Chapter 5
Elimination reactions
Elimination reactions involve the removal of a pair of atoms or
groups from two adjacent atoms to form a multiple bond
MECHANISMS
E1 mechanism (unimolecular)
E2 mechanism (bimolecular)
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E1 mechanism (unimolecular)
involving an initial cleavage of the carbon–halogen bond to form an
intermediate carbocation.
The reaction is first order, or unimolecular, as the rate depends on
the concentration of only the alkyl halide
does not require a particular geometry; the intermediate carbocation
can lose any proton from an adjacent position.
An E1 reaction is a first-order elimination reaction because the rate
of the reaction depends only on the concentration of the alkyl
halide(and not the base). 2
only the alkyl halide is involved in the rate-determining step of the
reaction. Therefore, there must be at least two steps in the reaction.
[Link] of the E1 reaction
3
The more substituted alkene is the more stable of the two alkenes
formed in the preceding reaction, and therefore, it has the more stable
transition state leading to its formation.
As a result, the more substituted alkene is formed more rapidly, so it
is the major product. To obtain the more substituted alkene, the
hydrogen is removed from the β carbon bonded to the fewest
hydrogens, in accordance with Zaitsev’s rule.
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E2 elimination Reaction
Concerted , one step reaction
Called “dehydrohalogenations’’
Called α / Eliminiation
Called 1-2 Elimination
The C-C bond begins to form at the same time as the C-H and C-X
bonds begin to break.
The reaction is second order (or bimolecular), as the rate depends
on the concentration of the base and the alkyl halide.
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Eg
The rate of an E2 reaction depends on the concentrations of both tert-
butyl bromide and hydroxide ion. It is, therefore, a second-order reaction
both tert-butyl bromide and hydroxide ion are involved in the rate-
determining step of the reaction.
The above mechanism agrees with the observed second-order kinetics.
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The proton and the bromide ion are removed in the same step, so no
intermediate is formed.
E1 versus E2
The mechanism of an elimination reaction is influenced by the nature
of the alkyl halide, the base and the solvent.
Primary alkyl halides undergo only E2 elimination reactions.
They cannot undergo E1 reactions because of the difficulty
encountered in forming primary carbocations.
Secondary and tertiary alkyl halides undergo both E2 and E1
reactions.
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The alkyl halide
Primary, secondary and tertiary alkyl halides can all undergo an E2
mechanism (hence, this is more common than E1).
Tertiary alkyl halides can react by an E1 mechanism.
The better the leaving group, the faster the rate of both E1 and E2
reactions (as CX bond cleavage is involved in both of the rate
determining steps).
The base
Increasing the strength of the base will increase the rate of an E2
elimination.
Strong bases such as HO− and RO− will favor an E2 elimination.
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Increasing the strength of the base will not increase the rate of an
E1 reaction.
The mechanism can shift from E1 to E2 on changing to a more
powerful base.
The solvent
• Increasing the polarity (i.e. the dielectric constant, ε) of the solvent
will result in a slight decrease in the rate of an E2 reaction.
• Increasing the polarity of the solvent will result in a significant
increase in the rate of an E1 reaction.
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Applications of elimination reactions
Dehydration of Alcohols
Heating most alcohols with a strong acid causes them to lose a
molecule of water and form an alkene
The reaction is an elimination and is favored at higher temperatures.
The most commonly used acids in the laboratory are Brønsted acids
proton donors such as sulfuric acid and phosphoric acid.
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Primary alcohols are the most difficult to dehydrate:
Secondary alcohols usually dehydrate under milder conditions:
Tertiary alcohols are usually dehydrated under extremely mild
conditions
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A secondary or tertiary alkyl halide is used if possible in order to
bring about an E2 reaction.
A high concentration of a strong, relatively no polarizable base,
such alkoxide ion, is used to avoid E1 reaction.
A relatively polar solvent such as an alcohol is employed.
To favor elimination generally, a relatively high temperature is
used.
Sodium ethoxide in ethanol and potassium tert-butoxide in tert-
butyl alcohol are typical reagents.
Potassium hydroxide in ethanol is used sometimes.
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Dehydrohalogenation of alkylhalides
Heating an alkyl halide with a strong base causes elimination to
happen
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Synthesis of an alkene by dehydrohalogenation is almost always better
achieved by an E2 reaction:
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Hofmann Elimination
The reaction of a quaternary ammonium ion with hydroxide
ion is known as a Hofmann elimination reaction.
The leaving group in a Hofmann elimination reaction is a tertiary
amine.
Because a tertiary amine is only a moderately good leaving group,
the reaction requires heat.
A Hofmann elimination reaction is an E2 reaction. Recall that an
E2 reaction is a concerted, one-step reaction—the proton and the
tertiary amine are removed in the same step .
Very little substitution product is formed.
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The Cope elimination
The “Cope Elimination” is a reaction where an amine is oxidized to
an intermediate called an “N-oxide”, which, when heated, acts as the
base in an intramolecular elimination reaction.
It used to form alkenes on heating.
These intramolecular eliminations proceed via cyclic transition
states, which require a synperiplanar arrangement of the leaving
groups (i.e. the leaving groups lie in the same plane on the same side
of the molecule).
This can be compared to an E2 elimination, which requires an
antiperiplanar arrangement of leaving groups
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Primary amine oxidized to hydroxylamine which intern oxidized
nitroso compound and further nitro compounds
Hydrogen peroxides,peroxy acids and other oxidizing agent can
be used to oxides amine.
Secondary amine oxidized to secondary hydroxylamine and
tertiary amines are oxidized to amine oxide.
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Amine oxidize under go reaction similar to Hoffman elimination
which is called cope elimination reaction.
It occurs under mild condition than Hoffman elimination.
Stronger base does not required because amine oxides acts as its
own base.
It is an intramolecular E2 reaction and it involves syn elimination.
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The Cope Elimination: Mechanism
The Cope proceeds through a concerted syn-elimination
mechanism.
The oxygen from the N-oxide acts a base, forming an O-H bond,
while the C-H and C-N bonds break to form the new C-C pi bond.
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The Cope Elimination vs. The “E2” Elimination:
Stereochemistry
The E2 always proceeds such that the two sigma bonds that
break [the C-H bond and the C-LG (leaving group) bond] are
oriented anti to each other.
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In the Cope elimination, the breaking C-H bond and the
breaking C-N bond are oriented syn to each other.
The E2 is almost always an intermolecular process, where the
rate depends both on the concentration of the substrate and the
concentration of the base.
The Cope is an intramolecular elimination reaction, the base (the
N-oxide) and the acid (the C-H bond) are always contained
within the same molecule.
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