ChemicalReactivity

ChemicalReactivity
Organicchemistryencompassesaverylargenumberofcompounds(manymillions),andourpreviousdiscussionandillustrationshave
focusedontheirstructuralcharacteristics.Nowthatwecanrecognizetheseactors(compounds),weturntotherolestheyareinclinedtoplay
inthescientificdramastagedbythemultitudeofchemicalreactionsthatdefineorganicchemistry.
Webeginbydefiningsomebasictermsthatwillbeusedfrequentlyasthissubjectiselaborated.
ChemicalReaction:Atransformationresultinginachangeofcomposition,constitutionand/orconfigurationofacompound(referredto
asthereactantorsubstrate).
ReactantorSubstrate:Theorganiccompoundundergoingchangeinachemicalreaction.Othercompoundsmayalsobeinvolved,and
commonreactivepartners(reagents)maybeidentified.Thereactantisoften(butnotalways)thelargerandmorecomplexmolecule
inthereactingsystem.Most(orall)ofthereactantmoleculeisnormallyincorporatedaspartoftheproductmolecule.
Reagent:Acommonpartnerofthereactantinmanychemicalreactions.Itmaybeorganicorinorganicsmallorlargegas,liquidor
solid.Theportionofareagentthatendsupbeingincorporatedintheproductmayrangefromalltoverylittleornone.
Product(s)Thefinalformtakenbythemajorreactant(s)ofareaction.
ReactionConditionsTheenvironmentalconditions,suchastemperature,pressure,catalysts&solvent,underwhichareaction
progressesoptimally.Catalystsaresubstancesthatacceleratetherate(velocity)ofachemicalreactionwithoutthemselvesbeing
consumedorappearingaspartofthereactionproduct.Catalystsdonotchangeequilibriapositions.

Chemicalreactionsarecommonlywrittenasequations:

ReactionClassification

ClassifyingOrganicChemicalReactions
Ifyouscananyorganictextbookyouwillencounterwhatappearstobeaverylarge,oftenintimidating,numberofreactions.Thesearethe
"tools"ofachemist,andtousethesetoolseffectively,wemustorganizetheminasensiblemannerandlookforpatternsofreactivitythat
permitusmakeplausiblepredictions.Mostofthesereactionsoccuratspecialsitesofreactivityknownasfunctionalgroups,andthese
constituteoneorganizationalschemethathelpsuscatalogandrememberreactions.
Ultimately,thebestwaytoachieveproficiencyinorganicchemistryistounderstandhowreactionstakeplace,andtorecognize
thevariousfactorsthatinfluencetheircourse.
Thisisbestaccomplishedbyperceivingthereactionpathwayormechanismofareaction.

1.ClassificationbyStructuralChange
First,weidentifyfourbroadclassesofreactionsbasedsolelyonthestructuralchangeoccurringinthereactantmolecules.Thisclassification
doesnotrequireknowledgeorspeculationconcerningreactionpathsormechanisms.
TheletterRinthefollowingillustrationsiswidelyusedasasymbolforagenericgroup.ItmaystandforsimplesubstituentssuchasHor
CH3,orforcomplexgroupscomposedofmanyatomsofcarbonandotherelements.

FourReactionClasses
Addition

Elimination

Substitution

Rearrangement

Inanadditionreactionthenumberofbondsinthesubstratemoleculeincreases,usuallyattheexpenseofoneormorebonds.Thereverse
istrueofeliminationreactions,i.e.thenumberofbondsinthesubstratedecreases,andnewbondsareoftenformed.Substitution
reactions,asthenameimplies,arecharacterizedbyreplacementofanatomorgroup(Y)byanotheratomorgroup(Z).Asidefromthese
groups,thenumberofbondsdoesnotchange.Arearrangementreactiongeneratesanisomer,andagainthenumberofbondsnormallydoes
notchange.
Theexamplesillustratedaboveinvolvesimplealkylandalkenesystems,butthesereactiontypesaregeneralformostfunctionalgroups,
includingthoseincorporatingcarbonoxygendoublebondsandcarbonnitrogendoubleandtriplebonds.Somecommonreactionsmayactually
beacombinationofreactiontypes.Thereactionofanesterwithammoniatogiveanamide,asshownbelow,appearstobeasubstitution
reaction(Y=CH3O&Z=NH2)however,itisactuallytworeactions,anadditionfollowedbyanelimination.

