Preliminary Research on Mechanism of the Isomerization/Chlorination of O, O-Dialkylthiophosphate (-onate)with Phosphorus Oxychloride

Abstract

Abstract: In the previous papers, we reported that O,O-dialkylthiophosphate(-onate) 1 reacted with phosphorus oxychloride to give S-alkyl thiophosphoro (-on-)chloridate 2 and Oalkyl phosphorodichloridate 3.Obviously both of isomerization and chlorination occurred in this reaction.The recent experimental results show that phosphorus oxychloride doesn' t react with O-alkyl thiophosphoro(-no)chlorldate 5 which is a desired chlorination product of 1,while it can smoothly react with O,S-dialkythiophosphate(-onate) 6 which is a desired isomerization product of 1 to give 2- Based on this fact we suggest that the isomerization may occur ahead of the chlorination in the isomerization/chlorination of 1.In the light of the above results and trigonal bipyramid (TBP) intermediate concept, the mechanism 0f the isomerization /chlorination of 1 is discussed.

Key words: Thiophosphate (-onate), Thiophosphoro(-no)chloridate, Isomerization, Chlorination, Reaction mechanism

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TANG Chu-Chi, MA Fu-Peng, HE Zheng-Jie. Preliminary Research on Mechanism of the Isomerization/Chlorination of O, O-Dialkylthiophosphate (-onate)with Phosphorus Oxychloride[J]. Chem. J. Chinese Universities, 1997, 18(2): 229.

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Preliminary Research on Mechanism of the Isomerization/Chlorination of O, O-Dialkylthiophosphate (-onate)with Phosphorus Oxychloride

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