CHAPTER1

HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006

15.1 : Introduction
Haloalkanes or alkyl halides

- compounds that contains halogen atom

bonded to an sp3 hybridized carbon atom.

General formula :

or
or

R-X
CnH2n+1X (acyclic)
CnH2n-1X (cyclic)

where X : halogen atom

(F, Cl, Br or I)
2

15.1.1 : Classification of
Haloalkanes
Haloalkanes are classified according

to
the nature of carbon atom bonded to the
halogen.
General Formula
Classification
CH 3X

methyl halide
- halogen is bonded
to methyl group

R CH 2 X

Primary (10) halide

- halogen is bonded
to 10 carbon atom

R
R CH X

Secondary (20) halide

- halogen is bonded
to 20 carbon atom 3

General Formula

Classification

Tertiary (30) halide

- halogen is bonded to 30
carbon atom

R C X
R
X

CH 2X

Aryl halide
- halogen is bonded to
aromatic ring

** Not a aryl halide

4

Example :
Classify the following haloalkanes :

No
.

Haloalkanes
CH 3CH 2Br

i.
ii.

Classification
10

CH 3CH(Cl)CH 3

20

(CH 3)3C(Br)
iii.

iv.

H 3C

Cl

30

30

15.1.2 : IUPAC Nomenclature

Haloalkanes are named as alkanes with

halogen as substituents.
Locate and number the parent chain from

the direction that gives the substituent

encountered first the lower number.
Show

halogen substituents by the

prefixes flouro-, chloro-, bromo- and
iodo-, and list them in alphabetical order
along with other substituents.
6

Example :
i.

CH 3CHCH 2CH 3
Br
2bromobutan
e

ii.

Cl
BrCH 2CH 2CHCHCH 2CH 3
CH 3

1-bromo-3-chloro-4methylhexane

Example :
iii.

CH 2CH 2F
CH 3CH 2CH 2CHCH 2CH 2CH 3
4-(2flouroethyl)heptane

iv.

H 3C

CH 3
Cl

2-chloro-1,1dimethylcyclopentane

Example :
v.

Br

4bromocyclohexe
ne
vi.

CH 2Cl

(chloromethyl)ben
zene

vii.

CH 3
Cl
2chlorotoluen

15.1.3 : Structure of
Haloalkane
The carbon halogen bond in haloalkene is polar

because halogens is more electronegative than

carbon.

+ C X

electrophi
lic site

The polar C X bond causes the carbon bearing

the halogen is susceptible to nucleophilic attack.

Haloalkanes are reactive and undergo nucleophilic

substitution and elimination reaction.

10

15.2 : Chemical
Properties
15.2.1 : Nucleophilic
Reaction

Substitution

Haloalkanes

undergo
nucleophilic
substitution reactions in which the halogen
atom is replaced by a nucleophile.

In this reaction, the nucleophile attacks

the partially positive charge (+) carbon

atom bonded to the halogen (-).

General
reaction_:
_

R X

Nu:

R _ Nu

_
X:
11

(a) :
Hydrolysis of Haloalkane with
Aqueous Solution of NaOH (H2O/NaOH)
Alkaline

hydrolysis is carried out by

boiling R-X with NaOH(aq) to form alcohol.

R_ X + NaOH

H 2O

R_ OH + NaX

Example :

CH 3
H 2O
_
_
CH 3 C Br + NaOH
CH 3

CH 3
CH 3_ C _OH + NaBr
CH 3
12

(b) :
Reaction of Haloalkane with
Potassium Cyanide (KCN)
When R-X is refluxed with KCN in alcohol,

the halogen atom is substituted by the

CN- to produce a nitrile compound.