Theadditionofwatertoanitriledoesnotseemtofitanyoftheabovereactiontypes,butitissimplyaslowadditionreactionfollowedbyarapid
rearrangement,asshowninthefollowingequation.Rapidrearrangementsofthiskindarecalledtautomerizations.

AdditionalexamplesillustratingtheseclassesofreactionmaybeexaminedbyClickingHere

2.ClassificationbyReactionType
Atthebeginning,itishelpfultoidentifysomecommonreactiontypesthatwillsurfacerepeatedlyasthechemicalbehaviorofdifferent
compoundsisexamined.Thisisnotintendedtobeacompleteandcomprehensivelist,butshouldsetthestageforfutureelaborations.

AcidityandBasicity
Itisusefultobeginadiscussionoforganicchemicalreactionswithareviewofacidbasechemistryandterminologyforseveralreasons.First,
acidbasereactionsareamongthesimplesttorecognizeandunderstand.Second,someclassesoforganiccompoundshavedistinctlyacidic
properties,andsomeotherclassesbehaveasbases,soweneedtoidentifytheseaspectsoftheirchemistry.Finally,manyorganicreactions
arecatalyzedbyacidsand/orbases,andalthoughsuchtransformationsmayseemcomplex,ourunderstandingofhowtheyoccuroftenbegins
withthefunctioningofthecatalyst.
Organicchemistsusetwoacidbasetheoriesforinterpretingandplanningtheirwork:theBrnstedtheoryandtheLewistheory.

BrnstedTheory
AccordingtotheBrnstedtheory,anacidisaprotondonor,andabaseisaprotonacceptor.Inanacidbasereaction,eachsideof
theequilibriumhasanacidandabasereactantorproduct,andthesemaybeneutralspeciesorions.
HA+B:()

A:()+BH

(acid1)(base1)

(base2)(acid2)

Structurallyrelatedacidbasepairs,suchas{HAandA:()}or{B:()andBH}arecalledconjugatepairs.Substancesthatcanserve
asbothacidsandbases,suchaswater,aretermedamphoteric.

HCl+H2O

Cl:()+H3O(+)

(acid)(base)

(base)(acid)

H3N:+H2O

NH4(+)+HO()

(base)(acid)

(acid)(base)

Therelativestrengthofagroupofacids(orbases)maybeevaluatedbymeasuringtheextentofreactionthateachgroupmember
undergoeswithacommonbase(oracid).Waterservesnicelyasthecommonbaseoracidforsuchdeterminations.Thus,foranacidH
A,itsstrengthisproportionaltotheextentofitsreactionwiththebasewater,whichisgivenbytheequilibriumconstantKeq.

H3O(+)+A:()

HA+H2O

Sincethesestudiesaregenerallyextrapolatedtohighdilution,themolarconcentrationofwater(55.5)isconstantandmaybeeliminated
fromthedenominator.TheresultingKvalueiscalledtheacidityconstant,Ka.Clearly,strongacidshavelargerKa'sthandoweaker
acids.Becauseoftheverylargerangeofacidstrengths(greaterthan1040),alogarithmicscaleofacidity(pKa)isnormallyemployed.
StrongeracidshavesmallerormorenegativepKavaluesthandoweakeracids.

Someusefulprinciplesofacidbasereactionsare:
Thestrongertheacidtheweakeritsconjugatebasethestrongerthebasetheweakeritsconjugateacid.
Acidbaseequilibriaalwaysfavortheweakestacidandtheweakestbase.

