The introduction of substituted vinyl groups V A rearrangement involving the migration of an allyl group in a three-carbon system
The introduction of substituted vinyl groups V A rearrangement involving the migration of an allyl group in a three-carbon system
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DOI：
10.1021/ja01859a055
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发表时间：
1940-01-01
影响因子：
15
通讯作者：
Hardy, EM
中科院分区：
文献类型：
--
作者：
Cope, AC;Hardy, EM
最近描述的（二基乙烯基）-烷基氰乙酸酯是稳定的化合物，在纯化过程中没有发生任何变化。然而，在制备（1-甲基丙烯）-丙烯基氰乙酸乙酯的过程中，形成了不稳定的产物，在真空中经过多次蒸馏后变成了沸点较高的稳定物质。这些化合物的结构和重排的性质现在已经确定，并在本文中报道。由（1-甲基丙基）氰乙酸乙酯制备的钠衍生物经烯丙基卤化物处理后形成的物质，在1mm压力下蒸馏，证明其足够稳定，可以在纯净状态下进行异构化。分析和分子折射结果与正常烷基化产物乙基（1-甲基丙烯）-乙基氰乙酸酯的结构一致。
The (dialkylvinyl)-alkylcyanoacetic esters de-scribed recently3 were stable compounds which were not alteredin any way during purification. However, in the preparation of ethyl (1-methylpropenyl)-allylcyanoacetate, which was studied but not reportedin the previous work, an un-stable product was formed, which changed into a stable substance of higher boilingpoint after sev-eral distillations in vacuum. The structures of these compounds and the nature ofthe rearrangement have now been determined, and are reported in this paper.The substance formed initially when the sodium derivative prepared from ethyl (1-methylpropylidene)-cyanoacetate was treated with allyl halides proved to be sufficiently stable to be iso-lated in a pure state if it was distilled at a pressure of 1 mm. Analysis and molecular refraction were in agreement with the structure of the normal alkylation product, ethyl (1-methylpropenyl)-al-lylcyanoacetate, I.