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化学学报
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化学学报 ›› 1998, Vol. 56 ›› Issue (9): 920-924. 上一篇    下一篇

研究论文

2-氯-2-氧代(硫代)-1, 3, 2-二氧磷杂环己烷的甲醇解及其开环 异构化反应

邵瑞链;杨光富;苗伟时;杨敏华;成俊然   

  1. 南开大学.天津(300071);元素有机化学国家重点实验室;南开大学元素有机化 学研究所.天津(300071)
  • 发布日期:1998-09-15

Methanolysis and ring-opening isomerization reaction of 2-chloro-4- phenyl-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane 2-oxide (2-sulfide)

Shao Ruilian;Yang Guangfu;Miao Weishi;Yang Minhua;Cheng Junran   

  1. Nankai Univ..Tianjin(300071);Nankai Univ, Elementoorgan Chem Lab. Tianjin(300071)
  • Published:1998-09-15

PDF

618

被引次数

21

报道了trans-2-氧代-2-氯-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷以及cis-2-硫代-2-氯-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷甲醇解反应的立体化学。结果表明,反应体系的酸碱性对前者甲醇解反应的立体化学有着重要影响。而硫代环磷酰氯在碱性条件下的甲醇解反应存在一个开环异构化过程。

关键词: 二氧磷芑烷P, 甲醇解, 异构化反应, 开环反应, 立体化学

The stereochemistry of methanolysis reaction of trans-2-chloro- 4- phenyl-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane 2-oxide (trans-1) and cis-2-chloro-4-phenyl-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane 2- sulfide (cis-2) were described. Trans-1 was treated with methanol to give inversion product at phosphorus. In contrast, retention is favored while the reaction employs methoxide ion as the nucleophile. Reaction of cis-2 with sodium methoxide in methanol under reflux led to a ring opening followed by ring closure to give a thermodynamically controlled mixture of diastereomeric isomers in which trans isomer was the major component. An acyclic intermediate is found to be involved in this process.

Key words: DIOXAPHOSPHORINANE P, ISOMERIZATION REACTION, RING CLEAVAGE REACTION, STEREOCHEMISTRY

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