Can Interact Cannot Interact

H2C CH X H2C CH CH2 X

3
(sp )

Allyl halide
Vinyl halide
Figure: In allyl halides, the p-orbital of the halogen atom cannot interact with the
 MO of the C-C double bond. This is because they are separated by a saturated sp
3

hybridized carbon atom.

(1) Substitution Reactions. Following are some of the important nucleophilic substitution
reactions of allyl iodide.
NaOH
H2O
CH2 = CHCH2OH + NaI
Allyl alcohol
CH2I CH 3ONa
CH2 = CHCH2OCH3 + NaI
CH Allyl methyl ether
CH2 KCN
CH2 = CHCH2CN + KI
Allyl iodide Allyl cyanide
NH3
CH2 = CHCH2NH2 + HI
Allylamine

(2) Addition Reactions. The carbon-carbon double bond in allyl iodide shows the usual
electrophilic addition reaction. Markovnikov rule is followed.
Br Br
Br2
CH2I CH2   CH CH2I
1,2-Dibromo-3-iodopropane
CH
CH2 H Br
HBr
Allyl iodide CH2   CH CH2I
2-Bromo-1-iodopropane

5.13 Aryl Halides

Aryl halides are the compounds that contain halogen atom directly attached to the benzene
ring. They have general formula ArX.
Cl Cl Cl Cl

chlorobenzene NO2
NO2 NH2
1-chloro-3-nitrobenzene
1-chloro-4-nitrobenzene 4-chloroaniline

Any halogen compound that contains a benzene ring is not classified as aryl halide.
e.g. Benzyl chloride is not an aryl halide, but is a substituted alkyl halide.
Preparation:
(i) By direct halogenation in presence of a halogen carrier such as Fe, chlorine or bromine
readily replaces nuclear halogen of aromatic hydrocarbons. Mono-, di- and trichloro or
bromo derivatives are obtained, depending upon the proportion of halogen to
hydrocarbon. o– and p- di- chloro di- bromo benzenes are formed on further
halogenation.

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 Similarly, toluene on chlorination gives o- and p- chlorotoluenes.
(ii) Nuclear halogenation of highly activated compounds, like amines and phenols do not
require any Lewis acid catalyst,

(iii) Strongly deactivated aromatic compounds require high temperature for the
reaction.

(iv) Halogens in presence of silver sulphate- This is very reactive halogenating agent for
strongly deactivated compounds.

(v) Decomposition of diazonium salts- When aqueous benzene diazonium chloride is

warmed at about 60aC with cuprous chloride (catalyst) in HC1, chlorobenzene is
formed. The reaction is known as Sandmeyer’s Reaction (1884).
(i) C6H5N2C1 + CuCl C6H5N2[CuCl2]– C6H5· + N2 + CuCl2
(ii) C6H5· + CuCl2 C6H5Cl + CuCl Chlorobenzene

(vi) Reaction of PCl5 on phenols- C6H5OH + PCl5 C6H5Cl + POCl3 + HCl

(vii) Action of HOBr -

C6H6 + HOBr C6H5Br + H2O
Benzene Bromobenzene
Properties
(i) Aryl halides are heavier than water. Among the halides, the melting points and boiling
points follow the order.
Aryl Iodides > Bromides > Chlorides > Fluorides
(ii) Among the isomeric halides (0-, m-, p-), the differences in their melting points are
much wider than those in their boiling points. The m.p. of o-, m-, p- dichlorobenzenes,

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