ExamplesofBrnstedAcidBaseEquilibria

AcidBaseReaction

HBr+H2O

H3O(+)+Br()

CH3CO2H+H2O

H3O(+)+CH3CO2()

C2H5OH+H2O

H3O(+)+C2H5O()

NH3+H2O

H3O(+)+NH2()

Conjugate
Acids

Conjugate
Bases

Ka

pKa

HBr

Br()
H2O

105

1.77*105

4.75

1016

16

1034

34

H3

O(+)

CH3CO2H

H3

O(+)

C2H5OH
H3O(+)
NH3
H3

O(+)

CH3CO2()
H2O
C2H5O()
H2O
NH2()
H2O

Inalltheaboveexampleswateractsasacommonbase.Thelastexample(NH3)cannotbemeasureddirectlyinwater,sincethe
strongestbasethatcanexistinthissolventishydroxideion.Consequently,thevaluereportedhereisextrapolatedfrommeasurements
inmuchlessacidicsolvents,suchasacetonitrile.
Sincemanyorganicreactionseithertakeplaceinaqueousenvironments(livingcells),orarequenchedorworkedupinwater,itis
importanttoconsiderhowaconjugateacidbaseequilibriummixturechangeswithpH.AsimplerelationshipknownastheHenderson
Hasselbalchequationprovidesthisinformation.

WhenthepHofanaqueoussolutionormixtureisequaltothepKaofanacidiccomponent,theconcentrationsoftheacidandbase
conjugateformsmustbeequal(thelogof1is0).IfthepHisloweredbytwoormoreunitsrelativetothepKa,theacidconcentration
willbegreaterthan99%.Ontheotherhand,ifthepH(relativetopKa)israisedbytwoormoreunitstheconjugatebaseconcentration
willbeover99%.Consequently,mixturesofacidicandnonacidiccompoundsareeasilyseparatedbyadjustingthepHofthewater
componentinatwophasesolventextraction.
Forexample,ifasolutionofbenzoicacid(pKa=4.2)inbenzylalcohol(pKa=15)isdissolvedinetherandshakenwithanexcessof
0.1Nsodiumhydroxide(pH=13),theacidiscompletelyconvertedtoitswatersoluble(etherinsoluble)sodiumsalt,whilethealcohol
isunaffected.Theethersolutionofthealcoholmaythenbeseparatedfromthewaterlayer,andpurealcoholrecoveredbydistillationof
thevolatileethersolvent.ThepHofthewatersolutionofsodiumbenzoatemaythenbeloweredto1.0byadditionofhydrochloricacid,at
whichpointpurebenzoicacidcrystallizes,andmaybeisolatedbyfiltration.

Basicity
Thebasicityofoxygen,nitrogen,sulfurandphosphoruscompoundsorionsmaybetreatedinananalogousfashion.Thus,wemaywrite
baseacidequilibria,whichdefineaKbandacorrespondingpKb.However,amorecommonprocedureistoreporttheaciditiesofthe
conjugateacidsofthebases(theseconjugateacidsareoften"onium"cations).ThepKa'sreportedforbasesinthissystemare
proportionaltothebasestrengthofthebase.Ausefulrulehereis:pKa+pKb=14.
Weseethisrelationshipinthefollowingtwoequilibria:

AcidBaseReaction

NH3+H2O

NH4(+)+OH()

NH4(+)+H2O

H3O(+)+NH3

Conjugate
Acids

Conjugate
Bases

NH4(+)

NH3

H2O

OH()

NH4(+)

NH3

O(+)

H2O

H3

pK

Kb=1.8*105

pKb=4.74

Ka=5.5*1010

pKa=9.25

TablesofpKavaluesforinorganicandorganicacids(andbases)areavailableinmanyreferencebooks,andmaybeexaminedhereby
clickingontheappropriatelink:
InorganicAcidityConstants
OrganicAcidityConstants
BasicityConstants
AlthoughitisconvenientandinformativetoexpresspKavaluesforacommonsolventsystem(usuallywater),thereareserious
limitationsforverystrongandveryweakacids.Thusacidsthatarestrongerthanthehydroniumcation,H3O(+),andweakacidshaving
conjugatebasesstrongerthanhydroxideanion,OH(),cannotbemeasureddirectlyinwatersolution.Solventssuchasaceticacid,
acetonitrileandnitromethaneareoftenusedforstudyingverystrongacids.Relativeaciditymeasurementsinthesesolventsmaybe
extrapolatedtowater.Likewise,veryweaklyacidicsolventssuchasDMSO,acetonitrile,toluene,aminesandammoniamaybeusedto
studytheaciditiesofveryweakacids.Forboththesegroups,thereportedpKavaluesextrapolatedtowaterareapproximate,andmany
havelargeuncertainties.AusefultableofpKavaluesinDMSOsolutionhasbeencompiledfromtheworkofF.G.Bordwell,andmaybe
reachedbyClickingHere.

