11.

1FreeRadicals
FreeradicalsformwhenbondsbreakHOMOLYTICALLY.

11.1FreeRadicals
Recalltheorbitalhybridizationincarbocations and
carbanions.

Notethesinglebarbedorfishhookarrowusedtoshow
theelectronmovement.

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11.1FreeRadicals
Freeradicalscanbethoughtofassp2 hybridizedor
quicklyinterconverting sp3 hybridized.

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11.1FreeRadicals Stability
Useargumentsthatinvolvehyperconjugation andan
energydiagramtoexplainthedifferencesinbond
dissociationenergy(BDE)below.

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11.1FreeRadicals Stability
Freeradicalsdonothaveaformalchargebutare
unstablebecauseofanincompleteoctet.
Groupsthatcanpush(donate)electronstowardthe
freeradicalwillhelptostabilizeit.WHY?HOW?
Considerhyperconjugation.

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11.1FreeRadicals Resonance
Drawingresonanceforfreeradicalsusingfishhook
arrowstoshowelectronmovement.
Remember,forresonance,thearrowsdontACTUALLY
showelectronmovement.WHY?
Drawtheresonancehybridforanallyl radical.

HOWandWHYdoesresonanceaffectthestabilityof
thefreeradical?
PracticewithCONCEPTUALCHECKPOINT11.1.
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11.1FreeRadicals Resonance

11.1FreeRadicals Resonance
Stabilization

Thebenzylic radicalisahybridthatconsistsoffour
contributors.

Howdoesresonanceaffectthestabilityofaradical?
WHY?

Drawtheremainingcontributors.
Drawthehybrid.

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Whatisabiggerfactor,hyperconjugation orresonance?
PracticewithSKILLBUILDER11.1.
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11.1FreeRadicals Resonance
Stabilization
Vinylic freeradicalsareespeciallyunstable.
Noresonancestabilization.

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11.2RadicalElectronMovement
Freeradicalelectronmovementisquitedifferentfrom
electronmovementinionicreactions.
Forexample,freeradicalsdontundergorearrangement.

Whattypeoforbitalisthevinylic freeradicallocatedin,
andhowdoesthataffectstability?
PracticewithSKILLBUILDER11.2.
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ThereareSIXkeyarrowpushingpatternsthatwewill
discuss.
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11.2RadicalElectronMovement
1. Homolytic cleavage,initiatedbylightorheat:
2. Additiontoapibond:
3. Hydrogenabstraction(NOTthesameasproton
transfer):
4. Halogenabstraction:
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Klein, Organic Chemistry 1e

11.2RadicalElectronMovement
5. Elimination:theradicalfromthe carbonispushed
towardthe carbontoeliminateagrouponthe
carbon(reverseofadditiontoapibond):

TheXgroupisNOTaleavinggroup.WHY?

6. Coupling,thereverseofhomolytic cleavage:

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11 -10

Notethatradicalelectronmovementgenerally
involvestwoorthreefishhookarrows.
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11.2RadicalElectronMovement

Notethereversibilityofradicalprocesses:

11.2RadicalElectronMovement

Radicalelectronmovementisgenerallyclassifiedas
eitherinitiation,termination,orpropagation.
INITIATION
occurswhen
radicalsare
created.

TERMINATION
occurswhen
radicalsare
destroyed.

PracticewithSKILLBUILDER11.3.
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11.2RadicalElectronMovement
PROPAGATIONoccurswhenradicalsaremovedfrom
onelocationtoanother.

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11.3RadicalReactions
ChlorinationofMethane
Letsapplyourelectronpushingskillstoareaction.

Wemustconsidereachpatternforanyfreeradicalthat
formsduringthereaction.

Ishomolytic cleavagealsolikelyforCH4?
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11.3RadicalReactions
ChlorinationofMethane

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11.3RadicalReactions
ChlorinationofMethane
Whyareterminationreactionslesscommonthan
propagationreactions?

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11.3RadicalReactions
ChlorinationofMethane
Thepropagationstepsgivethenetreaction:

1. InitiationproducesasmallamountCl radical.
2. HabstractionconsumestheCl radical.
3. Cl abstractiongeneratesaCl radical,whichcangoonto
startanotherHabstraction.

Propagationstepsareselfsustaining.
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Reactionsthathaveselfsustainingpropagationsteps
arecalledCHAINREACTIONS.
Inachainreaction,theproductsfromonestepare
reactantsforadifferentstepinthemechanism.
Polychlorination isdifficulttoprevent,especiallywhen
anexcessofCl2 ispresent.WHY?

