[(α-chloro)(methylthio)methyl]diphenylphosphine oxide | 123146-55-4

• 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: [(α-chloro)(methylthio)methyl]diphenylphosphine oxide
• 英文别名: [[Chloro(methylsulfanyl)methyl]-phenylphosphoryl]benzene
• CAS: 123146-55-4
• 化学式: C₁₄H₁₄ClOPS
• 分子量: 296.757
• InChiKey: VONWOQCCHHHEBE-UHFFFAOYSA-N

物化性质

• 沸点：
  368.3±32.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  [(α-chloro)(methylthio)methyl]diphenylphosphine oxide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以97%的产率得到[(α-chloro)sulfinylmethyl]diphenylphosphine oxide
  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 在 N-氯代丁二酰亚胺 作用下， 以 氯苯 为溶剂， 生成 [(α-chloro)(methylthio)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 approach to S,N-ketene acetals
  作者：Pieter A. Otten、Njord Oskam、Arne van der Gen

  DOI：10.1016/0040-4020(96)00626-6

  日期：1996.8

  The synthesis of S,N-acetals of formyldiphenylphosphine oxide 2 is described. The stable lithiated anions of these acetals were applied in a Horner-Wittig reaction with several structural types of aldehydes. The resulting S,N-ketene acetals 1 were obtained in excellent yields. Ketones and pivaldehyde did not react with the sterically hindered phosphine oxide anions. S,N-ketene acetals 1 were found

  描述了甲酰基二苯基膦氧化物2的S，N-缩醛的合成。这些缩醛的稳定锂化阴离子与几种结构类型的醛一起用于Horner-Wittig反应中。以优异的产率获得了所得的S，N-烯酮缩醛1。酮和四乙醛不会与空间受阻的氧化膦阴离子反应。发现S，N-乙烯酮缩醛1在中等酸性条件下被选择性水解为相应的（S）-硫酯5。S的先前未描述的反应性，Ñ -ketene缩醛1所允许的醛的两步转化成同源的（小号）-thioesters 5以良好的收率。
• 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.
• Costisella, Burkhard; Keitel, Iris, Phosphorus and Sulfur and the Related Elements, 1988, vol. 40, p. 161 - 166
  作者：Costisella, Burkhard、Keitel, Iris

  DOI：——

  日期：——
• 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：——