高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (7): 1047.

• 论文 • 上一篇    下一篇

α-氧代烯酮环二硫代缩酮化学(ⅩⅫ) --硫醇(酚)为亲核体的α-氧代烯酮环二硫代缩酮与2-甲基烯丙基氯化镁加成物的取代-环合芳构化反应

刘群, 徐柏玲, 杨智蕴, 赵洪武   

  1. 东北师范大学化学系, 长春, 130024
  • 收稿日期:1994-07-27 修回日期:1994-12-18 出版日期:1995-07-24 发布日期:1995-07-24
  • 通讯作者: 刘群,男,40岁,教授.
  • 作者简介:刘群,男,40岁,教授.
  • 基金资助:

    国家教育委员会优秀年轻教师基金

The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles

LIU Qun, XU Bai-Ling, YANG Zhi-Yun, ZHAO Hong-Wu   

  1. Dept. of Chem., Northeast Normal Univ., Changchun, 130024
  • Received:1994-07-27 Revised:1994-12-18 Online:1995-07-24 Published:1995-07-24

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摘要： 缩酮基为五元和六元环的α-氧代烯酮环二硫代缩酮与2-甲基烯丙基氯化镁反应得1,2-加成产物。所得加成产物在酸催化条件下以乙硫醇为亲核体时生成芳基乙基硫醚;苯硫酚为亲核体时,产物为芳基苯基硫醚。同样实验条件下,缩酮基为甲硫基的α-氧代烯酮二硫代缩酮与2-甲基烯丙基氯化镁的1,2-加成则生成芳构化产物芳基甲基硫醚。本实验从亲核体的选用上进一步拓展了所述取代-环合芳构化反应,并进一步验证了缩酮基结构对反应活性的影响。

关键词: &alpha, -氧代烯酮二硫代缩酮, 2-甲基烯丙基氯化镁, 加成物, 硫醇(酚), 取代-环合芳构化反应

Abstract: The 1,2-addition of α-oxoketene dithioacetals with methallyl Grignard reagent afforded the carbinols 2. 5 and 6 respectively. Catalyzed by sulfuric acid, 2 and 5 were converted to the same product (such as 3c)3 (or 4) when mercaptan (or phenyl-sulfohydrate) was used as the nucleophile. The above conversion was believed to proceed via a substitution cyclo aromatization mechanism. Under the same condition, compound 6 was converted to the cycloaromatization product 7. Based on the experimental facts, a reactivity order 1,3-propy-lenedithio>1,2-ethylenedithio>dimethylthio was proposed to the substitution cycloaromatization reaction.

Key words: α-Oxoketene dithioacetal, Methallyl Grignard reagent, Adduct, Mercaptan, Substitution cycloaromatization reaction

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