LewisTheory
AccordingtotheLewistheory,anacidisanelectronpairacceptor,andabaseisanelectronpairdonor.Lewisbasesarealso
Brnstedbaseshowever,manyLewisacids,suchasBF3,AlCl3andMg2+,arenotBrnstedacids.TheproductofaLewisacidbase
reaction,isaneutral,dipolarorchargedcomplex,whichmaybeastablecovalentmolecule.Asshownatthetopofthefollowing
drawing,coordinatecovalentbondingofaphosphorousLewisbasetoaboronLewisacidcreatesacomplexinwhichtheformalcharge
ofboronisnegativeandthatofphosphorousispositive.Inthiscomplex,boronacquiresaneonvalenceshellconfigurationand
phosphorousanargonconfiguration.Ifthesubstituents(R)ontheseatomsarenotlarge,thecomplexwillbefavoredatequilibrium.
However,sterichindranceofbulkysubstituentsmayprohibitcomplexformation.TheresultingmixtureofnonbondedLewisacid/base
pairshasbeentermed"frustrated",andexhibitsunusualchemicalbehavior.
TwoexamplesofLewisacidbaseequilibriathatplayaroleinchemicalreactionsareshowninequations1&2below.

Inthefirstexample,anelectrondeficientaluminumatombondstoacovalentchlorineatombysharingoneofitsnonbondingvalence
electronpairs,andthusachievesanargonlikevalenceshelloctet.Becausethissharingisunilateral(chlorinecontributesbothelectrons),
boththealuminumandthechlorinehaveformalcharges,asshown.Ifthecarbonchlorinebondinthiscomplexbreakswithboththe
bondingelectronsremainingwiththemoreelectronegativeatom(chlorine),thecarbonassumesapositivecharge.Werefertosuch
carbonspeciesascarbocations.CarbocationsarealsoLewisacids,asthereversereactiondemonstrates.
Manycarbocations(butnotall)mayalsofunctionasBrnstedacids.Equation3illustratesthisdualbehaviortheLewisacidicsiteis
coloredredandthreeofthenineacidichydrogenatomsarecoloredorange.InitsBrnstedacidrolethecarbocationdonatesaprotonto
thebase(hydroxideanion),andisconvertedtoastableneutralmoleculehavingacarboncarbondoublebond.
AterminologyrelatedtotheLewisacidbasenomenclatureisoftenusedbyorganicchemists.Herethetermelectrophilecorresponds
toaLewisacid,andnucleophilecorrespondstoaLewisbase.
Electrophile:Anelectrondeficientatom,ionormoleculethathasanaffinityforanelectronpair,andwillbondtoabaseor
nucleophile.
Nucleophile:Anatom,ionormoleculethathasanelectronpairthatmaybedonatedinbondingtoanelectrophile(orLewisacid).
Tolearnmoreabouttherelationshipofbasicityandnucleophilicity,
andforexamplesofacid/basecatalysisoforganicreactionsClickHere.

