Citation: Li Qianggen, Mao Shuang, Liu Liuxie, Cai Wanfei, Zheng Yan. Theoretical Study of the Alcoholysis Reaction Mechanism of Temazepam[J]. Chemistry, ;2016, 79(10): 968-974. shu

Theoretical Study of the Alcoholysis Reaction Mechanism of Temazepam

1.
College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610068

Corresponding author: Li Qianggen,
Received Date: 16 February 2016
Available Online: 20 April 2016
Fund Project:

Abuse of the large number sedative hypnotics has brought serious negative impacts to food safety, and also threatens people's health and life safety. In the present work, using temazepam (TMZ) as 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 indicated that the degradation reactions of TMZ by N1-C2 bond broken in neutral and acidic methanol solution (Path 2 and Path 3) are difficult to process based on the analysis of kinetics and thermodynamics, while the degradation reaction of TMZ by C3-N4 bond broken (Path 1) is feasible in neutral methanol solution according to the dynamic analysis. The reaction involves one (85.7kJ/mol (ΔG^≠)) or two explicit solvent molecules (81.6 kJ/mol (ΔG^≠)), which act(s) as proton acceptor and donor to accelerate the reaction. Thus, Path 1 should be the dominated alcoholysis reaction path of TMZ in methanol solution, and the results are consistent with the experimental results.
- Temazepam,
- Benzodiazepines,
- Alcoholysis,
- B3LYP,
- Solvent effect
1. [1]
  [1] 广州标点医药信息有限公司《2009年镇静催眠药市场研究报告》, http://www.docin.com/p-381984530.html.
2. [2]
  [2] 华平, 王关红, 沈承武等. 世界临床药物, 2009, 30(6):377~380.
3. [3]
  [3] 刘晓芳, 李锋, 刘国艳等. 中国动物检疫, 2009, 26(10):71~74.
4. [4]
  [4] 刘晓芳, 姚冰, 刘国艳等. 分析化学, 2010, 38(5):683~687.
5. [5]
  [5] 张玉洁, 张素霞, 程林丽等.安徽农业科学, 2009, 37(18):8316~8317.
6. [6]
  [6] 李秋生, 胥传来, 彭池方等. 食品科学, 2007, 28(8):521~524.
7. [7]
  [7] 汪丽萍, 李翔, 孙英等. 分析化学, 2005, 33(7):951~954.
8. [8]
  [8] 汤文利, 任爱丽, 梁萌等. 家禽科学, 2006, 7:11~13.
9. [9]
  [9] 井连平, 洪燕敏, 董伟林等. 中国法医学杂志, 1998, 13(3):141~143.
10. [10]
  [10] M L Bastos, M E Soares. J. Agric. Food Chem., 1993, 41(6):965~967.
11. [11]
  [11] C H Redshaw, M P Cooke, H M Talbot et al. J. Soils Sediments, 2008, 8(4):217~230.
12. [12]
  [12] K M Onesios, J T Yu, E J Bouwer. Biodegradation, 2009, 20(4):441~466.
13. [13]
  [13] J O Straub. Pharmaceuticals in the Environment, 2008, Part IV, Chapter 22, Deterministic and Probabilistic Environmental Risk Assessment for Diazepam, 343~383.
14. [14]
  [14] 李想, 蒋可心. 中国初级卫生保健, 2010, 24(7):60~61.
15. [15]
  [15] S K Yang. Chirality, 1999, 11:179~186.
16. [16]
  [16] A D Becke. J. Chem. Phys., 1993, 98(7):5648~5652.
17. [17]
  [17] C Lee, W Yang, R G Parr. Phys. Rev. B, 1988, 37(2):785~789.
18. [18]
  [18] B Miehlich, A Savin, H Stoll et al. Chem. Phys. Lett., 1989, 157(3):200~206.
19. [19]
  [19] 李强根, 郑妍, 毛双等. 化学通报, 2015, 78(1):w2015002.
20. [20]
  [20] Y Zeng, Y Xue, G S Yan. J. Phys. Chem. B, 2008, 112(34):10659~10667.
21. [21]
  [21] J I Mujika, J M Mercero, X Lopez. J. Am. Chem. Soc., 2005, 127(12):4445~4453.
22. [22]
  [22] J I Mujika, E Formoso, J M Mercero et al. J. Phys. Chem. B, 2006, 110(30):15000~15011.
23. [23]
  [23] T K Manojkumar, S B Suh, K S Oh et al. J. Org. Chem., 2005, 70(7):2651~2659.
24. [24]
  [24] Y Wu, Y Xue, D Q Xie et al. J. Phys. Chem. B, 2007, 111(9):2357~2364.
25. [25]
  [25] X Lopez, J I Mujika, G M Blackburn et al. J. Phys. Chem. A, 2003, 107(13):2304~2315.
26. [26]
  [26] L Zhang, D Q Xie, D Xu et al. Chem. Commun., 2007, 16:1638~1640.
27. [27]
  [27] J Y Gao, Y Zeng, Y Xue et al. J. Phy. Chem. A, 2009, 113(1):325~331.
28. [28]
  [28] L Jin, Y Xue, H Zhang et al. J. Phys. Chem. A, 2008, 112(19):4501~4510.
29. [29]
  [29] C Flinn, R A Poirier. J. Phys. Chem. A, 2003, 107(50):11174~11181.
30. [30]
  [30] M H Almatarneh, C G Flinn, R A Poirier. J. Phys. Chem. A, 2006, 110(26):8227~8234.
31. [31]
  [31] Y Wu, L Jin, Y Xue et al. Comput. Chem., 2008(8):29, 1222~1232.
32. [32]
  [32] J Tomasi, M Persico. Chem. Rev., 1994, 94(7):2027~2094.
