4-(二甲氧基磷酰基)-3-氧代丁酸乙酯 | 103517-82-4

• 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
• 中文名称: 4-(二甲氧基磷酰基)-3-氧代丁酸乙酯
• 英文名称: ethyl 4-(dimethoxyphosphinyl)-3-oxobutanoate
• 英文别名: 4-(dimethoxyphosphoryl)-3-oxobutanoic acid ethyl ester；ethyl 4-(dimethoxyphosphoryl)-3-oxobutanoate；ethyl 4-dimethoxyphosphoryl-3-oxobutanoate
• CAS: 103517-82-4
• 化学式: C₈H₁₅O₆P
• 分子量: 238.177
• InChiKey: SEGFHJCBKZOWCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  4-(二甲氧基磷酰基)-3-氧代丁酸乙酯 在 ammonium acetate 、 sodium hydride 、 sulfur 、 溶剂黄146 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  Novel aminophosphonothiophene derivatives from β-keto-δ-carbethoxyphosphonates and phosphineoxides

  摘要：

  The reaction of -keto--carbethoxyphosphonates and phosphineoxides with active methylene nitriles leads to the corresponding phosphonoalkylidenes. Treatment of these compounds with sulfur, under the classical Gewald reaction conditions, gives a ca. 1:1 mixture of novel aminophosphonothiophene derivatives 3 and 3'. In order to improve the regioselectivity of the reaction, novel conditions have been developed for the Gewald condensation, in which we used an inorganic base NaH in THF as the solvent. These conditions afforded exclusively the 3-regioisomer in good yield. [image omitted].

  DOI：

  10.1080/17415993.2011.570763
• 作为产物：
  描述：

  4-(Dimethoxy-phosphoryl)-3-(methoxycarbonyl-hydrazono)-butyric acid ethyl ester 在 盐酸 、 丙酮 作用下， 反应 3.0h， 以67%的产率得到4-(二甲氧基磷酰基)-3-氧代丁酸乙酯
  参考文献：
  名称：

  An Efficient Synthesis of Dialkyl 2-Oxoalkanephosphonates and Diphenyl-2-oxoalkylphosphine Oxides from 1-Chloralkyl Ketones

  摘要：

  介绍了通过三烷基亚磷酸酯或乙氧基二苯基膦与 1-氯烷基酮的甲氧基羰基肼衍生物的 Arbuzov 反应，然后进行羰基脱保护，合成 2-氧代烷基膦酸二烷基酯和 2-氧代烷基膦氧化物的过程。

  DOI：

  10.1055/s-1985-31424

文献信息

• Enantioselective reduction of dialkyl 4-(dialkoxyphosphoryl)-3-oxobutanoates by baker's yeast
  作者：Chengye Yuan、Ke Wang、Jinfeng Li、Zuyi Li

  DOI：10.1002/hc.10011

  日期：——

  Dialkyl 4-(dialkoxyphosphoryl)-3-oxobutanoates (1), upon yeast-mediated bioreduction, afforded chiral dialkyl 4-(dialkoxyphosphoryl)-3-hydroxybutanoates (2) in moderate to good yields and ee values. Significant improvement was reported for the preparation of dialkyl 4-(dialkoxyphosphoryl)-3-oxobutanoates (1), the key substrates of this bioreductive conversion. © 2002 Wiley Periodicals, Inc. Heteroatom

  4-(二烷氧基磷酰基)-3-氧代丁酸二烷基酯 (1) 在酵母介导的生物还原作用下以中等至良好的产率和 ee 值提供手性二烷基 4-(二烷氧基磷酰基)-3-羟基丁酸酯 (2)。据报道，4-（二烷氧基磷酰基）-3-氧代丁酸二烷基酯 (1) 的制备得到了显着改进，这是该生物还原转化的关键底物。© 2002 Wiley Periodicals, Inc. 杂原子化学 13:153–156, 2002; 在线发表于 Wiley Interscience (www.interscience.wiley.com)。DOI 10.1002/hc.10011
• Unusual Course of the Reaction of Lawesson’s Reagent with β-Phosphoryl- β’-carbethoxyhydrazones: First Synthesis of 5-Mercapto-3-(methylthiophosphoryl) pyrazoles
  作者：Emna Chebil、Soufiane Touil

