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

(http://www.sigmaaldrich.com/spectra/ftir/FTIR008555.PDF)

Youmightsaythatoctanehasnofunctionalgroups,sohowwouldanIRspectrumhelp?Well,sincenearly everymoleculeyouwillhavetoidentifywillhaveeitheralkane,alkene,oraromaticgroupsattached,youmust knowwhateachlookslike.Thisspectrumshowsyouwhatasimplealkylgrouplookslike,soyoushouldexpect thatANYmoleculewithCH3,CH2,orCHgroupsanywhereinitwouldcontainthesepeaksandyouwouldbe correct.TheonlythingIwantyoutonoticeinthisspectrumistheclusterofpeaksbelow3000cm1downto around2850cm1:thesearethepeaksfromthestretchingofsp3hybridizedCHbonds.Sowheneveryouseea spectrumwiththisclusterofpeaks,think:theremustberegularalkylchaincarbonsinthismolecule!Notethatthe manyotherpeaksyouseeatlowerwavenumberswillnotbereadilydistinguishableinallspectra,sowedonthave toworryaboutthem.

C=CandCHBonds:Alkenes ExampleSpectrumB:2methyl1hexene

(http://www.sigmaaldrich.com/spectra/ftir/FTIR000272.PDF)

Alkenespectrashouldshowbothregularalkanepeaks(fromallthesp3carbons)andpeaksforthesp2 carbons.Lookingatthespectrum,youshouldrecognizethealkanepeaksbelow3000cm1,buttherearetwo importantnewadditions:firstisapeakcloseto3100cm1,whichisthepeakforsp2hybridizedCHbonds;second isthesharppeakaround1650cm1,whichrepresentstheC=Cdoublebond.Thesearethetwosignsofanalkene.

ButoneothertypeofcompoundhasC=Cbondsthephenylring(benzeneetc.);howintheworldcan youtellthedifference?Onewayisbycalculatingtheunsaturationindex,butanotherisbyknowingexactlyhow alkeneC=CandphenylC=Cspectradiffer.

C=CandCHBonds:Benzene/PhenylRings ExampleSpectrumC:ethylbenzene (http://www.sigmaaldrich.com/spectra/ftir/FTIR007982.PDF)

Thiscompoundhasbothaphenylringandanalkylchain.Ofcourseyoucandetectthefamiliarsp3CH peaksbelow3000cm1,buttherearemanymorepeakstolookforthaninalkenespectra.Firstofall,whilethe alkeneabovehadasinglepeakcloseto3100cm1,thephenylringusuallyshowsmultipleCHpeaksbetween3100 and3000cm1.Second,whilethealkenespectrumshowedaC=Cpeakbetween1600and1700cm1,phenylrings almostalwaysshowaweakersharppeakrightat1600cm1.Wantthreemorepiecesofproofthatyouhavea phenylringinsteadofanalkene?Phenylringsgenerallyshowtwoverynarrowpeaksat1450and1500cm1 alkenesdont.Phenylringsalwayshaveastrong,sharppeakintheregionof700to800cm1alkenesdont.Also, phenylringsalmostalwaysshowjaggedcraziness(itsweak,butitsthere)between2000and1650cm1alkenes dont.Comparethesetwoexamplespectrauntilyouaretotallysureyoucantellthedifferenceataglance.

TripleBonds:Alkynes ExampleSpectrumD:1hexyne (http://www.sigmaaldrich.com/spectra/ftir/FTIR003743.PDF)

Thelastofthehydrocarbonfamilyconsistsofalkynes,compoundswithsphybridizedcarbonsintriple bonds.Theexamplespectrumhereshowsthefamiliaralkylchainsp3peaksbelow3000cm1,buttheC Cbond vibrationwillshowupasaweak,sharppeakbetween2100and2200cm1.(Note:thestrongsharppeakat3300 cm1ischaracteristicforCHbondsonsphybridizedcarbonsinalkynes,butyouarenotexpectedtoknowthisfor theexam.)Thisisreallynotconfusingwhenyoucomparewithalkenes,phenylrings,oralkanes,butthereisone otherfunctionalgroupthatshowsupinthisregiontheonlyotherfunctionalgroupyouknowwithtriplebonds!

TripleBonds:Nitriles ExampleSpectrumE:hexanenitrile (http://www.sigmaaldrich.com/spectra/ftir/FTIR001769.PDF)

Likealkynes,nitrilespossessatriplebondandthereforetheirpeaksappearinasimilarlocation,andit mayseemeasytoconfusethetwoonaproblemsetorexam.Butjustremembertwothings:youwillalwaysbe giventhemolecularformula,andnitrileshaveanitrogenatomwhilealkynesdonot;andalso,rememberthe number2200cm1:alkyneswillrarely,ifever,appearabove2200cm1,whilenitrileswillalwaysappearabove 2200cm1.Simple!

