Preparation of Alkyl Halides

2. Halogenation of hydrocarbons: alkyl halides can be prepared by the radical

reaction of an alkane with Cl2 or Br2 in the presence of ultraviolet light or heat.

Examples:
• Alkane halogenation is a poor synthetic method for preparing alkyl
halides because mixtures of products invariably result.
 Mechanism of the radical chlorination of methane
(Halogenation of hydrocarbons)

• Three kinds of steps are required

in radical substitution reactions:
initiation, propagation, and
termination
• Alkanes that have more than one kind of hydrogen, the chlorination reaction prefers
to occur on the most substituted carbon atom in alkane

Example:
• The observed reactivity order of alkane
hydrogens toward radical chlorination
can be explained the bond dissociation
energies.

• less energy is needed to break a tertiary

C−H bond than to break a primary or
secondary C−H bond, the resultant
tertiary radical is more stable than a
primary or secondary radical.