  DOI：10.2174/157017812801264764

  日期：2012.5.1

  It is well known that Lawesson’s reagent (LR) reacts with hydrazone derivatives at 80 °C to yield 3-thioxo- 1,2,3-diazaphospholine derivatives. We show, in the present investigation, that the reaction of LR with β- phosphoryl-β’-carbethoxyhydrazones under the same conditions, took an entirely different course and gave a new type of pyrazole derivatives, the 5-mercapto-3-(methylthiophosphoryl)pyrazoles

  众所周知，Lawesson试剂（LR）在80℃下与衍生物反应以产生3-硫代-1,2,3-二氮杂磷酸衍生物。在本研究中，我们表明，在相同条件下，LR与β-磷酰基-β'-乙氧基hydr肼的反应采用了完全不同的过程，并得到了一种新型的吡唑衍生物，即5-巯基-3-（甲硫基磷酰基）吡唑类。
• Synthesis of 6-styryldihydropyrimidinones and 6-styryldihydropyridinones via the respective 6-alkylphosphonates
  作者：Rufus Smits、Sergey Belyakov、Marina Petrova、Vladislav Kozhich、Ruslan Muhamadejev

  DOI：10.1007/s10593-023-03145-7

  日期：2022.12

  with 6-bromomethyl-3,4-dihydropyrimidin-2(1H)-one or analogous 6-bromomethyl-3,4-dihydropyridin-2(1H)-one provided the respective 6-alkylphosphonates in excellent yields. The heterocyclic alkylphosphonates are useful synthons in the Horner–Wadsworth–Emmons reaction for introducing a styryl moiety. Bromination of 6-methyl-4-phenyl-3,4-dihydropyridin-2(1H)-one with NBS in methanol resulted in an unexpected

  Arbuzov 反应中的亚磷酸三甲酯或三乙酯与 6-溴甲基-3,4-二氢嘧啶-2(1 H )-一或类似的 6-溴甲基-3,4-二氢吡啶-2(1 H )-一提供相应的 6-烷基膦酸盐以优异的收率。杂环烷基膦酸酯是 Horner-Wadsworth-Emmons 反应中用于引入苯乙烯基部分的有用合成子。在甲醇中用 NBS溴化 6-methyl-4-phenyl-3,4-dihydropyridin-2(1 H )-one 得到意想不到的化合物，而在氯仿中用溴溴化得到预期的 6-bromomethyl-3,4- dihydropyridin-2(1 H )-one，容易进行亲核取代。中间体和产物通过单晶X射线衍射验证。
• An Efficient Separation Method for Enol Phosphate and Corresponding β-Ketophosphonate from Their Mixtures Under Aqueous Conditions
  作者：Cornelis M. Moorhoff

  DOI：10.1081/scc-120021033

  日期：2003.7

  Separation of a mixture beta-ketophosphonate 3 and their corresponding enol phosphate 4 is efficiently carried out in aqueous alkaline solutions. Enol phosphate 4 is first extracted with hexanes:dichloromethane (19:1). Acidification of the aqueous layer followed by extraction of the beta-ketophosphonate 3 with dichloromethane completes the separation. Thus, when 1-bromo-2,4-pentadione 1a reacted with triethyl phosphite to give diethyl (2,4-dioxopentyl)phosphonate 3a (Arbuzov-product) and the corresponding enol phosphate 4a (Perkow-product), separation of the two compounds was carried out using this method.
• Behaviour of β-Keto-δ-carbethoxyphosphonates and Phosphine Oxides in the Biginelli Multicomponent Reaction: Regioselective Synthesis of 5-Carbethoxy-6-phosphonomethyl-3,4-dihydropyrimidin-2-ones
  作者：Soufiane Touil、Emna Chebil

  DOI：10.3987/com-12-12570

  日期：——

  An efficient one-pot synthesis of the novel 5-carbethoxy-6-phosphonomethyl-3,4-dihydropyrimidin-2-ones via a three-component Biginelli-type condensation of beta-keto-delta-carbethoxyphosphonates and phosphine oxides with aldehydes and urea in the presence of a catalytic amount of acetic acid, is described. The reaction proceeded efficiently at room temperature to afford regioselectively the title compounds in good to high yields. The factors governing the regioselectivity of the reaction are discussed.