PracticewithSKILLBUILDER11.4.
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11.3RadicalReactions
ChlorinationofMethane

11.3RadicalReactions
ChlorinationofMethane
Drawareasonablemechanismthatshowshoweachof
theproductsmightforminthefollowingreaction.

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11.3RadicalReactions Radical
Initiators
Aninitiatorstartsafreeradicalchainreaction
H = +159 kJ/mol

Cl
H = +243 kJ/mol

Cl2
heat

Cl

Cl

H = +121 kJ/mol

Cl

Whichoftheproductsabovearemajor,andwhichare
minor?
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11.3RadicalReactions Radical
Inhibitors
Inhibitorsactinareactiontoscavengefreeradicalsto
stopchainreactionprocesses.
Oxygenmoleculescanexistintheformofadiradical,
whichreactsreadilywithotherradicals.Usearrowsto
showtheprocess.

Howcanreactionconditionsbemodifiedtostop
oxygenfrominhibitingadesiredchainreaction?
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Whichinitiatoraboveinitiatesreactionsmostreadily?
WHY?
Theacyl peroxidewillbeeffectiveat80C.
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11.3RadicalReactions Radical
Inhibitors
Hydroquinoneisalsooftenusedasaradicalinhibitor.

Drawinnecessaryarrowsinthereactionsabove.

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11.4Halogenation Thermodynamics
Ifwewanttodeterminewhetheraprocessisproduct
favored,wemustdeterminethesign(+/)forG.

11.4Halogenation Thermodynamics
BecausetheTS termshouldbeclosetozero,wecan
simplifythefreeenergyequation
Consideringthebondsthatbreakandforminthe
reaction,estimateHhalogenation foreachofthehalogens
inthetablebelow.

Inahalogenation reaction,willH orTS haveabigger

effectonthesignofG?WHY?

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11.4Halogenation Thermodynamics

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11.4Halogenation Thermodynamics
Fluorinationissoexothermicthatitisimpractical.WHY
doesthatmakeitimpractical?
Iodinationisnonspontaneous,sodoesnotfavor
products.ThereactionisnotPRODUCTFAVORED.

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11.4Halogenation Thermodynamics
Considerchlorinationandbromination inmoredetail.

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11.4Halogenation Thermodynamics
Whichstepinthemechanismistheslowstep?Which
reactionhasafasterrate?Whichismoreproduct
favored?
Bothstepsare
exothermic

Chlorinationismoreproductfavoredthan
bromination.
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Klein, Organic Chemistry 1e

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Firststepisendothermic
Secondstepisexothermic

Klein, Organic Chemistry 1e

11.5Halogenation Regioselectivity

11.5Halogenation Regioselectivity

Withsubstratesmorecomplexthanethane,multiple
MONOHALOGENATIONproductsarepossible.

FortheCHLORINATIONprocess,theactualproduct
distributionfavors2chloropropaneover1
chloropropane.

Ifthehalogenwereindiscriminant,predicttheproduct
ratio?

Whichstepinthemechanismdeterminesthe
regioselectivity?
Showthearrowpushingforthatkeymechanisticstep.

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11.5Halogenation Regioselectivity
Inonereaction,a1 freeradicalforms,andintheother,a
2 radicalforms.
Isthechlorinationprocessthermodynamicallyor
kineticallycontrolled?
WHY?

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11.5Halogenation Regioselectivity
FortheBROMINATIONprocess,theproductdistribution
vastlyfavors2bromopropaneover1bromopropane.

Whichstepinthemechanismdetermines
regioselectivity?
Showthearrowpushingforthatkeymechanisticstep.

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11.5Halogenation Regioselectivity
Kineticvs.Thermodynamic
Isthekeystepinthebromination mechanism
kineticallyorthermodynamicallycontrolled?WHY?

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11.5Halogenation Regioselectivity
FocusontheHabstractionstep,andconsiderthe
Hammondpostulatespeciesontheenergydiagram
thataresimilarinenergyaresimilarinstructure.

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11.5Halogenation Regioselectivity

11.5Halogenation Regioselectivity
Whenthebromineradicalabstracts
thehydrogen,thecarbonmustbe
abletostabilizealargepartial
radical.
Whenthechlorineradicalabstracts
thehydrogen,thecarbondoesnot
carryasmuchofapartialradical.

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11.5Halogenation Regioselectivity

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11.5Halogenation Regioselectivity

Whichprocessismoreregioselective?WHY?

Bromination atthe3 positionhappens1600times

moreoftenthanatthe1 position.
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11.5Halogenation Regioselectivity
Whichprocessisleastregioselective?WHY?

