1-(phenylsulfinyl)-4-(phenylsulfonyl)-1,3-butadiene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(phenylsulfinyl)-4-(phenylsulfonyl)-1,3-butadiene
• 英文别名: [(1E,3E)-4-(benzenesulfonyl)buta-1,3-dienyl]sulfinylbenzene
• 化学式: C₁₆H₁₄O₃S₂
• 分子量: 318.417
• InChiKey: MMGHXXHLNDNLNB-FNCQTZNRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  78.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(phenylsulfinyl)-4-(phenylsulfonyl)-1,3-butadiene 在 Oxone 作用下， 以 甲醇 、 水 为溶剂， 反应 5.0h， 以97%的产率得到1,4-bis(phenylsulfonyl)-1,3-butadiene
  参考文献：
  名称：

  [2,3]-Sigmatropic rearrangement of .beta.-phenylsulfonyl propargylic sulfenates as a method for preparing 1,4-bis(phenylsulfonyl)-1,3-butadienes

  摘要：

  Several beta-sulfoxy-substituted acetylenic carbinols were prepared by the addition of thiyl radicals and oxygen to conjugated enynes. The products obtained are derived from thiyl radical attack at the olefinic bond to generate a propargylic radical. Capture of this radical by oxygen followed by hydrogen transfer from thiophenol gives a hydroperoxide intermediate, which undergoes oxygen transfer by both intra- and intermolecular pathways. The resultant beta-phenylsulfinyl propargylic alcohols proved to be versatile intermediates for the preparation of several different classes of compounds. The [2,3]-sigmatropic sulfinate to sulfoxide rearrangement was found to give 1,4-bis(phenylsulfonyl)-1,3-butadienes, alpha,beta-unsaturated phenylsulfoxy ketones, and beta-phenylsulfonyl alpha-allenic sulfoxides' Oxidation of the sulfoxy moiety to the sulfone followed by sulfinate formation with phenylsulfenyl chloride produces, after [2,3]-sigmatropic rearrangement, beta-phenylsulfonyl alpha-allenic sulfoxides. In certain cases these allenes could be isolated, but were usually isomerized in situ and further oxidized to give 1,4-bis(phenylsulfonyl)-1,3-butadienes. The [2,3]-sigmatropic rearrangement of beta-phenyl-sulfinyl-substituted propargylic alcohols proceeds by an entirely different course. With these systems, a double sigmatropic process occurs leading to the formation of vinyl sulfinates which are readily hydrolyzed to give alpha,beta-unsaturated phenylsulfoxy ketones.

  DOI：

  10.1021/jo00072a019
• 作为产物：
  描述：

  甲基苯基亚砜 在 Oxone 、 potassium carbonate 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 1-(phenylsulfinyl)-4-(phenylsulfonyl)-1,3-butadiene
  参考文献：
  名称：

  [2,3]-Sigmatropic rearrangement of .beta.-phenylsulfonyl propargylic sulfenates as a method for preparing 1,4-bis(phenylsulfonyl)-1,3-butadienes

  摘要：

  Several beta-sulfoxy-substituted acetylenic carbinols were prepared by the addition of thiyl radicals and oxygen to conjugated enynes. The products obtained are derived from thiyl radical attack at the olefinic bond to generate a propargylic radical. Capture of this radical by oxygen followed by hydrogen transfer from thiophenol gives a hydroperoxide intermediate, which undergoes oxygen transfer by both intra- and intermolecular pathways. The resultant beta-phenylsulfinyl propargylic alcohols proved to be versatile intermediates for the preparation of several different classes of compounds. The [2,3]-sigmatropic sulfinate to sulfoxide rearrangement was found to give 1,4-bis(phenylsulfonyl)-1,3-butadienes, alpha,beta-unsaturated phenylsulfoxy ketones, and beta-phenylsulfonyl alpha-allenic sulfoxides' Oxidation of the sulfoxy moiety to the sulfone followed by sulfinate formation with phenylsulfenyl chloride produces, after [2,3]-sigmatropic rearrangement, beta-phenylsulfonyl alpha-allenic sulfoxides. In certain cases these allenes could be isolated, but were usually isomerized in situ and further oxidized to give 1,4-bis(phenylsulfonyl)-1,3-butadienes. The [2,3]-sigmatropic rearrangement of beta-phenyl-sulfinyl-substituted propargylic alcohols proceeds by an entirely different course. With these systems, a double sigmatropic process occurs leading to the formation of vinyl sulfinates which are readily hydrolyzed to give alpha,beta-unsaturated phenylsulfoxy ketones.

  DOI：

  10.1021/jo00072a019

文献信息

• [2,3]-Sigmatropic rearrangement of .beta.-phenylsulfonyl propargylic sulfenates as a method for preparing 1,4-bis(phenylsulfonyl)-1,3-butadienes
  作者：Xiaoheng Wang、Zhijie Ni、Xiujing Lu、Andrea Hollis、Harold Banks、Augusto Rodriguez、Albert Padwa

  DOI：10.1021/jo00072a019

  日期：1993.9

  Several beta-sulfoxy-substituted acetylenic carbinols were prepared by the addition of thiyl radicals and oxygen to conjugated enynes. The products obtained are derived from thiyl radical attack at the olefinic bond to generate a propargylic radical. Capture of this radical by oxygen followed by hydrogen transfer from thiophenol gives a hydroperoxide intermediate, which undergoes oxygen transfer by both intra- and intermolecular pathways. The resultant beta-phenylsulfinyl propargylic alcohols proved to be versatile intermediates for the preparation of several different classes of compounds. The [2,3]-sigmatropic sulfinate to sulfoxide rearrangement was found to give 1,4-bis(phenylsulfonyl)-1,3-butadienes, alpha,beta-unsaturated phenylsulfoxy ketones, and beta-phenylsulfonyl alpha-allenic sulfoxides' Oxidation of the sulfoxy moiety to the sulfone followed by sulfinate formation with phenylsulfenyl chloride produces, after [2,3]-sigmatropic rearrangement, beta-phenylsulfonyl alpha-allenic sulfoxides. In certain cases these allenes could be isolated, but were usually isomerized in situ and further oxidized to give 1,4-bis(phenylsulfonyl)-1,3-butadienes. The [2,3]-sigmatropic rearrangement of beta-phenyl-sulfinyl-substituted propargylic alcohols proceeds by an entirely different course. With these systems, a double sigmatropic process occurs leading to the formation of vinyl sulfinates which are readily hydrolyzed to give alpha,beta-unsaturated phenylsulfoxy ketones.