| 李强根,郑妍,毛双,刘柳斜,蔡皖飞,李来才,李权.化学通报,2015,78(1):72. |
| 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 |
| 投稿时间：2014-07-15 修订日期：2014-09-18 |
| DOI： |
| 中文关键词: G型含氟有机磷神经毒剂 醇解 B3LYP 反应机理 |
| 英文关键词:G-type Fluoride organophosphorus nerve agents, Alcoholysis reaction, B3LYP, Reaction Mechanism |
| 基金项目:四川省教育厅基金（批准号：13ZB0160,13ZB0161）项目 |
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| 中文摘要: |
| 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. 研究结果显示: 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, 三个甲醇分子参与的分步路径(Path C)都是最优路径; 而一个甲醇阴离子参与的碱性条件下分步路径(Path A'), 其气相和液相反应决速步骤吉布斯自由能垒分别为14.6 kJ/mol和31.4 kJ/mol, 比中性条件下最优路径Path C分别低87.0 kJ/mol和59.8 kJ/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. |
| 英文摘要: |
| Fluoride organophosphorus nerve agents are inconvenient to experimental research due to its high toxicity. In present work, we investigate theoretically on the acoholysis reaction mechanism of G-type fluoride organophosphorus nerve agents in neutral and alkaline conditions by employing the B3LYP/6?311G** and MP2/6?311G** methods through a simplified model. The results indicate 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'), the activation energy barrier (ΔG≠) is 14.6 kJ/mol and 31.4 kJ/mol, respectively, which is lower 87.0 kJ/mol and 59.8 kcal/mol, respectively, than that of the most favorable pathway (Path C) in neutral environment. Thus, alcoholysis by alkali catalytic should be more efficient. |
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