OxidationandReductionReactions
Aparallelandindependentmethodofcharacterizingorganicreactionsisbyoxidationreductionterminology.Carbonatomsmayhave
anyoxidationstatefrom4(e.g.CH4)to+4(e.g.CO2),dependingupontheirsubstituents.Fortunately,weneednotdeterminethe
absoluteoxidationstateofeachcarbonatominamolecule,butonlythechangeinoxidationstateofthosecarbonsinvolvedina
chemicaltransformation.Todeterminewhetheracarbonatomhasundergonearedoxchangeduringareactionwesimplynoteany
changesinthenumberofbondstohydrogenandthenumberofbondstomoreelectronegativeatomssuchasO,N,F,Cl,Br,I,&Sthat
hasoccurred.Bondstoothercarbonatomsareignored.Thiscountshouldbeconductedforeachcarbonatomundergoinganychange
duringareaction.
1. Ifthenumberofhydrogenatomsbondedtoacarbonincreases,and/orifthenumberofbondstomoreelectronegativeatoms
decreases,thecarboninquestionhasbeenreduced(i.e.itisinaloweroxidationstate).
2. Ifthenumberofhydrogenatomsbondedtoacarbondecreases,and/orifthenumberofbondstomoreelectronegativeatoms
increases,thecarboninquestionhasbeenoxidized(i.e.itisinahigheroxidationstate).
3. Iftherehasbeennochangeinthenumberofsuchbonds,thenthecarboninquestionhasnotchangeditsoxidationstate.Inthe
hydrolysisreactionofanitrileshownabove,thebluecoloredcarbonhasnotchangeditsoxidationstate.
Theserulesareillustratedbythefollowingfouradditionreactionsinvolvingthesamestartingmaterial,cyclohexene.Carbonatoms
coloredbluearereduced,andthosecoloredredareoxidized.Intheadditionofhydrogenbothcarbonatomsarereduced,andthe
overallreactionistermedareduction.Peracidepoxidationandadditionofbromineoxidizebothcarbonatoms,sothesearetermed

oxidationreactions.AdditionofHBrreducesoneofthedoublebondcarbonatomsandoxidizestheotherconsequently,thereisno
overallredoxchangeinthesubstratemolecule.

ForadiscussionofhowoxidationstatenumbersmaybeassignedtocarbonatomsClickHere.

Sincemetalssuchaslithiumandmagnesiumarelesselectronegativethanhydrogen,theircovalentbondstocarbonarepolarizedso
thatthecarbonisnegative(reduced)andthemetalispositive(oxidized).Thus,Grignardreagentformationfromanalkylhalidereduces
thesubstitutedcarbonatom.Inthefollowingequationandhalfreactionsthecarbonatom(blue)isreducedandthemagnesium
(magenta)isoxidized.

3.ClassificationbyFunctionalGroup
Functionalgroupsareatomsorsmallgroupsofatoms(usuallytwotofour)thatexhibitacharacteristicreactivitywhentreatedwith
certainreagents.ToviewatableofthecommonfunctionalgroupsandtheirclassnamesClickHere.Aparticularfunctionalgroupwill
almostalwaysdisplayitscharacteristicchemicalbehaviorwhenitispresentinacompound.Becauseofthis,thediscussionoforganic
reactionsisoftenorganizedaccordingtofunctionalgroups.Thefollowingtablesummarizesthegeneralchemicalbehaviorofthe
commonfunctionalgroups.Forreference,thealkanesprovideabackgroundofbehaviorintheabsenceofmorelocalizedfunctional
groups.
FunctionalClass

Formula

CharacteristicReactions

Alkanes

CC,CH

Substitution(ofH,commonlybyClorBr)
Combustion(conversiontoCO2&H2O)

Alkenes

C=CCH

Addition
Substitution(ofH)

Alkynes

CCH

Addition
Substitution(ofH)

AlkylHalides

HCCX

Substitution(ofX)
Elimination(ofHX)

Alcohols

HCCOH

Substitution(ofH)Substitution(ofOH)
Elimination(ofHOH)Oxidation(eliminationof2H)

Ethers

()COR

Substitution(ofOR)Substitution(ofH)

Amines

CNRH

Substitution(ofH)
Addition(toN)Oxidation(ofN)

BenzeneRing

C6H6

Substitution(ofH)

Aldehydes

()CCH=O

Addition
Substitution(ofHorH)

Ketones

()CCR=O

Addition
Substitution(ofH)

CarboxylicAcids

()CCO2H

Substitution(ofH)Substitution(ofOH)
Substitution(ofH)Addition(toC=O)

CarboxylicDerivatives

()CCZ=O
(Z=OR,Cl,NHR,etc.)

