p-tert.-Butyl-benzyl-triphenyl-phosphoniumchlorid | 18880-06-3

• 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: p-tert.-Butyl-benzyl-triphenyl-phosphoniumchlorid
• 英文别名: [(4-tert-Butylphenyl)methyl](triphenyl)phosphanium chloride；(4-tert-butylphenyl)methyl-triphenylphosphanium;chloride
• CAS: 18880-06-3
• 化学式: C₂₉H₃₀P*Cl
• 分子量: 444.984
• InChiKey: AZWHQQNGJCOFRH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  p-tert.-Butyl-benzyl-triphenyl-phosphoniumchlorid 在 氟硼酸钠 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products

  摘要：

  Quaternary (arylmethyl)phosphonium salts of the general formula ArCH2-PR3+Y-(Ar = substituted phenyl or 1-naphthyl; R = phenyl, ferrocenyl, or butyl; Y- = BF4- or halide) have been photolyzed in acetonitrile or in methanol. Photolysis involved the cleavage of the P-CH2 bond and the products derived from both, the arylmethyl radical and the carbocation, were formed. The proportion of the radical- and carbocation-derived products was determined as a function of substituents in group Ar, of groups R, counterions Y-, and the solvent. For the nonoxidizable counterion (BF4-), the proposed mechanism of the reaction involves initial homolysis, followed by the escape of the radical products from a solvent cage, or by the electron transfer from carbon to phosphorus, yielding the corresponding arylmethyl carbocation. The latter can either react with the solvent to form the observed carbocation-derived product or can undergo recombination with the tertiary phosphine formed to yield the starting phosphonium ion. Some indication of the ''inverted substituent effect'' resulting from the inhibition of single electron transfer from an easily oxidized radical was obtained. For the oxidizable counterions (halides), an additional pathway is suggested, that involves electron transfer from the anion, yielding the arylmethyl radical and the phosphine, thus decreasing the ionic/radical products ratio.

  DOI：

  10.1021/jo00073a023
• 作为产物：
  描述：

  4-叔丁基苄醇 在 氯化亚砜 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 p-tert.-Butyl-benzyl-triphenyl-phosphoniumchlorid
  参考文献：
  名称：

  Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products

  摘要：

  Quaternary (arylmethyl)phosphonium salts of the general formula ArCH2-PR3+Y-(Ar = substituted phenyl or 1-naphthyl; R = phenyl, ferrocenyl, or butyl; Y- = BF4- or halide) have been photolyzed in acetonitrile or in methanol. Photolysis involved the cleavage of the P-CH2 bond and the products derived from both, the arylmethyl radical and the carbocation, were formed. The proportion of the radical- and carbocation-derived products was determined as a function of substituents in group Ar, of groups R, counterions Y-, and the solvent. For the nonoxidizable counterion (BF4-), the proposed mechanism of the reaction involves initial homolysis, followed by the escape of the radical products from a solvent cage, or by the electron transfer from carbon to phosphorus, yielding the corresponding arylmethyl carbocation. The latter can either react with the solvent to form the observed carbocation-derived product or can undergo recombination with the tertiary phosphine formed to yield the starting phosphonium ion. Some indication of the ''inverted substituent effect'' resulting from the inhibition of single electron transfer from an easily oxidized radical was obtained. For the oxidizable counterions (halides), an additional pathway is suggested, that involves electron transfer from the anion, yielding the arylmethyl radical and the phosphine, thus decreasing the ionic/radical products ratio.

  DOI：

  10.1021/jo00073a023

文献信息

• Silylcarbonium ions from the reaction of silylcarbinols with boron trifluoride
  作者：A. G. Brook、K. H. Pannell

  DOI：10.1139/v70-617

  日期：1970.12.1

  The behavior of silylcarbonium ions, Si—C+, generated from various types of α-silylcarbinol with boron trifluoride under a variety of conditions of temperature and solvent has been examined. Four distinct types of reaction have been observed, depending on the conditions and the structure of the carbinol. These are: 1,2-migration of aryl groups from silicon to carbon, yielding a fluorosilane; Friedel–Crafts

  已经研究了在各种温度和溶剂条件下由各种类型的 α-甲硅烷基甲醇与三氟化硼生成的甲硅烷基碳正离子 Si-C+ 的行为。根据条件和甲醇的结构，已观察到四种不同类型的反应。它们是： 芳基从硅到碳的 1,2-迁移，产生氟硅烷；芳族底物上碳正离子的 Friedel-Crafts 取代；消除水元素得到乙烯基硅烷；通过氢迁移异构化为β-甲硅烷基碳正离子，然后消除甲硅烷基，得到简单的氟硅烷和烯烃（即β-消除）。讨论了影响这些途径之间划分的因素。
• Photolysis of (arylmethyl)triphenylphosphonium salts. Substituent, counterion, and solvent effects on reaction products
  作者：C. Imrie、T. A. Modro、E. R. Rohwer、C. C. P. Wagener

  DOI：10.1021/jo00073a023

  日期：1993.10

  Quaternary (arylmethyl)phosphonium salts of the general formula ArCH2-PR3+Y-(Ar = substituted phenyl or 1-naphthyl; R = phenyl, ferrocenyl, or butyl; Y- = BF4- or halide) have been photolyzed in acetonitrile or in methanol. Photolysis involved the cleavage of the P-CH2 bond and the products derived from both, the arylmethyl radical and the carbocation, were formed. The proportion of the radical- and carbocation-derived products was determined as a function of substituents in group Ar, of groups R, counterions Y-, and the solvent. For the nonoxidizable counterion (BF4-), the proposed mechanism of the reaction involves initial homolysis, followed by the escape of the radical products from a solvent cage, or by the electron transfer from carbon to phosphorus, yielding the corresponding arylmethyl carbocation. The latter can either react with the solvent to form the observed carbocation-derived product or can undergo recombination with the tertiary phosphine formed to yield the starting phosphonium ion. Some indication of the ''inverted substituent effect'' resulting from the inhibition of single electron transfer from an easily oxidized radical was obtained. For the oxidizable counterions (halides), an additional pathway is suggested, that involves electron transfer from the anion, yielding the arylmethyl radical and the phosphine, thus decreasing the ionic/radical products ratio.