ethyl 2-(diethoxyphosphoryl)-3-oxopentanoate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: ethyl 2-(diethoxyphosphoryl)-3-oxopentanoate
• 英文别名: Ethyl 2-diethoxyphosphoryl-3-oxopentanoate
• 化学式: C₁₁H₂₁O₆P
• 分子量: 280.258
• InChiKey: PRIKDZLYROHSBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2-(diethoxyphosphoryl)-3-oxopentanoate 以 水 、 1,2-二氯乙烷 为溶剂， 反应 24.0h， 生成 diethyl (5-ethyl-1-methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)phosphonate
  参考文献：
  名称：

  Versatile Synthesis of 4-Methylidenepyrazolidin-3-ones Using a Horner–Wadsworth–Emmons Approach

  摘要：

  A new, versatile method for the synthesis of, so far unknown, variously substituted 4-methylidenepyrazolidin-3-ones as potential cytotoxic agents is described. Target compounds were synthesized from the corresponding 4-diethoxyphosphorylpyrazolidin-3-ones which were used as Horner-Wadsworth-Emmons reagents for the olefination of formaldehyde. 4-Phosphorylpyrazolidin-3-ones were, in turn, obtained starting from the sodium salt of ethyl 2-diethoxyphosphoryl-3-hydroxy-2-propenoate, ethyl 2-acyl-2-diethoxyphosphorylacetates, or 3-methoxy-2-diethoxyphosphorylacrylate and monosubstituted or 1,2-disubstituted hydrazines.

  DOI：

  10.1055/s-0033-1340071
• 作为产物：
  描述：

  亚磷酸三乙酯 、 丙酰乙酸乙酯 在 过氧化双月桂酰 、 溶剂黄146 、 copper(I) bromide 作用下， 以93%的产率得到ethyl 2-(diethoxyphosphoryl)-3-oxopentanoate
  参考文献：
  名称：

  一种制备2-膦酸酯基-1,3-二羰基衍生物的方 法

  摘要：

  本发明公开了一种制备2‑膦酸酯基‑1,3‑二羰基衍生物的方法，使用1,3‑二羰基衍生物和三烷基亚磷酸酯为起始物，原料易得、种类很多；利用本发明的方法得到的产物类型多样，既可以直接使用、又可以用于其他进一步的反应；此外，本发明公开的方法中，反应在空气中进行，条件温和，反应时间短，目标产物的收率高，污染小，反应操作和后处理过程简单，适于工业化生产。

  公开号：

  CN105503945B

文献信息

• Synthesis of 4,4-Disubstituted 3-Methylidenechroman-2-ones as Potent Anticancer Agents
  作者：Rafał Jakubowski、Dorota K. Pomorska、Angelika Długosz、Anna Janecka、Urszula Krajewska、Marek Różalski、Marek Mirowski、Tomasz Bartosik、Tomasz Janecki

  DOI：10.1002/cmdc.201700080

  日期：2017.4.20

  The synthesis of a new library of 4,4-disubstituted 3-methylidene-3,4-dihydro-2H-chroman-2-ones applying Horner-Wadsworth-Emmons methodology for the construction of an exo-methylidene moiety is reported. Corresponding 3-diethoxyphosphorylchroman-2-ones were synthesized in a three-step reaction sequence consisting of O-methylation of ethyl 2-diethoxyphosphoryl-3-oxoalkanoates, followed by reaction of

  报道了使用Horner-Wadsworth-Emmons方法合成4，4-二取代的3-亚甲基-3，4-二氢-2H-苯并二氢吡喃的新文库，用于构建外亚甲基部分。以三步反应顺序合成相应的3-二乙氧基磷酰基苯并二氢吡喃-2-酮，其由2-二乙氧基磷酰基-3-氧代链烷酸乙酯的O-甲基化组成，然后使所获得的2-二乙氧基磷酰基-3-甲氧基-2-链烯酸酯与酚或1-萘酚。在与各种格氏试剂的反应中，所得的3-二乙氧基磷酰铬-2-酮被证明是有效的迈克尔受体。初步生物学评估表明，许多合成的3-methylidenechroman-2-ones对NALM-6和HL-60癌细胞系具有非常高的细胞毒活性（IC50 <1。0μm）以及对MCF-7癌细胞系的高活性（IC50 <10μm）。此外，在针对人脐静脉内皮细胞（HUVEC）的测试中，两个在第4位具有双甲基和乙基取代基的高活性3-亚甲基苯并二氢吡喃-2-酮显示出令人鼓舞的10和13的治疗指数。
• Versatile Synthesis of 4-Methylidenepyrazolidin-3-ones Using a Horner–Wadsworth–Emmons Approach
  作者：Tomasz Janecki、Jakub Modranka、Rafał Jakubowski

  DOI：10.1055/s-0033-1340071

  日期：——

  A new, versatile method for the synthesis of, so far unknown, variously substituted 4-methylidenepyrazolidin-3-ones as potential cytotoxic agents is described. Target compounds were synthesized from the corresponding 4-diethoxyphosphorylpyrazolidin-3-ones which were used as Horner-Wadsworth-Emmons reagents for the olefination of formaldehyde. 4-Phosphorylpyrazolidin-3-ones were, in turn, obtained starting from the sodium salt of ethyl 2-diethoxyphosphoryl-3-hydroxy-2-propenoate, ethyl 2-acyl-2-diethoxyphosphorylacetates, or 3-methoxy-2-diethoxyphosphorylacrylate and monosubstituted or 1,2-disubstituted hydrazines.
• A New Synthesis of 2-Aryl-2-Oxoalkylphosphonates from Triethyl Phosphonoacetate
  作者：Dae Young Kim、Myeon Sik Kong、Dae Yong Rhie

  DOI：10.1080/00397919508011834

  日期：1995.9

  Acylation of triethyl phosphonoacetate using magnesium ethoxide affords acyl phosphonoacetates which, on treatment with catalytic p-TsOH in water, are converted into 2-aryl-2-oxoalkylphosphonates.
• A Practical Synthesis of β-Keto Phosphonates from Triethyl Phosphonoacetate
  作者：Dae Young Kim、Myeon Sik Kong、Taek Hyeon Kim

  DOI：10.1080/00397919608004561

  日期：1996.7

  An efficient and practical preparation of beta-keto phosphonates, via acylation reaction of triethyl phosphonoacetate with carboxylic acid chlorides in the presence of magnesium chloride-triethylamine followed by decarbethoxylation, is described.
• On A Safe and Practical Method for The Preparation of β-Keto Phosphonates¹
  作者：Bernard Corbel、Isabelle L'Hostis-Kervella、Jean-Pierre Haelters

  DOI：10.1080/00397919608004568

  日期：1996.7

  Acylations of the magnesium enolate derivatives of trimethyl and triethylphosphonoacetates, using a magnesium chloride-triethylamine system, lead to 2-acylphosphonoacetates which are decarbalkoxylated to give beta-keto phosphonates.