_
_
R X + CN

alcohol
reflux

_
_
R CN + X

Example :

CH 3CH 2Br + KCN

alcohol
reflux

CH 3CH 2CN + KBr

13

(c) :Reaction of Haloalkane with Ammonia

(NH3)
When

R-X
is
heated
with
excess
concentrated NH3, the halogen atom is
replaced by the amino group, NH2-.
R_ X

NH3

_
+
RNH3 X

NH3

_
_
+
R NH2 +NH4 X
(amin
e)

Example :
CH 3CH 2Cl + excess NH 3

_
+
CH 3CH 2NH 2 + NH 4 Cl
14

15.2.2

: Mechanisms of Nucleophilic
Substitution Reaction

They are 2 important mechanisms for the

substitution reaction:
(A).
Unimolecular
Nucleophilic
Substitution Reaction (SN1)
(B).
Bimolecular
Nucleophilic
Substitution Reaction (SN2)

15

(A)
: Unimolecular
Nucleophilic
Substitution
Reaction (SN1)
The term unimolecular means there is only one

molecule involved in the transition state of the

rate-limiting step.
S N1

reactions are governed mainly

relative stabilities of carbocations.

by

the

Relative reactivities of haloalkanes in an S N1

reaction :
R-X
1o

<

R-X <
2o

R-X
3o

increasing reactivity
16

 The rate of SN1 reaction does not depend

on the concentration of nucleophile.

The

rate
depends
concentration of the
halide.

only
on
the
substrate, alkyl

rate = k [R3C-X]

* SN1 is a first order reaction

17

 The mechanism of SN1 reaction involves 2

steps.
Step 1 : Formation of a carbocation (rate
determining
step)

R
R_ C _ X

slow

R
3o alkyl halide

R
_
_
R C+ + X
R

carbocation

halide ion

Step 2 : Nucleophilic attack on the carbocation

R
_
_
R C + + Nu:
R

fast

R
R_ C _ Nu
R

18

 Example 1 :

Reaction of
H2O.

2-bromo-2-methylpropane with

CH 3
CH 3_ C _ Br + H 2O
CH 3

CH 3
CH 3_ C _ OH + HBr
CH 3

SN1 mechanism :

Step 1 : Formation of a carbocation

CH 3
CH 3_ C _ Br
CH 3

slow

CH 3
_
_
CH 3 C +
+ Br
CH 3

19

 Step

2 : Nucleophilic
carbocation

attack

CH 3
fast
_
+
CH 3 C
+ H 2O
CH 3

on

the

CH 3
H
_
_
CH 3 C O
+ H
CH 3

Loss of proton, H+ to solvent

CH 3
H
_
_
CH 3 C O
+ H
CH 3

+ H 2O

CH 3
CH 3_ C _ OH + H 3O+
CH 3
20

 Example 2 :

Write the
reaction.

mechanism

CH 3
CH 3_ C _CH 2Br + NaOH(aq)
CH 3

for

the

following

CH 3
CH 3_ C _CH 2CH 3 + NaBr
OH

SN1 Mechanism :

Step 1 : Formation of carbocation

CH 3
CH 3_ C _ CH 2_ Br
CH 3

slow

CH 3
_
_
_
CH 3 C CH 2 + Br
+
CH 3

21

Rearrangement :
CH 3
CH 3_ C _ CH 2
+
CH 3

1,2-methyl shift

Step 2 : Nucleophilic
carbocation
CH 3
CH 3_ C _ CH2
+
CH 3

+ OH

fast

CH 3
CH 3_ C _ CH 2
+
CH 3

attack

on

the

CH 3
CH 3_ C _ CH 2CH 3
OH
22

Exercise 1 : (Feb 2003)

Write a reasonable structures of products
formed when 1-iodobutane reacts with
i.
ii.
iii.

KCN
NaOH/H2O
excess NH3

Write the mechanism for the reaction in

(ii).

23

Exercise 2 : (Mac 2002)

The structure of compound A is as follows:

CH3
CH3 C Br
CH3
i. Give IUPAC name for A
ii.Compound A react with OH- forming an alcohol.
Write the mechanism for the formation of this
alcohol and name the reaction.

