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5
HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006 1
15.1 : Introduction
Haloalkanes or alkyl halides
- compounds that contains halogen atom
bonded to an sp3 hybridized carbon atom.
2
15.1.1 : Classification of
Haloalkanes
Haloalkanes are classified according to
the nature of carbon atom bonded to the
halogen.
General Formula Classification
methyl halide
CH 3X - 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
R CH X 20 carbon atom 3
General Formula Classification
Aryl halide
X - halogen is bonded to
aromatic ring
4
Example :
Classify the following haloalkanes :
No. Haloalkanes Classification
CH 3CH 2Br
i. 10
ii. CH 3CH(Cl)CH 3 20
H 3C Cl
iv. 30
5
15.1.2 : IUPAC Nomenclature
i. CH 3CHCH 2CH 3
Br
2-
bromobutan
e
ii. Cl
BrCH 2CH 2CHCHCH 2CH 3
CH 3
1-bromo-3-chloro-4-
methylhexane 7
Example :
iii. CH 2CH 2F
CH 3CH 2CH 2CHCH 2CH 2CH 3
4-(2-
flouroethyl)heptane
iv. H 3C CH 3
Cl
2-chloro-1,1- 8
dimethylcyclopentane
Example :
v. Br
4-
bromocyclohexe
ne
vi. CH 2Cl vii. CH 3
Cl
(chloromethyl)ben 2-
zene chlorotoluen 9
15.1.3 : Structure of
Haloalkane
The carbon – halogen bond in haloalkene is polar
because halogens is more electronegative than
carbon.
δ+ δ- electrophi
C X
lic site
The polar C – X bond causes the carbon bearing the
halogen is susceptible to nucleophilic attack.
10
15.2 : Chemical
Properties
15.2.1 : Nucleophilic Substitution
Reaction
General reaction :
_ _
R_ X + Nu: R _ Nu + X:
11
(a) : Hydrolysis of Haloalkane with
Aqueous Solution of NaOH (H2O/NaOH)
H 2O
R_ X + NaOH R_ OH + NaX
Example :
CH 3 CH 3
_ _ H 2O
CH 3 C Br + NaOH CH 3_ C _OH + NaBr
CH 3 CH 3
12
(b) : Reaction of Haloalkane with
Potassium Cyanide (KCN)
_ _ alcohol _ _
R X + CN R CN + X
reflux
Example :
NH3 _ NH3 _
R_ X +
RNH3 X _ +
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
15
(A) : Unimolecular Nucleophilic
Substitution Reaction (SN1)
16
The rate of SN1 reaction does not depend
on the concentration of nucleophile.
∴ rate = k [R3C-X]
17
The mechanism of SN1 reaction involves 2 steps.
R R
slow _
R_ C _ X _
R C+ + X
R
3o alkyl halide R
carbocation halide ion
R R
_ _ fast
R C + + Nu: R_ C _ Nu
R R 18
Example 1 :
Reaction of 2-bromo-2-methylpropane with
H2O.
CH 3 CH 3
CH 3_ C _ Br + H 2O CH 3_ C _ OH + HBr
CH 3 CH 3
SN1 mechanism :
CH 3 CH 3
slow _
CH 3_ C _ Br _
CH 3 C + + Br
CH 3 CH 3 19
Step 2 : Nucleophilic attack on the
carbocation
CH 3 CH 3
_ fast _ _ H
CH 3 C + + H 2O CH 3 C O
+ H
CH 3 CH 3
CH 3 CH 3
H
_ _
CH 3 C O + H 2O CH 3_ C _ OH + H 3O+
+ H
CH 3 CH 3
20
Example 2 :
Write the mechanism for the following
reaction.
