20.

Sowhatinfodoyouget?
DoesthecompoundhaveanabsorptionintheUV
visibleregionoftheelectromagneticspectrum?
Yes indicatesthatthemoleculecontainsconjugation.
No indicatesthatthemoleculedoesnotcontain
conjugation.

45

TutorialQ#3

20.7

Example7
Whichofthesecompoundswouldyouexpecttobe
UVvisactive?

A,CandEareallconjugatedandwouldbeUVvis
active.BhasonlyonedoublebondandinDthe
twodoublebondsaretoofarapart thereisno
double/singlebondalternatingpattern hence
theyarenotconjugated.

46

RealWorldExample3
PlasticsolarcellsattheCommonwealthScientificand
IndustrialResearchOrganisation (CSIRO).
Theseconjugateddyesare
mixedinaplasticfilm,
similartoourbanknotes.

47

RealWorldExample3
PlasticsolarcellsattheCommonwealthScientificand
IndustrialResearchOrganisation (CSIRO).
Theseconjugateddyesare
mixedinaplasticfilm,
similartoourbanknotes.

DrScottWatkins
Teamleader,OrganicPhotovoltaicsCSIRO
B.Sc.inChemistryUNSW1995
B.Sc.(Hons)inChemistryUNSW1996
Ph.D.inChemistryUNSW2000

48

20.3

Infraredspectroscopy
Correspondstotransitionsbetweendifferent
vibrationalenergylevelsinamolecules.

49

20.3

Whatarethesemolecularvibrations?
EnergiesassociatedwithIR radiationcausemolecular
vibrations,eitherofthewholemolecularorindividual
functionalgroups withinthemolecule.

50

https://www.youtube.com/watch?v=HuSbLBDagdc (at1:00isCH CO H=aceticacid)

3

20.3

Theenergygapismuchsmaller!
2
3

E2

0
3

Energy

Therearemany
vibrational energy
levelsineach
electronic energy
level,thegapbetween
themissmallersothe
amountofenergy
requiredforexcitation
issmaller.Hencethe
wavelengthabsorbed
islonger.

E1

Rotational
levels
1

Eo

51

20.3

Infraredspectroscopy
Aspectrumgenerallylookslikethis

52

20.4

Infraredspectroscopy
Youinterpretthesespectrausingcorrelationtables.

Theregionfrom1500cm1 to3600cm1 isoften

referredtoasthegroupfrequencyregion.Below1500
cm1 isthefingerprintregion whichischaracteristic
53
foreachmolecule.

20.4

Infraredspectroscopy
Somegeneralthings
Thestrongerthebondthehigherthecm1
TheCYstretchingfrequencydecreaseswithan
increaseinmassofY
Bendingoccursatalowercm1 thanstretching.
Hybridisationeffectscausethestretchingcm1 to
increasefromsp3 tosp.
54

20.4

Infraredspectroscopy
Youinterpretthesespectrausingcorrelationtables.

Theregionfrom1500cm1 to3600cm1 isoften

referredtoasthegroupfrequencyregion.Below1500
cm1 isthefingerprintregion whichischaracteristic
55
foreachmolecules.

Infraredspectroscopy

20.4

Theprincipalonesarebelow
Functional group

Frequency / strength

O-H, N-H:

3200-3650 cm-1 (strong, often broad)

CH:

alkyl

2850-2960 cm-1 (strong)

alkenyl

3020-3100 cm-1 (medium)

alkynyl

3300 cm-1 (strong)

aromatic

3030 cm-1 (weak)

Not very
useful

1670-1780 cm-1 (strong)

C=O:
C=C:

Comments

alkenyl

1640-1680 cm-1 (medium)

aromatic

1450-1600 cm-1 (medium)

CN:

2210-2260 cm-1 (medium)

CC:

2100-2260 cm-1 (medium)

Not
Common

56

Infraredspectroscopy

20.4

Notetheregions thatshowyouinterpretIRspectra.
Functional group

Frequency / strength

O-H, N-H:

3200-3650 cm-1 (strong, often broad)

CH:

alkyl

2850-2960 cm-1 (strong)

alkenyl

3020-3100 cm-1 (medium)

alkynyl

3300 cm-1 (strong)

aromatic

3030 cm-1 (weak)

Not very
useful

1670-1780 cm-1 (strong)

C=O:
C=C:

Comments

alkenyl
aromatic

1640-1680 cm-1 (medium)

1450-1600 cm-1 ((medium))

CN:

2210-2260 cm-1 (medium)

CC:

2100-2260 cm-1 (medium)

Below1450cm1

=Fingerprintregion

Not
Common

57

Infraredspectroscopy

20.4

Notetheregions thatshowyouinterpretIRspectra.
OH
NH

CN
CC

C=O C=C

Fingerprintregion

58

Infraredspectroscopy
CharacteristicIRAbsorptions
(NB.allvaluesare approximate!)

