化学学报 ›› 1964, Vol. 30 ›› Issue (2): 197-204. 上一篇    下一篇

论文

硫醇对炔属化合物的加成反应Ⅲ.苯硫酚与硫醇乙酸对β-烷基苯乙炔的加成

刘有成, 张自义   

  1. 兰州大学化学系
  • 投稿日期:1963-07-22 发布日期:2013-06-03

THE ADDITION OF THIOLS TO ACETYLENIC COMPOUNDS Ⅲ. THE ADDITION OF THIOPHENOL TO β-ALKYLPHENYLACETYLENES

LIU YU-CHENG, CHANG TZI-YI   

  1. Department of Chemistry, Lanchow University
  • Received:1963-07-22 Published:2013-06-03

苯硫酚与1-苯基丙炔-1及1-苯基丁炔-1在苯甲酰过氧化物或紫外光引发下顺利加成.当反应物用量为等克分子比时,加成物分别为1-苯基-2-苯硫基丙烯-1(Ⅰ)及1-苯基-2-苯硫基丁烯-1(Ⅱ);当用量为2:1克分子比时,除生成上述1:1加成物外,尚得2:1加成物:1-苯基-2,2-二-(苯硫基)-丙烷(Ⅴ)及1-苯基-2,2-二-(苯硫基)-丁烷(Ⅵ).这些加成物的结构是借在酸性介质中与2,4-二硝基苯肼作用生成相应酮的2,4-二硝基苯腙而得到证明.这加成反应是按自由基机理进行,苯硫基联结在与烷基相邻的碳原子表明中间生成的自由基之稳定性是加成方向的决定因素,因为苯基的共轭效应比烷基为强.竞争试验的结果表明,苯硫基对苯乙炔的加成比对1-苯基丙炔-1的加成快得多,这可归因于甲基的空间效应.当以苯硫酚与1-苯基丙炔-1及苯乙烯进行竞争时,只得炔烃的加成物,这表明炔烃的加成活性比烯烃大得多.后一结果是由于断裂三键中的一个π-键所需要的能量较断裂双键中的π-键所需要的能量为低的缘故.

Under the initiation of benzoyl peroxide or ultraviolet light,thiophenol added smoothly to 1-phenylpropyne-1 and to 1-phenylbutyne-1.When equimolecular ratio of the reactants was used,the addition products were 1-phenyl-2-phenylthiopropene-1 (Ⅰ) and 1-phenyl-2-phenylthiobutene-1 (Ⅱ),respectively.When the amount of thiophenol used was doubled,there were obtained,besides the one-to-one adducts named,two-to-one adducts; 1-phenyl-2,2-di-(phenylthio)-propane (V) and 1-phenyl-2,2-di-(phenylthio)-butane (Vr),respectively.