G.D.

GOENKA PUBLIC SCHOOL, SARITA VIHAR

CLASS XII – CHEMISTRY
Ch 10. HALOALKANES AND HALOARENES – 3

1. From hydrocarbons:
❖ By free radical halogenation: (from alkanes)
Gives a complex mixture of isomeric mono- and polyhaloalkanes, which is difficult to separate as pure
compounds. Consequently, the yield of any one compound is low.

2. From alkenes:

Using hydrogen halides using halogens

❖ Using hydrogen halides (HCl, HBr, HI, HF)

• In such reactions there are two products formed: one minor and one major depending upon the
Markovnikov’s rule and Anti- Markovnikov’s rule.
• Markovnikov’s rule says that the negative part of the hydrogen halide will be attached to that carbon
of the double bond which has lesser number of hydrogen atoms.
• Anti-markovnikov’s rule is applied only in the presence of HBr and peroxide.
• If HCl and HI are reacting with the alkene in the presence of peroxide then Markovnikov’s rule will be
applied.

❖ Using halogens in the presence of CCL4 (Br2)

Addition of bromine in CCl4 to an alkene resulting in discharge of reddish brown colour of bromine
constitutes an important method for the detection of double bond in a molecule. The addition results in the
synthesis of vic-dibromides, which are colourless.

3. Halogen exchange:

Finkelstein reaction (for alkyl iodide) Swarts reaction (for alkyl fluoride)

(metal fluoride)
 ❖ Finkelstein reaction (for alkyl iodide)
• The reverse of this reaction i.e. R-I + NaCl/Br will not place because acetone is a covalent compound
and so covalent solvents will dissolve in this solvent.
• NaI, NaCl and NaBr are all ionic but do have some covalent character in them (Fajan’s rule)
• Out of these three NaI would have the maximum covalent character (small cation – big anaion – more
covalent character). Thus NaI will be soluble in acetone and the reaction would proceed but NaCl and
NaBr are insoluble and would precipitate out in acetone.
• Therefore only alkyl iodides are formed via this method.

✓ Few of the mechanisms of the reactions mentioned above are given below and the explanation is hand
written. The transfer of electrons, gaining and loosing of charge, attack of leaving group are explained
via arrows and I have tried to pen down the explanation of the mechanism as far as possible for you
understand as to how the reaction is taking place. Kindly give a thorough reading to the hand out.