Youwillreceivethiscorrelationtableinyourexam

Infraredspectroscopy
CharacteristicIRAbsorptions
(NB.allvaluesare approximate!)
OH
NH

CN
CC

C=O

Fingerprintregion

Youwillreceivethiscorrelationtableinyourexam

Infraredspectroscopy

20.4

Notetheregions thatshowyouinterpretIRspectra.
C=O

61

Infraredspectroscopy

20.4

Notetheregions thatshowyouinterpretIRspectra.
OH
NH

C=O

62

Infraredspectroscopy

20.4

Often
usefulfor
comparison
purposes!

63

20.3

Sowhatinfodoyouget?
Doesthecompoundhaveabsorbancesatkeyregionsin
theIRspectrumcorrespondingto,forexample,C=O,
OH,etc.functionalgroups?
Yes indicatesthatthefunctionalgroupispresentin
themolecule.
No indicatesthatthefunctionalgroupisnotpresentin
themolecules.
64

WorkedExample20.6

20.4

Example8a
WhichregionintheIRspectrumcouldbeusedto
distinguishbetweenbutanoicacidand2butanone?
a.32003600cm1
b.1600cm1
c.16801750cm1
d.25003300cm1
Checkthecorrelationtable.Youseethanthatwewould
expectbutanoicacidtohaveanOHpeakat32003600
cm1 andaC=Opeakat16801750cm1 while2butanone
wouldonlyhaveaC=Opeakat16801750cm1.
Theansweristhereforea.
TutorialQ#4

65

WorkedExample20.6

20.4

Example8
WhichregionintheIRspectrumcouldbeusedto
distinguishbetweenbutanoicacidand2butanone?
a.32003600cm1
b.1600cm1
c.16801750cm1
d.25003300cm1
Checkthecorrelationtable.Youseethanthatwewould
expectbutanoicacidtohaveanOHpeakat32003600
cm1 andaC=Opeakat16801750cm1 while2butanone
wouldonlyhaveaC=Opeakat16801750cm1.
Theansweristhereforea.
TutorialQ#4

66

WorkedExample20.7

Example9

20.4

ThemolecularformulaofcompoundAisC6H12O.

i)Identifythefunctionalgroup(s)presentbyinspectionoftheIRspectra
ii)Calculatetheindexofhydrogendeficiency(IHD)anddeterminethestructural
featuresthataccountfortheIRandIHD.

67

WorkedExample20.7

Example9

20.4

ThemolecularformulaofcompoundAisC6H12O.

i)Identifythefunctionalgroup(s)presentbyinspectionoftheIRspectra
Answer:Thepeakaround1700correspondstoC=O(seeredbox).
ii)Calculatetheindexofhydrogendeficiency(IHD)anddeterminethestructural
featuresthataccountfortheIRandIHD.
Answer:IHD=1.FromthiswecanconcludethatAcontainsadoublebondsora
ring.ButasweknowithasC=O
+severalstructural
=itcanthavearing.
68
Isomerspossible

RealWorldExample4
IRspectroscopyisthebasisofthermalimaging,which
typicallylooksintheregion800 1700cm1.Itobserves
energyreleasedfrommolecularrelaxation.Thisisuseful
innightvision,medicalimaging,volcanosand

Termiteinspection!Theheatsignalfromtermitesinside
thiswallisdetectedbythermalimaging.
69
www.pestec.com.au/technology

Howmuchheatis
pouringoutofyour
house?Wasted
energythatyoucan
see!

www.sustainableguernsey.info/blog/2011/02/building
energyefficiencyshouldbeapriorityforguernsey/

Whereareyou
hiding?
http://edition.cnn.com/2013/04/17/tech/mobile/bostonbombingevidencesearchverge

20.5

Nuclearmagneticresonancespectroscopy
Correspondstotransitionsbetweendifferentspin
statesinanucleus.