33. [33]
  [33] M J Frisch, G W Trucks, H B Schlegel et al. Gaussian 09, Revision A02, Gaussian, Inc., Wallingford C.T, 2009.
1. [1]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 2309027-0. doi: 10.3866/PKU.WHXB202309027
2. [2]
  Nengmin ZHU , Wenhao ZHU , Xiaoyao YIN , Songzhi ZHENG , Hao LI , Zeyuan WANG , Wenhao WEI , Xuanheng CHEN , Weihai SUN . Preparation of high-performance CsPbBr₃ perovskite solar cells by the aqueous solution solvent method. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1131-1140. doi: 10.11862/CJIC.20240419
3. [3]
  Yajin Li , Huimin Liu , Lan Ma , Jiaxiong Liu , Dehua He . Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst. Acta Physico-Chimica Sinica, 2024, 40(9): 2308005-0. doi: 10.3866/PKU.WHXB202308005
4. [4]
  Yinjie Xu , Suiqin Li , Lihao Liu , Jiahui He , Kai Li , Mengxin Wang , Shuying Zhao , Chun Li , Zhengbin Zhang , Xing Zhong , Jianguo Wang . Enhanced Electrocatalytic Oxidation of Sterols using the Synergistic Effect of NiFe-MOF and Aminoxyl Radicals. Acta Physico-Chimica Sinica, 2024, 40(3): 2305012-0. doi: 10.3866/PKU.WHXB202305012
5. [5]
  Zhilian Liu , Wengui Wang , Hongxiao Yang , Yu Cui , Shoufeng Wang . Ideological and Political Education Design for the Synthesis of Irinotecan Drug Intermediate 7-Ethyl Camptothecin. University Chemistry, 2024, 39(2): 89-93. doi: 10.3866/PKU.DXHX202306012
6. [6]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
7. [7]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
8. [8]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
9. [9]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029
10. [10]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-0. doi: 10.3866/PKU.WHXB202310013
11. [11]
  Mengfei He , Chao Chen , Yue Tang , Si Meng , Zunfa Wang , Liyu Wang , Jiabao Xing , Xinyu Zhang , Jiahui Huang , Jiangbo Lu , Hongmei Jing , Xiangyu Liu , Hua Xu . Epitaxial Growth of Nonlayered 2D MnTe Nanosheets with Thickness-Tunable Conduction for p-Type Field Effect Transistor and Superior Contact Electrode. Acta Physico-Chimica Sinica, 2025, 41(2): 2310029-0. doi: 10.3866/PKU.WHXB202310029
12. [12]
  Kexin Yan , Zhaoqi Ye , Lingtao Kong , He Li , Xue Yang , Yahong Zhang , Hongbin Zhang , Yi Tang . Seed-Induced Synthesis of Disc-Cluster Zeolite L Mesocrystals with Ultrashort c-Axis: Morphology Control, Decoupled Mechanism, and Enhanced Adsorption. Acta Physico-Chimica Sinica, 2024, 40(9): 2308019-0. doi: 10.3866/PKU.WHXB202308019
13. [13]
  Chengshan Yuan , Xiaolong Li , Xiuping Yang , Xiangfeng Shao , Zitong Liu , Xiaolei Wang , Yongwen Shen . Standardized Operational Guidelines for Mixed-Solvent Recrystallization in Organic Chemistry Experiment. University Chemistry, 2025, 40(5): 122-127. doi: 10.12461/PKU.DXHX202504073
14. [14]
  Yiling Wu , Peiyao Jin , Shenyue Tian , Ji Zhang . The Star of Sugar Substitutes: An Interview of Erythritol. University Chemistry, 2024, 39(9): 22-27. doi: 10.12461/PKU.DXHX202404034
15. [15]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
16. [16]
  Tieping CAO , Yuejun LI , Dawei SUN . Surface plasmon resonance effect enhanced photocatalytic CO₂ reduction performance of S-scheme Bi₂S₃/TiO₂ heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 903-912. doi: 10.11862/CJIC.20240366
17. [17]
  Chao Liu , Huan Yu , Jiaming Li , Xi Yu , Zhuangzhi Yu , Yuxi Song , Feng Zhang , Qinfang Zhang , Zhigang Zou . 具有光热效应的多级Ti₃C₂/Bi₁₂O₁₇Br₂肖特基异质结简单合成及其太阳能驱动抗生素光降解的研究. Acta Physico-Chimica Sinica, 2025, 41(7): 100075-0. doi: 10.1016/j.actphy.2025.100075
18. [18]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
19. [19]
  Tianlong Zhang , Chenjia Song , Wenmin Zhao , Hongsheng Tang , Yan Li , Hua Li . Dream as a Horse, Poem “Liquor” while the Age. University Chemistry, 2024, 39(9): 48-54. doi: 10.12461/PKU.DXHX202403076
20. [20]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1100)
HTML views(199)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142