Halogenation
Halogenation
Chlorination
may be brought about by light, heat or catalysis and the extent of chlorination
depends largely on the amount of chlorine used. A mixture of all possible
isomeria monochlorides is obtained, but the isomers are formed in unequal
amounts, due to the difference of the reactivity of primary, secondary and
tertiary hydrogen atoms. Markownik off
(1875) found experimentally that the order of ease of substitution is tertiary
hydrogen > secondary > primary; e.g.,
chlorination of isobutene at 300oC gives a mixture of two isomeric
monochlorides :
Isobutene
has one tertiary and nine primary hydrogen atoms. On the basis of equal rates
of substitution, the statistical results would be 90 per cent of (I) and 10 per
cent of (II). Actually, the results obtained were 67 per cent of (I) and 33 per
cent of (II). This tertiary hydrogen is replaced about 4.5 times as fast as
primary hydrogen.
Bromination
is similar to chlorination, but not so vigorous. Iodination is reversible, but
it may be carried out in the presence of an oxidizing agent, such as HIO3,
HNO3, HgO, etc., which destroys the hydrogen iodide as it is formed
and so drives the reaction to the right , e.g.,
CH4 + I2 ⇌ CH3I
+ HI
5HI + HIO3 → 3I2
+3H2O
Iodides are
more conveniently prepared by treating the chloro- or bromo-derivative with
sodium iodide in methanol or acetone solution, e.g.,
RCI + NaI acetone RI +NaCl
This reaction
is possible because sodium iodide is soluble in methanol or acetone, whereas
sodium chloride and sodium bromide are not. This reaction is known as the Finkelstein
or Conant-Finkelstein reaction.
Direct
fluorination is usually explosive; special conditions are necessary for the
preparation of the fluorine derivatives of the alkanes.
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