| 李强根,毛双,刘柳斜,蔡皖飞,郑妍.化学通报,2016,79(10):968-974. |
| 替马西泮醇解反应机理研究 |
| Theoretical Studies the Alcoholysis Reaction Mechanism of Temazepam |
| 投稿时间：2016-02-16 修订日期：2016-04-11 |
| DOI： |
| 中文关键词: 替马西泮 苯二氮卓类药物 醇解 B3LYP 溶剂效应 |
| 英文关键词:Temazepam, Benzodiazepines, Alcoholysis, B3LYP, Solvent effect |
| 基金项目:四川省教育厅基金项目 |
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| 中文摘要: |
| 大量镇静催眠药的滥用给食品安全带来了严重负面影响,时刻威胁着人们的身体健康和生命安全。本文采用B3LYP/6?311 G**和MP2/6?311 G**方法,研究了苯二氮卓类药物替马西泮(TMZ)在中性和酸性甲醇溶液中的醇解反应机理。结果显示：TMZ分子在中性和酸性甲醇溶液中N1?C2键断裂开环降解反应(Path 2和Path 3),无论从热力学还是动力学上分析,反应都很难发生；而中性甲醇溶液中断裂C3?N4键醇解开环降解反应(Path 1),从动力学上分析是可行的,反应涉及一个或两个显性甲醇溶剂分子参与反应,通过质子的受体与给体的酸碱催化作用促进反应的进行,液相能垒(ΔG≠) 分别为85.7 kJ/mol和81.6 kJ/mol,应该为TMZ分子在甲醇溶液中醇解的优势反应路径,研究结果与实验观察一致。 |
| 英文摘要: |
| Abuse of the large number sedative hypnoticsShas been bringing seriously negative impacts toSfood safety, and also threatening people"sShealth and life safety. In the present work, using temazepam (TMZ)Sas an example, we explore theoretically the alcoholysis of benzodiazepines in neutral and acidic methanol solvent by employing the B3LYP/6?311 G** and MP2/6?311 G** methods. The results indicate that the degradation reactions of TMZ by N1?C2 bond broken in neutral and acidicSmethanol solution (Path 2 and Path 3) are difficult to process base on the analysis of kinetics and thermodynamics. While the degradation reaction of TMZ by C3?N4 bondSbrokenS(Path 1) is feasible in neutralSmethanol solution according toSthe dynamicSanalysis,Sand the reaction involves one (85.7 kJ/mol (ΔG≠)) orStwo explicit solvent molecules (81.6 kJ/mol (ΔG≠)), which act(s) asS proton acceptor and donor to accelerate the reaction. Thus, Path 1 should beSthe dominated alcoholysis reaction pathSof TMZ in methanol solution,Sand the resultsSare consistent with the experimental results. |
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