ReactionsofAlkanes

AlkaneReactions
Thealkanesandcycloalkanes,withtheexceptionofcyclopropane,areprobablytheleastchemicallyreactiveclassof
organiccompounds.Despitetheirrelativeinertness,alkanesundergoseveralimportantreactionsthatarediscussedinthe
followingsection.

1.Combustion
Thecombustionofcarboncompounds,especiallyhydrocarbons,hasbeenthemostimportantsourceofheatenergyfor
humancivilizationsthroughoutrecordedhistory.Thepracticalimportanceofthisreactioncannotbedenied,butthe
massiveanduncontrolledchemicalchangesthattakeplaceincombustionmakeitdifficulttodeducemechanisticpaths.
Usingthecombustionofpropaneasanexample,weseefromthefollowingequationthateverycovalentbondinthe
reactantshasbeenbrokenandanentirelynewsetofcovalentbondshaveformedintheproducts.Noothercommon
reactioninvolvessuchaprofoundandpervasivechange,andthemechanismofcombustionissocomplexthatchemists
arejustbeginningtoexploreandunderstandsomeofitselementaryfeatures.
CH3CH2CH3+5O2>3CO2+4H2O+heat
Twopointsconcerningthisreactionareimportant:
1.Sinceallthecovalentbondsinthereactantmoleculesarebroken,thequantityofheatevolvedinthisreactionis
relatedtothestrengthofthesebonds(and,ofcourse,thestrengthofthebondsformedintheproducts).Precise
heatsofcombustionmeasurementscanprovideusefuliinformationaboutthestructureofmolecules.
2.Thestoichiometryofthereactantsisimportant.Ifinsufficientoxygenissuppliedsomeoftheproductswillconsist
ofcarbonmonoxide,ahighlytoxicgas.
CH3CH2CH3+4O2>CO2+2CO+4H2O+heat

HeatofCombustion
Fromthepreviousdiscussion,wemightexpectisomerstohaveidenticalheatsofcombustion.However,afewsimple
measurementswilldisabusethisbelief.Thus,theheatofcombustionofpentaneis782kcal/mole,butthatofits2,2
dimethylpropane(neopentane)isomeris777kcal/mole.Differencessuchasthisreflectsubtlestructuralvariations,
includingthegreaterbondenergyof1CHversus2CHbondsandstericcrowdingofneighboringgroups.Insmall
ringcycliccompoundsringstraincanbeamajorcontributortothermodynamicstabilityandchemicalreactivity.The
followingtablelistsheatofcombustiondataforsomesimplecycloalkanesandcomparesthesewiththeincreaseperCH2
unitforlongchainalkanes.
H25
RingStrain
H25
kcal/mole
kcal/mole perCH2Unit

Cycloalkane
(CH2)n

CH2Units

Cyclopropane

n=3

468.7

156.2

27.6

Cyclobutane

n=4

614.3

153.6

26.4

Cyclopentane

n=5

741.5

148.3

6.5

Cyclohexane

n=6

882.1

147.0

0.0

Cycloheptane

n=7

1035.4

147.9

6.3

Cyclooctane

n=8

1186.0

148.2

9.6

Cyclononane

n=9

1335.0

148.3

11.7

Cyclodecane

n=10

1481

148.1

11.0

CH3(CH2)mCH3

m=large

147.0

0.0

Thechiefsourceofringstraininsmallerringsisanglestrainandeclipsingstrain.Asnotedelsewhere,cyclopropaneand
cyclobutanehavelargecontributionsofbothstrains,withanglestrainbeingespeciallysevere.Changesinchemical
reactivityasaconsequenceofanglestrainaredramaticinthecaseofcyclopropane,andarealsoevidentforcyclobutane.
Someexamplesareshowninthefollowingdiagram.Thecyclopropanereactionsareadditions,manyofwhichare
initiatedbyelectrophilicattack.Thepyrolyticconversionofpinenetomyrceneprobablytakesplacebyaninitialrupture
ofthe1:6bond,givinganallylic3diradical,followedimmediatelybybreakingofthe5:7bond.

