ethyl methyl malonate | 6186-89-6

• 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: ethyl methyl malonate
• 英文别名: methyl ethyl malonate；1-Ethyl 3-methyl malonate；3-O-ethyl 1-O-methyl propanedioate
• CAS: 6186-89-6
• 化学式: C₆H₁₀O₄
• 分子量: 146.143
• InChiKey: LIRDIZPKBSSVBK-UHFFFAOYSA-N

物化性质

• 熔点：
  70-71.5 °C(Solv: ligroine (8032-32-4))
• 沸点：
  189 °C
• 密度：
  1.0637 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• 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：

  ethyl methyl malonate 在 二甲基硫 、 sodium hydride 、 臭氧 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 28.08h， 生成 Methyl (+/-)-(Z)-7-(ethoxycarbonyl)-7-methyl-2-octenedioate
  参考文献：
  名称：

  Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions

  摘要：

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.

  DOI：

  10.1021/jo00077a043
• 作为产物：
  描述：

  ethyl-3-imino-3-methoxy propionate hydrochloride 在 盐酸 作用下， 反应 0.25h， 以69%的产率得到ethyl methyl malonate
  参考文献：
  名称：

  Kavalek, Jaromir; Panchartek, Josef; Potesil, Tomas, Collection of Czechoslovak Chemical Communications, 1986, vol. 51, # 3, p. 677 - 683

  摘要：

  DOI：

文献信息

• One-by-one hydrogenation, cross-coupling reaction, and Knoevenagel condensations catalyzed by PdCl2 and the downstream palladium residue
  作者：Hu Wang、Li Li、Xing-Feng Bai、Wen-Hui Deng、Zhan-Jiang Zheng、Ke-Fang Yang、Li-Wen Xu

  DOI：10.1039/c3gc40991k

  日期：——

  A novel catalyst-economic strategy with a recovered palladium catalyst was successfully applied for multi-task and maximum reuse in different types of one-by-one downstream reactions, from catalytic hydrogenation to Suzuki and Sonogashira-type cross-coupling reactions, Knoevenagel condensations, and trans-Knoevenagel-like condensations.

  一种新型催化剂经济策略，采用回收的钯催化剂，成功应用于多种一一对应的下游反应中，实现了从催化氢化到铃木型、Sonogashira型交叉偶联反应、Knoevenagel缩合反应以及类似trans-Knoevenagel缩合反应的多任务和最大化重复利用。
• Décomposition du percarbonate de<i>O</i>,<i>O</i>-<i>t</i>-butyle et<i>O</i>-isopropényle en solution: Acétonylation des esters, acides et nitriles
  作者：Robert Lalande、Claude Filliatre、Jean-Jacques Villenave、Rabih Jaouhari

  DOI：10.1002/hlca.19840670118

  日期：1984.2.1

  The Free-Radical Decomposition of O,O-t-Butyl and O-Isopropenyl Peroxycarbonate in Solution: the Acetonylation of Esters, Acides and Nitriles

  的自由基分解Ø，Ô -牛逼丁基和Ø异丙烯氧化碳的解决方案：酯类的酸酐和腈的Acetonylation
• Copper-Mediated Trifluoromethylation of α-Diazo Esters with TMSCF₃: The Important Role of Water as a Promoter
  作者：Mingyou Hu、Chuanfa Ni、Jinbo Hu

  DOI：10.1021/ja307058c

  日期：2012.9.19

  Copper-mediated trifluoromethylation of α-diazo esters with TMSCF(3) reagent has been developed as a new method to prepare α-trifluoromethyl esters. This trifluoromethylation reaction represents the first example of fluoroalkylation of a non-fluorinated carbene precursor. Water plays an important role in promoting the reaction by activating the "CuCF(3)" species prepared from CuI/TMSCF(3)/CsF (1.0:1

  铜介导的 α-重氮酯与 TMSCF(3) 试剂的三氟甲基化已被开发作为制备 α-三氟甲酯的新方法。这种三氟甲基化反应代表了非氟化卡宾前体氟烷基化的第一个例子。水通过激活由 CuI/TMSCF(3)/CsF (1.0:1.1:1.1) 制备的“CuCF(3)”物种，在促进反应中发挥重要作用。这种三氟甲基化反应的范围很广，在合成各种芳基、苄基和烷基取代的 3,3,3-三氟丙酸酯中证明了其效率。
• Cu(II)-Catalyzed Coupling of Aromatic C–H Bonds with Malonates
  作者：Hong-Li Wang、Ming Shang、Shang-Zheng Sun、Zeng-Le Zhou、Brian N. Laforteza、Hui-Xiong Dai、Jin-Quan Yu

  DOI：10.1021/acs.orglett.5b00193

  日期：2015.3.6

  A new Cu(II)-catalyzed oxidative coupling of arenes with malonates has been developed using an amide-oxazoline directing group. The reaction proceeds via C(sp2)–H activation and malonate coupling, followed by intramolecular oxidative N–C bond formation. A variety of arenes bearing different substituents are shown to be compatible with this reaction.

  使用酰胺-恶唑啉指导基团开发了一种新的Cu（II）催化芳烃与丙二酸酯的氧化偶联。该反应通过C（sp 2）–H活化和丙二酸酯偶联进行，随后形成分子内氧化性N–C键。显示了带有不同取代基的多种芳烃与该反应相容。
• PEG/ZnBr2-Assisted Multicomponent Reactions: A Novel Procedure for the Synthesis of Functionalized 5,6-Dihydropyran-2-ones
  作者：Mehdi Khalaj、Nasrin Farahani、Mahdieh Sadeghpour、Halimeh Rajabzadeh、Seyed Khatami

  DOI：10.1055/s-0036-1591760

  日期：2018.4

  We report a catalytic multicomponent reaction of isocyanides, oxiranes, and malonates under mild conditions, allowing the transformation of a wide range of substrates into 5,6-dihydropyran-2-one products in acceptable yields. We have also examined the leaving group selectivity using an unsymmetrical malonate. This novel method demonstrates the benefits of combining different activation modes in oxiranes

  我们报告了异氰化物、环氧乙烷和丙二酸酯在温和条件下的催化多组分反应，允许以可接受的产率将各种底物转化为 5,6-二氢吡喃-2-one 产物。我们还使用不对称丙二酸酯检查了离去基团的选择性。这种新方法展示了在环氧乙烷中结合不同活化模式的好处。