Substitution(ofZ)Substitution(ofH)
Addition(toC=O)

Thistabledoesnotincludeanyreferencetorearrangement,duetothefactthatsuchreactionsarefoundinallfunctionalclasses,and
arehighlydependentonthestructureofthereactant.Furthermore,areviewoftheoverallreactionpatternspresentedinthistable
disclosesonlyabroadandrathernonspecificsetofreactivitytrends.Thisisnotsurprising,sincethethreeremainingcategoriesprovide
onlyacoarsediscrimination(comparabletoidentifyinganobjectasanimal,vegetableormineral).Consequently,apparentsimilarities
mayfailtoreflectimportantdifferences.Forexample,additionreactionstoC=CaresignificantlydifferentfromadditionstoC=O,and
substitutionreactionsofCXproceedinverydifferentways,dependingonthehybridizationstateofcarbon.

ReactionVariables

TheVariablesofOrganicReactions
Inanefforttounderstandhowandwhyreactionsoffunctionalgroupstakeplaceinthewaytheydo,chemiststrytodiscoverjusthow
differentmoleculesandionsinteractwitheachotherastheycometogether.Tothisend,itisimportanttoconsiderthevarious
propertiesandcharacteristicsofareactionthatmaybeobservedand/ormeasuredasthereactionproceeds.Themost
commonandusefulofthesearelistedbelow:

1.ReactantsandReagents
A.ReactantStructure:Variationsinthestructureofthereactantmayhaveamarkedinfluenceonthecourseofareaction,
eventhoughthefunctionalgroupisunchanged.Thus,reactionof1bromopropanewithsodiumcyanideproceedssmoothlyto
yieldbutanenitrile,whereas1bromo2,2dimethylpropanefailstogiveanyproductandisrecoveredunchanged.Incontrast,
bothalkylbromidesformGrignardreagents(RMgBr)onreactionwithmagnesium.

B.ReagentCharacteristics:Apparentlyminorchangesinareagentmayleadtoasignificantchangeinthecourseofa
reaction.Forexample,2bromopropanegivesasubstitutionreactionwithsodiummethylthiolatebutundergoespredominant
eliminationontreatmentwithsodiummethoxide.

2.ProductSelectivity
A.Regioselectivity:Itisoftenthecasethatadditionandeliminationreactionsmay,inprinciple,proceedtomorethanone
product.Thus1butenemightaddHBrtogiveeither1bromobutaneor2bromobutane,dependingonwhichcarbonofthe
doublebondreceivesthehydrogenandwhichthebromine.Ifonepossibleproductoutoftwoormoreisformedpreferentially,
thereactionissaidtoberegioselective.

Simplesubstitutionreactionsarenotnormallyconsideredregioselective,sincebydefinitiononlyoneconstitutionalproductis
possible.However,rearrangementsareknowntooccurduringsomereactions.

B.Stereoselectivity:Ifthereactionproductsaresuchthatstereoisomersmaybeformed,areactionthatyieldsone
stereoisomerpreferentiallyissaidtobestereoselective.Intheadditionofbrominetocyclohexene,forexample,cisandtrans
1,2dibromocyclohexanearebothpossibleproductsoftheaddition.Sincethetransisomeristheonlyisolatedproduct,this
reactionisstereoselective.

C.Stereospecificity:Thistermisappliedtocasesinwhichstereoisomericreactantsbehavedifferentlyinagivenreaction.
Examplesinclude:
(i)Formationofdifferentstereoisomericproducts,asinthereactionofenantiomeric2bromobutaneisomerswithsodium
methylthiolate,showninthefollowingdiagram.

Here,the(R)reactantgivestheconfigurationallyinverted(S)product,and(S)reactantproduces(R)product.The(R)
and(S)notationsforconfigurationaredescribedinalatersectionofthistext.
(ii)Differentratesofreaction,asinthebaseinducedeliminationofcis&trans4tertbutylcyclohexylbromide(equation1
below).
(iii)Differentreactionpathsleadingtodifferentproducts,asinthebaseinducedeliminationofcis&trans2
methylcyclohexylbromide(equation2below).

Themechanismsofthesesubstitutionandeliminationreactionsarediscussedinthealkylhalidesectionofthistext.