2.Halogenation
Halogenationisthereplacementofoneormorehydrogenatomsinanorganiccompoundbyahalogen(fluorine,chlorine,
bromineoriodine).Unlikethecomplextransformationsofcombustion,thehalogenationofanalkaneappearstobea
simplesubstitutionreactioninwhichaCHbondisbrokenandanewCXbondisformed.Thechlorinationof
methane,shownbelow,providesasimpleexampleofthisreaction.
CH4+Cl2+energy>CH3Cl+HCl
Sinceonlytwocovalentbondsarebroken(CH&ClCl)andtwocovalentbondsareformed(CCl&HCl),thisreaction
seemstobeanidealcaseformechanisticinvestigationandspeculation.However,onecomplicationisthatallthe
hydrogenatomsofanalkanemayundergosubstitution,resultinginamixtureofproducts,asshowninthefollowing
unbalancedequation.Therelativeamountsofthevariousproductsdependontheproportionofthetworeactantsused.In
thecaseofmethane,alargeexcessofthehydrocarbonfavorsformationofmethylchlorideasthechiefproductwhereas,
anexcessofchlorinefavorsformationofchloroformandcarbontetrachloride.
CH4+Cl2+energy>CH3Cl+CH2Cl2+CHCl3+CCl4+HCl
Thefollowingfactsmustbeaccomodatedbyanyreasonablemechanismforthehalogenationreaction.
1.Thereactivityofthehalogensdecreasesinthefollowingorder:F2>Cl2>Br2>I2.
2.Weshallconfineourattentiontochlorineandbromine,sincefluorineissoexplosivelyreactiveitisdifficultto
control,andiodineisgenerallyunreactive.
3.Chlorinationsandbrominationsarenormallyexothermic.

4.Energyinputintheformofheatorlightisnecessarytoinitiatethesehalogenations.
5.Iflightisusedtoinitiatehalogenation,thousandsofmoleculesreactforeachphotonoflightabsorbed.
6.Halogenationreactionsmaybeconductedineitherthegaseousorliquidphase.
7.Ingasphasechlorinationsthepresenceofoxygen(aradicaltrap)inhibitsthereaction.
8.Inliquidphasehalogenationsradicalinitiatorssuchasperoxidesfacilitatethereaction.
Themostplausiblemechanismforhalogenationisachainreactioninvolvingneutralintermediatessuchasfreeradicalsor
atoms.Theweakestcovalentbondinthereactantsisthehalogenhalogenbond(ClCl=58kcal/moleBrBr=46
kcal/mole)sotheinitiatingstepisthehomolyticcleavageofthisbondbyheatorlight,notethatchlorineandbromineboth
absorbvisiblelight(theyarecolored).Achainreactionmechanismforthechlorinationofmethanehasbeendescribed.
Brominationofalkanesoccursbyasimilarmechanism,butisslowerandmoreselectivebecauseabromineatomisaless
reactivehydrogenabstractionagentthanachlorineatom,asreflectedbythehigherbondenergyofHClthanHBr.
Toseeananimatedmodelofthebrominationfreeradicalchainreaction ClickHere

Selectivity
Whenalkaneslargerthanethanearehalogenated,isomericproductsareformed.Thuschlorinationofpropanegivesboth
1chloropropaneand2chloropropaneasmonochlorinatedproducts.Fourconstitutionallyisomericdichlorinatedproducts
arepossible,andfiveconstitutionalisomersexistforthetrichlorinatedpropanes.Canyouwritestructuralformulasforthe
fourdichlorinatedisomers?

ShowIsomers

Thehalogenationofpropanedisclosesaninterestingfeatureofthesereactions.Allthehydrogensinacomplexalkane
donotexhibitequalreactivity.Forexample,propanehaseighthydrogens,sixofthembeingstructurallyequivalent
primary,andtheothertwobeingsecondary.Ifallthesehydrogenatomswereequallyreactive,halogenationshouldgive
a3:1ratioof1halopropaneto2halopropanemonohalogenatedproducts,reflectingtheprimary/secondarynumbers.
Thisisnotwhatweobserve.Lightinducedgasphasechlorinationat25Cgives45%1chloropropaneand55%2
chloropropane.
CH3CH2CH3+Cl2>45%CH3CH2CH2Cl+55%CH3CHClCH3
Theresultsofbromination(lightinducedat25C)areevenmoresuprising,with2bromopropaneaccountingfor97%of
themonobromoproduct.
CH3CH2CH3+Br2>3%CH3CH2CH2Br+97%CH3CHBrCH3
Theseresultssuggeststronglythat2hydrogensareinherentlymorereactivethan1hydrogens,byafactorofabout3:1.
Furtherexperimentsshowedthat3hydrogensareevenmorereactivetowardhalogenatoms.Thus,lightinduced
chlorinationof2methylpropanegavepredominantly(65%)2chloro2methylpropane,thesubstitutionproductofthesole
3hydrogen,despitethepresenceofnine1hydrogensinthemolecule.
(CH3)3CH+Cl2>65%(CH3)3CCl+35%(CH3)2CHCH2Cl

