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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)


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6.1.1 : Classification of Haloalkanes


 Haloalkanes are classified according to the nature

of carbon atom bonded to the halogen. General Formula


CH 3

Classification methyl halide - halogen is bonded to methyl group Primary (10) halide - halogen is bonded to 10 carbon atom Secondary (20) halide - halogen is bonded to 20 3 carbon atom

CH 2

CH

General Formula R R R

Classification Tertiary (30) halide - halogen is bonded to 30 carbon atom Aryl halide halogen is bonded aromatic ring

to

CH 2 X

** Not a aryl halide


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Example :
 Classify the following haloalkanes :

No. i. ii. iii.

Haloalkanes CH 3CH 2Br C H 3 C H (C l)C H 3


(C H 3 ) 3 C( Br) H3C Cl

Classification 10 20 30

iv.

30
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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.
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Example :
i.
C 3C C Br C 3

-bromobutane

ii.
B rC C

Cl C C C C 3 C 3

1-bromo-3-chloro-4-methylhexane
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Example :
iii.
CH 2 CH 2 F C H 3 C H 2 C H 2 CH C H 2 C H 2 C H 3

4-(2-flouroethyl)heptane

iv.

H3C

CH3 Cl

2-chloro-1,1-dimethylcyclopentane

Example :
v. Br

4-bromocyclohexene

vi.

CH 2Cl

vii.

CH 3 Cl

(chloromethyl)benzene

2-chlorotoluene
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6.1.3 : Structure of Haloalkane


 The carbon halogen bond in haloalkene is polar

because halogens is more electronegative than carbon. + C X electrophilic 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.

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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 (+) carbon atom bonded to the halogen (-).
_ _ X:
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 General reaction :

R_X

Nu:

R _Nu

(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
 Example :

H2O

R_ OH + NaX

CH3 H2O _ _ CH3 C Br + NaOH CH3

CH3 CH3_ C _OH + NaBr CH3


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(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

alcoh ol reflu x

_ _ R CN + X

 Example : CH3CH2 Br + KCN alcoh ol reflu x CH 3CH2CN + KBr


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(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
(amine)

 Example :
CH3CH2Cl + excess NH3 CH3CH2NH2 + NH4+Cl
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15.2.2 :

Mechanisms of Nucleophilic Substitution Reaction


mechanisms for the

 They

are 2 important substitution reaction:

(A). Unimolecular Reaction (SN1) (B). Bimolecular Reaction (SN2)

Nucleophilic

Substitution

Nucleophilic

Substitution

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(A) :

Unimolecular Reaction (SN1)

Nucleophilic

Substitution

 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


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 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

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 The mechanism of SN1 reaction involves 2 steps.

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

R R_ C _ X R

s lo

R R_ C + R
carbocation

3o alkyl halide

halide ion

Step 2 : Nucleophilic attack on the carbocation

R _ _ R C + + Nu: R

fa st

R R_ C _ Nu R
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 Example 1 :

Reaction of 2-bromo-2-methylpropane with H2O.


CH 3 CH 3 _ C _ B r + H 2 O CH 3 CH 3 CH 3 _ C _ OH + HB r CH 3

 SN1 mechanism :

Step 1 : Formation of a carbocation


CH 3 CH 3 _ C _ B r CH 3 s l ow CH 3 CH 3 _ C + CH 3 _
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+ Br

 Step 2 : Nucleophilic attack on the carbocation

CH 3 CH 3 _ C + CH 3

+ H2

fa st

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

H2O

CH 3 CH 3 _ C _ O H + H 3 O + CH 3
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 Example 2 :

Write the mechanism for the following reaction.


CH3 _ C _C C 3
 SN1 Mechanism :

C 3

2Br + NaOH(aq)

CH3 CH3_ C _CH2CH3 + NaBr OH

Step 1 : Formation of carbocation


CH 3 C H 3 _ C _ CH 2 _ B r CH 3 s low CH3 _ _ _ CH 3 C C H 2 + B r + CH3

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Rearrangement :
CH3 CH 3_ C _ CH2 + CH 3 CH 3 CH3 _ C _ CH 2 + CH 3

, 2 -meth l s h if t

Step 2 : Nucleophilic attack on the carbocation


CH 3 CH 3 _ C _ C H 2 + CH3 CH 3 CH 3 _ C _ C H 2 CH 3 OH
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+ OH

fa st

Exercise 1 : 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).

