3-Methylthio-5-hydroxy-1,2,4-triazine(1c)reacted withsubstituted benzenesulfonyl chloride to give 3-methylthio-5-oxy-1,2,4-triazin-6-ylpyridinium betaine(4)in anhydrous pyridine.But when NaOH/H;O/CH;COCH;orNaOH/CH;OH were used as reactant and solvent,3-methylthio-4-substitutedbenzenesulfonyl-5-oxo-6-hydroxy-1,4,5,6-tetrahydro-1,2,4-triazine(6)or1-tosyl-3-methylthio-5-oxo-6-methyloxy-1,4,5,6-tetrahydro-1,2,4-triazine(7)wasobtained respectively.The above reactions show anomalous properties of nucleophilicattack on 6-carbon in 1,2,4-triazine ring.