Nomenclature

NamingOrganicCompounds
Theincreasinglylargenumberoforganiccompoundsidentifiedwitheachpassingday,togetherwiththefactthatmanyofthesecompoundsare
isomersofothercompounds,requiresthatasystematicnomenclaturesystembedeveloped.Justaseachdistinctcompoundhasauniquemolecular
structurewhichcanbedesignatedbyastructuralformula,eachcompoundmustbegivenacharacteristicanduniquename.
Asorganicchemistrygrewanddeveloped,manycompoundsweregiventrivialnames,whicharenowcommonlyusedandrecognized.Some
examplesare:
Name

Methane

Butane

Acetone

Toluene

Acetylene

EthylAlcohol

Formula

CH4

C4H10

CH3COCH3

CH3C6H5

C2H2

C2H5OH

Suchcommonnamesoftenhavetheirorigininthehistoryofthescienceandthenaturalsourcesofspecificcompounds,buttherelationshipofthese
namestoeachotherisarbitrary,andnorationalorsystematicprinciplesunderlytheirassignments.

TheIUPACSystematicApproachtoNomenclature
Arationalnomenclaturesystemshoulddoatleasttwothings.First,itshouldindicatehowthecarbonatomsofagivencompoundarebonded
togetherinacharacteristiclatticeofchainsandrings.Second,itshouldidentifyandlocateanyfunctionalgroupspresentinthecompound.Since
hydrogenissuchacommoncomponentoforganiccompounds,itsamountandlocationscanbeassumedfromthetetravalencyofcarbon,andneed
notbespecifiedinmostcases.
TheIUPACnomenclaturesystemisasetoflogicalrulesdevisedandusedbyorganicchemiststocircumventproblemscausedbyarbitrary
nomenclature.Knowingtheserulesandgivenastructuralformula,oneshouldbeabletowriteauniquenameforeverydistinctcompound.Likewise,
givenaIUPACname,oneshouldbeabletowriteastructuralformula.Ingeneral,anIUPACnamewillhavethreeessentialfeatures:
Arootorbaseindicatingamajorchainorringofcarbonatomsfoundinthemolecularstructure.
Asuffixorotherelement(s)designatingfunctionalgroupsthatmaybepresentinthecompound.
Namesofsubstituentgroups,otherthanhydrogen,thatcompletethemolecularstructure.
AsanintroductiontotheIUPACnomenclaturesystem,weshallfirstconsidercompoundsthathavenospecificfunctionalgroups.Suchcompounds
arecomposedonlyofcarbonandhydrogenatomsbondedtogetherbysigmabonds(allcarbonsaresp3hybridized).
AnexcellentpresentationoforganicnomenclatureisprovidedonaNomenclaturePage.createdbyDaveWoodcock.
AfullpresentationoftheIUPACRulesisalsoavailable.

Alkanes

Alkanes
Hydrocarbonshavingnodoubleortriplebondfunctionalgroupsareclassifiedasalkanesorcycloalkanes,dependingonwhetherthecarbonatoms
ofthemoleculearearrangedonlyinchainsoralsoinrings.Althoughthesehydrocarbonshavenofunctionalgroups,theyconstitutetheframeworkon
whichfunctionalgroupsarelocatedinotherclassesofcompounds,andprovideanidealstartingpointforstudyingandnamingorganiccompounds.
Thealkanesandcycloalkanesarealsomembersofalargerclassofcompoundsreferredtoasaliphatic.Simplyput,aliphaticcompoundsare
compoundsthatdonotincorporateanyaromaticringsintheirmolecularstructure.
ThefollowingtableliststheIUPACnamesassignedtosimplecontinuouschainalkanesfromC1toC10.Acommon"ane"suffixidentifiesthese
compoundsasalkanes.Longerchainalkanesarewellknown,andtheirnamesmaybefoundinmanyreferenceandtextbooks.Thenamesmethane
throughdecaneshouldbememorized,sincetheyconstitutetherootofmanyIUPACnames.Fortunately,commonnumericalprefixesareusedin
namingchainsoffiveormorecarbonatoms.

