ALKYL HALIDES

Haloalkanes:
The monohalogen derivatives of alkanes are called as ‘haloalkanes’ or ‘alkyl halides’. The
general formula of haloalkanes is C nH2n + 1X, where X is a halogen atom. They can be represented as R-
X, where R is an alkyl group.

Classification of Alkyl halides:

The alkyl halides are classified as primary (10), secondary (20) or tertiary (30) alkyl halides,
depending upon whether the halogen atom is attached to a primary, secondary or tertiary carbon
atom respectively.
CH3 CH3

CH3 – Cl CH3 – C – Cl CH3 – C – Cl

H CH3
Chloromethane 2-Chloropropane 2-Chloro-2-methylpropane
(10) (20) (30)

Nomenclature:
1. Trivial or common system: In the trivial system the haloalkanes are named as ‘alkyl halides’.
The name is derived by adding halide to the name of the corresponding alkyl group. The trivial
name is always written in two separate words. The prefixes such as n-, iso-, tert-, are used to
differentiate various isomers.
(a) The prefix n- : The prefix n- stands for normal. It is used to describe an alkyl group which
contains a continuous straight chain of carbon atoms.
e.g.
CH3–CH2–CH2–Br CH3–CH2–CH2–CH2–Br
n-propyl bromide n-butyl bromide

(b) The prefix iso- : The prefix iso- is used to describe an alkyl group which contains a methyl
(-CH3) branch at the end of the chain.
e.g.
CH3– CH – Br CH2–CH–CH2–Br

CH3 CH3
Isopropyl bromide isobutyl bromide

(c) The prefix tert- : The prefix ter- is used to describe those alkyl groups which contain two
methyl (-CH3) branches at the same carbon at the end of the chain.
e.g.
CH3

CH3– C – Br

CH3
tert-butyl bromide

2. IUPAC system: In IUPAC system the monohalogen derivatives of alkanes are named as
haloalkanes. The IUPAC name is always written as single word.
Alkyl halides 2

Formula Trivial name IUPAC name

CH3 – Cl Methyl chloride Chloromethane
CH3–CH2–Br Ethyl bromide Bromoethane
CH3–CH2–CH2–Cl n-propyl chloride 1-Chloro propane
CH3–CH2–CH2–CH2–Br n-butyl bromide 1-Bromo butane
CH2– CH–CH2–Br
iso-butyl bromide 1-Bromo-2-methylpropane
CH3
CH3
CH3– C – Br
tert-butyl bromide 2-Bromo-2-methylpropane
CH3

Mechanism of Nucleophilic Substitution reaction:

Nucleophilic substitutions may take place in two different mechanisms. They are S N1 mechanism
and SN2 mechanism.

1. SN1 mechanism:
SN1 stands for unimolecular nucleophilic substitution reaction. This reaction follows first order
kinetics in which the rate of the reaction depends only upon the concentration of alkyl halide and not
upon the concentration of the attacking nucleophile. Thus the rate equation is:
Rate  [Alkyl halide]
e.g. Hydrolysis of tertiary butyl bromide with aqueous KOH to form tert-butyl alcohol follows
SN1 mechanism.
CH3 CH3
CH3– C – Br + KOH → CH3– C – OH + KBr
CH3 CH3
tert-butyl bromide tert-butyl alcohol

The mechanism involves two steps:

Step 1: Tert-butyl bromide ionises to form a planar carbocation by the removal of the bromide ion.
This is a slow step.
CH3 CH3 CH3
CH3– C – Br Slow C+ + Br-
CH3 CH3
Tert-butyl bromide Carbocation

Step 2: The nucleophile OH – attacks the carbocation to form tert-butyl alcohol. This is a fast step.
CH3 CH3 CH3
C+ + OH- Fast CH3– C – OH
CH3 CH3
Carbocation tert-butyl alcohol
Alkyl halides 3
Since the rate determining step is the slow step (Step 1), and hence the rate depends only on the
concentration of haloalkane or alkyl halide.
2. SN2 mechanism:
SN2 stands for bimolecular nucleophilic substitution reaction. This reaction follows second
order kinetics in which the rate of the reaction depends upon both the concentration of alkyl halide and
nucleophile. Thus the rate equation is:
Rate  [Alkyl halide] [Nucleophile]
e.g. Hydrolysis of methyl bromide with aqueous KOH to form methyl alcohol follows S N2
mechanism.
CH3Br + KOH → CH3OH + KBr

The mechanism involves only one step.

