O-烷基S-烷基(芳基)硫代磷(膦)酸衍生物与三氯氧磷的氯化反应──合成S-烷基(芳基)硫代磷(膦)酰氯酯的新方法

在研究O,O二烷基O芳基硫代磷酸酯(1)与三氯氧磷的异构化氯化反应机理时,发现1的异构化产物O,S二烷基硫代磷酸酯(4)能顺利地与三氯氧磷反应,4中的烷氧基被氯原子取代,得到的产物S烷基硫代磷酰氯酯(2)和O烷基磷酰二氯酯3.当4中的R为烷基或苯基,R'为烷氧基、芳氧基、烷硫基、芳硫基、二烷基氨基、氮杂环基、苯基和甲基,R"为C_1-4烷基时,4的氯化反应也能顺利发生,并得到较高产率的预期产物.

The Chlorination of O-Alkyl S-Alkyl(aryl)Thiophosphoric(-nic)Acids Derivatives with Phosphorus Oxychloride-A New Method for Synthesis of S-Alkyl(aryl)Thiophosphoro(-no)chloridates

In The course of investigating The isomerization/chlorination mechanism of O, O-di-alkyl pHospHorot hionate 1 with pHospHorus oxychloride, it was found that The isomerization prod-uctof 1, O, S-dialkyl phosphorothiolate 4, can be smoothly chlorinated with phosphorus oxy-chloride to lead its one alkoxy to be replaced by chlorine atom and give S-alkyl thiophospho-rochloridate 2 and O-alkyl phosphorodichloridate 3.The further investigations indicate that when Risalkyl or pHenyl, R'is alkoxy, aryloxy, alkylthio, arylthio, dialkylamino, nitrogen hetero-cyclic group, pHenyl or methyl respectively and R'is C_1-4alkyl, this chlorination can also easilytake place and give The desired product in a fair yield.Thus, this constitutes a convenient newmethod for synthesis of asymmet ric pHospHoro(-no)chloridot hiolate 2.