71

20.5

Nuclearmagneticresonancespectroscopy
NobelPrizes(sofar!)forNMR:
OttoStern,USA: NobelPrizeinPhysics1943,
forhiscontributiontothedevelopmentofmolecularraymethodandhisdiscoveryofthemagnetic
momentoftheproton
Isidor I.Rabi,USA: NobelPrizeinPhysics1944,
forhisresonancemethodforrecordingthemagneticpropertiesofatomicnuclei
FelixBloch,USAandEdwardM.Purcell,USA: NobelPrizeinPhysics1952,
fortheirdiscoveryofnewmethodsfornuclearmagneticprecisionmeasurementsanddiscoveriesin
connectiontherewith
RichardR.Ernst,Switzerland: NobelPrizeinChemistry1991,.
forhiscontributionstothedevelopmentofthemethodologyofhighresolutionnuclearmagnetic
resonance(NMR)spectroscopy
KurtWthrich,Switzerland: NobelPrizeinChemistry2002,
forhisdevelopmentofnuclearmagneticresonancespectroscopyfordeterminingthethree
dimensionalstructureofbiologicalmacromoleculesinsolution
PaulC.Lauterbur,USAandPeterMansfield,UnitedKingdom: NobelPrizeinPhysiologyorMedicine
2003,
fortheirdiscoveriesconcerningmagneticresonanceimaging

TodayNMRremainsthemostpowerfulstructuraldetermination
72
toolforcompoundsinsolution!
Photos:www.rsc.org/chemistryworld/News/2010/July/13071002.asp,www.nobelprize.org/nobel_prizes/physics/laureates/1952/blochbio.htmltable:
http://www2.chemistry.msu.edu/facilities/nmr/900Mhz/MCSB_NMR_nobel.html

20.5

Nuclearmagneticresonancespectroscopy
Correspondstotransitionsbetweendifferentspin
statesinanucleus;somenucleicanexistindifferent
spinstateswheninaverystrongmagneticfield
(requiressuperconductingmagnet).
For1Hand13C,onlytwoorientationsareallowed.

73

20.5

Nuclearmagneticresonancespectroscopy
Resonanceistheabsorptionofelectromagnetic
radiationbyaspinningnucleusandtheresultingflipof
itsnuclearspinstate.

Notethattheenergyrequiredisvery small
0.02 0.3Jmol1 or106 xsmallerthanIR!

74

20.5

Nuclearmagneticresonancespectroscopy

75

76
http://www.nmr.unsw.edu.au/facility/nmr700.htm

20.5

NMR activenuclei
TobeNMRactive anucleimusthaveanuclear
spin therearemanyofthesebutthetwokey
nucleiare1Hand13C.(Bothhaveaspinofand
twospinstatesinamagneticfield.)
1HNMRspectroscopy

givesinformationaboutthehydrogenatoms.
13CNMRspectroscopy

givesinformationaboutthecarbonsatoms.
77

20.5

NMR spectra
Absorptionofradiationistranslatedtoaspectrum
containingaseriesofsignals.
Thisisatypical1HNMRspectrum.

78

20.5

NMR spectra
Absorptionofradiationistranslatedtoaspectrum
containingaseriesofsignals. Thenumberofsignals
givesanindicationofthesymmetry inthemolecule.
Testforequivalence:Replaceinturneachofthe
protonswithatestatom(e.g.,Cl) iftheproductis
alwaysthesametheyareequivalent ifyougeta
differentcompoundtheyarenot.
Equivalentprotonsareinthesameenvironment.The
numberofsignalscorrespondstothenumberof
79
environments.

20.5

Equivalentprotons?
Absorptionofradiationistranslatedtoaspectrum
containingaseriesofsignals. Thenumberofsignals
givesanindicationofthesymmetryinthemolecule.

NMRshowsAVERAGEenvironmentsontheNMRtimescale.Soif,forexample,conformational
isomerscouldexistiftheyinterconvertquickly(eg,aboutasingleCCbond)thenwewillonlysee
theaverageenvironment.ThisiswhyallthreeprotonsofaCH3 arealwaystheequivalent.

80

20.5

Equivalentprotons?
Absorptionofradiationistranslatedtoaspectrum
containingaseriesofsignals. Thenumberofsignals
givesanindicationofthesymmetryinthemolecule.
Forexample,considerthenumberofdifferent1H
environmentsandhencesignalsinthecompounds
below.Equivalentprotonsgivethesame1HNMR
signal.
3

4
81

20.5

Equivalentprotons?
Absorptionofradiationistranslatedtoaspectrum
containingaseriesofsignals. Thenumberofsignals
givesanindicationofthesymmetryinthemolecule.
Forexample,considerthenumberofdifferent1H
environmentsandhencesignalsinthecompounds
below.Equivalentprotonsgivethesame1HNMR
signal.

3
2

82

WorkedExample20.10

20.5

Example10
Identifythenumberofsetsofequivalentprotonsin
thesestructures.

TutorialQ#6

83

WorkedExample20.10

20.5

Identifythenumberofsetsofequivalentprotonsin
thesestructures.

TutorialQ#6

84

WorkedExample20.10

20.5

Identifythenumberofsetsofequivalentprotonsin
thesestructures.

