G型含氟有机磷神经毒剂醇解反应机理研究  

Theoretical Studies on the Alcoholysis Reaction Mechanism of G-type Fluoride Organophosphorus Nerve Agents

作　　者：李强根[1] 郑妍[1] 毛双[1] 刘柳斜[1] 蔡皖飞[1] 李来才[1] 李权[1] 

机构地区：[1]四川师范大学化学与材料科学学院,成都610068

出　　处：《化学通报》2015年第1期72-72,共1页Chemistry

摘　　要：含氟有机磷神经毒剂毒性强,危害大,给实验研究带来不便。本文采用B3LYP/6-311G**和MP2/6-311G**方法及一个简化计算模型,探讨了G型含氟有机磷神经毒剂在中性和碱性条件下的醇解反应机理。结果显示,中性环境下G型含氟有机磷神经毒剂的醇解,不管是气相还是液相反应,3个甲醇分子参与的分步路径(Path C)都是最优路径;而1个甲醇阴离子参与的碱性条件下的分步路径(Path A'),其气相和液相反应决速步骤的吉布斯自由能垒分别为14.6和31.4 k J/mol,比Path C分别低87.0和59.8 k J/mol。因此,强碱催化下的G型含氟有机磷神经毒剂的醇解更高效。Fluoride organophosphorus nerve agents are inconvenient to experimental research due to its high toxicity. In present work,we investigate theoretically on the alcoholysis reaction mechanism of G-type fluoride organophosphorus nerve agents in neutral and alkaline conditions by employing the B3 LYP /6- 311G**and MP2 /6- 311G**methods through a simplified model.The results indicated that the stepwise path in neutral conditions of three methanol molecules involved( Path C) is the most favorable pathway,due to lower activation energy barrier( ΔG≠) both in the gas phase and in methanol solution. Moreover,for the alcoholysis involving a methanol anion in alkaline conditions( Path A'),ΔG≠of the liquid phase reaction and gas phase reaction is 14. 6 and 31. 4 k J / mol,which is lower than that Path C in neutral environment 87. 0 and 59. 8 k J / mol,respectively.Thus,alkali catalytic alcoholysis should be more efficient.

关 键 词：G型含氟有机磷神经毒剂 醇解反应 B3LYP 反应机理 

分 类 号：O627.51[理学—有机化学] O643.1[理学—化学]