InterpretingInfraredSpectraPainlessly,Quickly,andCorrectly

Knowinghowtointerpretinfrared(IR)spectraisofimmensehelptostructuredetermination.
Notonlywillittellyouwhatfunctionalgroupsandstructuralelementsarethere,itwillalsoclarify
whichonesarenotthere,quicklyreducingyourlistofpossibilitiesbeforeyoueventhinkaboutglancing
attheNMR.Letstakeaquicklookatsomeexamplespectratogainmoreofanintuitivefeelforthis
technique.IhaveincludedthespectraaslinkstoPDFsonlineinordertopreventprohibitivefilesizes
andloadingtimes.Also,thiswayyoucanopenthespectruminaseparatebrowserwindowandposition
themoverthetextinsuchawaythatyoucanreadtheinformationandcomparewiththepeaksonthe
spectra.Ihopethiswillbeausefullearningtoolforyou.(RemembertopressandholdCTRLwhile
clickingthelinkstogetthemtoopen.)
OrganicCompoundsinGeneral:Alkanes
ExampleSpectrumA:octane
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R008555. PDF)

Youmightsaythatoctanehasnofunctionalgroups,sohowwouldanIRspectrumhelp?Well,sincenearly
everymoleculeyouwillhavetoidentifywillhaveeitheralkane,alkene,oraromaticgroupsattached,youmust
knowwhateachlookslike.Thisspectrumshowsyouwhatasimplealkylgrouplookslike,soyoushouldexpect
thatANYmoleculewithCH
3
,CH
2
,orCHgroupsanywhereinitwouldcontainthesepeaksandyouwouldbe
correct.TheonlythingIwantyoutonoticeinthisspectrumistheclusterofpeaksbelow3000cm
1
downto
around2850cm
1
:thesearethepeaksfromthestretchingofsp
3
hybridizedCHbonds.Sowheneveryouseea
spectrumwiththisclusterofpeaks,think:theremustberegularalkylchaincarbonsinthismolecule!Notethatthe
manyotherpeaksyouseeatlowerwavenumberswillnotbereadilydistinguishableinallspectra,sowedonthave
toworryaboutthem.
C=CandCHBonds:Alkenes
ExampleSpectrumB:2methyl1hexene
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R000272. PDF)

Alkenespectrashouldshowbothregularalkanepeaks(fromallthesp
3
carbons)andpeaksforthesp
2

carbons.Lookingatthespectrum,youshouldrecognizethealkanepeaksbelow3000cm
1
,buttherearetwo
importantnewadditions:firstisapeakcloseto3100cm
1
,whichisthepeakforsp
2
hybridizedCHbonds;second
isthesharppeakaround1650cm
1
,whichrepresentstheC=Cdoublebond.Thesearethetwosignsofanalkene.
ButoneothertypeofcompoundhasC=Cbondsthephenylring(benzeneetc.);howintheworldcan
youtellthedifference?Onewayisbycalculatingtheunsaturationindex,butanotherisbyknowingexactlyhow
alkeneC=CandphenylC=Cspectradiffer.
C=CandCHBonds:Benzene/PhenylRings
ExampleSpectrumC:ethylbenzene
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R007982. PDF)

Thiscompoundhasbothaphenylringandanalkylchain.Ofcourseyoucandetectthefamiliarsp
3
CH
peaksbelow3000cm
1
,buttherearemanymorepeakstolookforthaninalkenespectra.Firstofall,whilethe
alkeneabovehadasinglepeakcloseto3100cm
1
,thephenylringusuallyshowsmultipleCHpeaksbetween3100
and3000cm
1
.Second,whilethealkenespectrumshowedaC=Cpeakbetween1600and1700cm
1
,phenylrings
almostalwaysshowaweakersharppeakrightat1600cm
1
.Wantthreemorepiecesofproofthatyouhavea
phenylringinsteadofanalkene?Phenylringsgenerallyshowtwoverynarrowpeaksat1450and1500cm
1

alkenesdont.Phenylringsalwayshaveastrong,sharppeakintheregionof700to800cm
1
alkenesdont.Also,
phenylringsalmostalwaysshowjaggedcraziness(itsweak,butitsthere)between2000and1650cm
1
alkenes
dont.Comparethesetwoexamplespectrauntilyouaretotallysureyoucantellthedifferenceataglance.
TripleBonds:Alkynes
ExampleSpectrumD:1hexyne
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R003743. PDF)

Thelastofthehydrocarbonfamilyconsistsofalkynes,compoundswithsphybridizedcarbonsintriple
bonds.Theexamplespectrumhereshowsthefamiliaralkylchainsp
3
peaksbelow3000cm
1
,buttheC Cbond
vibrationwillshowupasaweak,sharppeakbetween2100and2200cm
1
.(Note:thestrongsharppeakat3300
cm
1
ischaracteristicforCHbondsonsphybridizedcarbonsinalkynes,butyouarenotexpectedtoknowthisfor
theexam.)Thisisreallynotconfusingwhenyoucomparewithalkenes,phenylrings,oralkanes,butthereisone
otherfunctionalgroupthatshowsupinthisregiontheonlyotherfunctionalgroupyouknowwithtriplebonds!

