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Elimination Reactions
of Alkyl Halides
Competition Between
Substitution and
Elimination
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In addition to substitution, an alkyl halide can undergo an
elimination reaction
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The E2 Reaction
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The removal of a proton and a halide ion is called
dehydrohalogenation:
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An E2 reaction is also called a b-elimination or a
1,2-elimination reaction:
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The Regioselectivity of the E2 Reaction
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Reaction coordinate diagram for the E2 reaction of
2-bromobutane and methoxide ion
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The Zaitsev Rule
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Conjugated alkene products are preferred over the
more substituted alkene product:
Zaitsev product
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Sect 9.9: bulky leaving groups -
- Hofmann Elimination
This give the anti-Zaitsev product (least
substituted product is formed)!
b b _
CH3 CH2 CH2 CH CH3 OH CH3 CH2 CH CH CH3 6%
CH3 N+ CH3 heat
CH3 +
H C H H
H C C
C H
CH3
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Consider the elimination of 2-fluoropentane…
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Therefore, the major product of an E2 elimination reaction
is the more stable alkene except if the reactants are
sterically hindered or the leaving group is poor
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The E1 Reaction
A unimolecular reaction:
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The E1 reaction, like the SN1 reaction, involves a
carbocation intermediate:
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How does a weak base like water remove a proton from
an sp3 carbon?
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The major product in an E1 reaction is generally the
more substituted alkene
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Reaction coordinate diagram for the E1 reaction of
2-chloro-2-methylbutane
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Because the first step is the rate-determining step, the rate of an
E1 reaction depends both on the ease with which the carbocation
is formed and how readily the leaving group leaves
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Because the E1 reaction forms a carbocation
intermediate, we need to consider carbocation
rearrangement
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Competition Between E2
and E1 Reactions
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When only one hydrogen is bonded to the b-carbon, the
major product of an E2 reaction depends on the structure
of the alkene
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Elimination from Cyclic Compounds
In an E2 reaction, groups to be eliminated must be in
axial positions
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The hydrogen that is removed and the leaving group
both have to be in the axial position, therefore…
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E1 Elimination from Cyclic Compounds
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A bulky alkyl halide or a sterically hindered nucleophile
encourages elimination over substitution
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High temperature favors elimination over substitution:
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The E2 reaction should be used if you want to
synthesize an alkene:
Hydroxide
Water
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