4differentHenvironments

6differentHenvironments

6differentHenvironments

WorkedExample20.10

20.5

Identifythenumberofsetsofequivalentprotonsin
thesestructures.
Br

Br

Br
Br

TutorialQ#6

86

WorkedExample20.10

20.5

Identifythenumberofsetsofequivalentprotonsin
thesestructures.
N

HO

TutorialQ#6

Br

87

WorkedExample20.10

20.5

Identifythenumberofsetsofequivalentprotonsin
thesestructures.

Diastereoisomers:eachhavethesamenumberofdifferentenvironments,butthey
areNOTthesame

89

20.5

1HNMRspectra

infoyouget

Foreachsignaltherearethreekeypiecesof
information.
1.Chemicalshift:thetypeofenvironmentand
thenatureofadjacentgroups.
2.Integration:thenumberofprotons(1Hnuclei)
inthatenvironment.
3.Multiplicity:thenumberofprotonsonthe
adjacentcarbonatom(s).

90

20.5

1HNMRspectra

1.ChemicalShift

AtypicalNMR spectrumisshownofmethylacetate+
tetramethylsilane (TMS) areferencecompound. NMR
spectraarealwaysscaledagainstsomereference.
91

20.5

1HNMRspectra

1.ChemicalShift

TMSgivesonesignal allprotonsareequivalent.
Methylacetategivestwosignals thetwomethyl
groupsareindifferentchemicalenvironments.
Whydotheyappearindifferentpartsofthespectrum?
92

20.5

1HNMRspectra

1.ChemicalShift

Nucleiaresaidtobeshielded ordeshielded,
dependingonadjacentgroups.
Electrondonatinggroupsresultinshielding
anupfieldshiftandalowerchemicalshift().

Electronwithdrawinggroupsresultin
deshielding adownfieldshiftandahigher
chemicalshift().
93

20.5

1HNMRspectra

1.ChemicalShift

Nucleiaresaidtobeshielded ordeshielded,
dependingonadjacentgroups.

94

20.5

1HNMRspectra

1.ChemicalShift

Thegreatertheelectrondonation/withdrawal,the
biggertheeffectonthechemicalshift.

Compound

CH3H

CH3I

CH3Br CH3Cl CH3F

Element X

Br

Cl

Electronegativity of X

2.1

2.5

2.8

3.1

4.0

Chemical shift ()

0.23

2.16

2.68

3.05

4.26

95

20.5

1HNMRspectra

1.ChemicalShift

b
b
a

Therearetwosetsofequivalentprotons,labelleda andb.

Protonsa aredeshieldedbytheC=O(C=sp2)next
neighbourcomparedtoC (C=sp3)nextneighbouronb.
Protona appearat 2whileb appearsat 1.5.

96

20.5

1HNMRspectra

1.ChemicalShift

Thechemicalshiftgivesanindicationofadjacent
functionalgroups.

97

20.5

1HNMRspectra

1.ChemicalShift

Thisisanexampleof
1HNMRcorrelation
table.
Valuesare
approximate!

98

20.5

1HNMRspectra

1.ChemicalShift

Chemicalshiftsarealso
approximatelyadditive.
eg:ConsiderCH2CH3 tobethe
startingpoint(0.8 1.0ppm).
Ifattachedtoanoxygen,theOCH3
mightbeexpectedtobeshiftedto
3.34.0ppm.
butifattachedtotwooxygens
(OCH2O),itwillbeshiftedeven
furtherdownfield(~4.5 5.5ppm)
i.e.eachneighbouringgroup
contributestotheoverallthe
chemicalshift,sothiscorrelation
tableisrough!

99

1HNMRspectra

correlationtable

Characteristic1HChemicalShifts
(NB.allvaluesare approximate!)

Youwillreceivethiscorrelationtableinyourexam

20.5

1HNMRspectra

2.SignalIntegrals

b
b
a

N
Notethatthesignalsforprotonsa andb areNOTequal
inintensity.Theintensityof1HNMR signalsisdirectly
proportionaltothenumberofequivalentprotons
givingrisetothatsignal.
101

20.5

1HNMRspectra

2.SignalIntegrals

b
b
a

Theblacklinehereshowsthe
signalintegration.Theheight
ofthislinecorrespondsto
theareaunderthepeak

N
Signalintegration(areaunderpeak)gives67forproton
b and23forprotona.Theintegrationratio istherefore
67/23or2.91/1(67/23).Thisisratioiscloseto3:1.
Theratioofequivalentprotons fora andb isalso3:1
(3protonsforaand9forb).
TutorialQ#7

WorkedExample20.12

102

1HNMRspectra

20.5

chemicalshiftandintegrationsummary
Howmanysignalsdowe
expectforeachofthese
compounds?

Whatratioofpeak
integralsdoweexpect?

103