5-methyl-2-bromophosphinine | 134654-74-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: 5-methyl-2-bromophosphinine
• 英文别名: 2-Bromo-5-methylphosphinine
• CAS: 134654-74-3
• 化学式: C₆H₆BrP
• 分子量: 188.991
• InChiKey: UZTXAGQZQKNOQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• 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：
  0

反应信息

• 作为反应物：
  描述：

  乙腈(五羰基)钨(0) 、 4-methyl-2-bromophosphinine 、 5-methyl-2-bromophosphinine 以 四氢呋喃 为溶剂， 生成 (4-methyl-2-bromophosphinine)pentacarbonyltungsten 、 (5-methyl-2-bromophosphinine)pentacarbonyltungsten
  参考文献：
  名称：

  2-lithiophosphinines的合成等价物：2-官能膦的新途径

  摘要：

  Two routes converting 2-bromophosphinines into 2-functional phosphinines are described. In the first one, a [2 + 4] cycloadduct between the 2-bromophosphinine, 2,3-dimethylbutadiene, and sulfur is first formed. On this adduct, a bromine to lithium exchange is performed by phenyllithium in THF at low temperature. This lithium derivative is converted into a functional derivative by reaction with an electrophile. Then, the 2-functional phosphinine is obtained by a combined reduction-cycloreversion using P(CH2CH2CN)3 as the reducing agent at ca. 180-degrees-C. A 2-(trimethylsilyl)- and a 2-(diphenylphosphino)phosphinine were thus prepared. In the second route, a bromine to lithium exchange is performed on a (2-bromophosphinine)pentacarbonyltungsten complex by phenyllithium in THF at -80-degrees-C. The 2-functional phosphinine is recovered from its complex by heating with Ph2PCH2CH2PPh2 at 110-degrees-C in toluene. A 2-iodo-, 2-(trimethylsilyl)-, and 2-[(diphenylphosphino)pentacarbonyltungsten]phosphinine were thus obtained. An intermediate [2-(ethoxycarbonyl)phosphinine]pentacarbonyltungsten complex readily adds water to give the corresponding 1-hydroxy-1,6-dihydrophosphinine complex.

  DOI：

  10.1021/om00053a055