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Substituent
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Inorganicchemistryandbiochemistry,asubstituentisanatomorgroupofatomswhichreplaceshydrogenatom
ontheparentchainofahydrocarbon,becomingamoietyoftheresultantnewmolecule.Thetermssubstituent,side
chain,group,branch,orpendantgroupareusedalmostinterchangeablytodescribebranchesfromaparent
structure,[1]thoughcertaindistinctionsaremadeinthecontextofpolymerchemistry.[2]Inpolymers,sidechains
extendfromabackbonestructure.Inproteins,sidechainsareattachedtothealphacarbonatomsoftheaminoacid
backbone.

Thesuffixylisusedwhennamingorganiccompoundsthatcontainasinglebondreplacingonehydrogenylidene
andylidyneareusedwithdoublebondsandtriplebonds,respectively.Inaddition,whennaminghydrocarbons
thatcontainasubstituent,positionalnumbersareusedtoindicatewhichcarbonatomthesubstituentattachesto
whensuchinformationisneededtodistinguishbetweenisomers.Thepolareffectexertedbyasubstituentisa
combinationoftheinductiveeffectandthemesomericeffect.Additionalstericeffectsresultfromthevolume
occupiedbyasubstituent.

Thephrasesmostsubstitutedandleastsubstitutedarefrequentlyusedtodescribemoleculesandpredicttheir
products.Inthisterminology,methaneisusedasareferenceofcomparison.Usingmethaneasareference,for
eachhydrogenatomthatisreplacedor"substituted"bysomethingelse,themoleculecanbesaidtobemorehighly
substituted.Forexample:

Markovnikov'srulepredictsthatthehydrogenaddstothecarbonofthealkenefunctionalgroupthathasthe
greaternumberofhydrogenatoms(feweralkylsubstituents).
Zaitsev'srulepredictsthatthemajorreactionproductisthealkenewiththemorehighlysubstituted(more
stable)doublebond.

Contents
1 Nomenclature
2 Methanesubstituents
3 Structures
4 Statisticaldistribution
5 Seealso
6 References

Nomenclature
Thesuffixylisusedinorganicchemistrytoformnamesofradicals,eitherseparateorchemicallybondedpartsof
molecules.Itcanbetracedbacktotheoldnameofmethanol,"methylene"(coinedfromGreekwordsmethy=
"wine"andhl="wood"),whichbecameshortenedto"methyl"incompoundnames.Severalreformsofchemical
nomenclatureeventuallygeneralizedtheuseofthesuffixtootherorganicsubstituents.

Theuseofthesuffixisdeterminedbythenumberofhydrogenatomsthatthesubstituentreplacesonaparent
compound(andalso,usually,onthesubstituent).Accordingto1993IUPACguidelines:[3]

ylmeansthatonehydrogenisreplaced.
ylidenemeansthattwohydrogensarereplacedbyadoublebondbetweenparentandsubstituent.
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ylidynemeansthatthreehydrogensarereplacedbyatriplebondbetweenparentandsubstituent.

Thesuffixylidine(with"ine"insteadof"yne"or"ene")isencounteredsporadically,andappearstobeavariant
spellingof"ylidene".[4]ItisnotmentionedinIUPACguidelines.

Formultiplebondsofthesametype,whichlinkthesubstituenttotheparentgroup,theprefixesdi,tri,tetra,
etc.areused:diyl(twosinglebonds),triyl(threesinglebonds),tetrayl(foursinglebonds),diylidene(two
doublebonds)

Formultiplebondsofdifferentbondtypes,multiplesuffixesareadded:ylylidene(onesingleandonedouble),
ylylidyne(onesingleandonetriple),diylylidene(twosingleandonedouble)

Theparentcompoundnamecanbealteredintwoways.

Formanycommoncompoundsthesubstituentislinkedatoneend(the1position),whichisthereforenot
explicitlynumberedintheformula.Thesubstituentnameismodifiedbystrippingane(seeAlkane)and
addingtheappropriatesuffix.Thisis"recommendedonlyforsaturatedacyclicandmonocyclichydrocarbon
substituentgroupsandforthemononuclearparenthydridesofsilicon,germanium,tin,lead,andboron".
Thus,ifthereisacarboxylicacidcalled"Xicacid",analcoholending"Xanol"(or"Xylalcohol"),oran
alkanecalled"Xane",then"Xyl"typicallydenotesthesamecarbonchainlackingthesegroupsbut
modifiedbyattachmenttosomeotherparentmolecule.
Themoregeneralmethodomitsonlytheterminal"e"ofthesubstituentname,butrequiresexplicit
numberingofeachylprefix,evenatposition1(exceptforylidyne,whichasatriplebondmustterminate
thesubstituentcarbonchain).Pentan1ylisanexampleofanamebythismethod,andissynonymouswith
Pentylfromthepreviousguideline.

Notethatsomepopulartermssuchas"vinyl"(whenusedtomean"polyvinyl")representonlyaportionofthefull
chemicalname.

Thesuffix"yl"arosebyextractingitfromtheword"methyl".