ExamplesofSimpleUnbranchedAlkanes
Name

Molecular
Formula

Structural
Formula

Isomers

Name

Molecular
Formula

Structural
Formula

Isomers

methane

CH4

CH4

hexane

C6H14

CH3(CH2)4CH3

ethane

C2H6

CH3CH3

heptane

C7H16

CH3(CH2)5CH3

propane

C3H8

CH3CH2CH3

octane

C8H18

CH3(CH2)6CH3

18

butane

C4H10

CH3CH2CH2CH3

nonane

C9H20

CH3(CH2)7CH3

35

pentane

C5H12

CH3(CH2)3CH3

decane

C10H22

CH3(CH2)8CH3

75

Someimportantbehaviortrendsandterminologies:
(i)TheformulasandstructuresofthesealkanesincreaseuniformlybyaCH2increment.
(ii)Auniformvariationofthiskindinaseriesofcompoundsiscalledhomologous.
(iii)TheseformulasallfittheCnH2n+2rule.ThisisalsothehighestpossibleH/Cratioforastablehydrocarbon.
(iv)SincetheH/Cratiointhesecompoundsisatamaximum,wecallthemsaturated(withhydrogen).
Beginningwithbutane(C4H10),andbecomingmorenumerouswithlargeralkanes,wenotetheexistenceofalkaneisomers.Forexample,thereare
fiveC6H14isomers,shownbelowasabbreviatedlineformulas(AthroughE):

Althoughthesedistinctcompoundsallhavethesamemolecularformula,onlyone(A)canbecalledhexane.Howthenarewetonametheothers?
TheIUPACsystemrequiresfirstthatwehavenamesforsimpleunbranchedchains,asnotedabove,andsecondthatwehavenamesforsimplealkyl
groupsthatmaybeattachedtothechains.Examplesofsomecommonalkylgroupsaregiveninthefollowingtable.Notethatthe"ane"suffixis
replacedby"yl"innaminggroups.ThesymbolRisusedtodesignateageneric(unspecified)alkylgroup.
Group CH3 C2H5 CH3CH2CH2 (CH3)2CH CH3CH2CH2CH2 (CH3)2CHCH2 CH3CH2CH(CH3) (CH3)3C

Name

Alkyl

Methyl

Ethyl

Propyl

Isopropyl

Butyl

Isobutyl

secButyl

tertButyl

IUPACRulesforAlkaneNomenclature
1.Findandnamethelongestcontinuouscarbonchain.
2.Identifyandnamegroupsattachedtothischain.
3.Numberthechainconsecutively,startingattheendnearestasubstituentgroup.
4.Designatethelocationofeachsubstituentgroupbyanappropriatenumberandname.
5.Assemblethename,listinggroupsinalphabeticalorderusingthefullname(e.g.cyclopropylbeforeisobutyl).
Theprefixesdi,tri,tetraetc.,usedtodesignateseveralgroupsofthesamekind,arenotconsideredwhenalphabetizing.

FortheaboveisomersofhexanetheIUPACnamesare:B2methylpentaneC3methylpentaneD2,2dimethylbutaneE2,3
dimethylbutane
Halogensubstituentsareeasilyaccommodated,usingthenames:fluoro(F),chloro(Cl),bromo(Br)andiodo(I).Forexample,
(CH3)2CHCH2CH2Brwouldbenamed1bromo3methylbutane.Ifthehalogenisbondedtoasimplealkylgroupanalternative"alkylhalide"name
maybeused.Thus,C2H5Clmaybenamedchloroethane(nolocatornumberisneededforatwocarbonchain)orethylchloride.Halogenatedalkyl
substituentssuchasbromomethyl,BrCH2,andtrichloromethyl,CCl3,maybelistedandarealphabetizedaccordingtotheirfullnames.
Foradditionalexamplesofhowtheserulesareusedinnamingbranchedalkanes,andforsomesubrulesofnomenclature ClickHere .

Cycloalkanes

Cycloalkanes
Cycloalkaneshaveoneormoreringsofcarbonatoms.Thesimplestexamplesofthisclassconsistofasingle,unsubstitutedcarbonring,and
theseformahomologousseriessimilartotheunbranchedalkanes.TheIUPACnamesofthefirstfivemembersofthisseriesaregiveninthe
followingtable.Thelast(yellowshaded)columngivesthegeneralformulaforacycloalkaneofanysize.Ifasimpleunbranchedalkaneisconvertedto

acycloalkanetwohydrogenatoms,onefromeachendofthechain,mustbelost.Hencethegeneralformulaforacycloalkanecomposedofn
carbonsisCnH2n.Althoughacycloalkanehastwofewerhydrogensthantheequivalentalkane,eachcarbonisbondedtofourotheratomssosuch
compoundsarestillconsideredtobesaturatedwithhydrogen.

