CP203 LecLure 21

CcLober 22, 2014

Pammond's osLulaLe
Allyllc halogenauon
2
8adlcal chaln reacuons - Pammond's osLulaLe
3
Pammond's osLulaLe: 1he Lransluon sLaLe ls more slmllar ln sLrucLure Lo Lhe specles Lo
whlch lL ls more slmllar ln energy.

LxoLhermlc reacuon: Lransluon sLaLe ls reacLanL-llke
LndoLhermlc reacuon: Lransluon sLaLe ls producL-llke
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ln an exoLhermlc reacuon, Lhe Lransluon sLaLe more closely resembles Lhe reacLanLs.
ln an endoLhermlc reacuon, Lhe Lransluon sLaLe more closely resembles Lhe producLs.
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ln an exoLhermlc reacuon wlLh Lwo producLs, Lhe Lransluon sLaLes are noL as dlerenL ln
energy as are Lhe producLs.
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ln an endoLhermlc reacuon wlLh Lwo producLs, Lhe Lransluon sLaLes are almosL as
dlerenL ln energy as are Lhe producLs.
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8adlcal chaln reacuons - Pammond's osLulaLe
8
8adlcal chaln reacuons - Pammond's osLulaLe
9
10
1he smaller !!C1 ls, Lhe less selecuve Lhe reacuon wlll be.
8adlcal halogenauon - sLereochemlsLry
11
When radlcal halogenauon generaLes a chlral cenLer ln an achlral sLarung maLerlal, Lhe
chlral cenLer ls equal amounLs of 8 and S. 1he producL ls a racemlc mlxLure.
8adlcal halogenauon - sLereochemlsLry
12
1he carbon radlcal lnLermedlaLe ls aL wlLh equal amounLs of elecLron denslLy ln each
lobe. 1he carbon radlcal can reacL by maklng a bond wlLh Lhe Lop lobe or Lhe bouom
lobe. 1he probablllLy of each ls equal.
Allyllc halogenauon
13
1he allyl C-P bond ls weak ln a homolyuc cleavage because Lhe resulung radlcal ls
delocallzed, and Lhus sLablllzed, by resonance.

1he vlnyl C-P bond ls so sLrong LhaL Lhe vlnyl P ls never absLracLed ln a homolyuc
reacuon.
Allyllc halogenauon
14
1reaung propene wlLh bromlne aL room LemperaLure glves a dlbromoalkane as producL,
buL when Lhe same reacuon ls run aL elevaLed LemperaLure, Lhe producL ls a
monobromoalkene.

1hese reacuons go by dlerenL mechanlsms.
Allyllc halogenauon
13
AL low LemperaLures, Lhe propene double bond auacks a bromlne, dlsplaclng bromlde
and formlng an lnLermedlaLe Lhree-membered rlng conLalnlng a bromonlum lon.

1he bromlde auacks aL one of Lhe C-8r+ bonds, formlng a new C-8r bond. 1he resulung
producL ls a 1,2-dlbromo compound.

1hls mechanlsm ls elecLrophlllc addluon of bromlne Lo an alkene.
Allyllc halogenauon
16
AL hlgh LemperaLures, dlaLomlc bromlne ls cleaved lnLo bromlne radlcals whlch auack
Lhe weakesL bond ln propene Lo glve an allyl radlcal.

1he allyl radlcal absLracLs a bromlne aLom from dlaLomlc bromlne Lo glve Lhe producL,
allyl bromlde, and a bromlne radlcal Lo conunue Lhe chaln reacuon.

1hls mechanlsm ls allyllc subsuLuuon vla a free radlcal chaln reacuon.
Allyllc halogenauon
17
A more pracucal way Lo run an allyllc subsuLuuon vla a free radlcal chaln reacuon ls Lo
use n-bromosucclnlmlde, a reagenL whlch reacLs wlLh moderaLe heaL or llghL Lo glve a
bromlne radlcal ln Lhe lnluauon sLep and also serves as a source of bromlne for Lhe allyl
radlcal Lo auack ln Lhe propagauon sLeps.
Allyllc bromlnauon wlLh n8S
18
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Allyllc bromlnauon wlLh n8S
19
1he reacuon of n8S and Lhe P8r generaLed ln one of Lhe propagauon sLeps produces a
consLanL buL very low concenLrauon of 8r
2
.

1hls amounL of 8r
2
ls enough Lo fuel Lhe second propagauon sLep buL Lhe 8r
2
never
reaches such a hlgh concenLrauon LhaL Lhe elecLrophlllc addluon mechanlsm becomes
posslble.