CAJ | 학술논문

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 kJ/mol，比Path C分别低87.0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。
함불유궤린신경독제독성강，위해대，급실험연구대래불편。본문채용 B3LYP/6?311G**화MP2/6?311G**방법급일개간화계산모형，탐토료G형함불유궤린신경독제재중성화감성조건하적순해반응궤리。결과현시，중성배경하G형함불유궤린신경독제적순해，불관시기상환시액상반응，3개갑순분자삼여적분보로경(Path C)도시최우로경；이1개갑순음리자삼여적감성조건하적분보로경(Path A')，기기상화액상반응결속보취적길포사자유능루분별위14.6화31.4 kJ/mol，비Path C분별저87.0화59.8 kJ/mol。인차，강감최화하적G형함불유궤린신경독제적순해경고효。
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 B3LYP/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 kJ/mol, which is lower than that Path C in neutral environment 87.0 and 59.8 kJ/mol, respectively. Thus, alkali catalytic alcoholysis should be more efficient.