ExamplesofSimpleCycloalkanes
Name
Molecular
Formula

Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane

C3H6

C4H8

C5H10

C6H12

C7H14

Structural
Formula

CnH2n

(CH2)n

Line
Formula
Substitutedcycloalkanesarenamedinafashionverysimilartothatusedfornamingbranchedalkanes.Thechiefdifferenceintherulesand
proceduresoccursinthenumberingsystem.Sinceallthecarbonsofaringareequivalent(aringhasnoendslikeachaindoes),thenumberingstarts
atasubstitutedringatom.

IUPACRulesforCycloalkaneNomenclature
1.Foramonosubstitutedcycloalkanetheringsuppliestherootname(tableabove)andthesubstituentgroupis
namedasusual.Alocationnumberisunnecessary.
2.Ifthealkylsubstituentislargeand/orcomplex,theringmaybenamedasasubstituentgrouponanalkane.
3.Iftwodifferentsubstituentsarepresentonthering,theyarelistedinalphabeticalorder,andthefirstcited
substituentisassignedtocarbon#1.Thenumberingofringcarbonsthencontinuesinadirection(clockwiseor
counterclockwise)thataffordsthesecondsubstituentthelowerpossiblelocationnumber.
4.Ifseveralsubstituentsarepresentonthering,theyarelistedinalphabeticalorder.Locationnumbersare
assignedtothesubstituentssothatoneofthemisatcarbon#1andtheotherlocationshavethelowestpossible
numbers,countingineitheraclockwiseorcounterclockwisedirection.
5.Thenameisassembled,listinggroupsinalphabeticalorderandgivingeachgroup(iftherearetwoormore)a
locationnumber.Theprefixesdi,tri,tetraetc.,usedtodesignateseveralgroupsofthesamekind,arenot
consideredwhenalphabetizing.

Forexamplesofhowtheserulesareusedinnamingsubstitutedcycloalkanes ClickHere .
Smallrings,suchasthreeandfourmemberedrings,havesignificantanglestrainresultingfromthedistortionofthesp3carbonbondanglesfromthe
ideal109.5to60and90respectively.Thisanglestrainoftenenhancesthechemicalreactivityofsuchcompounds,leadingtoringcleavage
products.Itisalsoimportanttorecognizethat,withtheexceptionofcyclopropane,cycloalkylringsarenotplanar(flat).Thethreedimensionalshapes
assumedbythecommonrings(especiallycyclohexaneandlargerrings)aredescribedanddiscussedintheConformationalAnalysisSection.
Hydrocarbonshavingmorethanoneringarecommon,andarereferredtoasbicyclic(tworings),tricyclic(threerings)andingeneral,polycyclic
compounds.ThemolecularformulasofsuchcompoundshaveH/Cratiosthatdecreasewiththenumberofrings.Ingeneral,forahydrocarbon
composedofncarbonatomsassociatedwithmringstheformulais:CnH(2n+22m).Thestructuralrelationshipofringsinapolycycliccompound
canvary.Theymaybeseparateandindependent,ortheymayshareoneortwocommonatoms.Someexamplesofthesepossiblearrangements
areshowninthefollowingtable.

ExamplesofIsomericC8H14Bicycloalkanes
IsolatedRings

SpiroRings

Nocommonatoms Onecommonatom

FusedRings

BridgedRings

Onecommonbond

Twocommonatoms

PracticeProblems

ChooseaProblem

Alkenes&Alkynes

AlkenesandAlkynes
Alkenesandalkynesarehydrocarbonswhichrespectivelyhavecarboncarbondoublebondandcarboncarbontriplebondfunctionalgroups.
Themolecularformulasoftheseunsaturatedhydrocarbonsreflectthemultiplebondingofthefunctionalgroups:
Alkane RCH2CH2R CnH2n+2 ThisisthemaximumH/Cratioforagivennumberofcarbonatoms.
Alkene RCH=CHR

CnH2n

Eachdoublebondreducesthenumberofhydrogenatomsby2.

Alkyne RCCR

CnH2n2

Eachtriplebondreducesthenumberofhydrogenatomsby4.

AsnotedearlierintheAnalysisofMolecularFormulassection,themolecularformulaofahydrocarbonprovidesinformationaboutthepossible
structuraltypesitmayrepresent.Forexample,considercompoundshavingtheformulaC5H8.Theformulaofthefivecarbonalkanepentaneis
C5H12sothedifferenceinhydrogencontentis4.Thisdifferencesuggestssuchcompoundsmayhaveatriplebond,twodoublebonds,aringplusa
doublebond,ortworings.Someexamplesareshownhere,andthereareatleastfourteenothers!

