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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(艹卓)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(艹卓)鎓中间体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。
2-Aryl-4-phenyl-2,3-dihydro-1,5-benzodiazepine was reacted with ethyl diazoacetate under the catalysis of copper powder to obtain a cyclic addition product of ethyleneimine And diaza (艹 Zhuo) Ⅰ, we also get an unexpected five-membered ring product pyrrolobenzodiazepine Ⅱ. The yield of compound Ⅱ can be up to 50% by changing the reaction conditions. Through the study of the reaction of the by-product of diethyl ether disulfonate Ⅲ and 4,5-dihydropyrazole-3,4,5-tricarboxylate Ⅳ, the initial proposed reaction of ethoxycarbonyl The mechanism of the cycloaddition reaction of the alkylated benzodiazepinium intermediates Ⅴ. Their stereochemistry was investigated by X-ray single crystal diffraction analysis and NMR analysis and found to be stereospecific reactions.