3-((Dimethoxyphosphonyl)methyl)-2-cyclohexenone | 153856-39-4

• 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: 3-((Dimethoxyphosphonyl)methyl)-2-cyclohexenone
• 英文别名: 3-<(dimethoxyphosphoryl)methyl>cyclohex-2-enone；dimethyl (3-oxocyclohex-1-enyl)methylphosphonate；3-(Dimethoxyphosphorylmethyl)cyclohex-2-en-1-one
• CAS: 153856-39-4
• 化学式: C₉H₁₅O₄P
• 分子量: 218.189
• InChiKey: HRQUFYRKUSDVER-UHFFFAOYSA-N

物化性质

• 沸点：
  332.7±31.0 °C(Predicted)
• 密度：
  1.178±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3-((Dimethoxyphosphonyl)methyl)-2-cyclohexenone 在 重水 、 sodium hydride 、 氘代硫酸 作用下， 以 苯 为溶剂， 生成 3-[Deuterio(dimethoxyphosphoryl)methyl]cyclohex-2-en-1-one
  参考文献：
  名称：

  A general approach to 3-phosphorylmethyl cycloalkenones by intramolecular Horner-Wittig reaction of bis-.beta.-ketophosphonates

  摘要：

  The reaction of dicarboxylic acid diesters with lithiomethylphosphonates was found to give bis-beta-keto phosphonates 1 [(RO)(2)P(O)CH2C(O)](2)(CH2)(n) (n = 2, 3, 4), a new class of compounds. Their cyclization under basic conditions provides an easy access to five-, six- and seven-membered 3-phosphorylmethyl cycloalkenones 2. The cyclization of 1,6-bis(dialkoxyphosphoryl)hexan-2,5-dione (1a,d) was found to be bidirectional in course and a competition between the intramolecular Horner-Wittig and Knoevenagel reaction was observed. It was demonstrated that the latter reaction is reversible which allows conversion of the Knoevenagel reaction product into the Horner-Wittig reaction product (for example 5b into 2d). Two efficient methods for the synthesis of 2- and 3-functionalized cycloalkenones 6 and 7 involving alkylation and olefination of the cycloalkenones 2 anion were devised.

  DOI：

  10.1021/jo00101a041
• 作为产物：
  描述：

  dimethyl ((3-oxo-2-(phenylsulfinyl)cyclohexyl)(trimethylsilyl)methyl)phosphonate 以 氯仿 为溶剂， 反应 5.0h， 以58%的产率得到3-((Dimethoxyphosphonyl)methyl)-2-cyclohexenone
  参考文献：
  名称：

  The sila-Pummerer reaction of γ-silyl substituted cycloalkanoyl sulfoxides: the first examples and a new approach to 3-substituted cycloalk-2-enones

  摘要：

  The thermal decomposition of 3-(alpha-trimethylsilyl)alkyl substituted 2-(phenylsulfinyl)cycloalkanones occurs via the gamma-sila-Pummerer reaction, affording 3-substituted cycloalk-2-enones and unstable trimethylsilyl benzenesulfenate as an elimination by-product. The starting gamma-silyl substituted cycloalkanoyl sulfoxides were obtained through the conjugate addition reaction of nucleophilic reagents to 2-(phenylsulfinyl)cycloalk-2-enones. The tandem conjugate addition/gamma-sila-Pummerer reaction investigated here provides a new route to 3-substituted cycloalk-2-enones. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.04.128

文献信息

• Straightforward synthesis of functionalized (E)-3-acylacrylic acids
  作者：Ivan Sivák、Jakub Václav、Dušan Berkeš、Andrej Kolarovič

  DOI：10.1016/j.tet.2015.10.003

  日期：2015.11

  An experimentally simple, mild and straightforward synthetic route towards diversely functionalized (E)-3-acylacrylic acids is described, with Horner–Wadsworth–Emmons (HWE) reaction as the key step. The substrate scope and limitations of the HWE reaction were investigated with a range of β-ketophosphonates. Glyoxylic acid monohydrate was demonstrated to be fully compatible with the HWE reaction conditions

  朝不同地官能化（通过实验简单，轻度和直接合成路线ë）-3- acylacrylic酸进行了说明，与霍纳-沃兹沃思-埃蒙斯（HWE）作为关键步骤反应。基板范围和HWE反应的局限性与一系列β-ketophosphonates的进行了研究。已证明乙醛酸一水合物与HWE反应条件完全相容，因此避免了最后一步中相应的3-丙烯酸丙烯酸酯的麻烦水解，并提供了有价值的合成捷径。
• 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。
• The First Observation of γ-Sila-Pummerer Rearrangement
  作者：Maciej Mikina

  DOI：10.1080/10426507.2012.744310

  日期：2013.4.1

  2-Sulfinyl-3-trimethylsilylmethylcycloalkanones unexpectedly undergo -sila-Pummerer rearrangement. The first examples of this new type of rearrangement are presented.
• A Synthesis of 3-Alkenylcycloalkenones
  作者：Ernest Wenkert、Matthias K. Schorp

  DOI：10.1021/jo00086a063

  日期：1994.4
• Mikolajczyk Marian, Mikina Maciej, J. Org. Chem., 59 (1994) N 22, S 6760-6765
  作者：Mikolajczyk Marian, Mikina Maciej

  DOI：——

  日期：——