Studies on the Syntheses of Pyrimidine Derivatives. II

Syntheses of Dipyrimidinylsulfone Derivatives and Diazotization of 6-(5-Amino-2-pyrimidinyl) aminohexanoic Acid

Abstract

By heating 6-(5-bromo-2-pyrimidinyl) aminohexanoic acid and thiourea in aqueous solution, it was derived to 6-(5-isothiouronyl-2-pyrimidinyl) aminohexanoic acid and application of sodium malonaldehyde to its hydrochloride in aqueous solution, with piperidine as the condensation agent, afforded 6-[5-(5-nitro-2-pyrimidinyl)thio-2-pyrimidinyl] aminohexanoic acid. This compound submitted to permanganate oxidation and the corresponding 5-(5-nitro-2-pyrimidinyl) sulfonyl compound was obtained. Its reduction with stannous chloride and conc. hydrochloric acid yielded the 5-amino compound.
Diazotization of 6-(5-amino-2-pyrimidinyl) aminohexanoic acid by the usual method afforded 6-(5-hydroxy-2-pyrimidinyl) aminohexanoic acid. In a similar manner, 5-bromo and 5-chloro compounds were obtained, besides two kinds of crystals; one of white needles whose molecular formula agreed with C₁₀H₁₅O₂N₄Cl⋅HCl and the other of white rhomboprisms agreeing with C₁₀H₁₅O₂N₄Br⋅HBr.
Both underwent condensation with anisaldehyde to form a hydrazone compound, so that they were determined as 6-[1-(5-chloro-2-pyrimidinyl) -hydrazino] hexanoic acid and its 5-bromo compound.