CHAPTER 6

HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006 1
6.1 : Introduction
 Haloalkanes or alkyl halides
- compounds that contains halogen atom bonded
to an sp3 hybridized carbon atom.

 General formula : R-X

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

where X : halogen atom

(F, Cl, Br or I)
2
6.1.1 : Classification of Haloalkanes
 Haloalkanes are classified according to the nature of
carbon atom bonded to the halogen.

General Formula Classification

methyl halide
CH 3 X - halogen is bonded to
methyl group
Primary (10) halide
R CH 2 X - halogen is bonded to 10
carbon atom
Secondary (20) halide
R
- halogen is bonded to 20
R CH X
carbon atom 3
General Formula Classification

R Tertiary (30) halide

R C X - halogen is bonded to 30 carbon
R atom

X Aryl halide
- halogen is bonded to aromatic
ring

CH 2 X
** Not a aryl halide
4
Example :
 Classify the following haloalkanes :

No. Haloalkanes Classification

i. CH 3 CH 2 Br 10

ii. CH 3 CH(Cl)CH 3 20

iii. (CH 3 ) 3 C(Br) 30

H3C Cl
iv. 30
5
6.1.2 : 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 3 CHCH 2 CH 3
Br

2-bromobutane

ii. Cl
BrCH 2 CH 2 CHCHCH 2 CH 3
CH 3

1-bromo-3-chloro-4-methylhexane
7
 Example :

iii. CH 2 CH 2 F
CH 3 CH 2 CH 2 CHCH 2 CH 2 CH 3

4-(2-flouroethyl)heptane

iv. H3C CH 3
Cl

2-chloro-1,1-dimethylcyclopentane 8
 Example :

v. Br

4-bromocyclohexene

vi. CH 2 Cl vii. CH 3
Cl

(chloromethyl)benzene 2-chlorotoluene
9
6.1.3 : Structure of Haloalkane
 The carbon – halogen bond in haloalkene is polar
because halogens is more electronegative than carbon.

δ+ δ- electrophilic
C X
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
6.2 : Chemical Properties
6.2.1 : Nucleophilic Substitution Reaction

 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 (δ+) carbon atom bonded to the halogen
(δ-).

 General reaction :
_ _
R_ X + Nu: R _N u + 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.

H2O
R _ X + N aOH R_ OH + N aX

 Example :

CH 3 CH 3
_ _ H2O
CH 3 C Br + N aOH CH 3 _ C _OH + N aBr
CH 3 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.

_ _ alcoh ol _
R X + CN R_ CN + X
reflu x

 Example :

CH 3 CH 2 Br + KCN alcohol CH 3 CH 2 CN + KBr

reflux
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-.

NH 3 _ NH 3 _
R_ X RNH 3 +X _ +
R N H2 + NH 4 X
(amine)

 Example :

+ _
CH 3 CH 2 Cl + exces s N H 3 CH 3 CH 2 N H 2 + N H 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.

 SN1 reactions are governed mainly by the relative

stabilities of carbocations.

 Relative reactivities of haloalkanes in an SN1 reaction :

R-X < R-X < R-X
1o 2o 3o
increasing reactivity

16
 The rate of SN1 reaction does not depend on the
concentration of nucleophile.

 The rate depends only on the concentration of the

substrate, alkyl halide.

 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
s low _
R_ C _ X _
R C+ + X
R R
3o alkyl halide carbocation halide ion

Step 2 : Nucleophilic attack on the carbocation

R R
_ _ fas t
R C+ + Nu: R_ C _ N u
R R 18
 Example 1 :
Reaction of 2-bromo-2-methylpropane with H2O.

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

 SN1 mechanism :

Step 1 : Formation of a carbocation

CH 3 CH 3
s low _
CH 3 _ C _ Br CH 3 _ C + + Br
CH 3 CH 3 19
  Step 2 : Nucleophilic attack on the carbocation

CH 3 CH 3
H
CH 3 _ C + + H 2 O fas t _ _
CH 3 C O
+ H
CH 3 CH 3

Loss of proton, H+ to solvent

CH 3 CH 3
H
_ _
CH 3 C O + H2O CH 3 _ C _ OH + H 3 O +
+ H
CH 3 CH 3
20
 Example 2 :
Write the mechanism for the following reaction.

CH 3 CH 3
CH 3 _ C _CH 2 Br + N aOH(aq) CH 3 _ C _CH 2 CH 3 + N aBr
CH 3 OH

 SN1 Mechanism :

Step 1 : Formation of carbocation

CH 3 CH 3
_
CH 3 _ C _ CH 2 _Br s low _ _
CH 3 C CH 2 + Br
+
CH 3 CH 3 21
Rearrangement :

CH 3 CH 3
CH 3 _ C _ CH 2 1,2-meth yl s hift CH 3 _ C _ CH 2
+ +
CH 3 CH 3

Step 2 : Nucleophilic attack on the carbocation

CH 3 CH 3
_
CH 3 _ C _ CH2 + OH fas t CH 3 _ C _ CH 2 CH 3
+
CH 3 OH

22
Exercise 1 :

Write a reasonable structures of products formed when 1-

iodobutane reacts with

i. KCN
ii. NaOH/H2O
iii. excess NH3

Write the mechanism for the reaction in (ii).

