diethyl [2-(methoxycarbonyl)ethyl]malonate | 5331-68-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl [2-(methoxycarbonyl)ethyl]malonate
• 英文别名: (Diethyl-3-methyl)-1,1,3-propantricarboxylat；diethyl (2-methoxycarbonylethyl)malonate；propane-1,1,3-tricarboxylic acid-1,1-diethyl ester-3-methyl ester；Propan-1,1,3-tricarbonsaeure-1,1-diaethylester-3-methylester；Propan-1.1-dicarbonsaeurediaethylester-3-carbonsaeuremethylester；β-Carbmethoxy-ethylmalonsaeure-diethylester；1,1-Diethyl 3-methyl propane-1,1,3-tricarboxylate；1-O,1-O-diethyl 3-O-methyl propane-1,1,3-tricarboxylate
• CAS: 5331-68-0
• 化学式: C₁₁H₁₈O₆
• 分子量: 246.26
• InChiKey: HRDIKQFHFOTXDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  17
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  diethyl [2-(methoxycarbonyl)ethyl]malonate 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 0.5h， 生成 1-bromo-propane-1,1,3-tricarboxylic acid-1,1-diethyl ester-3-methyl ester
  参考文献：
  名称：

  Michael additions: a regioselective approach to the synthesis of spirothiazolidinones

  摘要：

  Novel routes to the synthesis of spirothiazolidinones have been designed using a Michael addition reaction Followed by a Dieckmann condensation and a Claisen type condensation reaction. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00973-5
• 作为产物：
  描述：

  在 碘 作用下， 以 二甲基亚砜 为溶剂， 反应 0.5h， 以51%的产率得到diethyl [2-(methoxycarbonyl)ethyl]malonate
  参考文献：
  名称：

  First Iodine-Catalyzed Deallylation of Reactive Allyl Methylene Esters

  摘要：

  C-Allyl cleavage has been developed using the inexpensive and mild reagent iodine in dimethylsulfoxide. A variety of compounds with active methylene groups were C-deallylated using this reagent. This method is efficient and operationally simple in comparison to the methods using transition-metal complexes. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications (R) to view the free supplemental file.

  DOI：

  10.1080/00397911.2012.682245

文献信息

• Merrifield Resin−C₆H₄CH₂N₃P(MeNCH₂CH₂)₃N:  An Efficient Reusable Catalyst for Room-Temperature 1,4-Addition Reactions and a More Convenient Synthesis of Its Precursor P(MeNCH₂CH₂)₃N
  作者：Reddy、John G. Verkade

  DOI：10.1021/jo062505z

  日期：2007.4.1

  donors were efficiently catalyzed at room temperature by the title reusable Merrifield resin-supported catalyst. Advantages of this catalyst include a simple workup (filtration of the reaction mixture) and good to excellent product yields. We also report a substantially simplified synthesis of the commercially available strong nonionic base 1, a precursor to the title polymer-bound catalyst.

  室温下，标题为可重复使用的Merrifield树脂负载的催化剂可有效地催化1,4-加成物中具有多种供体的多种Michael受体。该催化剂的优点包括简单的后处理（反应混合物的过滤）和良好至极好的产物产率。我们还报告了商业上可获得的强非离子碱1的大幅简化合成，该碱是标题聚合物结合的催化剂的前体。
• Preparation and Reactivities of (η³-1- and 2-Trimethylsiloxyallyl)Fe(CO)₂NO Complexes. Intermediates Functioning as Equivalents of β- and α-Acyl Carbocations and Acyl Carbanions
  作者：Keiji Itoh、Saburo Nakanishi、Yoshio Otsuji

  DOI：10.1246/bcsj.64.2965

  日期：1991.10

  (η3-1- and 2-Trimethylsiloxyallyl)Fe(CO)2NO complexes were prepared by the reaction of the corresponding siloxyallylic halides with Bu4N[Fe(CO)3NO]. These complexes reacted with both of carbon nucleophiles and carbon electrophiles preferentially at the less hindered sites of the allylic ligands. In these reactions, (η3-1-trimethylsiloxyallyl)Fe(CO)2NO complexes served as synthetically equivalent synthons