Whatisthegeneralrelationshipbetweenreactivityand
selectivity?WHY?

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11.5Halogenation Regioselectivity
Forthereactionbelow,drawthestructureforEVERY
possiblemonobromination product.

Ranktheproductsinorderfrommostmajortomost
minor.

PracticewithSKILLBUILDER11.5.
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11.6Halogenation Stereochemistry
Thehalogenation ofbutaneormorecomplexalkanes
formsanewchirality center.

11.6Halogenation Stereochemistry
Whetherthefreeradicalcarbonissp2 orarapidly
interconverting sp3,thehalogenabstractionwilloccur
oneithersideoftheplanewithequalprobability.

2chlorobutanewillformasaracemic mixture.
Whichstepinthemechanismisresponsibleforthe
stereochemical outcome?
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11.6Halogenation Stereochemistry
Threemonosubstituted productsforminthe
halogenation ofbutane.

Drawallofthemonosubstituted productsthatwould
forminthehalogenation of2methylbutaneincluding
allstereoisomers.
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11.6Halogenation Stereochemistry
Drawallofthemonosubstituted productsthatwould
forminthehalogenation belowincludingall
stereoisomers.

Br2

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11.6Halogenation Stereochemistry
Inthehalogenation of(S)3methylhexane,thechirality
centeristhemostreactivecarboninthemolecule.
WHY?

Nametheproductandpredictthestereochemical
outcome.
PracticewithSKILLBUILDER11.6.
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11.7Allylic Halogenation
WhenanC=Cdoublebondispresent,itaffectsthe
regioselectivity ofthehalogenation reaction.
Giventhebonddissociationenergiesbelow,which
positionofcyclohexene willbemostreactivetoward
halogenation?

light

Classifyanystereoisomerpairsaseitherenantiomers or
diastereomers.
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11.7Allylic Halogenation
Whenanallylic hydrogenisabstracted,itleavesbehind
anallylic freeradicalthatisstabilizedbyresonance.

11.7Allylic Halogenation withNBS

ToavoidthecompetinghalogenADDITIONreaction,
NBScanbeusedtosupplyBr radicals.

Basedonthehighselectivityofbromination thatwe
discussed,youmightexpectbromination tooccuras
shown:
Whatothersetofsideproductsislikelyto
forminthisreaction?Hint:additionreaction.
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11.7Allylic Halogenation withNBS

Showhowresonancestabilizesthesuccinimide radical.
HeatorlightINITIATEStheprocess.
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11.7Allylic Halogenation withNBS

Thesuccinimide radicalthatisproducedintheinitiation
stepcanalsoundergopropagationwhenitcollideswith
anHBrmolecule.Showamechanism.

PropagationproducesnewBr radicalstocontinuethe
chainreaction.
WheredoestheBrBr abovecomefrom?Theamount
ofBrBr insolutionisminimal,sothecompeting
additionreactionisminimized.
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11.7Allylic Halogenation withNBS

Giveamechanismthatexplainsthefollowingproduct
distribution.Hint:resonance.

H-Br

Givesomeexamplesofsometerminationstepsthat
mightoccur.
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11.8Applications
AtmosphericChemistryandO3

Ozoneisbothcreatedanddestroyedintheupperatmosphere.
O3 moleculesabsorbharmfulUVradiation.
O3 moleculesarerecycledasheatenergyisreleased.

PracticewithSKILLBUILDER11.7.

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11.8Applications
AtmosphericChemistryandO3

Forthisprocesstobespontaneous,theentropyofthe
universemustincrease.
Heatisamoredisorderedformofenergythanlight.WHY?

11.8Applications
AtmosphericChemistryandO3
O3 depletion(about6%eachyear)remainsaserious
healthandenvironmentalissue.
Compoundsthataremostdestructivetotheozonelayer:
1. Arestableenoughtoreachtheupperatmosphere.
2. FormfreeradicalsthatinterferewiththeO3 recyclingprocess.

CHLOROFLUOROCARBONs (CFCs)fitbothcriteria.

AtmosphereO3isvitalforprotection,butwhat
effectdoesO3 haveattheearthssurface?
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11.8Applications
AtmosphericChemistryandO3
CFCsubstitutesthatgenerallydecomposebefore
reachingtheO3 layerincludehydrochlorofluorocarbons.

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11.8Applications
CombustionandFirefighting
Likemostreactions,combustioninvolvesbreaking
bondsandformingnewbonds:
AfuelisheatedwiththenecessaryEact tobreakbonds(CC,C
H,andO=O)homolytically.
TheresultingfreeradicalsjointogethertoformnewOHand
C=Obonds.

