4,5-Dimethyl-2-(ethoxycarbonyl)phosphinine | 133983-62-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4,5-Dimethyl-2-(ethoxycarbonyl)phosphinine
• 英文别名: 2-ethoxycarbonyl-4,5-dimethylphosphinine；Ethyl 4,5-dimethylphosphinine-2-carboxylate
• CAS: 133983-62-7
• 化学式: C₁₀H₁₃O₂P
• 分子量: 196.186
• InChiKey: DFKMCUCOBYUNGH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3,4-dimethyl-1-phenylphosphole-1-sulfide 在 镍 作用下， 以 甲苯 、 均三甲苯 为溶剂， 反应 1100.5h， 生成 4,5-Dimethyl-2-(ethoxycarbonyl)phosphinine
  参考文献：
  名称：

  Reaction of phosphole sulfides with diazoalkanes as a new route to phosphinines

  摘要：

  The reaction of ethyl diazoacetate with 1-(methylthio)-3,4-dimethylphosphole 1-sulfide (6) in refluxing xylene leads to the corresponding diene-carbene [2 + 1] cycloadduct 7. The sterochemistry of 7 was established by X-ray crystal structure analysis. Compound 7 is converted into 2-(ethoxycarbonyl)-4,5-dimethylphosphinine (4) upon reaction with triphenyl phosphite at 160-degrees-C. On the basis of the X-ray data, the proposed mechanism includes the opening of the cyclopropane ring of 7 with selective phosphorus-assisted migration of the ethoxycarbonyl group. This kind of chemistry can be transposed to a 2,2'-biphosphole to prepare a 2,2'-biphosphinine.

  DOI：

  10.1021/jo00012a042

文献信息

• Investigating the Phospholylcarbene to Phosphinine Conversion
  作者：Hui Chen、Jin Li、Huaiqiu Wang、Hui Liu、Zheng Duan、François Mathey

  DOI：10.1002/ejic.201100098

  日期：2011.4

  study suggests that the conversion of arsolylcarbenes into arsenines as described by Markl proceeds via arsabenzvalenes. A similar conversion does not work with phospholylcarbenes. However, we have found that, in some cases, 1-diazoalkylphosphole sulfides are converted into phosphinine sulfides whose in situ reduction by triphenylphosphite affords the dicoordinate phosphinines.

  DFT 研究表明，如 Markl 所描述的，arsolylcarbenes 向砷的转化是通过 arsabenzvalenes 进行的。类似的转化不适用于磷酸卡宾。然而，我们发现，在某些情况下，1-重氮烷基磷硫化物会转化为硫化膦，其被亚磷酸三苯酯原位还原得到双配位膦。