3.ReactionCharacteristics
A.ReactionRates:Somereactionsproceedveryrapidly,andsomesoslowlythattheyarenotnormallyobserved.Amongthe
variablesthatinfluencereactionratesaretemperature(reactionsareusuallyfasteratahighertemperature),solvent,and
reactant/reagentconcentrations.Usefulinformationaboutreactionmechanismsmaybeobtainedbystudyingthemannerin
whichtherateofareactionchangesastheconcentrationsofthereactantandreagentsarevaried.Thisfieldofstudyiscalled
kinetics.
B.Intermediates:Manyreactionsproceedinastepwisefashion.Thiscanbeconvincinglydemonstratedifanintermediate
speciescanbeisolatedandshowntoproceedtothesameproductsunderthereactionconditions.Someintermediatesare
stablecompoundsintheirownrighthowever,somearesoreactivethatisolationisnotpossible.Nevertheless,evidencefor
theirexistencemaybeobtainedbyothermeans,includingspectroscopicobservationorinferencefromkineticresults.

4.FactorsthatInfluenceReactions
Itishelpfultoidentifysomegeneralfeaturesofareactionthathaveasignificantinfluenceonitsfacility.Someofthemostimportantof
theseare:
A.Energetics:Thepotentialenergyofareactingsystemchangesasthereactionprogresses.Theoverallchangemaybe
exothermic(energyisreleased)orendothermic(energymustbeadded),andthereisusuallyanactivationenergy
requirementaswell.TablesofStandardBondEnergiesarewidelyusedbychemistsforestimatingtheenergychangeina
proposedreaction.Asarule,compoundsconstructedofstrongcovalentbondsaremorestablethancompoundsincorporating
oneormorerelativelyweakbonds.
B.ElectronicEffects:Thedistributionofelectronsatsitesofreaction(functionalgroups)isaparticularlyimportantfactor.
Electrondeficientspeciesorgroups,whichmayormaynotbepositivelycharged,areattractedtoelectronrichspeciesor
groups,whichmayormaynotbenegativelycharged.Werefertothesespeciesaselectrophiles&nucleophiles
respectively.Ingeneral,oppositesattractandlikerepel.
Thechargedistributioninamoleculeisusuallydiscussedwithrespecttotwointeractingeffects:Aninductiveeffect,whichis
afunctionoftheelectronegativitydifferencesthatexistbetweenatoms(andgroups)andaresonanceeffect,inwhich
electronsmoveinadiscontinuousfashionbetweenpartsofamolecule.
C.StericEffects:Atomsoccupyspace.Whentheyarecrowdedtogether,vanderWaalsrepulsionsproduceanunfavorable
sterichindrance.Sterichindrancemayinfluenceconformationalequilibria,aswellasdestabilizingtransitionstatesof
reactions.
D.StereoelectronicEffects:Inmanyreactionsatomicormolecularorbitalsinteractinamannerthathasanoptimal
configurationalorgeometricalalignment.Departurefromthisalignmentinhibitsthereaction.
E.SolventEffects:Mostreactionsareconductedinsolution,notinagaseousstate.Thesolventselectedforagivenreaction
mayexertastronginfluenceonitscourse.Remember,solventsarechemicals,andmostundergochemicalreactionunderthe
rightconditions.

ReactionMechanisms

MechanismsofOrganicReactions
Adetaileddescriptionofthechangesinstructureandbondingthattakeplaceinthecourseofareaction,andthesequenceofsuch
eventsiscalledthereactionmechanism.Areactionmechanismshouldincludearepresentationofplausibleelectronreorganization,as
wellastheidentificationofanyintermediatespeciesthatmaybeformedasthereactionprogresses.Thesefeaturesareelaboratedinthe
followingsections.