  (η3-1-和2-三甲基甲硅烷氧基烯丙基)Fe(CO)2NO配合物是通过相应的甲硅烷氧基烯丙基卤化物与Bu4N[Fe(CO)3NO]反应制备的。这些配合物优先与碳亲核试剂和碳亲电试剂在烯丙基配体的受阻较小的位点反应。在这些反应中，(η3-1-三甲基甲硅烷氧基烯丙基)Fe(CO)2NO 配合物作为 β-酰基碳正离子和 j8-酰基碳负离子和 (η3-2-三甲基甲硅烷氧基烯丙基)Fe(CO)2NO 配合物的合成等效合成子α-酰基碳正离子和α-酰基碳负离子。描述了反应的立体化学过程。
• Carbon dioxide as a reversible amine-protecting agent in selective Michael additions and acylations
  作者：Annelies Peeters、Rob Ameloot、Dirk E. De Vos

  DOI：10.1039/c3gc40568k

  日期：——

  solution of a sufficiently basic primary amine at room temperature and atmospheric pressure. This reaction is employed for the protection of the amine functionality in several reactions at room temperature where inter- or intramolecular selectivity is desired. The concept is demonstrated for the selective Michael additions to methyl acrylate of a normally less reactive sulfonamide in the presence of a strong

  二氧化碳可以用作下列物质的临时保护基 胺类。一个氨基甲酸当CO 2鼓泡通过足够碱性的溶液时，可逆地形成伯胺在室温和大气压下。该反应在需要分子间或分子内选择性的室温下的几个反应中用于保护胺官能度。该概念已针对迈克尔的选择性添加而得到了证明。丙烯酸甲酯 通常反应性较小的 磺酰胺 在强大的存在下 胺 亲核试剂或环状 仲胺 在脂肪族存在下 伯胺，或在以下条件下存在的β-酮酸酯 胺类。选择性的酰化 的 酒精 在一个 胺也可以在CO 2气氛下实现。
• Michael addition approach for the synthesis of novel spiro compounds and 2-substituted malonic acid derivatives from Meldrum’s acid
  作者：Madhukar S. Chande、Rahul R. Khanwelkar

  DOI：10.1016/j.tetlet.2005.09.030

  日期：2005.11

  Novel routes for the synthesis of spiro derivatives of Meldrum’s acid and 2-substituted malonic acid derivatives have been developed. Meldrum’s acid was monoalkylated using a Michael addition reaction. Mono-Michael adducts were then alkylated using substituted haloalkanes, which on condensation gave spiro derivatives of Meldrum’s acid. Bis Michael addition of Meldrum’s acid with 1,5-diaryl-1,4-pentadien-3-one

  已经开发了用于合成Meldrum的酸和2-取代的丙二酸衍生物的螺环衍生物的新途径。使用迈克尔加成反应将麦德鲁姆酸单烷基化。然后使用取代的卤代烷烃将单迈克尔加成物烷基化，该缩合的卤代烷烃在缩合后产生麦德鲁姆酸的螺环衍生物。Meldrum酸与1,5-二芳基-1,4-pentadien-3-one的Bis Michael加成直接得到Meldrum酸的螺环衍生物。这些化合物和双烷基化的麦德鲁姆酸衍生物，在酸性甲醇分解作用下，得到2-取代的丙二酸。
• Diversity in Modes of Reactions of (η³-1-Trimethylsiloxyallylic)Fe(CO)₂NO Complexes. Nucleophilic Addition and Cyclization on the Allylic Ligands
  作者：Keiji Ito、Saburo Nakanishi、Yoshio Otsuji

  DOI：10.1246/cl.1988.473

  日期：1988.3.5

  The titled iron complexes derived from 3-iodo-1-trimethylsiloxypropenes and [Bu4N][Fe(CO)3NO] reacted with carbon nucleophiles such as NaCH(CO2Et)2 to give the corresponding nucleophile addition products in high yields. The addition occurred at the 3-position of the ligands with high regioselectivity. However, the iron complexes derived from 2-alkyl-3-iodo-1-trimethylsiloxypropenes underwent cyclization

  源自 3-iodo-1-trimethylsiloxypropenes 和 [Bu4N][Fe(CO)3NO] 的标题铁配合物与碳亲核试剂如 NaCH(CO2Et)2 反应，以高产率得到相应的亲核试剂加成产物。添加发生在具有高区域选择性的配体的 3 位。然而，衍生自 2-烷基-3-碘-1-三甲基甲硅烷氧基丙烯的铁配合物与相同的甲硅烷氧基丙烯发生环化反应，得到二氢吡喃衍生物。讨论了铁配合物反应模式的多样性。