Methanesubstituents
Accordingtotheaboverules,acarbonatominamolecule,consideredasasubstituent,hasthefollowingnames
dependingonthenumberofhydrogensboundtoit,andthetypeofbondsformedwiththeremainderofthe
molecule:

CH4 methane nobonds


CH3 methylgroup onesinglebondtoanonhydrogenatom
=CH2 methylenegroupormethylidene onedoublebond
CH2 methylenebridgeormethanediyl twosinglebonds
CH methylidynegroup onetriplebond
=CH methinegroup,methanylylidene,methylylidene onesinglebondandonedoublebond
>CH methanetriylgroup threesinglebonds
C methylylidynegroup onetriplebondandonesinglebond
=C= methanediylidenegroup twodoublebonds
>C= methanediylylidenegroup twosinglebondsandonedoublebond
>C< methanetetraylgroup foursinglebonds

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Structures
Inachemicalstructuralformula,anorganicsubstituentsuchasmethyl,ethyl,orarylcanbewrittenasR(orR1,
R2,etc.)Tisagenericplaceholder,theRderivedfromradicalorrest,whichmayreplaceanyportionofthe
formulaastheauthorfindsconvenient.ThefirsttousethissymbolwasCharlesFrdricGerhardtin1844.[5]

ThesymbolXisoftenusedtodenoteelectronegativesubstituentssuchasthehalides.[6][7]

Statisticaldistribution
Onecheminformaticsstudyidentified849,574uniquesubstituentsupto12nonhydrogenatomslargeand
containingonlycarbon,hydrogen,nitrogen,oxygen,sulfur,phosphorus,selenium,andthehalogensinasetof
3,043,941molecules.Fiftysubstituentscanbeconsideredcommonastheyarefoundinmorethan1%ofthisset,
and438arefoundinmorethan0.1%.64%ofthesubstituentsarefoundinonlyonemolecule.Thetop5most
commonarethemethyl,phenyl,chlorine,methoxy,andhydroxylsubstituents.Thetotalnumberoforganic
substituentsinorganicchemistryisestimatedat3.1million,creatingatotalof6.71023molecules.[8]Aninfinite
numberofsubstituentscanbeobtainedsimplybyincreasingcarbonchainlength.Forinstance,thesubstituents
methyl(CH3)andpentyl(C5H11).

Seealso
Functionalgroupsareasubsetofsubstituents

References
1.D.R.Bloch(2006).OrganicChemistryDemystified.ISBN9780071459204.
2."PAC,1996,68,2287.Glossaryofbasictermsinpolymerscience(IUPACRecommendations1996)".IUPACGold
Book.doi:10.1351/pac199668122287.Thisdistinguishesapendantgroupasneitheroligomericnorpolymeric,whereasa
pendantchainmustbeoligomericorpolymeric.
3."R2.5SubstituentPrefixNamesDerivedfromParentHydrides".IUPAC.1993.
4.ThePubChemdatabaselists740,110resultsfor"ylidene",ofwhich14havesynonymswherethesuffixisreplacedby
"ylidine".Another4resultscontain"ylidine"withoutlisting"ylidene"asasynonym.
5.See:
CharlesGerhardt,Prcisdechimieorganique(Summaryoforganicchemistry),vol.1(Paris,France:Fortinet
Masson,1844),page29.Frompage29:(https://books.google.com/books?id=sjlBAAAAYAAJ&pg=PA29#v=onep
age&q&f=false)"Endsignant,parconsquent,leslmentscombustiblesparR,sanstenircomptesdes
proportionsatomiquesdecarboneetd'hydrogne,onpeutexprimerd'unemaniregnrale:ParR.Les
hydrognescarbons."(Consequently,bydesignatingcombustiblecomponentsbyR,withoutconsideringthe
atomicproportionsofcarbonandhydrogen,onecanexpressinageneralway:ByRhydrocarbons.)
WilliamB.Jensen(2010)"AsktheHistorian:WhyisRUsedforHydrocarbonSubstituents?,"Journalof
ChemicalEducation,87:360361.Availableat:UniversityofCincinnati.(http://www.che.uc.edu/jensen/W.%20
B.%20Jensen/Reprints/163.%20Origin%20of%20R.pdf)
6.Jensen,W.B.(2010)."WhyIs"R"UsedToSymbolizeHydrocarbonSubstituents?".JournalofChemicalEducation.87
(4):360361.doi:10.1021/ed800139p.
7.ThefirstuseoftheletterXtodenoteunivalentelectronegativegroupsappearedin:
StanislaoCannizzaro(1858)"Suntodiuncorsodifilosofiachimica,fattonellaR.UniversitadiGenova"(https://b
ooks.google.com/books?id=VQOrAAAAIAAJ&pg=PA321#v=onepage&q&f=false)(Sketchofacourseof
chemicalphilosophy,offeredattheRoyalUniversityofGenoa),IlNouvoCimento(TheNewExperiment),7:
321366.Frompage355:(https://books.google.com/books?id=VQOrAAAAIAAJ&pg=PA355#v=onepage&q&f=fa
lse)"Xindicatuttocichevinellamolecola,oltrel'idrogenometallico"(Xstandsforallthatisin
themolecule,aswellasmetallichydrogen).
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8.Ertl,P.(2003)."CheminformaticsAnalysisofOrganicSubstituents:IdentificationoftheMostCommonSubstituents,
CalculationofSubstituentProperties,andAutomaticIdentificationofDruglikeBioisostericGroups".Journalof
ChemicalInformationandModeling.43(2):374.doi:10.1021/ci0255782.

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