E1-
Mechanism:
This
elimination takes place (without the participation of a base) in 2 steps, unimolecular ionization, being rate-determining step.
The main feature of this mechanism
is that under the influence of solvation forces the electron attracting group
(leaving group) breaks away along with the bonding electrons. The resulting
Carbocation subsequently loses a proton to the solvent or to some other proton
acceptor.
The reaction has 2 stages, of
which the first is the rate determining step and as a result, the reaction rate
depends only on the concentration of the first reactant. In E1 reactions,
a Proton is eliminated from the carbon adjacent to the positive, electron
deficient carbon and the pair of electrons formerly shared by this hydrogen is
available for the formation of a π-Bond.
The Carbocations are
planar species and their formation at the bridgehead position will be a
difficult process. Thus, bicyclic structures prevent the bridgehead
carbon becoming planar even though the cation would be tertiary. It is
not formed due to very high energy. Such compounds will not undergo E1
reactions.
The direction of elimination:
2-Bromo-2-methylbutane on
reaction with water in ethanol gives substitution as the major product when
both water and ethanol can act as a nucleophile to give an alcohol or an
ether. The major alkene formed is more highly substituted.
Thus, from among alkyl halides
with the same alkyl group the alkyl fluorides display the least reactivity in
E1 reaction.
RF < RCl <
RBr < RI
E1 elimination from cyclic
compound:
Since a carbon is formed in the first
step of the E1 reaction, the relative stereochemistry of the leaving
groups (anti coplanarity) is not important. When menthyl
chloride undergoes E2 reaction only one alkene is formed in hundred percent
yield due to the need for the departed group to attend diaxial positions. When
menthyl chloride is subjected to E1 reaction conditions 2 alkenes are formed,
the major product is in accord with the saytzeff rule.
Curtin-Hammett principle:
That Curtin Hammett principle
applies to a conformationally heterogeneous reactant where the products must be
non-equilibrating. The Curtin Hammett principle implies that in a
chemical reaction which gives one product from one conformer and a different
product from another conformer. The product composition is not determined
by the relative population of the ground state conformer but largely depends on
the relative energies of the corresponding transition state involved.
E1cB
Mechanism:
In
the E1cB mechanism, the base rapidly removes the proton from the β
carbon resulting in the formation of carbanion, which loses the leaving group
in the rate-determining step. Since the conditions of base catalysed
elimination reaction does not allow the formation of an unstabilized
carbanion, it is reasonable to presume that if
formed, they must be either rapidly reconverted to the substrate is
converted to the alkene. In this mechanism, the overall rate is
limited to that of the slower state 2nd stage, which depends only on
the concentration of the conjugate base of the reactant. This
mechanism is called as E1cB as the leaving group is lost from the
conjugate base of the starting material and the reaction is Unimolecular.
The
first step of is reversible, and hence, when the reaction is carried out
in C2H5OD instead of C2H5OH,
the intermediate carbanion should pick up deuterium.
If
the E1cB mechanism is correct, we recover 2-phenyl-ethyl
bromide after a partial transformation to styrene. On the
other hand, there should be no incorporation of deuterium if the E2
mechanism is operative. Actual experiments have shown that there is
no deuterium incorporation and hence the E1cB mechanism does not operate
in this case.
However,
this mechanism does operate under special
circumstances. 1,1,1-trifluoro-2,2-dichloroethane (3), for instance,
undergoes a base-catalyzed exchange of β hydrogen atom with the solvent deuterium
faster than dehydrofluorination.
A
strong carbon-fluorine bond (and the consequent poor leaving ability of
fluoride ion) coupled with the electron-withdrawing effect of halogens explains
the formation of carbanion before elimination.
The
removal of a proton and loss of the leaving group
occurs simultaneously in E2 mechanism whereas removal of a
Proton is the first step in the E1cB reaction. In the subsequent
rate-determining step of the E1cB reaction, the leaving group
departs from the conjugate base of the substrate.
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