Hydrofluorocarbons dontevenformthechlorine
radicalsthatinterferewiththeO3 cycle.

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11.8Applications
CombustionandFirefighting
WaterdeprivesthefireoftheEact neededbyabsorbing
theenergy.
CO2 andargongasdeprivethefireofneededoxygen.
Halons areveryeffectivefiresuppressionagents.

Whydoestheprocessreleaseenergyoverall?
Whattypesofchemicalsmightbeusedinfire
extinguisherstoinhibittheprocess?

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11.8Applications
CombustionandFirefighting
Halons suppresscombustioninthreemainways:
1. Asagas,theycansmotherthefireanddepriveitofO2.
2. TheyabsorbsomeoftheEact forthefirebyundergoing
homolytic cleavage.

3. ThefreeradicalsproducedcancombinewithC andH free

radicalstoterminatethecombustionchainreaction.

Halons suppresscombustioninthreemainways.
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11.8Applications
CombustionandFirefighting

11.9Autooxidation vs.Antioxidation
Autooxidation

Howdoyouthinktheuseofhalons tofightfiresaffects
theozonelayer?

Autooxidation istheprocessbywhichcompoundsreact
withmolecularoxygen.

FM200isanalternativefirefightingagent.

Theprocessisgenerallyveryslow.
PracticewithCONCEPTUALCHECKPOINT11.18.
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11.9Autooxidation vs.Antioxidation
Autooxidation Mechanism
Themechanism
illustratesthe
needfora
morerefined
definitionof
initiationand
propagation.
HOW?

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11.9Autooxidation vs.Antioxidation
Autooxidation Mechanism
Propagationcanbemorepreciselydefinedasthesteps
thataddtogethertogivetheNETchemicalequation.

StepsinthemechanismthatarenotpartoftheNET
equationmustbeeitherinitiationortermination.
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11.9Autooxidation vs.Antioxidation
Autooxidation
Somecompoundssuchasethersareparticularly
susceptibletoautooxidation.

Becausehydroperoxides canbeexplosive,etherslike
diethylethermustnotbestoredforlongperiodsof
time.
Theyshouldbedatedandusedinatimely
fashion.
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11.9Autooxidation vs.Antioxidation
Autooxidation
Lightacceleratestheautooxidation process.
Darkcontainersareoftenusedtostoremany
chemicalssuchasvitamins.
Intheabsenceoflight,autooxidation is
usuallyaslowprocess.
Compoundsthatcanformarelativelystable
C radicaluponHabstractionareespecially
susceptibletoautooxidation.WHY?
Considertheautooxidation ofcompounds
withallylic orbenzylic hydrogen.

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11.9Autooxidation vs.Antioxidation
Antioxidants
Triglyceridesareimportanttoahealthydiet.

Autooxidation canoccurattheallylic positions

causingthefoodtobecomerancidandtoxic.
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11.9Autooxidation vs.Antioxidation
Antioxidants
Foodswithunsaturatedfattyacidshaveashortshelf
lifeunlesspreservativesareused.

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11.9Autooxidation vs.Antioxidation
Antioxidants

11.9Autooxidation vs.Antioxidation
NaturalAntioxidants

PreservativescanundergoHabstractiontoquenchthe
C radicalsthatforminthefirststepofautooxidation.

VitaminsCishydrophilic.
VitaminEishydrophobic.
Whatpartsofthebodydothese
vitaminsprotect?
Foreachvitamin,showitsoxidationmechanism,and
explainhowthatprotectsthebodyfromautooxidation.

OnemoleculeofBHTcanpreventthousandsof
autooxidation reactionsbystoppingthechainreaction.
HowdoesBHTs structuremakeitgoodattakingona
freeradical?Considerresonanceandsterics.
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11.10Addition AntiMarkovnikov
Addition
WelearnedinChapter9thatHXwilladdacrossaC=C
doublebondwithantiMarkovnikov regioselectivity
whenperoxidesarepresent.

Nowthatwehavediscussedfreeradicals,wecan
explainthemechanismforthe
antiMarkovnikov addition.
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11.10Addition AntiMarkovnikov
Addition
TheOOsinglebondcanbreakhomolytically witha
relativelylowEact.

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11.10Addition AntiMarkovnikov
Addition
TheBr radicalreactstogivethemorestableC radical.

11.10Addition AntiMarkovnikov
Addition
Mostoftheradicalsinsolutionatanygivenmoment
willbeBr radical.WHY?

