[3-Methoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide | 183994-96-9

• 分子结构分类: 有机化合物 - 有机磷化合物 - 四烷基鏻化合物
• 英文名称: [3-Methoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide
• 英文别名: [3-methoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide
• CAS: 183994-96-9
• 化学式: C₁₄H₂₆NO₂P
• 分子量: 271.34
• InChiKey: CSXDKEHCCWHTQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  27.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  异氰酸间甲苯酯 、 [3-Methoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide 以 二氯甲烷 为溶剂， 以50%的产率得到1--2-(triisopropylphosphonio)-1-cyanoethan-1-ide
  参考文献：
  名称：

  A novel electrophilic rearrangement with migration of an alkoxycarbonyl group from carbon to a nitrogen anionic center

  摘要：

  DOI：

  10.1007/bf02495716
• 作为产物：
  描述：

  2-氰基丙烯酸甲酯 、 三异丙基膦 以 乙醚 、 正己烷 为溶剂， 以48%的产率得到[3-Methoxy-3-oxo-2-[tri(propan-2-yl)phosphaniumylmethyl]prop-1-enylidene]azanide
  参考文献：
  名称：

  ZWITTERIONIC SPECIES FROM TRIISOPROPYLPHOSPHINE AND 2-CYANOACRYLATES: SYNTHESIS, STRUCTURE AND PROPERTIES

  摘要：

  Triisopropylphosphine reacts with 2-cyanoacrylates with formation of the P-zwitterionic species 2a and 2b. The reaction of 2b with trimethylsilyltriflate, in the presence of traces of water, leads to the phosphonium triflate 3. 2b is alkylated at the carbon atom with methyl iodide with formation of the phosphonium iodide 4. The initially formed adducts of the zwitterionic species 2a and 2b with tosyl azide and with tosyl isocyanate are thermodynamically unstable. In the first case, the final products of the reaction are tosyl iminotriisopropylphosphine imide 6 and 2-cyanoacrylate polymers. In the second case, the reaction leads to the zwitterionic product 8, and, in the presence of traces of water, to the molecular complexes 9a and 9b. The reaction of the zwitterionic species 2a and 2b with methylisocyanate proceeds in an unusual way, resulting in the formation of the zwitterionic species 12a and 12b, as a result of the insertion of methylisocyanate into the C-C bond of the starting zwitterionic adducts. The identity and structure of all the new products were established by elemental analysis, IR spectroscopy, H-1-, C-13-, and P-31-NMR spectroscopy, as well as by single-crystal X-ray structure analyses for 2b, 8, 9a and 12b. The structures of 2b, 9a and 12b are closely similar as regards the molecular backbone. In all four structures there is evidence for some delocalisation of negative charge to the C(:O) and CN group.

  DOI：

  10.1080/10426509608037951

文献信息

• ZWITTERIONIC SPECIES FROM TRIISOPROPYLPHOSPHINE AND 2-CYANOACRYLATES: SYNTHESIS, STRUCTURE AND PROPERTIES
  作者：Yuri G. Gololobov、Vastly A. Pinchuk、Holger Thönnessen、Peter G. Jones、Reinhard Schmutzler

  DOI：10.1080/10426509608037951

  日期：1996.8.1

  Triisopropylphosphine reacts with 2-cyanoacrylates with formation of the P-zwitterionic species 2a and 2b. The reaction of 2b with trimethylsilyltriflate, in the presence of traces of water, leads to the phosphonium triflate 3. 2b is alkylated at the carbon atom with methyl iodide with formation of the phosphonium iodide 4. The initially formed adducts of the zwitterionic species 2a and 2b with tosyl azide and with tosyl isocyanate are thermodynamically unstable. In the first case, the final products of the reaction are tosyl iminotriisopropylphosphine imide 6 and 2-cyanoacrylate polymers. In the second case, the reaction leads to the zwitterionic product 8, and, in the presence of traces of water, to the molecular complexes 9a and 9b. The reaction of the zwitterionic species 2a and 2b with methylisocyanate proceeds in an unusual way, resulting in the formation of the zwitterionic species 12a and 12b, as a result of the insertion of methylisocyanate into the C-C bond of the starting zwitterionic adducts. The identity and structure of all the new products were established by elemental analysis, IR spectroscopy, H-1-, C-13-, and P-31-NMR spectroscopy, as well as by single-crystal X-ray structure analyses for 2b, 8, 9a and 12b. The structures of 2b, 9a and 12b are closely similar as regards the molecular backbone. In all four structures there is evidence for some delocalisation of negative charge to the C(:O) and CN group.
• A novel electrophilic rearrangement with migration of an alkoxycarbonyl group from carbon to a nitrogen anionic center
  作者：Yu. G. Gololobov、M. A. Galkina、I. Yu. Kuz'mintseva、P. V. Petrovskii

  DOI：10.1007/bf02495716

  日期：1998.9