Dimethyl (Z)-(2-cyano-1-vinyl)phosphonate | 161186-13-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: Dimethyl (Z)-(2-cyano-1-vinyl)phosphonate
• 英文别名: (Z)-3-dimethoxyphosphorylprop-2-enenitrile
• CAS: 161186-13-6
• 化学式: C₅H₈NO₃P
• 分子量: 161.097
• InChiKey: QUEHUARSEVSJEB-HYXAFXHYSA-N

物化性质

• 沸点：
  237.645±32.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.194±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Dimethyl (Z)-(2-cyano-1-vinyl)phosphonate 在 indium(III) chloride 、 sodium tetrahydroborate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以84%的产率得到dimethyl (2-cyanoethyl)phosphonate
  参考文献：
  名称：

  InCl 3 -NaBH 4试剂系统还原活化的共轭烯烃

  摘要：

  乙腈中催化量的氯化铟（III）和硼氢化钠的组合可选择性降低共轭烯烃（如α，α-二氰基烯烃，α，β-不饱和腈，氰基酯，氰基膦酸酯和二羧酸酯）中的碳-碳双键。但是，减少查耳酮几乎没有什么不同。如果将反应混合物用H 2 O淬灭，则它们会还原为饱和酮和醇的混合物，而用MeOH淬灭只会产生饱和醇。

  DOI：

  10.1016/j.tet.2003.08.022
• 作为产物：
  描述：

  2-溴丙烯腈 、 三甲氧基磷 反应 3.0h， 生成 Dimethyl (Z)-(2-cyano-1-vinyl)phosphonate 、 (E)-3-dimethoxyphosphorylprop-2-enenitrile
  参考文献：
  名称：

  Synthesis, Molecular Structure, and Spectroscopical Properties of Alkenylphosphonic Derivatives. 1. Vinyl-, Propenyl-, (Bromoalkenyl)-, and (Cyanoalkenyl)phosphonic Compounds

  摘要：

  Several vinyl-, propenyl-, (bromoalkenyl)-, and (cyanoalkenyl)phosphonate derivatives have been synthesized. The (2-cyanovinyl)phosphonates have been obtained with an important improvement in the yield (40% versus 6%). The separation of the E and Z isomers of the cyano derivatives and their hydrolysis to the corresponding phosphonic acids have been studied. The bromination and dehydrobromination of some alkenylphosphonic derivatives have also been studied. Spectroscopical studies from UV, IR, Raman, and H-1, C-13, and P-31 NMR have been performed in most of these derivatives. The C=C/P-O pi conjugation exists but it is weak in all these compounds. Dipole moments and C=C/P=O conformational populations have been calculated theoretically by ab initio methods. The effect of the solvent polarity on the conformational population has been observed by IR spectroscopy disclosing two C=C/P=O conformers. Experimental and theoretical results have been compared, a high level of agreement has been found.

  DOI：

  10.1021/jo00106a017

文献信息

• Use of indium hydride (Cl2InH) for chemoselective reduction of the carboncarbon double bond in conjugated alkenes
  作者：Brindaban C. Ranu、Sampak Samanta

  DOI：10.1016/s0040-4039(02)01668-4

  日期：2002.10

  Indium hydride (Cl2InH) generated in situ from a combination of a catalytic amount of indium(III) chloride and sodium borohydride selectively reduces the carboncarbon double bond in conjugated alkenes such as α,α-dicyano olefins, α,β-unsaturated nitriles, cyano esters, cyanophosphonate, diesters and ketones.

  催化量的氯化铟（III）和硼氢化钠的组合就地生成的氢化铟（Cl 2 InH）有选择地还原共轭烯烃（如α，α-二氰基烯烃，α，β-不饱和腈，氰基酯，氰基膦酸酯，二酯和酮。
• Synthesis of Substituted 2-Alkoxycarbonyl or 2-Cyano-1,3-butadienes
  作者：Yu-Xiu Liu、Cheng-Fu Xu、Ru-Zhen Cao、Lun-Zu Liu

  DOI：10.1081/scc-120024875

  日期：2003.10

  A series of 2-butoxycarbonyl-1,4-diaryl-1,3-butadienes and 2-cyano-1,4-diaryl-1,3-butadienes are synthesized by one pot reaction of 2-butoxycarbonyl or 2-cyanoethenylphosphonate with aromatic aldehyde and tributylphosphine.
• Synthesis, Molecular Structure, and Spectroscopical Properties of Alkenylphosphonic Derivatives. 1. Vinyl-, Propenyl-, (Bromoalkenyl)-, and (Cyanoalkenyl)phosphonic Compounds
  作者：C. I. Sainz-Diaz、E. Galvez-Ruano、A. Hernandez-Laguna、J. Bellanato

  DOI：10.1021/jo00106a017

  日期：1995.1

  Several vinyl-, propenyl-, (bromoalkenyl)-, and (cyanoalkenyl)phosphonate derivatives have been synthesized. The (2-cyanovinyl)phosphonates have been obtained with an important improvement in the yield (40% versus 6%). The separation of the E and Z isomers of the cyano derivatives and their hydrolysis to the corresponding phosphonic acids have been studied. The bromination and dehydrobromination of some alkenylphosphonic derivatives have also been studied. Spectroscopical studies from UV, IR, Raman, and H-1, C-13, and P-31 NMR have been performed in most of these derivatives. The C=C/P-O pi conjugation exists but it is weak in all these compounds. Dipole moments and C=C/P=O conformational populations have been calculated theoretically by ab initio methods. The effect of the solvent polarity on the conformational population has been observed by IR spectroscopy disclosing two C=C/P=O conformers. Experimental and theoretical results have been compared, a high level of agreement has been found.
• Reduction of activated conjugated alkenes by the InCl3–NaBH4 reagent system
  作者：Brindaban C Ranu、Sampak Samanta

  DOI：10.1016/j.tet.2003.08.022

  日期：2003.9

  catalytic amount of indium (III) chloride and sodium borohydride in acetonitrile reduces selectively the carbon–carbon double bonds in conjugated alkenes such as α,α-dicyano olefins, α,β-unsaturated nitriles, cyanoesters, cyanophosphonate and dicarboxylic esters. However, reduction of chalcones is little different. They are reduced to a mixture of saturated ketones and alcohols if the reaction mixture is quenched

  乙腈中催化量的氯化铟（III）和硼氢化钠的组合可选择性降低共轭烯烃（如α，α-二氰基烯烃，α，β-不饱和腈，氰基酯，氰基膦酸酯和二羧酸酯）中的碳-碳双键。但是，减少查耳酮几乎没有什么不同。如果将反应混合物用H 2 O淬灭，则它们会还原为饱和酮和醇的混合物，而用MeOH淬灭只会产生饱和醇。