Givesomeexamplesofotherterminationstepsthat
mightoccurbutthatwouldbelesscommon.
A3 radicalformsthroughalowertransitionstatethan
a2 radical.
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11.10AdditionThermodynamics
AntiMarkovnikov radicaladditionofHBr isgenerally
spontaneous(productfavored).
Yet,radicaladditionofHCl andHIaregenerally
nonspontaneous (reactantfavored).

Wewillexaminethethermodynamicsofeach
propagationstep.
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11.10AdditionThermodynamics

TheHIreactionwillneverfavorproducts.WHY?
Howcanthetemperaturebeadjustedtofavorproducts
fortheHCl andHBr reaction?
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Gobackthrougheachstepinthemechanismtoexplain
theH valueforeachstep.
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11.10Addition Thermodynamics
Explainthesign(+/)fortheentropytermineach
process.

Willtheentropychangefavorproductsorreactants?
WHY?
Theenthalpychangeisaffectedmostbythe
relativestabilityofthetworadicalspecies.
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11.10Addition Thermodynamics

Forthesecondpropagationstep,whyistheentropy
termapproximatelyzero?
Whatsmalldifferencesinentropybetweenproducts
andreactantsmightaccountforentropychangesbeing
slightly+or?
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11.10Addition Thermodynamics

11.10Addition Stereochemistry
Additionreactionsoftenformanewchiral center.

`
`
ForHCl andHI,thesecondpropagationstepwillnotbe
productfavored.WHY?
HBr istheonlyreactantthatfavorsproductformationfor
bothpropagationsteps.

MighttheoverallpropagationinvolvingHCl beproduct
favorediftheG ofstep1outweighsthe+G
ofstep2?
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11.11RadicalPolymerization
InChapter9,welearnedhowsomeionic
polymerizationsoccur.
Freeradicalconditionsarealsofrequentlyusedtoform
polymers.
Recallthatapolymerizationprocessjoinstogether
manysmallunitscalledmonomersinalongchain.

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11.11RadicalPolymerization
Radicalpolymerizationsgenerallyproceedthrougha
chainreactionmechanism.

Recallthatatleastonereagentinthereactionmustbe
chiral forthereactiontobestereoselective.
Predicttheproductdistributionforthereactionbelow
andexplainthestereochemical outcome.

PracticewithSKILLBUILDER11.8.
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11.11RadicalPolymerization
Radicalpolymerizationsgenerallyproceedthrougha
chainreactionmechanism.

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11.11RadicalPolymerization
Radicalpolymerizationsgenerallyproceedthrougha
chainreactionmechanism.

Notehowthesumofthepropagationsteps
yieldstheoverallreaction.
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11.11RadicalPolymerization
Radicalpolymerizationsgenerallyproducechainsof
monomerswithawidedistributionoflengths.
Howmightexperimentalconditionsbeoptimizedto
controltheaveragelengthofthechains?
Becausethemechanismwejustlearnedproceeds
through1 carbonfreeradicalintermediates,itis
usuallynotfacile.
InChapter27,wewilldiscussspecializedcatalyststhat
canbeusedtocontrolsuchpolymerizationreactions.
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11.11RadicalPolymerization

11.11RadicalPolymerization
Branchingiscommoninsomeradicalpolymerizations.

Branchingmakespolymermaterials
moreflexible,suchasapolyethylene
usedforsqueezebottles.
Whencatalystsareusedtominimize
branching,morerigidmaterialsareproduced,suchas
thematerialusedforsqueezebottlecaps.
Whydoesbranchingaffectrigidity?
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11.11RadicalPolymerization

Manyderivativesofethylenearealsopolymerized.

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11.12RadicalPetroleumProcesses
RecalltheCRACKINGandREFORMINGprocessesfrom
chapters4and8.
CrudeoilisCRACKEDtoproducesmalleralkanes and
alkenes.

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11.13SyntheticUtilityof
Halogenation
Radicalchlorinationandbromination arebothuseful
processes.
Recallthatbromination ismoreselective.WHY?

Temperaturecanbeusedtohelpavoid
polysubstitution.HOW?
Reformingincreasesbranching.Proposeamechanism.

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11.13SyntheticUtilityof
Halogenation
Chlorinationcanbeusefulwithhighlysymmetrical
substrates.

11.13SyntheticUtilityof
Halogenation
Synthesizingatargetmoleculefromanalkane is
challengingbecauseofitslimitedreactivity.
Oftenhalogenation isthebestoption.

Itisdifficulttoavoidpolysubstitution.WHY?
Thesyntheticutilityofhalogenation islimited:
Chlorinationisdifficulttocontrol.
Bromination requiresasubstratewithonesitethatis
significantlymorereactivethanallothers.

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