H. Kawabe, M. Yanagita
Apr 1, 1971
Citations
0
Influential Citations
14
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The amination of chloromethylated polystyrene with 2-aminobutanol in dioxane was studied. The apparent rate constatns, kapp, as computed by the simple second-order equation, were found to increase linearly with the degree of amination; this was in contrast with the amination with n-butylamine, in which the kapp decreased as the amination proceeded. By assuming that the reactivity of the chloromethyl group is enhanced when it is situated next to the already-aminated group as a result of the “hydrophilic effect” of the hydroxyl group, rate equations which give the elementary rate constants were derived. In the presence of a large excess of amine, the over-all kinetics can be expressed by:dx⁄dt=[ab⁄(3k1−k2)][3k1(k1−k2)e−3k1at+2k1k2e−k2at]where x is the concentration of chloride ions at time t; where a is the initial concentration of amine, and b, that of the chloromethyl group, and where k1 and k2 are the rate constants of the elementary reactions which are independent of the neighboring group and under the ...