HALOGENATION

Halogenation is a chemical reaction that involves the reaction of a compound, usually

an organic compound, with a halogen. The pathway and stoichiometry of halogenation
depends on the structural features and functional groups of the organic substrate as
well as the halogen.

The organic halogen compounds can be prepared by a number of methods. The

conditions and procedures differ not only for each member of halogen but also type and
structure of the compound undergoing halogenation.

Chlorine derivatives because of low cost production are most important whereas
bromine derivatives possess certain pharmaceutical or dyeing properties. Fluorine
derivatives are mostly used as refrigerants and aerosol propellants.

There are several processes for the halogenation of organic compounds, including
 free radical halogenation, (substitution halogenation)
 replacement halogenation, and
 halogen addition reaction.

The determining factors are the functional groups.

Saturated hydrocarbons typically do not add halogens but undergo free radical
halogenation, involving substitution of hydrogen atoms by halogen.

CH4 + Cl2 CH3Cl + CH2Cl + HCl

CH CH + 2Cl2 Cl2HC-CHCl2

Unsaturated compounds, especially alkenes and alkynes, add halogens.

(UV)
Ethene + Bromine Water Bromoethane + Hydrogen bromide

CH3COOH + Cl2 PCl5 CH2ClCOOH + HCl

C2H5OH + HCl ZnCl2 C2H5Cl + H2O

It may clear from the above examples that all the reactions not only need different
halogenating agent but also need suitable activator or catalyst. Many of the catalysts
are halogen carrier which exists in two valencies as halogen compounds and they give
up halogen when they move from higher valency (less stable) to lower valency.

Halogenation reactions may be classified in a number of ways but the principal

classification is based on the halogenating agent used
CHLORINATION:

Direct action of chlorine gas

FeCl3
H2C=CH2 + Cl2 Cl-H2C-CH2-Cl
400-500 oC
4CH4 + 10Cl2 CH3Cl + CH2Cl2 + HCCl3 + CCl4 + 10HCl

FeCl3 Cl
+ Cl2
30-100 oC

Hydrochloric acid as chlorinating agent

Addition reaction

Substitution reaction

Replacement reaction

Sodium hypochloride as chlorinating agent

Chlorination with phosgene

Chlorination with Sulfuryl Chloride

Chlorination with Phosphorous Chloride

BROMINATION:

In many cases bromination is carried out similar to chlorination. Thus bromine,

bromides, bromates may be used as in case of chlorination. Reactions involving
addition & substitution are common. Bromine water is very frequently used as a
brominating agent. Potassium bromide is generally added to aqueous bromine solution
to increase the concentration of soluble molecular bromine.

Br2 + KBr KBr3

Addition Reaction

Replacement Reaction

Substitution Reaction