Ifyouareuncertainaboutthetermsprimary(1),secondary(2)&tertiary(3)ClickHere.
Itshouldbeclearfromareviewofthetwostepsthatmakeupthefreeradicalchainreactionforhalogenationthatthefirst
step(hydrogenabstraction)istheproductdeterminingstep.Onceacarbonradicalisformed,subsequentbondingtoa
halogenatom(inthesecondstep)canonlyoccurattheradicalsite.Consequently,anunderstandingofthepreferencefor
substitutionat2and3carbonatomsmustcomefromananalysisofthisfirststep.
FirstStep:R3CH+X>R3C+HX
SecondStep:R3C+X2>R3CX+X
SincetheHXproductiscommontoallpossiblereactions,differencesinreactivitycanonlybeattributedtodifferencesin
CHbonddissociationenergies.Inourpreviousdiscussionofbondenergyweassumedaveragevaluesforallbondsofa
givenkind,butnowweseethatthisisnotstrictlytrue.Inthecaseofcarbonhydrogenbonds,therearesignificant
differences,andthespecificdissociationenergies(energyrequiredtobreakabondhomolytically)forvariouskindsofCH
bondshavebeenmeasured.Thesevaluesaregiveninthefollowingtable.

R(inRH)

methyl

ethyl

ipropyl

tbutyl

phenyl

benzyl

allyl

vinyl

BondDissociationEnergy
(kcal/mole)

103

98

95

93

110

85

88

112

ThedifferenceinCHbonddissociationenergyreportedforprimary(1),secondary(2)andtertiary(3)sitesagreeswith
thehalogenationobservationsreportedabove,inthatwewouldexpectweakerbondstobebrokenmoreeasilythanare
strongbonds.Bythisreasoningwewouldexpectbenzylicandallylicsitestobeexceptionallyreactiveinfreeradical
halogenation,asexperimentshaveshown.Themethylgroupoftoluene,C6H5CH3,isreadilychlorinatedorbrominatedin
thepresenceoffreeradicalinitiators(usuallyperoxides),andethylbenzeneissimilarlychlorinatedatthebenzyliclocation
exclusively.Thehydrogensbondedtothearomaticring(referredtoasphenylhydrogensabove)haverelativelyhighbond
dissociationenergiesandarenotsubstituted.
C6H5CH2CH3+Cl2>C6H5CHClCH3+HCl
Sincecarboncarbondoublebondsaddchlorineandbrominerapidlyinliquidphasesolutions,freeradicalsubstitution
reactionsofalkenesbythesehalogensmustbecarriedoutinthegasphase,orbyotherhalogenatingreagents.Onesuch
reagentisNbromosuccinimide(NBS),showninthesecondequationbelow.ByusingNBSasabrominatingagent,allylic
brominationsarereadilyachievedintheliquidphase.

Thecovalentbondhomolysesthatdefinethebonddissociationenergieslistedabovemayaredescribedbythegeneral
equation:
R3CH+energy>R3C+H

Sincethehydrogenatomiscommontoallthecasescitedhere,wecanattributethedifferencesinbonddissociation
energiestodifferencesinthestabilityofthealkylradicals(R3C)asthecarbonsubstitutionchanges.Thisleadsustothe
conclusionthat:

alkylradicalstabilityincreasesintheorder:phenyl<primary(1)<secondary(2)<tertiary(3)<allylbenzyl.
Becausealkylradicalsareimportantintermediatesinmanyreactions,thisstabilityrelationshipwillprovetobeveryuseful
infuturediscussions.Theenhancedstabilityofallylandbenzylradicalsmaybeattributedtoresonancestabilization.Ifyou
wishtoreviewtheprinciplesofresonanceClickHere.
Formulasfortheallylandbenzylradicalsareshownbelow.Drawstructuralformulasforthechiefcanonicalforms
contributingtotheresonancehybridineachcase.

ShowContributingStructures

Thepoorstabilityofphenylradicals,C6H5,mayinturnbeattributedtothedifferenthybridizationstateofthecarbon
bearingtheunpairedelectron(sp2vs.sp3).
BondDissociationEnergyandRadicalStability
TheargumentthatthestabilityofalkylradicalsissimplyderivedfromRHbonddissociationenergiesisflawed.
Forabriefexplanationofthiserror,andareferencetoamorecompletediscussionClickHere.

PracticeProblems

Threeproblemsconcerningtheidentificationofstructurallyequivalentgroupingsandvariousalkanereactionsare
presentedhere.
ChooseaProblem

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