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化学学报
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化学学报 ›› 1964, Vol. 30 ›› Issue (3): 283-289. 上一篇    下一篇

论文

硫醇对炔属化合物的加成反应——Ⅳ.苯硫酚对苯基丙炔酸、丙炔酸乙酯、丁炔-2-酸乙酯的加成

刘有成, 王序昆, 朱申杰   

  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——Ⅳ.THE ADDITION OF THIOPHENOL TO PHENYLPROPIOLIC ACID,ETHYL PROPIOLATE AND ETHYL BUT-2-YNOATE

LIU YU-CHENG, WANG SUE-KWUNG, CHU SHEN-JE   

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

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苯硫酚对苯基丙炔酸及其乙酯在苯甲酰过氧化物引发下的自由基加成产生α-苯硫基肉桂酸(酯),加成的方向与在乙醇钠催化下的加成方向相反.苯硫酚与丙炔酸乙酯及丁炔-2-酸乙酯在苯甲酰过氧化物引发下进行加成时,苯硫基均加到羧基的β-碳上.苯硫酚与苯基丙炔酸在乙醇钠催化下的加成可以朝两个方向进行,生成α-及β-苯硫基肉桂酸.苯硫酚与丙炔酸及丁炔-2-酸在相同条件下进行加成时,与预期的结果一致,分别产生β-取代产物.从自由基加成与负离子加成的糖果比较看来,苯硫基自由基的加成取向不是取决于炔烃分子中的极化状态,而是取决于中间生成的自由基的稳定性.从本文及前一文中报导的结果,可以看出,三键上取代基对自由基的稳定性的影响顺序为:C6H5>COOH≌COOC2H5>CH3,C2H5.

Under the initiation of benzoyl peroxide the free radical addition of thiophenol to phenylpropiolic acid and its ethyl ester yielded α-phenylthiocinnamic acid (ester), the direction of addition being opposite to that observed with ethoxide-catalysed addition When the reaction with ethyl propiolate and ethyl but-2-ynoate was conducted under the initiation of benzoyl peroxide, the phenylthiyl radical was added to the β-carbon atom.