[(p-tolylthio)methyl]diphenylphosphine oxide | 31238-58-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [(p-tolylthio)methyl]diphenylphosphine oxide
• 英文别名: 1-(Diphenylphosphorylmethylsulfanyl)-4-methylbenzene
• CAS: 31238-58-1
• 化学式: C₂₀H₁₉OPS
• 分子量: 338.41
• InChiKey: NYZULXCXEICEKJ-UHFFFAOYSA-N

物化性质

• 沸点：
  458.0±28.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(p-tolylthio)methyl]diphenylphosphine oxide 在 N-氯代丁二酰亚胺 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯苯 为溶剂， 反应 48.0h， 生成 1-chlorovinyl p-tolyl sulfoxide
  参考文献：
  名称：

  Stereoselective Horner-Wittig synthesis of (Z)-1-chlorovinyl sulfoxides

  摘要：

  This paper describes the synthesis of (Z)-I-chlorovinyl sulfoxides 1 by the Horner-Wittig reaction. The required [(alpha-chloro)sulfinylmethyl]diphenylphosphine oxides 2 (R-1=Me, c-Hex, Ph, p-Tol, p-(CF3)Ph), were prepared in high yields by selective monochlorination and subsequent mono-oxidation of (thiomethyl)diphenylphosphine oxides 3. The stable lithiated anions of 2 gave an efficient reaction with all structural types of aldehydes. Aromatic and alpha,beta-unsaturated aldehydes gave 1 with excellent Z-selectivity (>98%), irrespective of the nature of the substituent R-1 at sulfur. With straight chain aliphatic aldehydes, an aromatic substituent at sulfur was required to obtain high Z-selectivity. A mechanistic explanation for these observations is presented. An X-ray analysis of 1, R-1=Me, R-2=4-MeOC6H4 confirmed the Z-disposition of the chloro and aryl substituents. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00665-0
• 作为产物：
  描述：

  二苯基乙氧基膦 、 氯甲基对甲苯硫醚 以98%的产率得到[(p-tolylthio)methyl]diphenylphosphine oxide
  参考文献：
  名称：

  A Horner-Wittig Synthesis of 1-Chlorovinyl Sulfoxides.

  摘要：

  DOI：

  10.1080/10426509608545187

文献信息

• A Horner-Wittig synthesis of 1-chlorovinyl sulfoxides
  作者：Pieter A. Otten、Honorine M. Davies、Arne van der Gen

  DOI：10.1016/0040-4039(94)02367-k

  日期：1995.1

  1-Chlorovinyl sulfoxides 1 were prepared by a Horner-Wittig reaction of [(alpha-chloro)sulfinylmethyl]diphenylphosphine oxides 2 with aldehydes. Excellent Z-selectivity was observed in most cases.
• A Horner-Wittig Synthesis of 1-Chlorovinyl Sulfoxides.
  作者：P.A. Otten、H.M. Davies、A. Van Der Gen

  DOI：10.1080/10426509608545187

  日期：1996.1
• Otten Pieter A., Davies Honorine M., van der Gen Arne, Tetrahedron Lett, 36 (1995) N 5, S 781-784
  作者：Otten Pieter A., Davies Honorine M., van der Gen Arne

  DOI：——

  日期：——
• US5591881A
  申请人：——

  公开号：US5591881A

  公开（公告）日：1997-01-07
• Stereoselective Horner-Wittig synthesis of (Z)-1-chlorovinyl sulfoxides
  作者：Pieter A. Otten、Honorine M. Davies、Jan Hein van Steenis、Syb Gorter、Arne van der Gen

  DOI：10.1016/s0040-4020(97)00665-0

  日期：1997.7

  This paper describes the synthesis of (Z)-I-chlorovinyl sulfoxides 1 by the Horner-Wittig reaction. The required [(alpha-chloro)sulfinylmethyl]diphenylphosphine oxides 2 (R-1=Me, c-Hex, Ph, p-Tol, p-(CF3)Ph), were prepared in high yields by selective monochlorination and subsequent mono-oxidation of (thiomethyl)diphenylphosphine oxides 3. The stable lithiated anions of 2 gave an efficient reaction with all structural types of aldehydes. Aromatic and alpha,beta-unsaturated aldehydes gave 1 with excellent Z-selectivity (>98%), irrespective of the nature of the substituent R-1 at sulfur. With straight chain aliphatic aldehydes, an aromatic substituent at sulfur was required to obtain high Z-selectivity. A mechanistic explanation for these observations is presented. An X-ray analysis of 1, R-1=Me, R-2=4-MeOC6H4 confirmed the Z-disposition of the chloro and aryl substituents. (C) 1997 Elsevier Science Ltd.