23
Exercise 2 :

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 haloalkanes in an SN2 reaction :

R-X < R-X < CH3-X

2o 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 R R
slow fast Nu C
C X Nu C X + X-
Nu:- H H
H H H H
27
transition state
 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 from the original configuration.

* 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 3 CH 2 Br + N aOH (aq) CH 3 CH 2 OH + N aBr

 SN2 Mechanism :

CH3 CH3 CH3

:OH- C Br
slow
OH C Br
fast
OH C + Br-
H H
H H H H
transition state
29
 Comparison of SN1 and SN2 Reactions

SN 1 SN 2

A two-step mechanism A one-step mechanism

A unimolecular rate- A bimolecular rate-
determining step determining step
Second order : First order :
rate = k [RX] [Nu] rate = k [RX]
Strong nucleophile Weak nucleophile
No carbocation
Carbocation rearrangement
rearrangement
Reactivity order : Reactivity order :
3 o > 2o > 1o methyl > 1o > 2o 30
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 _ _
C C + X
_

X
haloalkane base alkene
31
 Example :
Br
CH 3 CH 2 ON a
i. CH 3 CHCHCH 3 CH 3 C CH CH 3
CH 3 CH 2 OH
CH 3 CH 3
major
+

CH 3 CHC CH 2
CH 3
ii. minor

Br CH 3 CH 2 ON a CH 3 CH 2
CH 3 CH 3 CH 2 OH +
major minor 32
6.2.4 : Synthesis of Organomagnesium
Compound ( Grignard Reagent )

 Prepared by the reaction of haloalkanes with

magnesium metal in anhydrous ether as a solvent.

R-X + Mg eth er R-MgX

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

ii.
eth er
Cl + Mg MgCl
33
6.2.4.1 : 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 2 O R-H + Mg(OH)X

34
Example :

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

ii.

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

H 2 O/H +
CH 2 MgCl CH 3
+ Mg(OH)Cl
35
(ii). Synthesis of 1o alcohol

Methanal reacts with the Grignard reagent,

followed by the hydrolysis produces primary alcohol.

O H
R-MgX + H-C-H R-C-OMgX
H

H 2 O,H +

H
R-C-OH + Mg(OH)X
H 36
  Example :

i.
O H
H 3 O+
CH 3 MgBr + H-C-H CH 3 -C-OH + Mg(OH)Br
H

ii.

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

37
(iii). Synthesis of 2o alcohol

Grignard reagent reacts with aldehydes to

produce secondary alcohol.
O R'
R-MgX + H-C-R' R-C-OMgX
H

H 2 O,H +

R'
R-C-OH + Mg(OH)X
H 38
 Example :

O
i.
CH 3 CH 2 MgBr + CH 3 CH 2 -C-H

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

CH 3
O
MgCl H 2 O/H + C-OH
+ CH 3- C-H + Mg(OH)Cl
H
39
(iv). Synthesis of 3o alcohol

Grignard reagent reacts with ketons to produce

the tertiary alcohol.
O R'
R-MgX + R'-C-R" R-C-OMgX
R"

H 2 O,H +

R'
R-C-OH + Mg(OH)X
R" 40
 Example :

i.
O
CH 3 CH 2 MgBr + CH 3 -C-CH 3

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

CH 3
O
MgCl
H 3 O+ C-OH
+ CH 3- C-CH 3 + Mg(OH)Cl
CH 3 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 R-C-O-MgX

O O
H+
R-C-O-MgX + H 2 O R-C-OH + Mg(OH)X

42
  Example :

O
CH 3 CH 2Mg I + CO 2 CH 3 CH 2- C-O-MgI

O O
H +
CH 3 CH 2- C-O-MgI + H 2 O CH 3 CH 2 COH + Mg(OH)I

43
6.2.5 : 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

dry ether
2RX + 2Na  RR + 2NaX

Example:

2CH3CH2Br + 2Na  CH3CH2CH2CH3 + 2NaBr

44
ii. To prepare a odd number of carbon atoms
alkane

RX + R’X + 6Na  RR + RR’ + R’R’

+ 6NaX

Example:

CH3CH2Br + CH3Br + 6Na  CH3CH2CH2CH3

+ CH3CH2CH3

+ CH3CH3 + 6NaBr

45
6.2.6 : Importance of Haloalkanes as Inert
Substance
Haloalkanes Uses
CCl4 solvent for dry
cleaning, spot
(carbon tetrachloride) removing
CHCl3 solvent for cleaning
(chloroform) and degreasing work
CF2Cl2 , Freon-12 propellants in aerosol
(dichlorodifluoromethane) sprays
CFC
refrigerant gas
(chloroflourocarbons)
DDT
insecticide protects
46

(DichloroDiphenylTrichloroethane)