6

HALOALKANES
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6.1Haloalkanes or alkyl halides : Introduction

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 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 carbon atom 3

CH3X

R CH2 X
R R CH X

General Formula

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

R R C X R
X

to

CH 2 X

** Not a aryl halide

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Example :
Classify the following haloalkanes :

No.

Haloalkanes

Classification

i.
ii. iii.

CH3CH2Br CH3CH(Cl)CH3 (CH3)3C(Br)

H3C Cl

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.

Example :
i.

CH3CHCH2CH3 Br
2-bromobutane

ii.

Cl BrCH 2 CH 2 CHCHCH 2 CH 3 CH 3

1-bromo-3-chloro-4-methylhexane
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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
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Example :
v.
Br

4-bromocyclohexene

vi.

CH 2 Cl

vii.

CH 3 Cl
2-chlorotoluene
9

(chloromethyl)benzene

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 (-).

General reaction : _ X + Nu:_ R

R _ Nu

_ X:
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(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 _ C _Br + NaOH H 2O CH3 CH 3

CH 3 CH 3 _ 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.

_ X + CN _ R

alcohol reflux

_ CN + X _ R

Example :
CH 3 CH 2 Br + KCN alcohol reflux CH 3 CH 2 CN + 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 _ NH + NH +X_ R 4 2
(amine)

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

Mechanisms of Nucleophilic Substitution Reaction

mechanisms for the

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 ratelimiting 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

slow

R _C+ + X_ R R
carbocation halide ion

3o alkyl halide

Step 2 : Nucleophilic attack on the carbocation

R _ C + + Nu: _ R R

fast

R R_ C _ Nu R
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 Example 1 :

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

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

 Step 2 : Nucleophilic attack on the carbocation

CH 3 CH 3 _ C + CH 3

+ H 2 O fast

CH 3 _ C _O H CH 3 + H CH 3

Loss of proton, H+ to solvent

CH 3 _ C _O H CH 3 + H CH 3

H2O

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

Write the mechanism for the following reaction.

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

1,2-methyl shift

Step 2 : Nucleophilic attack on the carbocation

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

fast

(B) : Bimolecular Nucleophilic Reaction (SN2)

Substitution

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 nucleophile.

and

the

concentration

of

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 R
H

+ X-

transition state

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 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.

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 Example 3 :

Reaction of ethyl bromide with aqueous sodium hydroxide.

CH3CH2Br + NaOH(aq)

CH3CH2OH + NaBr

SN2 Mechanism :
CH3 H C Br H CH3 OH C Br H H CH3 OH C H H

:OH-

slow

fast

+ Br-

transition state
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Comparison of SN1 and SN2 Reactions S N1 A two-step mechanism

S N2

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 Weak nucleophile

Carbocation rearrangement Reactivity order : 3o > 2o > 1o

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 _ + :B _ X
haloalkane base

_ C C
alkene

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 Example :
Br

i.

CH 3 CHCHCH 3 CH 3

CH 3CH 2ONa CH 3CH 2OH

CH 3 C CHCH 3 CH 3

major
+ CH 3 CHC CH 2

ii.
Br CH3
CH3CH2ONa CH3CH2OH

minor
CH 3 + CH2

CH 3

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 + Mg ether 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.

Cl + Mg

ether

MgCl
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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.
RMgX + H2O H+ R-H + Mg(OH)X

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Example : i.

H+ CH3 CH2 MgBr + H 2O

CH 3 CH 3 + Mg(OH)Br

ii.

CH3CH-MgBr + H2O CH3

iii.

H+

CH3CH2CH3 + Mg(OH)Br

CH2MgCl

H2O/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-MgX + H-C-H H R-C-OMgX H H 2 O,H + H R-C-OH + Mg(OH)X H
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 Example :

i.
O CH 3 MgBr + H-C-H H3 O+

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

ii.
MgBr O + H-C-H H3O+ CH 2 OH + 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-OMgX H H 2 O,H + R' R-C-OH + Mg(OH)X H
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 Example :

i.

O 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 H 2 O/H + C-OH + Mg(OH)Cl H
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MgCl

O + CH 3- C-H

(iv).

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

to

 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 OH

CH 3 H3O+ C-OH CH 3 + Mg(OH)Cl
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ii.

MgCl

O + CH 3- C-CH 3

(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 + H2O O R-C-OH + Mg(OH)X

R-C-O-MgX

H+

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 Example :
O CH 3 CH 2MgI + CO2 CH 3 CH 2- C-O-MgI

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

H+

O CH 3 CH 2 COH + 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
dry ether

RR + 2NaX

Example:

2CH3CH2Br + 2Na CH3CH2CH2CH3 + 2NaBr

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6.2.6 : Importance of Haloalkanes as Inert Substance

Haloalkanes
CCl4 (carbon tetrachloride) CHCl3 (chloroform)

Uses
solvent for dry cleaning, spot removing solvent for cleaning and degreasing work

CF2Cl2 , Freon-12 (dichlorodifluoromethane) CFC (chloroflourocarbons) DDT (DichloroDiphenylTrichloroethane)

propellants in aerosol sprays

refrigerant gas insecticide protects
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