高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (11): 1538.

• 研究论文 • 上一篇    下一篇

α-羰基烯酮环二硫代缩醛化学(Ⅹ)——β,β-1,5-亚丙二硫基-α,β-不饱和酮与烯丙基Grignard试剂加成物的酸催化反应取向研究

刘群1, 朱再明1, 杨智蕴1, 胡玉兰1, 景凤英2, 孝延文2   

  1. 1. 东北师范大学化学系, 长春 130024;
    2. 中国科学院长春应用化学研究所
  • 收稿日期:1992-12-12 修回日期:1993-06-23 出版日期:1993-11-24 发布日期:1993-11-24
  • 通讯作者: 刘群, 男, 38岁, 硕士, 副教授.
  • 作者简介:刘群, 男, 38岁, 硕士, 副教授.
  • 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(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents

LIU Qun1, ZHU Zai-Ming1, YANG Zhi-Yun1, HU Yu-Lan1, JING Feng-Ying2, XIAO Yan-Wen2   

  1. 1. Department of Chemistry, Northeast Normal University, Changchun, 130024;
    2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun
  • Received:1992-12-12 Revised:1993-06-23 Online:1993-11-24 Published:1993-11-24

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摘要： β,β-1,5-亚丙二硫基-α,β-不饱和酮2b和2-甲基烯丙基氯化镁加成可得醇3b.在BF3·Et2O催化下,3b经分子内环合芳构化生成芳硫醚5b.2和烯丙基溴化镁反应得醇4,4在BF3·Et2O催化下经β-消除脱水生成共轭多烯类化合物6.二硫缩醛基以环和非环结构及环的大小对2与烯丙基Grignard试剂加成物在酸催化下的反应取向有重要影响.

关键词: &alpha, -羰基烯酮二硫代缩醛, 烯丙基Grignard试剂, 加成物, 酸催化, 反应取向

Abstract: Addition of aliphatic title compounds 2b with 2-methyl allyl Grignard reagent afforded the corresponding carbinols 3b.Catalyzed by BF3 · Et2O, 3b were converted to the arylthio ether 5b via a cyclization-aromatization process.When water or methanol was present in the reaction mixture, 3b were converted to the phenols or arylether 5'b via a substitution-cyclization aromati-zation process under similar conditions as above.The adducts 4 formed by the addition of 2 with magnesium allyl bromide, were converted to the conjugate polyenes 6 under the above conditions either in the presence or in the absence of the nucleophile.The mechanism was discussed according to the effects of different dialkylthio groups to the carbon cation intermediates 12, 13 and 14.

Key words: α-Oxo ketene dithioacetal, Allyl Grignard reagent, Adduct, Acid catalysis, Reaction orientation

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