diethyl <(1-hydroxy-3-chloro-2-cyclohexen-1-yl)methyl>phosphonate | 173171-39-6

• 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: diethyl <(1-hydroxy-3-chloro-2-cyclohexen-1-yl)methyl>phosphonate
• 英文别名: 3-Chloro-1-(diethoxyphosphorylmethyl)cyclohex-2-en-1-ol
• CAS: 173171-39-6
• 化学式: C₁₁H₂₀ClO₄P
• 分子量: 282.704
• InChiKey: SDDRCCAQMFMKQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl <(1-hydroxy-3-chloro-2-cyclohexen-1-yl)methyl>phosphonate 在 硫酸 作用下， 以 氯仿 为溶剂， 反应 0.08h， 以80%的产率得到3-<(diethoxyphosphoryl)methyl>cyclohex-2-enone
  参考文献：
  名称：

  Reaction of Phosphonate-Stabilized Carbanions with Cyclic Enones Bearing a .beta.-Leaving Group

  摘要：

  Reaction between alpha-lithiated alkylphosphonic esters and alpha,beta-unsaturated cyclopentenones and cyclohexenones carrying a heteroatom substituent Y in the beta-position was studied. Complete chemoselectivity was observed as a function of substituent Y. For Y = OMe exclusive addition-elimination at the beta-carbon was observed, yielding alpha,beta-unsaturated delta-ketophosphonates. The beta-chloro-substituted substrates (Y = Cl) derived from cyclohexenone reacted exclusively at the carbonyl carbon, yielding (2-hydroxyalkyl)phosphonates with the retained chlorovinyl function. The alcohols, depending on the conditions, could be dehydrated to two different products. The reaction of 3-chlorocyclopent-2-en-1-one with diethyl (lithiomethyl)phosphonate occurred at the beta-carbon, but the ketophosphonate product was isolated in a stable enolic form.

  DOI：

  10.1021/jo00130a024
• 作为产物：
  描述：

  3-氯环己-2-烯酮 、 甲基膦酸二乙酯 在 正丁基锂 作用下， 生成 diethyl <(1-hydroxy-3-chloro-2-cyclohexen-1-yl)methyl>phosphonate
  参考文献：
  名称：

  Reaction of Phosphonate-Stabilized Carbanions with Cyclic Enones Bearing a .beta.-Leaving Group

  摘要：

  Reaction between alpha-lithiated alkylphosphonic esters and alpha,beta-unsaturated cyclopentenones and cyclohexenones carrying a heteroatom substituent Y in the beta-position was studied. Complete chemoselectivity was observed as a function of substituent Y. For Y = OMe exclusive addition-elimination at the beta-carbon was observed, yielding alpha,beta-unsaturated delta-ketophosphonates. The beta-chloro-substituted substrates (Y = Cl) derived from cyclohexenone reacted exclusively at the carbonyl carbon, yielding (2-hydroxyalkyl)phosphonates with the retained chlorovinyl function. The alcohols, depending on the conditions, could be dehydrated to two different products. The reaction of 3-chlorocyclopent-2-en-1-one with diethyl (lithiomethyl)phosphonate occurred at the beta-carbon, but the ketophosphonate product was isolated in a stable enolic form.

  DOI：

  10.1021/jo00130a024

文献信息

• Reaction of Phosphonate-Stabilized Carbanions with Cyclic Enones Bearing a .beta.-Leaving Group
  作者：Malose J. Mphahlele、Tomasz A. Modro

  DOI：10.1021/jo00130a024

  日期：1995.12

  Reaction between alpha-lithiated alkylphosphonic esters and alpha,beta-unsaturated cyclopentenones and cyclohexenones carrying a heteroatom substituent Y in the beta-position was studied. Complete chemoselectivity was observed as a function of substituent Y. For Y = OMe exclusive addition-elimination at the beta-carbon was observed, yielding alpha,beta-unsaturated delta-ketophosphonates. The beta-chloro-substituted substrates (Y = Cl) derived from cyclohexenone reacted exclusively at the carbonyl carbon, yielding (2-hydroxyalkyl)phosphonates with the retained chlorovinyl function. The alcohols, depending on the conditions, could be dehydrated to two different products. The reaction of 3-chlorocyclopent-2-en-1-one with diethyl (lithiomethyl)phosphonate occurred at the beta-carbon, but the ketophosphonate product was isolated in a stable enolic form.