ORGANIC CHEMISTRY

(BT 304)
Course Co-ordinator
Dr Mahera Moin
Assistant Professor
Dow College of Biotechnology
Dow University of Health Sciences

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CHAPTER 6
CHEMISTRY OF
HALOALKANES

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HALOALKANES

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 Introduction

Classification of Halogenated Organic Compounds

Halogenated
Organic
Compounds

Vinyl
Haloalkanes Aryl Halides
Halides

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 Introduction

Haloalkanes:

Organic molecules containing a halogen atom bonded to an

sp3 hybridised carbon of the alkyl group

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Introduction- Some Important Haloalkanes

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 Synthesis of Haloalkanes

Haloalkanes are synthesised by the following methods

Synthesis of
Haloalkanes

1. From Alkenes 2. From Alkynes 3. From Alcohols

Addition of Halogen
a. Addition of Acids ( Refer to the Addition of Halogen
Halogens Mode of Action of Acids
Alkynes)

b. Addition of Halogen
Acids( Refer to the
Mode of Action of
Alkenes)

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

a. Addition of Halogens

Halogens add to alkenes to form vicinal dihalides.

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

Mechanism of Halogen Addition

Neither bromine nor ethylene is a polar molecule, but both are polarizable,

and an induced-dipole/induced-dipole force causes them to be mutually

attracted to each other. This induced-dipole/induced-dipole attraction sets

the stage for Br2 to act as an electrophile. Electrons flow from the system of

ethylene to Br2, causing the weak bromine–bromine bond to break.

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

Mechanism of Halogen Addition

Step 1: Reaction of ethylene and bromine to form a bromonium ion

intermediate:

Step 2: Nucleophilic attack of bromide anion on the bromonium ion:

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

Mechanism of Halogen Addition- Important Features

Formation of Bromonium Ion Vs Carbonium Ion

Such a carbocation, however, has been demonstrated to be less stable than

an alternative structure called a cyclic bromonium ion, in which the positive
charge resides on bromine, not carbon

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

Mechanism of Halogen Addition- Important Features

Stereochemistry Of Halogen Addition

The reaction of chlorine and bromine with cycloalkenes illustrates an

important stereochemical feature of halogen addition. Anti addition is
observed; the two bromine atoms of Br2 or the two chlorines of Cl2 add to
opposite faces of the double bond

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 Synthesis of Haloalkanes
1. Preparation Of Haloalkanes From Alkenes

Mechanism of Halogen Addition

Practice Problems

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 Synthesis of Haloalkanes
3. Preparation Of Alkyl Halides From Alcohols And Hydrogen Halides

The reaction of an alcohol with a hydrogen halide is a substitution. A

halogen, usually chlorine or bromine, replaces a hydroxyl group as a
substituent on carbon. Protonation converts the hydroxyl group from a poor
leaving group (OH-) to a good leaving group (H2O).

The order of reactivity of the hydrogen halides is:

Among the various classes of alcohols, tertiary alcohols are observed to be

the most reactive and primary alcohols the least reactive

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 Synthesis of Haloalkanes
Practice Problems

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 Mode of Action of Haloalkanes

Basic Terminology
• Reaction Mechanism

• Nucleophile and Electrophile

• Nucleophilicity

• Substrate and Leaving Group

• Inversion of Configuration

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 Mode of Action of Haloalkanes
Organic Reaction Mechanism

In organic chemistry the arrows tells us how and where the electrons are
moving during the course of a reaction. This process is called the reaction’s
reaction mechanism

Types of Organic Reaction Mechanisms

1. Ionic or Heterolytic Reaction Mechanisms ( 2 Electrons)

Double barbed arrow shows the movement of 2 electrons

2. Homolytic Reaction Mechanisms ( 1 Electron)

Single barbed arrow shows the movement of 1 electron

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 Mode of Action of Haloalkanes
Nucleophile and Electrophile

Nucleopilicity

Nucleophilic strength, or nucleophilicity, is a measure of how fast a Lewis base

displaces a leaving group from a suitable substrate

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 Mode of Action of Haloalkanes
Nucleophile and Electrophile

Nucleophiles possess a negative charge or have a lone pair of electrons or have

a pi bond

Electrophiles possess a positive charge or have an empty p orbital

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 Mode of Action of Haloalkanes
Practice Question: Identify each of the circled atom as electrophile, nucleophile
or neither

1. Neither 2. Electrophile 3. Nucleophile 4. Nucleophile

5. Nucleophile 6. Nucleophile 7. Electrophile 8. Electrophile

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 Mode of Action of Haloalkanes
Substrate and Leaving Groups

Substrate: A substrate is a chemical entity that contains a leaving group

Leaving Group: Groups that best stabilize a negative charge are the best
leaving groups. The weakest bases are most stable as anions and are the best
leaving groups

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 Mode of Action of Haloalkanes
The Inversion Of Configuration: It resembles the way an umbrella turns
inside out in the wind. It happens because the nucleophile attacks from the
back side ( the side opposite to the leaving group) and turns the tetrahedron of
the carbon inside out

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Mode of Action of Haloalkanes

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 Mode of Action of Haloalkanes

In the Nucleophilic substitution reactions of alkyl halides the carbon–halogen

bond of the alkyl halide is broken heterolytically and the pair of electrons in
that bond are lost with the leaving group

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Mode of Action of Haloalkanes

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 Mode of Action of Haloalkanes

The term “kinetics” refers to how the rate of a reaction varies with changes
in concentration. Consider the nucleophilic substitution in which sodium
hydroxide reacts with methyl bromide to form methyl alcohol and sodium
bromide:

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 Mode of Action of Haloalkanes

Hughes and Ingold observed that the hydrolysis of tert-butyl bromide, which
occurs readily, is characterized by a first-order rate law:

They found that the rate of hydrolysis depends only on the concentration of tert-

butyl bromide. Adding the stronger nucleophile hydroxide ion, moreover,

causes no change in the rate of substitution, nor does this rate depend on the

concentration of hydroxide.

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 Mode of Action of Haloalkanes

The SN1 mechanism for hydrolysis of tertbutylbromide

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 Mode of Action of Haloalkanes

The SN1 mechanism for hydrolysis of tertbutylbromide

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 Mode of Action of Haloalkanes

FUNCTIONAL GROUP TRANSFORMATION BY NUCLEOPHILIC

SUBSTITUTION

The anionic portion of the salt substitutes for the halogen of an alkyl
halide. The metal cation portion becomes a lithium, sodium, or
potassium halide

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 Mode of Action of Haloalkanes
FUNCTIONAL GROUP TRANSFORMATION BY NUCLEOPHILIC
SUBSTITUTION

Practice Question: Complete the following functional group transformations

using the nucleophilic substitution of alkyl halides

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 Mode of Action of Haloalkanes
FUNCTIONAL GROUP TRANSFORMATION BY NUCLEOPHILIC
SUBSTITUTION

Practice Question: Complete the following functional group transformations

using the nucleophilic substitution of alkyl halides

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• Reference

• Francis A. Carey

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Thank You

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