The kinetics of the
reaction between methyl radicals and anisole have been studied at temperatures
between 453 and 539�K and total pressures between 10 and 30 torr.
The concentrations of methyl radicals ranged from 2 x 10-12 to 5 x
10-11 mole and those of anisole from 10-7 to mole cm-3.
The reaction proceeds mainly by the mechanism
������������������ C6H5OCH3+CH3·
→ C6H5OCH2·+CH4���������������� (1)����������������� C6H5OCH2·+CH3·
→ C6H5OC2H5�������������������� (2)���������������� ���������C6H5OCH2·
→ C6H5CHO+H·������������������ (3)
At 487�K attack on the
aromatic ring to yield methyl anisoles is about twelve times slower than
reaction (1). The Arrhenius parameters for reactions (1) and (8) are: log10(A1 cm3
mole-1 sec-1) = 11.7 � 0.3, and E1 = 10.5 �
0.8 kcal mole-1; log10(A8
sec-1) = 12.5, and E8 = 21 kcal mole-1. The
last two values are based on the assumption that the kinetics of reaction (2)
are similar to those of the recombination of methyl radicals. The rate of
reaction (1) is about half that of the corre- sponding reaction with toluene and about five times that of
the reaction with ethane in the above temperature range.
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