Peroxide Effect
Peroxide Effect
The Peroxide
effect (Kharasch, 1933). The presence of oxygen or peroxide that are formed
when the alkene stands exposed to the air, or added peroxide such as benzoyl
peroxide, causes the addition of hydrogen bromide to take place in the
direction opposite to that predicted by Markovnikov’s rule. This departure from
the rule is known as the ‘abnormal’ reaction, and was shown to be due to the
‘peroxide effect’ (Kharasch et al., 1933). Hydrogen chloride, hydrogen
iodide and hydrogen fluoride do not exhibit the abnormal reaction. It has been
found that the addition of hydrogen bromide is ‘abnormally’ effected
photochemically as well as by peroxide catalysts.
The
mechanism of the peroxide effect is a free-radical chain reaction, the peroxide
generating the free radical R1 (cf. polymerization. Below):
(R1CO2)2 → 2R1CO2.
→ 2R1. + 2CO2
R1. + HBr → R1H
+ Br.
R2CH=CH2 + Br. → R2CHCH2Br
HBr R2CH2CH2Br +
Br., etc.
In the photochemical addition, the bromine atom is produced by absorption of a quantum of light:
a bell et al. (1962), using ESR spectroscopy, showed that the photochemical addition of HBr produces free radicals which appear to be best represented as bridged structures. They also showed, using DBr, that the bromine atom is the initial event in the attack.
The reason
for the addition being contrary to Markovnikov’s rule is not certain. A
favourted theory is that the order of stability of free radicals is the same as
that for corbonium ions, i.e.,
t > s > primary. One explanation for this order is no bound resonance. Thus the
reaction proceeds as shown in the equations above, the primary free-radical, R2CHBrCH2.,
being much less favoured energetically than the secondary, R2CHCH2Br.
It has
previously been pointed out that, among other factors, the energy of activation
in a given reaction is lower the greater the strength of the new bond formed.
Now, the bond broken is the –bond, and so this energy change will not affect
the activation energy whichever way the free-radical addition occurs. Also, the
strength of a C—H bond is not the order p > s > t; this order also applies to
bonds other than C—H. hence, on this basis, it can be expected that the
intermediate free radical will be preferably RCHCH2X rather than
RCHXCH2.. This, then, is possible explanation for
free-radical occurring contrary to Markovnikov’s rule.
The abnormal
reaction in the presence of peroxides can be prevented by the addition, in
sufficient amount, of an inhibitor such as diphenylamine, catechol, etc.
inhibitors combine with free radicals, and so prevent propagation of the
chain-reaction. Thus an inhibitor produces (if present in small amount only) an
induction period, i.e., a period
when apparently no reaction is occurring. When the inhibitor is used up, it is
than possible for the chain reaction to proceed in the normal fashion.
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