Introduction to Elimination Reaction

Elimination reaction, is a class of organic chemical reactions that involves the

removal of a pair or group of atoms from a molecule, generally through the movement
of acids, bases, or metals and in few cases, by means of heating to a high temperature. It
is the main process with the aid of which natural/organic compounds containing
saturated compounds are transformed to unsaturated compounds.

Mechanisms of Elimination Reaction:

An elimination reaction is a type of organic reaction in which two substituents
are removed from a molecule in either one or two-step mechanism. The one-step
mechanism is known as the E2 reaction, and the two-step mechanism is known as the
E1 reaction. The number refer not to the number of steps in the mechanism, but rather
to the kinetics of the reaction: E2 is bimolecular (second-order) while E1 is unimolecular
(first-order).

Characteristics of E1 Mechanism
1. Unimolecular (depends on concentration of substrate)
2. 3°>2°>1° (formation of carbocation)
3. Two-step process of elimination:
a. Ionization: the carbon-halogen bond breaks to give a formation of carbocation.
b. Deprotonation of the carbocation.
4. Reactions occurs in the complete absence or the presence of only a week base.
5. In competition with SN1 because they share a common carbocation intermediate.
6. Highly polar ionizing
7. Follows Zaitsev’s Rule (the most substituted alkene is usually the major
product)
8. Method of Elimination: Dehydrohalogenation and Dehalogenation
9. Examples:
a.

b.

c. dehydrohalogenation of iodoethane with potassium hydroxide to form

potassium iodide and water.
 d. Dehydrohalogenation
elimination of hydrochloric acid from
1,2-dichloroethane to form
chloroethene.

e. Dehalogenation of vicinal
dibromides (two bromines on adjacent
carbon
atoms are converted to alkenes by
reduction with iodide ion in acetone)

f. Acetate, for example, is a

weak base but a reasonably good
nucleophile,
and will react with 2-bromopropane
mainly as a nucleophile.

Characteristics of E2 Mechanism
1. Bimolecular (depends on concentration of substrate and base)
2. Single step elimination, with a single transition state (the double bond begins
to form and the H and X groups are leaving)
3. It requires strong base. It must be strong enough to remove a weakly acidic
hydrogen.
4. Competes with SN2 mechanism if the base can also act as a nucleophile which
are true with common bases.
5. Solvent polarity not important.
6. Follows Hoffman Elimination (the least substituted alkene that is
predominantly product in which the leaving group is quartenary amine)
7. Involves Cope Elimination (involving an amine oxide)
8. Method of Elimination: dehydrohalogenation, dehalogenation, dehydration,
and dehydrogenation
9. Examples:
a. Dehydration of ethanol to
form ethene

b. 2-Bromopropane will react with

ethoxide, for example, to give
propene.
 c. Alcohol is reacted with a catalyst to
produce an alkene and water
(dehydration- removes a water molecule from
the alcohol)

d. Dehydrogenation of alkanes

Elimination reactions are commonly known by the kind of atoms or group of

atoms leaving the molecule. The following are the methods of elimination reaction and
their important products and preparations:
Alkenes: Addition Reactions
Addition reaction can be categorized as either symmetrical or unsymmetrical.
A Symmetrical reaction is an addition in which the same atoms (or groups of atoms)
are added to each multiple carbon bond. An unsymmetrical addition reaction is an
addition reaction that adds different atoms (or groups of atoms) to a multiple carbon
bond's carbon.

Symmetrical Addition Reactions

The hydrogenation and halogenation are the two most common examples of
symmetrical addition reactions.

Hydrogenation reaction: Addition of H2

In a Hydrogenation reaction:
 Hydrogen (H2) is added over the double bond, transforming the unsaturated
molecule into a saturated molecule. Note that this reaction name contains the
word hydrogen, which makes it easier to remember and recognize:
hydrogenation. In a hydrogenation reaction, the final product is the saturated
alkane.
 A catalyst such as Pt or Ni is used to speed up reaction.
 Heat and/or pressure may also be needed

Halogenation reaction: Adding (Halogens)

In a Halogenation reaction:
 Group 7A (Halogens) elements are added across the double bond.
 Chlorine (Cl2), bromine (Br2), and iodine (I2) are the most common halogens
incorporated. Note that this reaction name contains the term halogen, making it
easier to remember and recognize: halogen-ation.
 Haloalkane is the final product.
 Chlorination (Cl2) and bromination (Br2) are the two most frequently observed
halogenation processes.
 This reaction occurs easily and requires no catalyst.
Examples:
Unsymmetrical Addition Reaction
Hydrohalogenation and hydration are two important types of unsymmetrical
addition reactions.
Hydrohalogenation reaction: Addition of one Hydrogen and one Halogen
In Hydrohalogenation:
 Alkenes react with one hydrogen and one halogen-containing molecules.
Therefore, the name is Hydro – Halogen-ation.
 A haloalkane is the final product.
 A hydrogen halide (HCl, HBr, HI) is introduced into organic compound
molecules. One C atom of a double bond receives a halogen another C atom
receives a H atom.
 There is no need for a catalyst.
 Follows the Markovnikov's rule.

Hydration reaction: Addition of H20

Hydration involves adding water to a molecule, such like when you feel fully
hydrated or full of water, while dehydration means reducing or withdrawing water,
much as when you feel dehydrated and need some water to drink.
In Hydration reaction:
 It requires an acid H+ catalyst
 Water (HOH) adds to a double bond
 The H atom bonds to one C in the double bond
 OH bonds to the other C
 The law of Markovnikov applies
 When an alkene involved in a hydrohalogenation or hydration reaction is itself

unsymmetrical there will be more than one possible product. (An unsymmetrical alkene
is one in which two carbon atoms of the double bond are not replaced equivalently.) For
example, adding HCl to propene (an unsymmetrical alkene) may produce either 1-
chloropropane or 2-chloropropane, depending on whether the H from the HCl is
attached to carbon 2 or carbon 1.

When two isomeric products are possible, typically one product predominates. The
dominant product can be predicted using a rule named after the Russian Chemist
Vladimir Markovnikov, the” Markovnikov’s Rule”.
Markovnikov’s”rule- ‘the rich get richer’
It states that when an unsymmetrical molecule of the form HQ
adds to an unsymmetrical alkene, the hydrogen atom from the
HQ becomes attached to the unsaturated carbon atom that
already has the most hydrogen atoms.