propadienyltriphenylphosphonium bromide | 54599-99-4

• 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: propadienyltriphenylphosphonium bromide
• 英文别名: Phosphonium,2-propadienyl-, bromide；triphenyl(propa-1,2-dienyl)phosphanium;bromide
• CAS: 54599-99-4
• 化学式: Br*C₂₁H₁₈P
• 分子量: 381.252
• InChiKey: IEJSECDWUIWJNJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.28
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  炔丙基三苯基溴化膦 以 二氯甲烷-D2 为溶剂， 反应 120.0h， 生成 propadienyltriphenylphosphonium bromide
  参考文献：
  名称：

  Synthesis of Phosphonium-Substituted Vinylidene Complexes from [HC≡CCH₂PPh₃]⁺: Exploring the Competition between Allene and Vinylidene Formation.

  摘要：

  Reaction of the alkenyl-substituted carbene complex [Ru(kappa(2)-O2CMe)(OC{Me}O(=CCH=CH2)(PPh3)(2)](+) with PPh3 results in the formation of the vinylidene-containing species [Ru(kappa(1)-O2CMe)(kappa(2)-O2CMe)(=C=CHCH2PPh3)(PPh3)(2)](+), among other products. This complex could also be obtained by reaction of [Ru(kappa(2)-O2CR)(PPh3)(2)] (R = Me, Ph) with [HC=CCH2PPh3](+) although in this instance competitive formation of allene-containing [Ru(kappa(1)-O2CR)(kappa(2)-O2CR)(kappa(2)-H2C=C=CHPPh3)(PPh3)(2)] occurred. Reaction of [Ru(kappa(2)-O2CMe)(2)(PPh3)(2)] with [H2C=C=CHPPh3](+) gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PiPr(3))(2)](2) was used as the metal precursor. The reaction with [H2C-C-CHPPh3](+) gave [RhCl(kappa(2)-H2C=C=CHPPh3)((PPr3)-Pr-i)(2)](+), whereas treatment with [HC=C=CH2PPh3](+) afforded a mixture of the same complex and [RhCl(kappa(2)-HC=CCH2PPh3)((PPr3)-Pr-i)(2)](+), which subsequently isomerized to vinylidene-containing [RhCl(-C-C=HCH2PPh3)((PPr3)-Pr-i)(2)](+) via the alkynyl hydride complex [RhCl(H)(C=C=CH2PPh3)((PPr3)-Pr-i)(2)](+). Consistent with previous findings [HC=C=CH2PPh3](+) isomerizes to [H2C=C=CHPPh3](+) in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.

  DOI：

  10.1021/om5010429

文献信息

• Synthesis and transformations of triphenylpropargylphosphonium bromide
  作者：G. B. Bagdasaryan、P. S. Pogosyan、G. A. Panosyan、M. G. Indzhikyan

  DOI：10.1134/s1070363208060133

  日期：2008.6

  A method of the s,mthesis of triphenylpropargylphosphonium bromide is developed. Its isomerization and hydration in various solvents are studied, and reactions with secondary arnines, tricthylamine, and triphenylphosphine are carried out. It is established that secondary arnines add to the intermediate allene isomer with subsequent migration ofthe formed double bond to the phosphorus atorn. The reaction of triethylamine with trir.henylpropargyl and triphenylethynyl bromides occurs similarly to alkaline hydrolysis involving attack of' the amine on the phosphorus atom. Triphenylphosphine fornis with triphenylpropar-ylphosphonium biomide a bis-salt with a terminal methylene group. Experimental evidence is obtained showinc -, that for plioi;phoxazole derivatives to form from oxiines derived from triphenyl(oxomethyl)phosphonium salts tha latter should bear an aryl substituent at the keto group.
• Synthesis of Phosphonium-Substituted Vinylidene Complexes from [HC≡CCH₂PPh₃]⁺: Exploring the Competition between Allene and Vinylidene Formation.
  作者：Elizabeth J. Smith、Natalie E. Pridmore、Adrian C. Whitwood、Jason M. Lynam

  DOI：10.1021/om5010429

  日期：2014.12.22

  Reaction of the alkenyl-substituted carbene complex [Ru(kappa(2)-O2CMe)(OCMe}O(=CCH=CH2)(PPh3)(2)](+) with PPh3 results in the formation of the vinylidene-containing species [Ru(kappa(1)-O2CMe)(kappa(2)-O2CMe)(=C=CHCH2PPh3)(PPh3)(2)](+), among other products. This complex could also be obtained by reaction of [Ru(kappa(2)-O2CR)(PPh3)(2)] (R = Me, Ph) with [HC=CCH2PPh3](+) although in this instance competitive formation of allene-containing [Ru(kappa(1)-O2CR)(kappa(2)-O2CR)(kappa(2)-H2C=C=CHPPh3)(PPh3)(2)] occurred. Reaction of [Ru(kappa(2)-O2CMe)(2)(PPh3)(2)] with [H2C=C=CHPPh3](+) gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PiPr(3))(2)](2) was used as the metal precursor. The reaction with [H2C-C-CHPPh3](+) gave [RhCl(kappa(2)-H2C=C=CHPPh3)((PPr3)-Pr-i)(2)](+), whereas treatment with [HC=C=CH2PPh3](+) afforded a mixture of the same complex and [RhCl(kappa(2)-HC=CCH2PPh3)((PPr3)-Pr-i)(2)](+), which subsequently isomerized to vinylidene-containing [RhCl(-C-C=HCH2PPh3)((PPr3)-Pr-i)(2)](+) via the alkynyl hydride complex [RhCl(H)(C=C=CH2PPh3)((PPr3)-Pr-i)(2)](+). Consistent with previous findings [HC=C=CH2PPh3](+) isomerizes to [H2C=C=CHPPh3](+) in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.