1.TheArrowNotationinMechanisms
Sincechemicalreactionsinvolvethebreakingandmakingofbonds,aconsiderationofthemovementofbonding(andnonbonding)
valenceshellelectronsisessentialtothisunderstanding.Itisnowcommonpracticetoshowthemovementofelectronswithcurved
arrows,andasequenceofequationsdepictingtheconsequencesofsuchelectronshiftsistermedamechanism.Ingeneral,twokinds
ofcurvedarrowsareusedindrawingmechanisms:
Afullheadonthearrowindicatesthemovementorshiftofanelectronpair:
Apartialhead(fishhook)onthearrowindicatestheshiftofasingleelectron:
Theuseofthesesymbolsinbondbreakingandbondmakingreactionsisillustratedbelow.Ifacovalentsinglebondisbrokensothat
oneelectronofthesharedpairremainswitheachfragment,asinthefirstexample,thisbondbreakingiscalledhomolysis.Ifthebond
breakswithbothelectronsofthesharedpairremainingwithonefragment,asinthesecondandthirdexamples,thisiscalled
heterolysis.
BondBreaking

BondMaking

OtherArrowSymbols
Chemistsalsousearrowsymbolsforotherpurposes,anditisessentialtousethemcorrectly.
TheReactionArrow

TheEquilibriumArrow

TheResonanceArrow

Thefollowingequationsillustratetheproperuseofthesesymbols:

ForfurtherinformationabouttheuseofcurvedarrowsinreactionmechanismsClickHere.

2.ReactiveIntermediates
Theproductsofbondbreaking,shownabove,arenotstableintheusualsense,andcannotbeisolatedforprolongedstudy.Such
speciesarereferredtoasreactiveintermediates,andarebelievedtobetransientintermediatesinmanyreactions.Thegeneral
structuresandnamesoffoursuchintermediatesaregivenbelow.
Apairofwidelyusedterms,relatedtotheLewisacidbasenotation,shouldalsobeintroducedhere.
Electrophile:Anelectrondeficientatom,ionormoleculethathasanaffinityforanelectronpair,andwillbondtoabaseornucleophile.
Nucleophile:Anatom,ionormoleculethathasanelectronpairthatmaybedonatedinbondingtoanelectrophile(orLewisacid).
Usingthesedefinitions,itisclearthatcarbocations(calledcarboniumionsintheolderliterature)areelectrophilesandcarbanionsare
nucleophiles.Carbeneshaveonlyavalenceshellsextetofelectronsandarethereforeelectrondeficient.Inthissensetheyare
electrophiles,butthenonbondingelectronpairalsogivescarbenesnucleophiliccharacter.Asarule,theelectrophiliccharacter
dominatescarbenereactivity.Carbonradicalshaveonlysevenvalenceelectrons,andmaybeconsideredelectrondeficienthowever,
theydonotingeneralbondtonucleophilicelectronpairs,sotheirchemistryexhibitsuniquedifferencesfromthatofconventional
electrophiles.Radicalintermediatesareoftencalledfreeradicals.
Theimportanceofelectrophile/nucleophileterminologycomesfromthefactthatmanyorganicreactionsinvolveatsomestagethe
bondingofanucleophiletoanelectrophile,aprocessthatgenerallyleadstoastableintermediateorproduct.Reactionsofthiskindare
sometimescalledionicreactions,sinceionicreactantsorproductsareofteninvolved.Somecommonexamplesofionicreactionsand
theirmechanismsmaybeexaminedbyClickingHere

Theshapesideallyassumedbytheseintermediatesbecomesimportantwhenconsideringthestereochemistryofreactionsinwhichthey
playarole.Asimpletetravalentcompoundlikemethane,CH4,hasatetrahedralconfiguration.Carbocationshaveonlythreebondsto
thechargebearingcarbon,soitadoptsaplanartrigonalconfiguration.Carbanionsarepyramidalinshape(tetrahedraliftheelectron
pairisviewedasasubstituent),butthesespeciesinvertrapidlyatroomtemperature,passingthroughahigherenergyplanarformin
whichtheelectronpairoccupiesaporbital.Radicalsareintermediateinconfiguration,theenergydifferencebetweenpyramidaland
planarformsbeingverysmall.Sincethreepointsdetermineaplane,theshapeofcarbenesmustbeplanarhowever,thevalence
electrondistributionvaries.

PracticeProblems
Thefollowingproblemsincludeacidbaserelationships,recognitionofdifferentfunctionalgroups,recognitionofnucleophilesandelectrophiles,
classificationofreactionsbystructuralchangeandoxidation/reductionchange,andtheuseofcurvedarrownotation.

ChooseaProblem

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