformula
C5H10O
133
133
Example17 20.6
Aplanforinterpretingspectra
Step3: Patternofchemicalshifts:
The 1.1isinthealkylregionandbasedon
integrationmostlikelya2xCH3 (possible3xCH2
butchemicalshiftseemsunlikely)
The 2.4isdownfieldfromnormalalkylHbut
consistentwithCH2,mostlikely2xCH2 (or
possibly4xCH)fromintegrationnexttoaC=O
group.
Notethattheabsenceofasignalinthe35ppm
regionindicatesthatthereisnoCH2/CHnextto
theO.
134
Example17 20.6
Aplanforinterpretingspectra
Step4: Integration:
48:33=1.45:13:2.Butbecausewehave10Hwe
concludetheratiomustbe6:4.
Outcome 1.1(6H,t)and2.4(4H,q)
Molecularformula
C5H10O
135
135
Example17 20.6
Aplanforinterpretingspectra
Step5: Thesplittingpattern:
Triplet at 1.1musthavetwoequivalentprotons(CH2)
nexttoitandthequartet at 2.4musthavethree
protons(CH3)nexttoit.
ThisisconsistentwithaCH3CH2 chain.
Withthedatafromsteps14wenowconcludethatwe
havethefollowingfragments:2xCH3CH2 and(C=O).
136
Example17 20.6
Aplanforinterpretingspectra
Together:
Startbyseeingifanyelementsaremissing:
The2xCH3CH2 +(C=O)fragmentsgiveamolecular
formulaofC5H10Owhichmeansnothingismissing.
Nowwejustassemblethesefragmentssothefitthe
data.Tomaintainthesymmetry,weputthetwoCH3CH2
chainsoneachsiteoftheC=O group.Thisgivesus
pentan3one.
137
SpectralExample2
TutorialQ#10,11
20.6
Example18
DeducethestructureofcompoundLwithmolecular
formulaC15H24O.
138
SpectralExample2
TutorialQ#10,11
20.6
Example18
Step1: IHD is(3224)/2=4.
Ringand3doublebonds=benzeneringismostobvious.
139
SpectralExample2
TutorialQ#10,11
20.6
Example18
Step2: Numberofsignals
1Hspectra.Thereareonly4differentHenvironments.
140
SpectralExample2
TutorialQ#10,11
20.6
Example18
Step3: Integration
6.9(s,2H),5.0(s,1H),2.3(s,3H)and1.5(s,18H).
2+1+3+18=24Hasinmolecularformula
141
SpectralExample2
TutorialQ#10,11
Example18
20.6
Step4: Chemicalshifts
6.9isaromatic(Ar)Hx2.MoreC=Ccanberuledout
fromIHDso 5.0isOH.
ThisrulesoutC=Oso 2.3isCH3 onAr.
1.5isalkyl(CH3/CH2/CH),mostlikely6xCH3 (or9x
CH2).
142
SpectralExample2
TutorialQ#10,11
20.6
Example18
Step5: Splittingpattern
AllsingletsThisrulesout9xCH2(or18xCH)
becausetheywouldhavetobecoupled(cause
splitting).
143
SpectralExample2
TutorialQ#10,11
20.6
Example18
Alltogether:
Withtheinformationabovewehaveanaromaticring
with2symmetricalHandoneCH3 whichtomaintain
symmetrymusthavethisarrangement:
Thisaccountsonlyfor7Cof15C.With6xCH3 wehave
2Cmissing.
144
TheymustbequaternaryC!e.g.2xC(CH3)3
SpectralExample2
TutorialQ#10,11
20.6
Example18
Alltogether:
Wehavealltheatomsintheformula.Tomaintain
symmetryweplacethetwogroupsC(CH3)3 oneachside
ofthecentralsymmetryaxisofthearomaticgroupwith
OHontheaxisgivingusstructuresA andB.
Withtheinformationavailable
BOTHAandBareOK
However,Bisunlikelyonsteric
ground(Aisactuallythe
compoundhere).
145
20.6
Aplanforinterpretingspectra
Step1:MolecularformulaandIHD
Step2:Numberofsignals(symmetry?)
Step3:Chemicalshifts(typesofenvironments?)
Step4:Integration(no.ofprotons?)
Step5:Splittingpattern(spinsystems?)
Together:Structuralformula!
Letsdemonstratethiswithsomeexamples
Molecularformula
C5H10O
146
146
Quiz6,Q1
C4H10O
a) Howmanydifferent1Hchemicalenvironmentsdoesthis
moleculehave?
b)Whatistheratioofthenumberof1Hineachenvironment?
c)Howmanyneighbouring1Hdoeseachenvironmenthave?
d)Identifythecorrectmoleculefromthoseshown.
1:3:6
6:0:1
RealWorld:drugs
NMR(incombinationwithmassspectrometry),is
commonlyusedtoidentifyillicitdrugs
FromMS:
O nocorrectionneeded
2x11 + 1 + 2 - 15
N add1H
IHD =
2
= 5 multiple bonds/rings
MW:193.24
C11H15NO2
148
RealWorld:drugs
NMR(incombinationwithmassspectrometry),is
commonlyusedtoidentifyillicitdrugs
MW:193.24
C11H15NO2
5multiplebond/rings
1HNMR(inCDCl )
3
RealWorld:drugs
NMR(incombinationwithmassspectrometry),is
commonlyusedtoidentifyillicitdrugs
MW:193.24
C11H15NO2
5multiplebond/rings
RCH3
ie,aliphaticchain
Trisubsituted
aromaticring
NCH3
(orArCH3)?
OCH2O
CHR
ie,aliphaticchain
CH2R
1HNMR(inCDCl )
3
RealWorld:drugs
NMR(incombinationwithmassspectrometry),is
commonlyusedtoidentifyillicitdrugs
MW:193.24
C11H15NO2
5multiplebond/rings
H2N
Whereisthe
CH2R?Not
correct!
O
CH3
N
H
CH3
CH2 notcoupled, CH
2xCH
3notcorrect!!
2O,notcorrect!!
notcorrect!!
3,4Methylenedioxymethamphetamine(MDMA)
Photo:drugaware.com.au/DrugInformation/Ecstasy/
(ecstasy)
NB:Thisisonlyasimulatedspectrum noneedtocallthepolice,please!
LearningObjectives
Knowthecommontoolsusedtodeterminethestructureof
compounds.
Massspectrometry(MS)
UVVisspectroscopy
Infraredspectroscopy(IR)
Nuclearmagneticresonancespectroscopy(NMR)
GoodluckinyourMidSemesterexam,
andhopetoseeyounextyear
(inSecondYear!)!!