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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。
Fluorine-containing organophosphate nerve agents are highly toxic and harmful, which brings inconvenience to experimental research. In this paper, B3LYP / 6-311G ** and MP2 / 6-311G ** methods and a simplified computational model were used to investigate the mechanism of alcoholysis reaction of G-type organophosphorus poison agents under neutral and alkaline conditions. The results showed that in the neutral environment, the alcoholysis of G-type organophosphorus poison agents, either in the gas phase or in the liquid phase, was the optimal path for the three methanol molecules involved in the pathway (Path C) The pathways (A ’’) under alkaline conditions involving anions are Gibbs free energy barriers of 14.6 and 31.4 kJ / mol for gas-phase and liquid-phase reactions, respectively, which are 87.0 and 47.0 lower than that of Path C respectively 59.8 k J / mol. Thus, alcoholysis of the G-type fluorinated organophosphate nerve agents catalyzed by strong bases is more efficient.