24

(B)
: Bimolecular
Nucleophilic
Substitution Reaction (SN2)
The term bimolecular means that the

transition state of the rate limiting step

involves the collision of two molecules.

SN2 reactions are governed mainly by

steric factors (steric effect).

Steric effect

- is an effect on relative rates caused

by the space-filling properties of those
parts of a
molecule attached at or
near to the reacting
site.
25

 The reactivity on SN2 reaction depends on the size of

atoms or groups attached to a C X.

The presence of bulky alkyl groups will prevent the

nucleophilic attack and slow the reaction rate.

Relative

reactivities

of

R-X

R-X

haloalkanes

in

an

S N2

reaction :

2o

<

<

CH3-X

1o

increasing reactivity

26

 The

rate of reaction depends on the

concentration of the haloalkane and the
concentration of nucleophile.
rate = k [R-X] [Nu:-]

* SN2 is a second order reaction.

The mechanism of SN2 occurs in a single

step.

General Mechanism :
R

Nu:-

C X
H

slow

Nu C X
H H

transition

fast Nu C

+ X27

 In SN2 reaction, the nucleophile attacks from the

back side of the electrophilic carbon, that is, from

the side directly opposite bonded to the halogen.

The

transition state involves partial bonding

between the attacking nucleophile and the
haloalkane.

Back-side attack causes the product formed has

inverse
configuration
configuration.

from

the

original

* turns the tetrahedron of the carbon atom

inside out, like umbrella caught by the wind.

28

 Example 3 :

Reaction of ethyl bromide with aqueous

sodium hydroxide.

CH 3CH 2Br + NaOH (aq)

CH 3CH 2OH + NaBr

SN2 Mechanism :

:OH-

CH3
H

C Br
H

slow

CH3
OH C Br
H H

transition
state

fast

CH3
OH C
H

+ Br-

29

Comparison of SN1 and SN2 Reactions

SN 1
A two-step
mechanism

SN 2
A one-step mechanism

A unimolecular
A bimolecular
rate-determining step rate-determining step
Second order :
rate = k [RX] [Nu]

First order :
rate = k [RX]

Strong nucleophile

Weak nucleophile

Carbocation
rearrangement

No carbocation
rearrangement

Reactivity order :
3o > 2o > 1o

Reactivity order :
o
methyl > 1o > 230

15.2.3 : Elimination Reaction

(dehydrohalogenation of
haloalkanes)
Halogen can be removed from one carbon

of a haloalkane and hydrogen from an

adjacent carbon to form a carbon-carbon
double bond in the presence of a strong
base.
General reaction :

H
_ C _ C _ + :B_
X

_
C C

haloalka
ne

alken
e

base

+ X

31

 Example :

Br

i.

CH 3CHCHCH 3

CH 3CH 2ONa
CH 3CH 2OH

CH 3C CHCH 3
CH 3

CH 3

major
+
CH 3CHC CH 2
CH 3

mino
r

ii.

Br
CH 3

CH 3CH 2ONa
CH 3CH 2OH

CH 3

CH 2
+

major

mino

32

15.2.4 : Synthesis of
Organomagnesium
Compound ( Grignard Reagent )
Prepared by the reaction of haloalkanes

with magnesium metal in anhydrous ether

as a solvent.
R-X + Mg ether R-MgX

Grignard Reagent
( alkylmagnesium
halide)
Example :
CH 3CH 2CH 2Br + Mg ether CH 3CH 2CH 2MgBr
i.
ii.

Cl + Mg

ether

MgCl
33

15.2.4.1 :
Synthesis of Alkanes,
Alcohols and
Carboxylic Acids
from Grignard
Reagents.
The

Grignard reagents undergo many

reactions that make them useful as a
starting materials in the synthesis of
other organic compounds.

(i).

