bromo-1 diphenyl-2,5 phosphole | 83085-55-6

• 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: bromo-1 diphenyl-2,5 phosphole
• 英文别名: 1-bromo-2,5-diphenylphosphole
• CAS: 83085-55-6
• 化学式: C₁₆H₁₂BrP
• 分子量: 315.149
• InChiKey: AIEARCYKPUJDSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  18
• 可旋转键数：
  2
• 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：
  0

反应信息

• 作为反应物：
  描述：

  Na[W(CO)3(cyclopentadienyl)] 、 bromo-1 diphenyl-2,5 phosphole 以 二乙二醇二甲醚 、 苯 为溶剂， 以70%的产率得到(η1(P)-2,5-diphenylphospholyl)(η5-cyclopentadienyl)tricarbonyltungsten
  参考文献：
  名称：

  Synthesis and chemical reactivity of tungsten P-substituted phospholes

  摘要：

  Two tungsten-substituted phospholes were prepared by reaction of CpW(CO)3Na with 1-cyano-3,4-dimethylphosphole and 1-bromo-2,5-diphenylphosphole, respectively. According to a X-ray crystal structure analysis, the 3,4-dimethyl-substituted compound is more planar and displays a higher electronic delocalization than an ordinary phosphole such as 1-benzylphosphole. In both cases, the lone pair at phosphorus retains a substantial nucleophilicity, with oxidation, sulfurization, and quaternization being easily achieved. Reaction with carboxylic acids leads to a tungsten-substituted 2,5-dihydrophosphole oxide via an initial protonation at phosphorus followed by a [1,5]-sigmatropic shift of hydrogen. [4 + 2] cycloadditions with N-phenylmaleimide are possible with the phosphole oxides or sulfides. The reaction with dimethyl acetylenedicarboxylate yields a spirocyclic compound containing a P-C=C-C(O)-W ring whose structure was established by X-ray analysis. The thermolysis of the 3,4-dimethyl-substituted phosphole leads to a normal mu-phosphido P2W2 dimer by loss of CO, whereas the more congested 2,5-diphenyl derivative gives a mu-phosphido, mu-hydrido complex with a W-W bond.

  DOI：

  10.1021/om00025a020
• 作为产物：
  描述：

  1,2,5-triphenyl-1H-phosphole 在 溴 、 lithium 作用下， 以 苯 为溶剂， 反应 22.0h， 生成 bromo-1 diphenyl-2,5 phosphole
  参考文献：
  名称：

  合成及专有的d 5-磷酸基-钴-二羰基

  摘要：

  光气与2,5-二苯基膦酰基阴离子反应，得到2,2'，5,5'-四苯基联膦酰基。在与羰基钴沸腾的甲苯，以收率此化合物反应（η 5 -2,5- diphenylphospholyl）dicarbonylcobalt其示出了在乙炔的环低聚没有催化活性。它也与溴和醇反应生成1-烷氧基磷脂。我们还幸运地观察到，苯基锂与1,2,5-三苯基磷脂的反应生成了2,5-二苯基-和2,3,5-三苯基-磷酰基阴离子的混合物。

  DOI：

  10.1016/s0022-328x(00)81213-9

文献信息

• A la recherche des ferrocénylphospholes
  作者：Eliane Deschamps、François Mathey

  DOI：10.1016/0022-328x(87)85133-1

  日期：1987.9
• Synthese et proprietes d'un η5-phospholyl-cobalt-dicarbonyle
  作者：Claude Charrier、Hubert Bonnard、François Mathey、Denis Neibecker

  DOI：10.1016/s0022-328x(00)81213-9

  日期：1982.6

  The reaction of phosgene with the anion 2,5-diphenylphospholyl gives 2,2′,5,5′-tetraphenylbiphospholyl. This compound reacts in boiling toluene with cobalt carbonyl to yield (η5-2,5-diphenylphospholyl)dicarbonylcobalt which shows no catalytic activity in the cyclooligomerization of acetylenes. It also reacts with bromine and alcohols to give 1-alkoxyphospholes. We have also fortuitously observed that

  光气与2,5-二苯基膦酰基阴离子反应，得到2,2'，5,5'-四苯基联膦酰基。在与羰基钴沸腾的甲苯，以收率此化合物反应（η 5 -2,5- diphenylphospholyl）dicarbonylcobalt其示出了在乙炔的环低聚没有催化活性。它也与溴和醇反应生成1-烷氧基磷脂。我们还幸运地观察到，苯基锂与1,2,5-三苯基磷脂的反应生成了2,5-二苯基-和2,3,5-三苯基-磷酰基阴离子的混合物。
• Synthesis and chemical reactivity of tungsten P-substituted phospholes
  作者：Francois Mercier、Louis Ricard、Francois Mathey

  DOI：10.1021/om00025a020

  日期：1993.1

  Two tungsten-substituted phospholes were prepared by reaction of CpW(CO)3Na with 1-cyano-3,4-dimethylphosphole and 1-bromo-2,5-diphenylphosphole, respectively. According to a X-ray crystal structure analysis, the 3,4-dimethyl-substituted compound is more planar and displays a higher electronic delocalization than an ordinary phosphole such as 1-benzylphosphole. In both cases, the lone pair at phosphorus retains a substantial nucleophilicity, with oxidation, sulfurization, and quaternization being easily achieved. Reaction with carboxylic acids leads to a tungsten-substituted 2,5-dihydrophosphole oxide via an initial protonation at phosphorus followed by a [1,5]-sigmatropic shift of hydrogen. [4 + 2] cycloadditions with N-phenylmaleimide are possible with the phosphole oxides or sulfides. The reaction with dimethyl acetylenedicarboxylate yields a spirocyclic compound containing a P-C=C-C(O)-W ring whose structure was established by X-ray analysis. The thermolysis of the 3,4-dimethyl-substituted phosphole leads to a normal mu-phosphido P2W2 dimer by loss of CO, whereas the more congested 2,5-diphenyl derivative gives a mu-phosphido, mu-hydrido complex with a W-W bond.