TripleBonds:Nitriles
ExampleSpectrumE:hexanenitrile
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R001769. PDF)

Likealkynes,nitrilespossessatriplebondandthereforetheirpeaksappearinasimilarlocation,andit
mayseemeasytoconfusethetwoonaproblemsetorexam.Butjustremembertwothings:youwillalwaysbe
giventhemolecularformula,andnitrileshaveanitrogenatomwhilealkynesdonot;andalso,rememberthe
number2200cm
1
:alkyneswillrarely,ifever,appearabove2200cm
1
,whilenitrileswillalwaysappearabove
2200cm
1
.Simple!
OHBonds:Alcohols
ExampleSpectrumF:2butanol
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R007377. PDF)

AlcoholsareoneoftheeasiestgroupstoidentifyonIRspectra.TheirOHbondstretchingshowsupasa
strong,broadpeakupwardsof3300cm
1
,whichyoucantmiss.Alsonotetheusualalkanesp
3
CHpeaksjust
below3000cm
1
.
OHandC=OBonds:CarboxylicAcids
ExampleSpectrumG:cyclopentanecarboxylicacid
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R007437. PDF)

SometimesstudentsgetconfusedabouthowtodifferentiatealcoholsfromcarboxylicacidsonIRthey
bothhaveOHgroups,right?Well,thewaythesecompoundsbehaveonIRisverydifferent.Inthespectrumof
thealcoholabove,theOHbondisastrong,broadpeakaroundorabove3300cm
1
;inthiscarboxylicacid
spectrum,theOHpeakisstillstrongbutshallower,andisMUCHbroader,startingaround3400cm
1
and
stretchingallthewaydownto2400cm
1
orso.Alsonotethatyoucanconfirmthisasacarboxylicacidbythe
strong,sharpcarbonylC=Opeak(alcoholshavenocarbonyl),whichforcarboxylicacidsshowsuprightaround
1700cm
1
.Tellingthedifferenceiseasyaspie!

Speakingofcarbonyls,letsshiftourattentioncompletelytoadiscussionofhowtodifferentiatethe
differentfunctionalgroupsthatallcontaincarbonyls,startingwiththesimplesttheketones.
C=OBonds:Ketones
ExampleSpectrumH:pinacolone
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R008683. PDF)
O

Ketonespectraaresoeasythattheybecomedifficultinotherwords,theylackmuchinformationatall,
andstudentstendtotryandreadmoreintothemthantheyshould.KetoneshaveonlyacarbonylC=Oastheir
functionalgroup,andthusyouwouldexpectthattheyshowaC=Ostretchpeakrightaround1700cm
1
,maybea
littlehigher.Alltheotherpeaksonthespectrumarisefromwhatevergroupsareattachedtothecarbonylcarbon
hereonlyalkylgroups.Simplesofar.Butwhathappenswhenothergroupsareattached?
MultipleFunctionalGroupsExample:PhenylRingandKetone
ExampleSpectrumI:propiophenone
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R008713. PDF)

Thisketonepossessesonealkanesidechainandonephenylringsidechain.Youshouldpredictthatyou
willseenotonlytheC=Opeak,butalsosp
3
CHpeaksandalltheexpectedphenylringpeaks.Soletstakealook!
KetoneC=Opeakaround1700cm
1
?Check.Alkanesp
3
CHpeaksbelow3000cm
1
?Check.Phenylringsp
2
CH
peaksbetween3000and3100cm
1
?Check.PhenylC=Cpeaksat1600,1500,and1450cm
1
?Sortofitlookslike
thelasttwopeakshavebeenshifteddownbyabout50cm
1
,buttheystilllookthesame,socheck.Strong,sharp
phenylpeakbetween700and800cm
1
?Check.Bizarrejaggedcrazinessbetween2000and1650cm
1
?Check.
Lookslikeweregoodtogowithanalkylarylketone!

C=OandCHBonds:Aldehydes
ExampleSpectrumJ:isobutyraldehyde
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R008179. PDF)

Atfirstblushitwouldseemthatdifferentiatingaldehydesandketoneswouldbetough,becauseanIR
spectrumcanttellyouhowmanyalkylsidechainsarepresent,justwhethertheyarepresent.Luckilyforyou,that
singlehydrogenattachedtothecarbonylcarbonhasataletotellLookatthespectrumofcourseyouseethe
carbonylC=Oaround1730cm
1
orso,butlookverycarefullyatthealkylCHpeakregion.Therearetwoextra
peaksthere,around2800and2700cm
1
,thatlooklikevampirefangs;thesearethepeaksthatarethedead
giveaway(badpunintended)foranaldehyde!Now,thereasonwhythissinglealdehydehydrogengivestwopeaks
isbeyondourscoperightnow,butthisisanexcellentwaytodistinguishaldehydesfromothercarbonyl
compounds,especiallyketones.
C=OandCOBonds:Esters
ExampleSpectrumK:cyclohexylpropionate
(ht t p: / / www. si gmaal dr i ch. com/ spect r a/ f t i r / FTI R009103. PDF)

Esterscanbetoughsometimestoo,becausetheycanappearasjustanothernondescriptcarbonyl
compoundintheIR.Ofcourse,themolecularformulawillusuallygiveitaway(therewillbetwooxygensinthe
compound),buttakealookattheexamplespectrumformoreevidence.Hereweseetheexpectedcarbonylpeak
around1740cm
1
andthealkylCHpeaksbelow3000cm
1
nosurprises.UsuallyNMRgivesthebestevidenceof
esterfunctionality,butyouwillalmostalwaysseeaverystrongpeakaround1200cm
1
foresters,representingthe
COsinglebondvibration.Justanotherhintthatcouldspeedyouonyourway.