20.

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

InterpretingNMR spectra alkenes

1Hshiftstypicallyfallinthed4.65.7region

119

20.6

InterpretingNMR spectra aromatics

Thisincludesbenzeneandotherrelatedcompounds.1H
shiftstypicallyfallinthed6.58.5region.1Hsignalscan
bequitecomplexduetooverlapand/ormultipletsignal
splitting.

Q:Whatwouldthespectrumlooklike
iftheCH3 groupwasreplacewithH?

120

20.6

InterpretingNMR spectra aldehydes

Thealdehydeprotonappearsdownfieldatd9.510.1.Asthereare
noprotonsontheneighbouringgroup(C=O),aldehydesignals
normallyappearassinglets.

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)

UnderstandhowMS,UVVis,IR andNMR canbeusedto

identifydifferentfunctionalgroupsorstructuralmotifs.
Interprettheinformationprovidedbyspectrawithfocuson
combininginformationfromdifferenttechniques(e.g.IR and
NMR).
Becomeawareofadditionaltoolsalsoavailableforstructural
determination.
152

GoodluckinyourMidSemesterexam,

andhopetoseeyounextyear
(inSecondYear!)!!