Synthesis of alkane

The Grignard reagent is hydrolyzed to

an alkane when warmed with H2O.
H+
RMgX + H 2O
R-H + Mg(OH)X
34

Example :
i.

+
H
CH 3CH 2MgBr + H 2O
CH 3CH 3 + Mg(OH)Br

ii.

CH 3CH-MgBr + H 2O

H+

CH 3CH 2CH 3 + Mg(OH)Br

CH 3
iii.

CH 2MgCl

H 2O/H +

CH 3
+ Mg(OH)Cl
35

(ii).

Synthesis of 1o alcohol

Methanal reacts with the Grignard

reagent,
followed by the hydrolysis
produces primary alcohol.
H

O
R-MgX + H-C-H

R-C-OMgX
H
H 2O,H +

H
R-C-OH + Mg(OH)X
H

36

 Example :

i.

CH 3MgBr + H-C-H

H 3O+

H
CH 3-C-OH + Mg(OH)Br
H

ii.
MgBr

O
+ H-C-H

H 3O+

CH 2OH

+ Mg(OH)Br

37

(iii). Synthesis of 2o alcohol

Grignard
reagent
reacts
with
aldehydes to produce secondary alcohol.
R'

O
R-MgX + H-C-R'

R-C-OMgX
H
H 2O,H +

R'
R-C-OH + Mg(OH)X
H

38

 Example :

i.

CH 3CH 2MgBr + CH 3CH 2-C-H

H 2O/H +
H
CH 3CH 2-C-CH 2CH 3 + Mg(OH)Br

ii.

MgCl

OH

O
+ CH 3-C-H

CH 3
H 2O/H +

C-OH
+ Mg(OH)Cl
H
39

(iv). Synthesis of 3o alcohol

Grignard reagent reacts with ketons
to produce the tertiary alcohol.
R'

O
R-MgX + R'-C-R"

R-C-OMgX
R"

H 2O,H +
R'
R-C-OH + Mg(OH)X
R"

40

 Example :

i.

O
CH 3CH 2MgBr + CH 3-C-CH 3
H 2O/H +
CH 3

ii.

CH 3CH 2-C-CH 3 + Mg(OH)Br

MgCl

OH

O
+ CH 3-C-CH 3

CH 3
H 3O+

C-OH
CH 3

+ Mg(OH)Cl
41

(v).

Synthesis of carboxylic acid

Grignard reagent reacts with carbon

dioxide (CO2) followed by hydrolysis to
form carboxylic
acid.

O
RMgX + O C O
O
R-C-O-MgX + H 2O

H+

R-C-O-MgX
O
R-C-OH + Mg(OH)X
42

 Example :
O
CH 3CH 2MgI + CO2

O
CH 3CH 2-C-O-MgI + H 2O

CH 3CH 2-C-O-MgI

H+

O
CH 3CH 2COH + Mg(OH)I

43

15.2.5 : Wurtz Reaction

Reaction of haloalkane (RX) with an alkali

metal (usually Na) to synthesise longer alkane.

i. To prepare an even number of carbon
atoms alkane
2RX + 2Na dry

RR + 2NaX

ether

Example:
2CH3CH2Br + 2Na

CH3CH2CH2CH3 + 2NaBr
44

ii.To prepare a odd number of carbon atoms

RX + RX + 6Na

alkane

RR + RR + RR
+

6NaX
Example:
CH3CH2Br + CH3Br + 6Na

CH3CH2CH2CH3
+ CH3CH2CH3
+ CH3CH3 + 6NaBr

45

15.2.6 : Importance of Haloalkanes

as Inert
Substance
Haloalkanes

Uses

CCl4

solvent for dry

cleaning, spot
removing

(carbon tetrachloride)
CHCl3
(chloroform)
CF2Cl2 , Freon-12
(dichlorodifluoromethane)
CFC
(chloroflourocarbons)
DDT

solvent for
cleaning and
degreasing work
propellants in
aerosol sprays
refrigerant gas
insecticide

46