(2-carboxyprop-2-enyl)(triphenyl)phosphonium bromide | 72707-67-6

• 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: (2-carboxyprop-2-enyl)(triphenyl)phosphonium bromide
• 英文别名: (2-carboxyallyl)triphenylphosphonium bromide；(2-Carboxy-2-propenyl)triphenylphosphonium；2-Carboxyprop-2-enyl(triphenyl)phosphanium;bromide
• CAS: 72707-67-6
• 化学式: Br*C₂₂H₂₀O₂P
• 分子量: 427.277
• InChiKey: MENGFLMXTWKTDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.63
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2-carboxyprop-2-enyl)(triphenyl)phosphonium bromide 在 sodium hydroxide 、 氢溴酸 作用下， 反应 5.17h， 生成 3-(diphenylphosphoryl)-2-((diphenylphosphoryl)methyl)propanoic acid
  参考文献：
  名称：

  Tautomerization of α,β-and β,γ-unsaturated phosphonium salts resulting from the reaction of triphenylphosphine with β-bromomethacrylic acid. Nucleophilic addition at the γ position of the allyl group in phosphonium salt

  摘要：

  Temperature factor was found to be determining in the isomerization of 2-carboxyprop-1-en-1-yl and 2-carboxyprop-2-en-1-yl(triphenyl)phosphonium bromides. Elevated temperature favors formation of isomer with the double bond in the beta,gamma position with respect to the phosphonium group. Alkaline hydrolysis at room temperature promotes the reverse isomerization. The isomerization of 2-carboxyprop-1-en-1-yl(triphenyl)phosphonium bromide is hampered by addition of hydrobromic acid, as well as by carrying out its synthesis in the presence of aqueous HBr. Alkaline hydrolysis of 2-carboxyprop-1-enyl(triphenyl)phosphonium bromide and (E)-(2-carboxyvinyl)triphenylphosphonium chloride is accompanied by phenyl group migration to the alpha-position with formation of 2-methyl-3-(diphenylphosphoryl)-3-phenylpropionic acid and 3-(diphenylphosphoryl)-3-phenylpropionic acid, respectively. The possibility for nucleophilic addition at the gamma position of the allyl group in 2-carboxyprop-2-enyl(triphenyl)phosphonium bromide was demonstrated using the reaction with triphenylphosphine as an example.

  DOI：

  10.1134/s1070363206100070
• 作为产物：
  描述：

  (2-carboxyprop-1-en-1-yl)(triphenyl)phosphonium bromide 以 乙腈 为溶剂， 反应 60.0h， 以70%的产率得到(2-carboxyprop-2-enyl)(triphenyl)phosphonium bromide
  参考文献：
  名称：

  Tautomerization of α,β-and β,γ-unsaturated phosphonium salts resulting from the reaction of triphenylphosphine with β-bromomethacrylic acid. Nucleophilic addition at the γ position of the allyl group in phosphonium salt

  摘要：

  Temperature factor was found to be determining in the isomerization of 2-carboxyprop-1-en-1-yl and 2-carboxyprop-2-en-1-yl(triphenyl)phosphonium bromides. Elevated temperature favors formation of isomer with the double bond in the beta,gamma position with respect to the phosphonium group. Alkaline hydrolysis at room temperature promotes the reverse isomerization. The isomerization of 2-carboxyprop-1-en-1-yl(triphenyl)phosphonium bromide is hampered by addition of hydrobromic acid, as well as by carrying out its synthesis in the presence of aqueous HBr. Alkaline hydrolysis of 2-carboxyprop-1-enyl(triphenyl)phosphonium bromide and (E)-(2-carboxyvinyl)triphenylphosphonium chloride is accompanied by phenyl group migration to the alpha-position with formation of 2-methyl-3-(diphenylphosphoryl)-3-phenylpropionic acid and 3-(diphenylphosphoryl)-3-phenylpropionic acid, respectively. The possibility for nucleophilic addition at the gamma position of the allyl group in 2-carboxyprop-2-enyl(triphenyl)phosphonium bromide was demonstrated using the reaction with triphenylphosphine as an example.

  DOI：

  10.1134/s1070363206100070

文献信息

• Duettmann,H.; Weyerstahl,P., Chemische Berichte, 1979, vol. 112, p. 3480 - 3485
  作者：Duettmann,H.、Weyerstahl,P.

  DOI：——

  日期：——
• Reaction of Haloacrylic Acids with Phosphorus Nucleophiles
  作者：R. A. Khachatryan、S. Yu. Kotikyan、R. Dzh. Hachikyan、G. A. Panosyan、R. A. Mirzakhanyan、M. G. Indzhikyan

  DOI：10.1023/b:rugc.0000016011.48284.9f

  日期：2003.10

  alpha-Chloroacrylic acid reacts with triphenylphosphine to give (E)-(2-carboxyvinyl)triphenylphos-phonium chloride. The same reaction with beta-halomethacrylic acids yields, depending on the temperature, either (2-carboxypropenyl)triphenylphosphonium halides or their isomeric (2-carboxyallyl)triphenylphosphonium halides. The possibility of "unusual" isomerization of-the first compounds to the latter is shown. Synthesis of 1,2-(diphenylphosphinoyl)ethane from alpha-chloroacrylic acid is carried out.
• US6169209B1
  申请人：——

  公开号：US6169209B1

  公开（公告）日：2001-01-02
• Tautomerization of α,β-and β,γ-unsaturated phosphonium salts resulting from the reaction of triphenylphosphine with β-bromomethacrylic acid. Nucleophilic addition at the γ position of the allyl group in phosphonium salt
  作者：R. Dzh. Khachikyan、N. V. Tovmasyan、G. A. Panosyan、M. G. Indzhikyan

  DOI：10.1134/s1070363206100070

  日期：2006.10

  Temperature factor was found to be determining in the isomerization of 2-carboxyprop-1-en-1-yl and 2-carboxyprop-2-en-1-yl(triphenyl)phosphonium bromides. Elevated temperature favors formation of isomer with the double bond in the beta,gamma position with respect to the phosphonium group. Alkaline hydrolysis at room temperature promotes the reverse isomerization. The isomerization of 2-carboxyprop-1-en-1-yl(triphenyl)phosphonium bromide is hampered by addition of hydrobromic acid, as well as by carrying out its synthesis in the presence of aqueous HBr. Alkaline hydrolysis of 2-carboxyprop-1-enyl(triphenyl)phosphonium bromide and (E)-(2-carboxyvinyl)triphenylphosphonium chloride is accompanied by phenyl group migration to the alpha-position with formation of 2-methyl-3-(diphenylphosphoryl)-3-phenylpropionic acid and 3-(diphenylphosphoryl)-3-phenylpropionic acid, respectively. The possibility for nucleophilic addition at the gamma position of the allyl group in 2-carboxyprop-2-enyl(triphenyl)phosphonium bromide was demonstrated using the reaction with triphenylphosphine as an example.