The permanganate oxidation of thymidine and thymidylic acid

Abstract

1. 1. Oxidation of thymidine with permanganate under mild conditions brought about the formation of thymidine glycol (5,6-dihydroxy-5,6-dihydrothymidine) and 5-hydroxy-5-methylbarbituric acid deoxyriboside. 2. 2. The oxidation at pH 8.6 resulted in a preferential formation of thymidine glycol, while at pH 4.3 it brought about a predominant formation of the barbituric acid derivative. 3. 3. These features are quite analogous to those of the permanganate oxidation of thymine. However, the hydrolysis of 5-hydroxy-5-methylbarbituric acid deoxyriboside occurs more readily than that of 5-hydroxy-5-methylbarbituric acid, and the ring cleavage takes place between N 1 and C 6, giving N-(2- deoxy- d-ribofuranosyl )-N′- methyltartronylurea . 4. Dephosphorylation of N-methyltartronylurea dexoyriboside 5′ (and 3′)-phosphate was effected by successive treatment with alkali and with diphenylamine in aqueous formic acid. Treatment of this nucleotide derivative with alkali at an elevated temperature also resulted in its dephosphorylation. These conditions of the dephosphorylation are similar to those under which thymidine glycol phosphate can be dephosphorylated.