ALKYL HALIDES

Alkyl halides are organic

compounds which contain
halogens (X) in the
molecules
 CH3Br CH2 CHBr
Methyl bromide Vinyl bromide

CH3 CH3
H3C C CH2Br H3C C CH3
CH3 Cl
Neopentyl bromide tert-Butyl chloride

CH3
Cl Cl

Cyclohexyl chloride 1-Chloro-1-methylcyclohexane

Preparation of Alkyl Halides
 1. Reactions of Alcohols with Hydrogen
Halides or Phosphorous Halides

The General reaction

HX
ROH RX
or PX3
Examples:
HBr (conc.)
HBr (pekat)
CH3CH2CH2OH CH3CH2CH2Br
Propanol Propyl bromide

PBr3 CHCH2CH3
CHCH2CH3
OH Br

1-Phenyl-1-propanol 1-Bromo-1-phenylpropane
 The Reactions
of Alkyl Halides
 Most alkyl halides will undergo the nucleophilic
substitution reactions. Nucleophiles (Nu-) are
electrons rich species which like to attack and attach
themselves to the carbon atoms of organic
compounds. Nucleophiles are Lewis bases and
usually have negative charges. Some examples of
nucleophiles are,
and many more.
 - - -
The sources of nucleophiles like F , Cl , Br ,
and I- can be obtained from the dissociation
of hydrogen halides in the solution of the
reactions. There are two important reactions
where nucleophiles can react with organic
compounds.
 1. Nucleophilic Substitution Reaction

In this type of reaction the nucleophile attacks and

becomes bonded to the carbon atom and causes the
halogen X to leave the carbon atom. In the
nucleophilic substitution reaction the breaking of
CX is replaced by forming the CNu through a
substitution mechanism.
 -
Nu- + C X C Nu + X
 Polarity and Reactivity

Halogens are more electronegative than C.

Carbonhalogen bond is polar, so carbon has partial positive
charge.
Carbon can be attacked by a nucleophile.
Halogen can leave with the electron pair.

Chapter 1 13
 2. Elimination Reaction

In this type of reaction a halogen X in

the organic compound has been
eliminated by a base, B-. In the process
of the reaction a base abstract a proton
from the compound and eliminate the
halogen X of the compound and gives
alkene as the product.
 --
NuB:
H
C C C BH + X
C + NuH
X

(Note: a nucleophile can interchange to a

base property and vice versa depending on
the nature of the reaction. A nucleophile
attacks a carbon centre. A base reacts with a
proton).
 Nucleophilic Substitution
Reaction: SN2 and SN1

There are two types of nucleophilic

substitution reaction mechanisms. The first
mechanism is called SN2: Substitution
Nucleophilic Bimolecular. The second
mechanism is called SN1: Substitution
Nucleophilic Unimolecular.
 Mechanism for the SN2 Reaction

In the SN2 reaction mechanism the

-
formation of bond by the nucleophile (Nu )
and the breaking of bond by X occur
simultaneously
Nu- + Nu X
X

Nu + X-
It is observed that the nucleophilic substitution
reaction between methyl bromide (CH3Br) and the
nucleophile OH- is the SN2 reaction mechanism.

CH3Br + OH- CH3OH + Br -

Rate of reaction = k[CH3Br][OH-]

The rate of reaction depends on both the

concentrations of CH3Br and OH-. The order of the
reaction is first order in CH3Br and OH-. It is SN2
and second order.
Characteristics of the SN2 reaction
 (i) The rate law of the reaction

The rate law of the reaction depends on the

concentrations of the alkyl halide and Nu-. It
is a second order rate law reaction.
 (ii) Nature of the group attached to the
carbon atom

It is observed that the larger the groups

bonded to the carbon atom the slower the
rate of SN2 reaction. The bulkiness of the
groups attached to carbon atom can
influence the rate of the SN2 reaction. This is
called the steric factor which is related to the
bulkiness of the group which influences the
rate of the SN2 reaction.
Because of the steric hindrance of the bulky groups
it is difficult for the Nu- to approach closer and
makes a bond to the carbon atom. No bond
breaking of CX occurs until the NuC bonded to
the carbon atom. That is, in the SN2 reaction
mechanism requires the formation of a bond by the
Nu- and the breaking of a bond by the X occur
simultaneously. For example, it favourable for
H3CX to undergo the SN2 reaction because it has
less steric hindrance than (CH3)3CX. Figure 7.1
shows that H3CX has less crowding groups
around the carbon atom, and thus it is easier for the
Nu- to approach and makes a bond to the carbon
atom.
 H H

Nu- X

Less steric hindrance for H3CX and favoured the

SN2 reaction mechanism.
 CH3 CH3

Nu- X

CH3

The crowding around the (CH3)3CX molecule increased

steric hindrance and disfavoured SN2 reaction mechanism.
 (CH3)3CX has more bulky groups and
increased the crowding around the carbon
atom and difficult for the Nu- to approach
and makes a bond to the carbon atom. The
rate of reaction for SN2 reaction is,
0 0 0
CH3X > 1 > 2 > 3
(iii) Stereochemistry of SN2 reaction

H5C2
C2H5
NaOH
H Br
SN2 HO H
H3C CH3
R Configuration S Configuration

Total inversion of configuration of the product of

the reaction
(iv) Type of alkyl halides

The order of increasing rate of SN2 reaction is,

RI > RBr > RCl > RF

This is consistent with the bond strength between RX in

the halogen series.
(v) Type of nucleophile

The type of nucleophile can influence the SN2 reaction. For

example, a strong nucleophile like OH- favours the SN2
reaction.

