1,2-diphenyl-2-(phenylseleno)-1-ethenol p-toluenesulfonate | 133295-67-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1,2-diphenyl-2-(phenylseleno)-1-ethenol p-toluenesulfonate
• 英文别名: [(E)-1,2-diphenyl-2-phenylselanylethenyl] 4-methylbenzenesulfonate
• CAS: 133295-67-7
• 化学式: C₂₇H₂₂O₃SSe
• 分子量: 505.496
• InChiKey: XKUABEIECGIYAH-CYYJNZCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.26
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  silver(I) 4-methylbenzenesulfonate 以 乙腈 为溶剂， 反应 4.08h， 生成 1,2-diphenyl-2-(phenylseleno)-1-ethenol p-toluenesulfonate
  参考文献：
  名称：

  Formation and electrophilic reactions of benzeneselenenyl p-toluenesulfonate. Preparation and properties of addition products with acetylenes

  摘要：

  Benzeneselenenyl p-toluenesulfonate (1) was generated in situ by the reaction of silver p-toluenesulfonate with benzeneselenenyl chloride in acetonitrile. The reagent reacted with acetylenes by electrophilic 1,2-addition to afford the beta-(phenylseleno)vinyl p-toluenesulfonates 2-12, generally in high yield. The latter were formed preferentially by anti addition, but with poor regioselectivity, unless a strongly orienting group (e.g., phenyl) was present. Selenenyl sulfonate 1 was also unexpectedly produced via radical pathways by heating p-toluenesulfonic acid with AIBN in the presence of diphenyl diselenide, or from the pyrolysis of sulfinyl sulfone 15 with the diselenide. The regioisomeric adducts 3 and 4 were prepared from 1 and 1-decyne, and both underwent elimination with potassium tert-butoxide to afford the acetylenic selenide 19 initially, which isomerized to a 6:1 mixture of the propargylic and allenic selenides 20 and 21 upon further equilibration. A Fritsch-Buttenberg-Wiechell rearrangement is proposed for the elimination of 4. The syn elimination of the selenoxide of 4 required forcing conditions and afforded only ca. 20% of the corresponding allenic sulfonate 22. The electrophile 1 induced the efficient cyclization of 5-hexen-1-ol and 4-pentenoic acid to the corresponding pyran 24 and lactone 25, respectively. It failed to cyclize alkynols, but afforded the lactones 28 and 29 from 4-pentynoic acid in low yield.

  DOI：

  10.1021/jo00008a039

文献信息

• Formation and electrophilic reactions of benzeneselenenyl p-toluenesulfonate. Preparation and properties of addition products with acetylenes
  作者：Thomas G. Back、K. Raman Muralidharan

  DOI：10.1021/jo00008a039

  日期：1991.4

  Benzeneselenenyl p-toluenesulfonate (1) was generated in situ by the reaction of silver p-toluenesulfonate with benzeneselenenyl chloride in acetonitrile. The reagent reacted with acetylenes by electrophilic 1,2-addition to afford the beta-(phenylseleno)vinyl p-toluenesulfonates 2-12, generally in high yield. The latter were formed preferentially by anti addition, but with poor regioselectivity, unless a strongly orienting group (e.g., phenyl) was present. Selenenyl sulfonate 1 was also unexpectedly produced via radical pathways by heating p-toluenesulfonic acid with AIBN in the presence of diphenyl diselenide, or from the pyrolysis of sulfinyl sulfone 15 with the diselenide. The regioisomeric adducts 3 and 4 were prepared from 1 and 1-decyne, and both underwent elimination with potassium tert-butoxide to afford the acetylenic selenide 19 initially, which isomerized to a 6:1 mixture of the propargylic and allenic selenides 20 and 21 upon further equilibration. A Fritsch-Buttenberg-Wiechell rearrangement is proposed for the elimination of 4. The syn elimination of the selenoxide of 4 required forcing conditions and afforded only ca. 20% of the corresponding allenic sulfonate 22. The electrophile 1 induced the efficient cyclization of 5-hexen-1-ol and 4-pentenoic acid to the corresponding pyran 24 and lactone 25, respectively. It failed to cyclize alkynols, but afforded the lactones 28 and 29 from 4-pentynoic acid in low yield.
• Back, Thomas G., Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 67, # 1-4, p. 203 - 218
  作者：Back, Thomas G.

  DOI：——

  日期：——