Elimination Reactions

➢ Reactions in which two atoms or atom groups X and Y are removed from a compound without their being
replaced by other atoms or groups, are referred to as eliminations.

➢ If the carbon bonded to the leaving group is called carbon 1, then the proton is lost from carbon 2. The
reaction is therefore termed a 1,2-elimination.

• Smaller atoms / groups are eliminated

• Saturated Unsaturated
• Reverse process of addition
➢ Three different simple mechanisms can be envisaged for 1,2- eliminations, differing from each other in the timing
of H-C and C-Y bond breaking.

1. Elimination, bimolecular (E2):

A one step process, passing through a single T.S. (4) and is some what reminiscent of SN2.

2. Elimination. Unimolecular (E1):

The H-C and C-Y bonds can be broken separately in two-step processes. It is reminiscent of SN1.
 3. Elimination, from conjugate base (E1cB):
The H-C bond could be broken first, involving a carbanion intermediate.

E1 Mechanism:
The reaction that takes place depends upon three variables: the substrate, the leaving group, and the solvent.
The reaction rate is first order in substrate and independent of the concentration of base:

reaction rate = k[substrate]

The initial, rate-determining step is heterolytic cleavage of the carbon–halogen bond to give a carbocation and a
halide anion. The stability of carbocations is 3◦> 2◦> 1◦ and, therefore, 3◦ alkyl halides are more reactive than 2◦
alkyl halides.
When two elimination products can be formed in an E1 reaction, the major product is generally the more
substituted alkene.
ZAITSEV’S RULE
The major alkene product is the one with more alkyl groups on the carbons of the double bond
(the more highly substituted product).
DEHYDRATION OF ALCOHOLS
In the dehydration of alcohols, the H and OH are lost from adjacent carbons. An acid catalyst is necessary.
REGIOSELECTIVITY IN ALCOHOL DEHYDRATION: THE ZAITSEV RULE

E2 Mechanism
An E2 reaction is a concerted, one-step reaction: The proton and the bromide ion are removed in the same step.
The rate of this elimination is proportional to the concentrations of both the alkyl halide and the base, giving a
second-order rate equation. This is a bimolecular process, with both the base and the alkyl halide participating in
the transition state, so this mechanism is abbreviated E2 for Elimination, bimolecular.

E2 rate = k[RX] [B]

Factors:
➢ The strength of base

➢ The rate of elimination depends on the halogen, the reactivity of alkyl halides increasing with decreasing
strength of the carbon–halogen bond.
Stereoselectivity in E2
➢ The stereoelectronic requirements occur because the orbitals that are going to form the new bonds must begin
to overlap at the very start of the reaction. As the reaction proceeds, this overlap increases and provides
significant stabilization in the transition state to help offset the energy cost of breaking the other bonds.

➢ In the case of the E2 reaction the carbon sp3 orbital of the carbon–hydrogen sigma bond and the carbon sp3
orbital of the carbon-leaving group sigma bond must begin to overlap to form the pi bond. This requires that
these two sigma bonds lie in the same plane; they must be coplanar. The two bonds may be on the same side of
the C-C bond (syn-periplanar conformation) or on opposite sides of the C-C bond (anti-periplanar
conformation).
➢ The two carbons begin to change hybridization from sp3 to sp2.
Three possible grounds can be stated for favoring elimination from the anti-periplanar conformation:
(a) Elimination would than be taking place from the lower energy ‘staggered’ conformation rather than from the
higher energy ‘ eclipsed’ conformation.
(b) The attacking base, B:, and the departing leaving group, Y-, would be as far apart from each other as possible in
the T.S.
(c) The electron pair developing from the initial C-H bond would be attacking the α-carbon atom from the side
opposite to that from which the electron pair of the initial C-Y bond will be departing.
Orientation in E2: Saytzev v. Hofmann
In substrates which have alternative β-hydrogen atoms available, it is possible to obtain more than one alkene
on elimination, e.g. (36) where there are two possibilities:

Saytzev: (Working on R-Br compounds, i.e. Y=Br) stated ‘that alkene will predominate which has most alkyl
substituents on the double bonds carbons’.

Hofmann: (Working on RN+Me3 compounds, i.e. Y= N+Me3 ) stated ‘that alkene will predominate which has least
alkyl substituents on the double bonds carbons’.
The least substituted alkene is always formed preferentially, i.e. (40) rather than (41).
Competition between Substitution and Elimination Reactions (Elimination V.
Substitution)

Four possible reaction mechanisms (SN1, SN2, E1, and E2) can result from the reaction of nucleophiles or bases
with halogenated substrates. Here are some guidelines that can be used to predict the major reaction pathway.
• Primary alkyl halides undergo only SN2 reactions with good nucleophiles. A good nucleophile that is also a
strong bulky base, such as tert-butoxide, tends to give E2 reactions.
• Tertiary alkyl halides undergo SN1, E1, and E2 reactions. E1 reactions are favored with weak bases (e.g., H2O) in
polar protic solvents. E2 reactions are favored with strong bases (OH−) and polar aprotic solvents. SN1 reactions
occur with good nucleophiles in polar protic solvents.
• Secondary alkyl halides are more difficult to predict since they can undergo all four mechanisms. Conditions
favoring SN1/E1 reactions are weak nucleophiles bases and polar protic solvents. Conditions that favor SN2 and E2
reactions are strong nucleophiles/bases and polar aprotic solvents.
The E1cb Mechanism
In the E1 mechanism the bond to the leaving group breaks during the first step and the bond to the hydrogen
breaks in a second step. In the E2 mechanism, both of these bonds break in a single step. There is a third
possible mechanism in which the bond to the hydrogen breaks during the first step and the bond to the leaving
group breaks in a second step, as illustrated in this equation:

Rate= k [RY] [B]

This is kinetically indistinguishable from the concerted E2. But it is possible to distinguish between them by
observing exchange of isotope label.
➢ Electronegative halogen atoms on the β-carbon to make the β-H more acidic
➢ Stabilisation of the carbanion (16) through electron-withdrawal by the halogen atoms on the carbanion carbon
atom
➢ A poor leaving group

Effect of activating group

➢ Through making the β-H more acidic (55), and hence more easily removable by a base
➢ Through stabilisation of a developing carbanion by electron-withdrawal (56)
➢ Through stabilization of the developing double bond by conjugation with it (57)
A good example of elimination promotion is by the CHO group in aldol (58) making possible a base catalysed
dehydration to an αβ-unsaturated aldehyde(59)

1,1-(α)Elimination: H.W
Pyrolytic SYN elimination / Elimination, intramolecular (Ei)
➢ There are a number of organic compounds including esters- especially acetates, xanthates-amine oxide and
halides that undergo pyrolytic elimination of HY, in the absence of added reagents, either in inert solvents
or in the absence of solvent-in some cases in the gas phase.

Rate = k [substrate]
➢ SYN elimination
➢ Cyclic T.S
➢ The reaction that is perhaps of the greatest synthetic utility-because it proceeds at relatively low
temperatures – is the Cope reaction of tertiary amine oxides, e.g. (82)