有机化学 ›› 2000, Vol. 20 ›› Issue (2): 218-223. 上一篇    下一篇

研究论文

2 - 芳基 -4- 苯基 -2, 3- 二氢 -1, 5- 苯并二氮杂卓与重氮乙酸乙酯反应机 理和 立体化学的研究

王洪钟;淳炯;金声   

  1. 北京大学化学与分子工程学院
  • 发布日期:2000-04-25

Studies on the mechanism and stereochemistry of the reaction of 2- phenyl-4- aryl-2,3-dihydro-1, 5-benzodiazepine with ethyl diazoacetate

Wang Hongzhong;Chun Jiong;Jin Sheng   

  • Published:2000-04-25

2-芳基-4-苯基-2,3-二氢-1,5-苯并二氮杂卓与重氮乙酸乙酯在铜粉催化下反应,得到环加成产物吖丙啶并苯并二氮杂卓I外,还得到一个非预期的五员环产物吡咯并苯并二氮杂卓II。改变反应条件可以使化合物II的收率达到50%。通过研究反应过程中分离出的副产物反丁烯酸二乙酯III和4,5-二氢吡唑-3,4,5-三羧酸乙酯IV,初步提出了反应经过乙氧羰基甲基化苯并二氮杂卓翁中间体V再发生环加成反应的机制。通过X-射线单晶衍射分析和NMR分析研究了它们的立体化学,发现为立体专一性反应。

关键词: 苯并二氮杂卓, 乙酸乙酯P, 重氮化合物, 铜, X射线衍射分析, 核磁共振谱法, 立体化学

The reaction of 2-phenyl -4- aryl -2,3 -dihydro- 1,5- benzodiazepine with ethyl diazoacetate using power Cu as a catlyst gives a normal cycloaddition product, azirino-benzodiazepine (I), and an unprecedent product pyrro - benzodiazepine (II). The yield of (II) was increased to 50% under the optimum condition.From the reaction mechanism, which involved formation of benzodiazepinium ethoxycarbonylmethylate (V), the reaction mechanism, which involved formation of benzodiazepinium ethoxycarbonyl- methylate (V) followed by cycloaddition reaction, was tentatively proposed. The reaction was proved to be stereospecific based on the analysis of X - ray and NMR spectra.

Key words: DIAZEPAM, ETHYL ACETATE P, DIAZO COMPOUNDS, COPPER, X-RAY DIFFRACTION ANALYSIS, NMR SPECTROMETRY, STEREOCHEMISTRY

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