The nucleophile OH- attacks the methyl bromide to from a transition state in which the C-
OH bond is half formed and C-Br bond is half broken. The transition state simultaneously releases the
Br- ion to form methyl alcohol.
H H H H
OH- + H – C – Br → HOδ-…...C…..Br δ- → HO – C – H + Br-
H H H
Methyl bromide Transition state Methyl alcohol

Hence in SN2 mechanism the attack of nucleophile and the release of halide ion take place
simultaneously. There fore substitution reaction involves a single step.

Characteristics of SN1 and SN2 reactions:

SN1 Reactions SN2 Reactions
1. It is a two step mechanism. 1. It is a one step mechanism.
2. The rate depends only on the concentration of 2. The rate depends on the concentration of
alkyl halide. alkyl halide and nucleophile.
3. It is unimolecular. 3. It is bimolecular.
4. The rate depends on the structure of alkyl 4. The rate depends on the structure of alkyl
halide. halide. CH3X > 10 > 20 > 30
30 > 20 > 10 > CH3X 5. It is favoured by non-polar solvents.
5. It is favoured by polar solvents 6. It requires strong bases.
6. It can occur with weak bases.

Elimination reaction – Dehydrohalogenation:

Reaction with alcoholic potash: When alkyl halides are heated with alcoholic potassium
hydroxide, it undergoes dehydrohalogenation to form an alkene. The hydrogen atom removed is a β-
hydrogen (i.e. at the carbon atom next to that carrying the halogen atom). Therefore such reactions are
also referred to as β-elimination reactions.
H H H H
R – C β – Cα – H + KOH (alc.) → R –C C – H + KX + H2O
H X alkene
Alkylhalide

H H H H
H – Cβ – Cα – H + KOH (alc.) → H–C C – H + KBr + H2O
Alkyl halides 4
H Br Ethene
Bromoethane

Saytzeff’s rule: “If the dehydrohalogenation of an alkyl halide can yield more than one alkene, then the
major product is the most highly substituted one”.

CH2 CH– CH2– CH3

1-Butene (20%) (Minor product)
CH3–CH– CH2– CH3 alc.KOH
∆
Br CH3-CH CH–CH3

2-Bromobutane 2-Butene (80%) (Major product)

Mechanism of Elimination reactions:

Elimination reactions are reverse of addition reactions. Here two or four atoms or groups
attached to the adjacent carbon atoms in the substrate molecule are eliminated to form a multiple bond.
The dehyrohalogenation of alkyl halides with alcoholic alkalis is an example of elimination.
These reactions are divided into two types:
1. E1 Reactions.
2. E2Reactions.

E1 Reactions:
E1 stands for unimolecular elimination. Here the rate of the reaction depends only on the
concentration of the substrate and hence it is a first order reaction and designated as E 1. Tertiary alkyl
halides undergo this reaction more readily.
e.g. Reaction of Tert-butylbromide with alcoholic potash to give 2-Methyl propene.

CH3 CH3 CH2

CH3– C – Br + KOH(alc.) → C + KBr + H2O
CH3 CH3
tert-butyl bromide 2-Methyl propene

E1 reactions like SN1 reactions involve two steps.

Step 1: The alkyl halide ionises to give the carbocation

CH3 CH3 CH3
CH3– C – Br Slow C+ + Br-
CH3 CH3
Tert-butyl bromide Carbocation

Step 2: A proton is abstracted by the base from the adjacent β-carbon atom to give the alkene.

CH3 CH2 – H CH3 CH2

Alkyl halides 5
+ -
C + OH → C + H2O

CH3 CH3

Carbocation 2-Methylpropene

E2 Reactions:
E2 stands for bimolecular elimination. Here the rate of the reaction depends on the concentration
of the substrate and the nucleophile and hence it is a second order reaction and designated as E 2.
Primary and secondary alkyl halides preferably undergo this reaction.

e.g. Reaction of ethyl bromide with alcoholic potash to give ethene.

CH3CH2Br + KOH (alc.) → CH2=CH2 + KBr + H2O

E2 reactions like SN2 reactions involve only one step. The mechanism involves the formation of a
transition state in which the nucleophile OH - is abstracting a proton from alkyl halide and at the same
time bromine atom is leaving the molecule as a bromide ion.

-
HO + H – CH 2 – CH2
δ-
– Br → HO···· H·· CH2 – CH2 ···· Br δ- → CH2=CH2 + H2O + Br-
Ethyl bromide Transition state Ethene
Alkyl halides 6