Kinetische untersuchungen zur reaktionsfähighkeit von chlormethylgruppen in methylendiphenolen

The chloromethyl derivatives of 16 differently substituted methylenediphenols were synthesized for the first time. To compare their reactivity, the solvolysis in methanol and the animolysis with an excess of p-nitroaniline in dimethyl sulfoxide were studied kinetically at 25°C. The rate constants for the methanolysis do not differ very much, beside of the fact that para-chloromethyl derivatives react about 100 times faster than ortho-chloromethyl derivatives. However, for the aminolysis a large acceleration up to 10³ was found for compounds having both hydroxyl groups in ortho-position to the methylene bridge. Obviously, the cleavage of the O? H bond, which occurs in the rate determining step of the aminolysis, is strongly favoured by an intramolecular hydrogen bond between the phenolic hydroxyl groups.