关环反应合成鸢尾酮

doi:10.3724/SP.J.1095.2014.40024

摘要/Abstract

摘要： 研究了以9,10-环亚甲基假紫罗兰酮为原料，经关环反应合成鸢尾酮的工艺，并对该关环反应机理进行了初步探讨。实验结果表明，适宜的工艺条件为：反应温度-70 ℃，物料摩尔比n(9,10-环亚甲基假紫罗兰酮)∶n(氯磺酸)为1∶4，反应45 min，鸢尾酮的收率为90.1%。产品中α-鸢尾酮、β-鸢尾酮和γ-鸢尾酮的含量分别为60.2%、29.0%和8.0%（GC，峰面积归一化法）；采用NMR确证了α-鸢尾酮的结构。关环反应机理的初步探讨表明关环反应应在低温下快速完成。

关键词: 鸢尾酮, 关环反应, 环亚甲基假紫罗兰酮, &, alpha, -鸢尾酮选择性

Abstract: The synthesis of irone was investigated by cyclization reaction from raw material 9,10-cyclomethylene pseudoionones. The cyclization mechanism was preliminarily studied. The optimal cyclization conditions for irone are to keep the reaction time within 45 min, the reaction temperature at -70 ℃, and the molar ratio of 9,10-cyclomethylene pseudoionones to chlorosulfonic acid at 1∶4. The combined yield of irone isomers can reach 90.1%, and the content of α-irone, β-irone and γ-irone are 60.2%, 29.0% and 8.0%, respectively, under the optimal cyclization conditions(determined by GC with area normalization method). The structures of irone isomers were also confirmed by 1H NMR and 13C NMR. Preliminary mechanism study indicates that the cyclization reaction for the synthesis of irone can finish rapidly at low temperature.

Key words: irone, cyclization reaction, cyclomethylene pseudoionones, selectivity of &, alpha, -irone

中图分类号:

O622.4

胡铁, 黎继烈, 王烨, 高海丽, 皮少峰, 孙汉洲. 关环反应合成鸢尾酮[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.40024.

HU Tie1,2, PI Shaofeng1, WANG Ye1, GAO Haili1, SUN Hanzhou1*, LI Jilie1*. Synthesis of Irone by Cyclization Reaction[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.40024.

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