Synthesis of 1,2,3-Triazine Derivatives by Deoxygenation of 1,2,3-Triazine 1-Oxides

A convenient, efficient, and inexpensive method has been developed for the synthesis of 1,2,3-triazine derivatives via deoxygenation of 1,2,3-triazine 1-oxide using trialkyl phosphites. Triethyl phosphite is more reactive than trimethyl phosphite, and both phosphites form their corresponding phosphates in these reactions. This procedure provides a range of aromatic and aliphatic substituted 1,2,3-triazine-4-carboxylate derivatives cleanly in high yields. Unexpected 1,2,4-triazine derivatives were also obtained as minor products during deoxygenation of 1,2,3-triazine-4-carboxylate 1-oxides having an aliphatic substituent at the 5-position.