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CHAPTER1

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.

 General formula : R-X


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

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

Tertiary (30) halide


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

Aryl halide
X - halogen is bonded to
aromatic ring

** Not a aryl halide


CH 2X

4
Example :
 Classify the following haloalkanes :
No. Haloalkanes Classification

CH 3CH 2Br
i. 10

ii. CH 3CH(Cl)CH 3 20

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

H 3C Cl
iv. 30
5
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

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.

 Haloalkanes are reactive and undergo nucleophilic


substitution and elimination reaction.

10
15.2 : Chemical
Properties
15.2.1 : 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 _ 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.

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)

 When R-X is refluxed with KCN in alcohol,


the halogen atom is substituted by the
CN- to produce a nitrile compound.

_ _ alcohol _ _
R X + CN R CN + X
reflux

 Example :

CH 3CH 2Br + KCN alcohol CH 3CH 2CN + 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-.

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

 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
slow _
R_ C _ X _
R C+ + X
R
3o alkyl halide R
carbocation halide ion

Step 2 : Nucleophilic attack on the carbocation

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 :

Step 1 : Formation of a carbocation

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

Loss of proton, H+ to solvent

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 :

Step 1 : Formation of carbocation

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

Step 2 : Nucleophilic attack on the


carbocation
CH 3 CH 3
_
CH 3_ C _ CH2 + OH fast CH 3_ C _ CH 2CH 3
+
CH 3 OH

22
Exercise 1 : (Feb 2003)

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 : (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 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
 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 3CH 2Br + NaOH (aq) CH 3CH 2OH + NaBr

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

Strong nucleophile Weak nucleophile


Carbocation No carbocation
rearrangement rearrangement
Reactivity order : Reactivity order :
3o > 2o > 1o methyl > 1o > 2o30
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
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.

R-X + Mg ether R-MgX


Grignard Reagent

( 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.

(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.

H 2O/H +
CH 2MgCl 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 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

Grignard reagent reacts with


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

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

Grignard reagent reacts with ketons


to produce the tertiary alcohol.
O R'
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
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

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 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

 Reaction of haloalkane (RX) with an alkali metal


(usually Na) to synthesise longer alkane.

i. To prepare an even number of carbon atoms


alkane

2R−X + 2Na → R−R + 2NaX


dry
ether
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
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