OHBonds:Alcohols ExampleSpectrumF:2butanol (http://www.sigmaaldrich.com/spectra/ftir/FTIR007377.PDF)

AlcoholsareoneoftheeasiestgroupstoidentifyonIRspectra.TheirOHbondstretchingshowsupasa strong,broadpeakupwardsof3300cm1,whichyoucantmiss.Alsonotetheusualalkanesp3CHpeaksjust below3000cm1.

OHandC=OBonds:CarboxylicAcids ExampleSpectrumG:cyclopentanecarboxylicacid (http://www.sigmaaldrich.com/spectra/ftir/FTIR007437.PDF)

SometimesstudentsgetconfusedabouthowtodifferentiatealcoholsfromcarboxylicacidsonIRthey bothhaveOHgroups,right?Well,thewaythesecompoundsbehaveonIRisverydifferent.Inthespectrumof thealcoholabove,theOHbondisastrong,broadpeakaroundorabove3300cm1;inthiscarboxylicacid spectrum,theOHpeakisstillstrongbutshallower,andisMUCHbroader,startingaround3400cm1and stretchingallthewaydownto2400cm1orso.Alsonotethatyoucanconfirmthisasacarboxylicacidbythe strong,sharpcarbonylC=Opeak(alcoholshavenocarbonyl),whichforcarboxylicacidsshowsuprightaround 1700cm1.Tellingthedifferenceiseasyaspie!

 Speakingofcarbonyls,letsshiftourattentioncompletelytoadiscussionofhowtodifferentiatethe differentfunctionalgroupsthatallcontaincarbonyls,startingwiththesimplesttheketones.

C=OBonds:Ketones ExampleSpectrumH:pinacolone (http://www.sigmaaldrich.com/spectra/ftir/FTIR008683.PDF)

O

Ketonespectraaresoeasythattheybecomedifficultinotherwords,theylackmuchinformationatall, andstudentstendtotryandreadmoreintothemthantheyshould.KetoneshaveonlyacarbonylC=Oastheir functionalgroup,andthusyouwouldexpectthattheyshowaC=Ostretchpeakrightaround1700cm1,maybea littlehigher.Alltheotherpeaksonthespectrumarisefromwhatevergroupsareattachedtothecarbonylcarbon hereonlyalkylgroups.Simplesofar.Butwhathappenswhenothergroupsareattached?

MultipleFunctionalGroupsExample:PhenylRingandKetone ExampleSpectrumI:propiophenone (http://www.sigmaaldrich.com/spectra/ftir/FTIR008713.PDF)

Thisketonepossessesonealkanesidechainandonephenylringsidechain.Youshouldpredictthatyou willseenotonlytheC=Opeak,butalsosp3CHpeaksandalltheexpectedphenylringpeaks.Soletstakealook! KetoneC=Opeakaround1700cm1?Check.Alkanesp3CHpeaksbelow3000cm1?Check.Phenylringsp2CH peaksbetween3000and3100cm1?Check.PhenylC=Cpeaksat1600,1500,and1450cm1?Sortofitlookslike thelasttwopeakshavebeenshifteddownbyabout50cm1,buttheystilllookthesame,socheck.Strong,sharp phenylpeakbetween700and800cm1?Check.Bizarrejaggedcrazinessbetween2000and1650cm1?Check. Lookslikeweregoodtogowithanalkylarylketone!

C=OandCHBonds:Aldehydes ExampleSpectrumJ:isobutyraldehyde (http://www.sigmaaldrich.com/spectra/ftir/FTIR008179.PDF)

Atfirstblushitwouldseemthatdifferentiatingaldehydesandketoneswouldbetough,becauseanIR spectrumcanttellyouhowmanyalkylsidechainsarepresent,justwhethertheyarepresent.Luckilyforyou,that singlehydrogenattachedtothecarbonylcarbonhasataletotellLookatthespectrumofcourseyouseethe carbonylC=Oaround1730cm1orso,butlookverycarefullyatthealkylCHpeakregion.Therearetwoextra peaksthere,around2800and2700cm1,thatlooklikevampirefangs;thesearethepeaksthatarethedead giveaway(badpunintended)foranaldehyde!Now,thereasonwhythissinglealdehydehydrogengivestwopeaks isbeyondourscoperightnow,butthisisanexcellentwaytodistinguishaldehydesfromothercarbonyl compounds,especiallyketones.

C=OandCOBonds:Esters ExampleSpectrumK:cyclohexylpropionate (http://www.sigmaaldrich.com/spectra/ftir/FTIR009103.PDF)

Esterscanbetoughsometimestoo,becausetheycanappearasjustanothernondescriptcarbonyl compoundintheIR.Ofcourse,themolecularformulawillusuallygiveitaway(therewillbetwooxygensinthe compound),buttakealookattheexamplespectrumformoreevidence.Hereweseetheexpectedcarbonylpeak around1740cm1andthealkylCHpeaksbelow3000cm1nosurprises.UsuallyNMRgivesthebestevidenceof esterfunctionality,butyouwillalmostalwaysseeaverystrongpeakaround1200cm1foresters,representingthe COsinglebondvibration.Justanotherhintthatcouldspeedyouonyourway.