(vi) Rearrangement of product of SN2 reaction.

There is no rearrangement in the product of the SN2 reaction

because the mechanism of this reaction does not involve in
the formation of carbocation.
(vii) Type of solvent

OCH3
H

-
OCH3 H X H OCH3

H
OCH3
In polar solvent such as methanol the reaction of
SN2 will be slower. This is because the charge of the
nucleophile in the transition state is dispersed and
the attacking of the carbon atom becomes slower.
The charge of the nucleophile becomes less
concentrated as a result of solvation by the polar
solvent. However, by using a neutral nucleophile
such as NH3 it will increase the rate of SN2 reaction.
In the transition state the neutral nucleophile is
solvated by the polar solvent and develops electrical
charge and stabilizes the intermediate of the
reaction.
Mechanism for the SN1 Reaction

In this SN1 reaction mechanism the bond between

CX must be broke first before the nucleophile
makes a bond with the carbon atom. For example,
the nucleophilic substitution reaction between tert-
butyl chloride is SN1 reaction and involves in two
steps mechanism
 CH3 CH3
CH3 C CH3 + - OH CH3 C CH3 + Cl-
CH3 OH
The first step (slow)

The formation carbocation

CH3 CH3
-
CH3 C CH3 CH3 C CH3 + Cl
+
Cl
The second step (fast)

The attack of the nucleophile to the carbocation.

CH3 CH3
CH3 C CH3 + - OH CH3 C CH3
+
OH
The rate of reaction is,

Rate of reaction = k[(CH3)3CCl]

The rate of reaction depends only on the concentration of the

(CH3)3CCl
Characteristics of the SN1 reaction

(i) The rate law of the reaction

The rate law of the reaction depends only on the

concentration of the alkyl halide. It is a first order rate law
reaction
(ii) Nature of the group attached to the carbon atom

The first step of the SN1 reaction mechanism involves in the

formation of carbocation.
0 0 0 +
The stability of the carbocation: 3 > 2 > 1 > CH ,3
Therefore, the rate of reaction for SN1 should be increased in
the order,

(CH3)3CX > (CH3)2HCX > (CH3)H2CX > H3CX

Bulky substituents at the carbon favour the formation of

stable carbocation and increase the rate of SN1 reaction.
(iii) Stereochemistry of SN1 reaction
OH-

H
CH3
+

C2H5

H H

H5C2 OH HO
C2H5
CH3 CH3
S Configuration R Configuration

Racemic products

Figure 7.3 The flat structure of carbocation resulted in the

racemic modification in SN1 reaction mechanism.
The order of increasing rate of SN1 reaction is,

RI > RBr > RCl > RF

This is similar to that of the SN2 reaction.

(v) Type of nucleophile

Weak or low concentration of nucleophile favour SN1

reaction. This is because such nucleophile attacks the
carbocation after the bond between CX has broken.
(vi) Rearrangement of product of the SN1 reaction.

R
R C CH2Br
R

C2H5OH

R R
R C CH2CH3 R C CH2R
R (II)

(I)

Figure 7.5 The rearrangement of the product in SN1

reaction mechanism.
(vii) Type of solvent

H3C H
O
H H

O C+ O
H3C H3C
O
H3C H
Polar solvent such as methanol will increase the SN1
reaction. This is because the transition state of SN1
reaction involves in the formation of the positive
charge of the carbocation which can be stabilized by
the polar solvent through solvation. This speeds up
the ionization of the carbocation and increases the
rate of the SN1 reaction.
 E2-Elimination Mechanism

--
NuB:
H
C C C BH + X
C + NuH
X

Rate of reaction = k[RX][ B:]

It is a second order rate law (E2-Elimination Bimolecular).

Characteristics of the E2 reaction

(i) The rate law of the reaction

The rate law of E2 reaction is second order.

(ii) Equation of reactions

The E2 has a similar trend of reactions as SN2.

E1-Elimination Mechanism

The E1 reaction involves two steps mechanism similar to

that of the SN1 reaction mechanism. No abstraction of the H
atom from the alkyl halide until a carbocation is formed in
the reaction
The first step (slow)

The formation of carbocation in the reaction.

X
+
C C C C + X+- X-
H
The second step (slow)

The attack of the base to abstract the hydrogen atom from

the alkyl halide.

+
C C C C + BH
H
B-

The rate of reaction = k[RX]

It is a first order rate law (E1-elimination unimolecular).

Characteristics of the E1 reaction

(i) The rate law of the reaction

The rate law of E1 reaction is first order.

(ii) Equation of reactions

The E1 has a similar trend of reactions as SN1.

END ALKYL HALIDES