化学学报 ›› 1987, Vol. 45 ›› Issue (4): 344-353. 上一篇    下一篇

研究论文

3-疏基香豆素及其衍生物的研究

邢其毅;王文江;何大淹   

  1. 北京大学化学系
  • 发布日期:1987-04-15

3-thiolcoumarin and its derivatives

XING QIYI;WANG WENJIANG;HE DAYAN   

  • Published:1987-04-15

研究了3-疏基香豆素(8)、3,3'-二硫代双香豆素的合成及8与一系列Michael受体的反应.按受体结构不同,除都能发生分子间的加成反应外,有些还可进一步发生第二次分子内的加成反应,关环后得到一系列四氢噻吩并[2,3-C][1]苯并吡喃-4(H)-酮的衍生物.对这些化合物的立体化学及结构进行了鉴定.8分别和烯丙基溴、肉桂基溴缩合,前者在N,N-二甲苯胺内发生正常的Claisen重排,得到1,2-二氢-2-甲基噻吩并[2,3-C][1]苯并吡喃-4-(H)-酮及1,2,3,5-四氢硫代吡喃并[2,3-C][1]苯并吡喃-5-酮,但后者的反应产物是3-(ρ-N,N-二甲氨基)苄硫基香豆素.

关键词: 硫醇, 分子结构, 溴代烃, 苯并吡喃 P, 香豆素 P, 二硫化物, 立体化学, 加成反应, 噻吩 P, 丙烯 P

3-Thiolcoumarin (I) and 3,3'-dithiobis(coumarin) were prepared When I was reacted with various Michael acceptors, some of the intermol. primary addition products reacted further through a sequential intramol. Michael addition with ring closure forming a series of tetrahydrothienobenzopyranone derivatives (e.g. II). The stereochem. of the tricyclic compounds was determine and discussed. The allyl thioethers of I were prepared and subjected to Claisen rearrangement in N,N-dimethylaniline, the expected rearranged products III and IV being obtained. However 3-cinnamylcoumarin thioether under the same condition gives 3-(p-N,N-dimethylamino)thiobenzylcoumarin and other products. Ph cinnamyl thioether reacts similarly giving p-(N,N-dimethylamino)benzyl Ph thioether.

Key words: MERCAPTAN, MOLECULAR STRUCTURE, BROMOHYDROCARBON, BENZOPYRAN P, COUMARIN P, DISULFIDE, STEREOCHEMISTRY, ADDITION REACTION, THIOPHENE P, PROPENE P

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