应用化学 ›› 2009, Vol. 26 ›› Issue (08): 890-893.

• 研究论文 • 上一篇    下一篇

吡啶与GCLE碘取代物在不同溶剂中亲核取代反应动力学研究

付德才1*,张静1,2,李志伟1,哈婧1   

  1. (1.河北科技大学化学与制药工程学院 石家庄 050018;2.河北化工医药职业技术学院制药工程系 石家庄 050026)
  • 收稿日期:2008-08-18 修回日期:2008-11-28 出版日期:2009-08-10 发布日期:2009-08-10
  • 通讯作者: 付德才,男,博士,教授; E-mail:dc6310@sina.com; 研究方向:药物中间体及药物合成工艺
  • 基金资助:
    河北省科学技术研究与发展计划项目(06547003D-2)

Synthesis and Kinetics of 7-phenylacetamido-3-pyridiniummethylcephem-4-carboxylic acid p-methoxybenzyl ester

FU De-Cai1*, ZHANG Jing1,2, LI Zhi-Wei1, HA Jing1   

  1. (1.College of Chemical and Pharmaceutical Engineering,Hebei University of
    Science and Technology,Shijiazhuang 050018;
    2.Department of Pharmaceutical Engineering,Hebei Chemical and Pharmaceutical
    Vocational Technology College,Shijiazhuang 050026)
  • Received:2008-08-18 Revised:2008-11-28 Published:2009-08-10 Online:2009-08-10

摘要:

以7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯(GCLE)和吡啶为原料合成头孢他啶中间体7-苯乙酰氨基-3-吡啶甲基头孢-4-羧酸对甲氧苄酯,用高效液相色谱仪监测了吡啶与GCLE碘取代物在二氯甲烷、丙酮、四氢呋喃、乙酸乙酯和DMF混合液中的亲核取代反应,反应的动力学行为可用SN2机理来解释。在一定的溶剂中不同温度的速率常数可用Arrhenius方程很好的关联。根据Arrhenius方程求得了指前因子,进一步讨论了该反应的溶剂效应,得出在不同溶剂中亲核取代反应顺序为:乙酸乙酯-DMF混合液>二氯甲烷>四氢呋喃>丙酮。

关键词: 苯乙酰氨基氯甲基头孢烷烯酸对甲氧基苄酯,苯乙酰氨基吡啶甲基头孢羧酸对甲氧苄酯,合成,动力学,溶剂效应

Abstract:

7-Phenylacetamido-3-pyridiniummethylcephem-4-carboxylic acid p-methoxybenzyl ester was prepared by reaction of GCLE with pyridine. The reaction process was inspected by HPLC in dichloromethane,acetone, tetrahydrofuran, the mixture of ethyl acetate and DMF. It was determined that the nucleophilic substitution reaction was 2nd order reaction. In a given solvent the rates can be perfectly related with Arrhenius's equation within the experimental temperature of 25℃and 35℃.The activation energy and the preexponential factor according to Arrhenius's equation were gained,and the solvent effects were discussed.The order of the nucleophilicity in different solvents was as follows: the mixture of ethyl acetate and DMF>dichloromethane>tetrahydrofuran>acetone.

Key words: phenylacetamidochloridecephemcarboxylic acid p-methoxybenzyl ester iodid, phenylacetamidopyridiniummethylcephemcarboxylic acid p-methoxybenzyl ester,synthesis,kinetics,solvent effect

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