Acid-catalyzed Cyclization of 3-Acetyl-3-(3, 4-dimethoxyphenyl) adiponitrile
Acid-catalyzed Cyclization of 3-Acetyl-3-(3, 4-dimethoxyphenyl) adiponitrile
复制标题
3-乙酰基-3-(3, 4-二甲氧基苯基)己二腈的酸催化环化
DOI：
10.1248/cpb.18.291
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发表时间：
1970
影响因子：
1.7
通讯作者：
H. Kugita
中科院分区：
文献类型：
--
作者：
T. Oh;H. Kugita
3-乙酰基-3-（3,4 -二甲氧基苯基）己二腈(V)在65%硫酸中在140°下水解环化得到3a-（3,4 -二甲氧基苯基）- 2,3,3,3,4,5,6 -六氢吲哚- 2,6 -二酮（VI），其结构通过光谱性质和转化得到dl-膜（=3a-（3,4 -二甲氧基苯基）-1-甲基过氢吲哚）（XI）。V在65%硫酸中室温反应生成五种产物XIII， XIV， XV， XVI和XVII作为该环化反应的中间体，在酸中加热至140°后全部转化为最终环化产物（VI）。提出了VI及其中间体形成的可能反应机理。以3,4 -二甲氧基苯基丙酮为原料，经3-（2-氰乙基）-3-（3,4 -二甲氧基苯基）乙酰丙酸甲酯（XIX）合成了VI。
Hydrolytic cyclization of 3-acetyl-3-(3, 4-dimethoxyphenyl) adiponitrile (V) in 65% sulfuric acid at 140° was found to yield 3a-(3, 4-dimethoxyphenyl)-2, 3, 3a, 4, 5, 6-hexahydroindol-2, 6-dione (VI), whose structure was confirmed by spectral properties and transformation into dl-mesembrane (=3a-(3, 4-dimethoxyphenyl)-1-methylperhydroindol) (XI). Reactions of V in 65% sulfuric acid at room temperature yielded five products, XIII, XIV, XV, XVI and XVII as intermediates of this cyclization reaction, all of which were converted to the final cyclization product (VI) by heating to 140°in the acid. Possible reaction mechanisms of the formation of VI and the intermediates were proposed. An alternate synthesis of VI from 3, 4-dimethoxyphenyl acetone via methyl 3-(2-cyanoethyl)-3-(3, 4-dimethoxyphenyl) levulinate (XIX) was also described.