Abstract
N, N-Dimethylalkylamines and N-alkylmorpholines with C6-C12 alkyl chain were photochlorinated with chlorine in hydrochloric acid and the reaction conditions and the isomer composition of the chlorinated compounds were investigated.
Different from the case of primary amines, tertiary amines were observed to be slowly chlorinated even in relatively dilute (2N) hydrochloric acid.
It was found that the reactive isomers in the chlorinated tertiary amines, such as 2-, 4- and 5-chloro derivatives, can be readily converted to the stable cyclic quaternary ammonium salts when heated in methanol and the other isomers were recovered unreacted.
With the aims of clarifying the selectivity for hydrogen abstraction by chlorine atoms, the quaternary ammonium compounds and the recovered chlorinated amine obtained from monochlorinated N, N-dimethyl-hexylamine were analyzed by NMR and by GLC and NMR, respectively.
From the above results, the approximate isomer composition of the chlorinated N, N-dimethylhexylamine was determined and the differences in isomer composition between primary and tertiary amines were discussed.