CH 3 CH 3
CH 3_ C _CH 2Br + NaOH(aq) CH 3_ C _CH 2CH 3 + NaBr
CH 3 OH
SN1 Mechanism :
CH 3 CH 3
_
CH 3_ C _ CH 2_ Br slow _ _
CH 3 C CH 2 + Br
+
CH 3 CH 3 21
Rearrangement :
CH 3 CH 3
1,2-methyl shift
CH 3_ C _ CH 2 CH 3_ C _ CH 2
+ +
CH 3 CH 3
22
Exercise 1 : (Feb 2003)
i. KCN
ii. NaOH/H2O
iii. excess NH3
23
Exercise 2 : (Mac 2002)
CH3
CH3 C Br
CH3
i. Give IUPAC name for A
24
(B) : Bimolecular Nucleophilic
Substitution Reaction (SN2)
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.
increasing reactivity
26
The rate of reaction depends on the
concentration of the haloalkane and the
concentration of nucleophile.
General Mechanism :
R R R
slow fast Nu C
C X Nu C X + X-
Nu:- H
H
H H H H
27
transition
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.
28
Example 3 :
Reaction of ethyl bromide with aqueous
sodium hydroxide.
SN2 Mechanism :
A unimolecular A bimolecular
rate-determining step rate-determining step
Second order : First order :
rate = k [RX] [Nu] rate = k [RX]
General reaction :
H
_ C _ C _ + :B_ _
C C + X
_
X
alken
haloalka base
e
ne 31
Example :
Br
CH 3CH 2ONa
i. CH 3CHCHCH 3 CH 3C CHCH 3
CH 3CH 2OH
CH 3 CH 3
major
+
CH 3CHC CH 2
CH 3
ii. mino
r
Br CH 3CH 2ONa CH 3 CH 2
CH 3 CH 3CH 2OH +
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.
( alkylmagnesium
Example :
halide)
i.
CH 3CH 2CH 2Br + Mg ether CH 3CH 2CH 2MgBr
ii.
ether
Cl + Mg 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.
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.
H 2O/H +
CH 2MgCl CH 3
+ Mg(OH)Cl
35
(ii). Synthesis of 1o alcohol
O H
R-MgX + H-C-H R-C-OMgX
H
H 2O,H +
H
R-C-OH + Mg(OH)X
H 36
Example :
i.
O H
H 3O+
CH 3MgBr + H-C-H CH 3-C-OH + Mg(OH)Br
H
ii.
MgBr O CH 2OH
H 3O+
+ H-C-H + Mg(OH)Br
37
(iii). Synthesis of 2o alcohol
H 2O,H +
R'
R-C-OH + Mg(OH)X
H 38
Example :
O
i.
CH 3CH 2MgBr + CH 3CH 2-C-H
H 2O/H +
H
CH 3CH 2-C-CH 2CH 3 + Mg(OH)Br
ii. OH
CH 3
O
MgCl H 2O/H + C-OH
+ CH 3-C-H + Mg(OH)Cl
H
39
(iv). Synthesis of 3o alcohol
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
CH 3CH 2-C-CH 3 + Mg(OH)Br
ii.
OH
CH 3
O
MgCl
H 3O+ C-OH
+ CH 3-C-CH 3 + Mg(OH)Cl
CH 3 41
(v). Synthesis of carboxylic acid
O
RMgX + O C O R-C-O-MgX
O O
H+
R-C-O-MgX + H 2O R-C-OH + Mg(OH)X
42
Example :
O
CH 3CH 2MgI + CO2 CH 3CH 2-C-O-MgI
O O
H+
CH 3CH 2-C-O-MgI + H 2O CH 3CH 2COH + Mg(OH)I
43
15.2.5 : Wurtz Reaction
44
ii.To prepare a odd number of carbon atoms alkane
Example:
45
15.2.6 : Importance of Haloalkanes
as Inert Substance
Haloalkanes Uses
CCl4 solvent for dry
(carbon tetrachloride) cleaning, spot
removing
CHCl3 solvent for
(chloroform) cleaning and
degreasing work
CF2Cl2 , Freon-12 propellants in
(dichlorodifluoromethane) aerosol sprays
CFC refrigerant gas
(chloroflourocarbons)
DDT insecticide 46
(DichloroDiphenylTrichloroet protects