IUPACRulesforAlkeneandCycloalkeneNomenclature
1.Theenesuffix(ending)indicatesanalkeneorcycloalkene.
2.Thelongestchainchosenfortherootnamemustincludebothcarbonatomsofthedoublebond.
3.Therootchainmustbenumberedfromtheendnearestadoublebondcarbonatom.Ifthedoublebondisinthe
centerofthechain,thenearestsubstituentruleisusedtodeterminetheendwherenumberingstarts.
4.Thesmallerofthetwonumbersdesignatingthecarbonatomsofthedoublebondisusedasthedoublebond
locator.Ifmorethanonedoublebondispresentthecompoundisnamedasadiene,trieneorequivalentprefix
indicatingthenumberofdoublebonds,andeachdoublebondisassignedalocatornumber.
5.Incycloalkenesthedoublebondcarbonsareassignedringlocations#1and#2.Whichofthetwois#1maybe
determinedbythenearestsubstituentrule.
6.Substituentgroupscontainingdoublebondsare:
H2C=CHVinylgroup
H2C=CHCH2Allylgroup

IUPACRulesforAlkyneNomenclature

1.Theynesuffix(ending)indicatesanalkyneorcycloalkyne.
2.Thelongestchainchosenfortherootnamemustincludebothcarbonatomsofthetriplebond.
3.Therootchainmustbenumberedfromtheendnearestatriplebondcarbonatom.Ifthetriplebondisinthecenter
ofthechain,thenearestsubstituentruleisusedtodeterminetheendwherenumberingstarts.
4.Thesmallerofthetwonumbersdesignatingthecarbonatomsofthetriplebondisusedasthetriplebondlocator.
5.Ifseveralmultiplebondsarepresent,eachmustbeassignedalocatornumber.Doublebondsprecedetriplebonds
intheIUPACname,butthechainisnumberedfromtheendnearestamultiplebond,regardlessofitsnature.
6.Becausethetriplebondislinear,itcanonlybeaccommodatedinringslargerthantencarbons.Insimple
cycloalkynesthetriplebondcarbonsareassignedringlocations#1and#2.Whichofthetwois#1maybedetermined
bythenearestsubstituentrule.
7.Substituentgroupscontainingtriplebondsare:
HCCEthynylgroup
HCCCH2Propargylgroup

Forexamplesofhowtheserulesareusedinnamingalkenes,alkynesandcyclicanalogs ClickHere .

BenzeneDerivatives

BenzeneDerivatives
Thenomenclatureofsubstitutedbenzeneringcompoundsislesssystematicthanthatofthealkanes,alkenesandalkynes.Afewmonosubstituted
compoundsarenamedbyusingagroupnameasaprefixto"benzene",asshownbythecombinednameslistedbelow.Amajorityofthese
compounds,however,arereferredtobysingularnamesthatareunique.Thereisnosimplealternativetomemorizationinmasteringthesenames.

Twocommonlyencounteredsubstituentgroupsthatincorporateabenzeneringarephenyl,abbreviatedPh,andbenzyl,abbreviatedBn.These
areshownherewithexamplesoftheiruse.Becarefulnottoconfuseaphenyl(pronouncedfenyl)groupwiththecompoundphenol(pronounced
feenol).AgeneralandusefulgenericnotationthatcomplementstheuseofRforanalkylgroupisArforanarylgroup(anyaromaticring).

Whenmorethanonesubstituentispresentonabenzenering,therelativelocationsofthesubstituentsmustbedesignatedbynumberingthering
carbonsorbysomeothernotation.Inthecaseofdisubstitutedbenzenes,theprefixesortho,meta&paraarecommonlyusedtoindicatea1,2or
1,3or1,4relationshiprespectively.Inthefollowingexamples,thefirstrowofcompoundsshowthisusageinred.Somedisubstitutedtolueneshave

singularnames(e.g.xylene,cresol&toluidine)andtheirisomersarenormallydesignatedbytheortho,metaorparaprefix.Afewdisubstituted
benzeneshavesingularnamesgiventospecificisomers(e.g.salicylicacid&resorcinol).Finally,iftherearethreeormoresubstituentgroups,thering
isnumberedinsuchawayastoassignthesubstituentsthelowestpossiblenumbers,asillustratedbythelastrowofexamples.Thesubstituentsare
listedalphabeticallyinthefinalname.Ifthesubstitutionissymmetrical(thirdexamplefromtheleft)thenumberingcorrespondstothealphabetical
order.

PracticeProblems

Sevenquestionsconcerningnomenclaturearepresentedhere.
ChooseaProblem

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