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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.
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(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.
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 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 2o

< R-X 1o

< CH3-X

increasing reactivity
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 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:H C X H slow R Nu C X H H fast Nu C H
H
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R + X-

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 haloalkane.

attacking

nucleophile

and

the

 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.
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 Example 3 :

Reaction of ethyl bromide with aqueous sodium hydroxide.

CH3CH2Br + NaOH(aq)

CH3CH2OH + NaBr

 SN2 Mechanism :
CH3 :OHH C Br H slow CH3 OH C Br H H fast OH C H H
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CH3 + Br-

transition state

Comparison of SN1 and SN2 Reactions SN1 A two-step mechanism SN2 A one-step mechanism

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

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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_ X
haloalkane

+ :B

_ C C
alkene

base

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 Example :
Br

i.

CH 3CHCH CH3 CH3

CH 3 CH 2O N a C H 3 C H 2OH

CH 3 C CH CH 3 CH 3

major
+ CH 3CHC CH 2

minor ii.
Br CH 3
C H 3 CH 2O N a C H 3 CH 2 OH

CH3

CH 3 +

CH2

major

minor

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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 + g eth er R- gX Grignard Reagent ( alkylmagnesium halide)

 Example :

i. CH 3 CH2 CH 2Br + ii.


Cl + g

g eth er C H 3C H 2C H 2 gB r

eth er

g Cl
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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.
RMg X + H 2 O H+ R - H + M g( OH ) X
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Example :
+ H i. C H 3 C H 2 Mg Br + H 2 O C H 3 CH 3 + Mg(OH) Br

ii.
C H 3 C H- Mg B r + H 2 O CH 3 H+ C H 3 C H 2 C H 3 + Mg(OH) B r

iii.
C H 2 Mg Cl

H 2 O/H +

CH3 + Mg(OH) Cl
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(ii).

Synthesis of 1o alcohol Methanal reacts with the Grignard reagent, followed by the hydrolysis produces primary alcohol.
O R -Mg X + H- C -H H R - C -OMg X H H 2 O,H + H R - C -OH + Mg(OH) X H
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 Example :

i.
O C H 3 MgB r + H- C-H H3O+ H C H 3 - C-OH + Mg(OH) B r H

ii.
MgB r O + H- C-H H3O+ C H 2OH + Mg(OH) Br

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(iii).

Synthesis of 2o alcohol Grignard reagent reacts with aldehydes to produce secondary alcohol.
O R-MgX + H -C-R' R' R-C- O MgX H H 2O,H + R' R-C- OH + Mg( OH )X H
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 Example :

i.

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

ii.
MgCl O + C H 3 - C -H CH 3 H2O/H+ C -OH + Mg (OH) Cl H
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(iv).

Synthesis of 3o alcohol Grignard reagent reacts with produce the tertiary alcohol.
O R - M g X + R '- C- R" R' R- C-O M gX R" H 2 O,H + R' R- C -OH + M g(OH) X R"
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ketons

to

 Example :

i.

O C H 3 C H 2 MgBr + C H 3 - C - C H 3 H 2 O/H + CH3 C H 3C H 2 - C - C H 3 + Mg(OH) Br OH

ii.
Mg Cl O + C H 3 - C- C H 3 H3O+

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

H+

 Example :
O C H 3 C H 2 MgI + C O 2 C H 3 C H 2 - C- O -MgI

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

H+

O C H 3 C H 2 C OH + Mg( OH )I

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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 2RX + 2Na Example: 2CH3CH2Br + 2Na p CH3CH2CH2CH3 + 2NaBr
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dry ether

RR + 2NaX

ii.

To prepare a odd number of carbon atoms alkane RX + RX + 6Na p RR + RR + RR + 6NaX

Example: CH3CH2Br + CH3Br + 6Na p CH3CH2CH2CH3 + CH3CH2CH3 + CH3CH3 + 6NaBr

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6.2.6 : Importance of Haloalkanes as Inert Substance


Haloalkanes CCl4 (carbon tetrachloride) Uses solvent for dry cleaning, spot removing

CHCl3 solvent for cleaning and degreasing work (chloroform) CF2Cl2 , Freon-12 propellants in aerosol sprays (dichlorodifluoromethane) CFC refrigerant gas (chloroflourocarbons) DDT 46 insecticide protects (DichloroDiphenylTrichloroethane)

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