diethyl <1-(3-oxo-1-cyclohexen-1-yl)ethyl>phosphonate | 173171-34-1

• 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-(3-oxo-1-cyclohexen-1-yl)ethyl>phosphonate
• 英文别名: 3-(1-Diethoxyphosphorylethyl)cyclohex-2-en-1-one
• CAS: 173171-34-1
• 化学式: C₁₂H₂₁O₄P
• 分子量: 260.27
• InChiKey: XYZGYPWKDOFSKS-UHFFFAOYSA-N

物化性质

• 沸点：
  368.2±31.0 °C(Predicted)
• 密度：
  1.118±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl <1-(3-oxo-1-cyclohexen-1-yl)ethyl>phosphonate 在 咪唑 、 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  氧化裂解条件下烯丙基膦酸酯的环扩，环收缩和环化反应

  摘要：

  环烯基烷基膦酸酯1的氧化裂解，然后用碱处理，可以得到高产率或高产率的同系环烯酮2。使环烷-2-烯基膦酸酯3在相同条件下以优异的产率提供与一碳环缩合的化合物4。γ，δ-不饱和酮膦酸酯6的氧化裂解，然后用碱处理，可得到具有良好总收率的2-环戊烯-1-酮7。该方法可以为实现单碳环膨胀，环收缩和环化反应的现有方法提供一种实用的替代方法。

  DOI：

  10.1021/acs.orglett.8b00791
• 作为产物：
  描述：

  乙基磷酸二乙酯 在 正丁基锂 、 硫酸 作用下， 以 氯仿 为溶剂， 反应 0.83h， 生成 diethyl <1-(3-oxo-1-cyclohexen-1-yl)ethyl>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

• NEBER REARRANGEMENT OF O-MESYLOXIME DERIV ATIVES OF THE RING AND SIDE CHAIN SUBSTITUTED 3-PHOSPHONOMETHYLCYCLOHEXENONES
  作者：Malose J. Mphahlele、Tomasz A. Modro

  DOI：10.1080/10426509708040503

  日期：1997.8.1

  derivatives of the ring and side chain substituted 3-phosphonomethylcyclohexenones undergo basic aluminum oxide–promoted Neber rearrangement to afford the corresponding vinyl aminocyclohexenonealkylphosphonates, regioselectively. No products resulting from the expected Beckmann rearrangement were detected.

  摘要 环和侧链取代的 3-膦酰基甲基环己烯酮的 O-甲磺酰肟衍生物经过碱性氧化铝促进的 Neber 重排，区域选择性地得到相应的乙烯基氨基环己烯酮烷基膦酸酯。没有检测到预期的贝克曼重排产生的产物。
• Mphahlele, Malose J.; Pienaar, Andre; Modro, Tomasz A., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1996, vol. 7, p. 1455 - 1460
  作者：Mphahlele, Malose J.、Pienaar, Andre、Modro, Tomasz A.

  DOI：——

  日期：——
• Ring Expansion, Ring Contraction, and Annulation Reactions of Allylic Phosphonates under Oxidative Cleavage Conditions
  作者：Dupre Orr、Nikolas Yousefi、Thomas G. Minehan

  DOI：10.1021/acs.orglett.8b00791

  日期：2018.5.18

  followed by treatment with base affords 2-cyclopenten-1-ones 7 in good overall yields. This method may offer a practical alternative to existing methods for effecting one-carbon ring expansion, ring contraction, and annulation reactions.

  环烯基烷基膦酸酯1的氧化裂解，然后用碱处理，可以得到高产率或高产率的同系环烯酮2。使环烷-2-烯基膦酸酯3在相同条件下以优异的产率提供与一碳环缩合的化合物4。γ，δ-不饱和酮膦酸酯6的氧化裂解，然后用碱处理，可得到具有良好总收率的2-环戊烯-1-酮7。该方法可以为实现单碳环膨胀，环收缩和环化反应的现有方法提供一种实用的替代方法。
• 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.