Simple pyrimidines. XV. The synthesis, piperidinolysis and hydrolysis of simple 2- and 4-(Halogenomethyl)pyrimidines

Abstract

The 2-and 4-bromomethyl-, dibromomethyl- and (impure) tribromomethyl-pyrimidines, as well as their chloro analogues, were made by direct halogenation of 2- or 4-methylpyrimidine (3m) and (3e) with the appropriate N-halogenosuccinimide. Rates were measured spectrometrically for piperidinolysis and alkaline hydrolysis of the monohalogenomethylpyrimidines which reacted much more rapidly than 2- and 4-halogenopyrimidines. 4,6-Dimethylpyrimidin-2-ylmethanol and 2,6-dimethyl- pyrimidin-4-ylmethanol were made by reduction of the corresponding esters (1 and 2; R = CO₂Et). The u.v., n.m.r, and mass spectra of the compounds are discussed.