Documente Academic
Documente Profesional
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4th Edition
Paula Yurkanis Bruice
Chapter 11
Elimination Reactions
of Alkyl Halides
Competition Between
Substitution and
Elimination
Irene Lee
Case Western Reserve University
Cleveland, OH
2004, Prentice Hall
In addition to substitution, an alkyl halide can undergo an
elimination reaction
The E2 Reaction
The weaker the base, the better it is as a leaving group
The Regioselectivity of the E2 Reaction
R R R H
R C: - < R C: - < H C: - < H C: -
R H H H
tertiary secondary primary methyl
carbanion carbanion carbanion anion
least most
stable stable
The E1 Reaction
Reaction coordinate diagram for the E1 reaction of
2-chloro-2-methylbutane
Because the E1 reaction forms a carbocation
intermediate, we need to consider carbocation
rearrangement
Competition Between E2 and E1
Reactions
Stereochemistry of the E2 Reaction
The bonds to the eliminated groups (H and X) must be
in the same plane
HX H
X
the more stable conformation
H H
Br Br
E1 Elimination from Cyclic Compounds
kD
CD2CH2Br -
+ CH3CH2O CD CH2 + Br- + CH3CH2OD
Cl OCH2CH3
+ CH3CH CH2 + CH3CH2OH
CH3CHCH3 + CH3CH2O- CH3CHCH3
+ Cl-
strong
base
O
Cl O OCCH3
CH3CHCH3 + CH3C O- CH3CHCH3 + Cl-
weak
base
Consider SN1/E1 conditions
Substitution and Elimination Reactions
in Synthesis
In synthesizing an ether, the less hindered group should
be provided by the alkyl halide
CH3 CH3
CH3CH2Br + CH3CO- Br- + CH3COCH2CH3 + CH2 CH2
CH3 CH3
CH3 CH3
CH3CH2O- + CH3CBr Br- + CH3C CH2 + CH3CH2OH
CH3
However, the most hindered alkyl halide
should be used if you want to synthesize an alkene
Consecutive E2 Elimination Reactions
Intermolecular Versus Intramolecular
Reactions
?
CH3 CH3
? Br
Br