dimethyl (diethylamino)ethylene-1,2-dicarboxylate | 17459-44-8

• 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: dimethyl (diethylamino)ethylene-1,2-dicarboxylate
• 英文别名: 2-(diethylamino)dimethyl succinate；N,N-Diaethyl-asparaginsaeure-dimethylester；N,N-diethyl-D,L-aspartic acid dimethyl ester；N,N-diethyl-aspartic acid dimethyl ester；dimethyl 2-(diethylamino)butanedioate
• CAS: 17459-44-8
• 化学式: C₁₀H₁₉NO₄
• 分子量: 217.265
• InChiKey: PQHYYXVASCGPFJ-UHFFFAOYSA-N

物化性质

• 沸点：
  64 °C(Press: 0.3 Torr)
• 密度：
  1.043±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  二乙胺 、 1,4-dimethyl but-2-enedioate 在 poly((2-methyl-5-sulfonylphenyl)methyl) 作用下， 反应 0.42h， 以93%的产率得到dimethyl (diethylamino)ethylene-1,2-dicarboxylate
  参考文献：
  名称：

  Highly efficient procedure for the conjugate addition of amines to electron deficient alkenes

  摘要：

  The novel efficient procedure has been developed for the conjugate addition of amines to electron deficient alkenes. The results showed that the catalyst was very efficient for the reactions with the excellent yields in several minutes. Operational simplicity, without need of any solvent, low cost of the catalyst used, high yields, reusability, excellent chemoselectivity, applicability to large-scale reactions are the key features of this methodology. The article is published in the original.

  DOI：

  10.1134/s0023158410020096

文献信息

• Formation of Acyl-Substituted Nitrile Ylides by Rh₂(OAc)₄-Catalyzed Decomposition of<i>α</i>-Diazocarbonyl Compounds in Nitriles
  作者：Kazuaki Fukushima、Toshikazu Ibata

  DOI：10.1246/bcsj.68.3469

  日期：1995.12

  The Rh2(OAc)4-catalyzed reactions of α-diazocarbonyl compounds in nitrile in the presence of dimethyl acetylenedicarboxylate (DMAD) gave oxazole and pyrrole derivatives. The formation of the oxazole derivatives is explained in terms of the 1,5-cyclization of an acyl-substituted nitrile ylide intermediate, and the formation of the pyrrole derivatives is explained by the 1,3-dipolar cycloaddition of

  在乙炔二羧酸二甲酯 (DMAD) 存在下，α-重氮羰基化合物在腈中的 Rh2(OAc)4 催化反应得到恶唑和吡咯衍生物。恶唑衍生物的形成通过酰基取代的腈叶立德中间体的 1,5-环化来解释，吡咯衍生物的形成通过相同中间体与 DMAD 的 1,3-偶极环加成来解释。酰基取代的腈叶立德与丙炔酸甲酯的环加成反应的区域化学表明，丙炔基型共振结构的贡献在酰基取代的腈叶立德反应中起重要作用。
• An efficient biomaterial supported bifunctional organocatalyst (ES-SO3− C5H5NH+) for the synthesis of β-amino carbonyls
  作者：Sanny Verma、Suman L. Jain、Bir Sain

  DOI：10.1039/c0ob00965b

  日期：——

  A biomaterial supported organocatalyst, readily synthesized by the reaction of chemically modified sulfonic group containing expanded corn starch with pyridine exhibited excellent catalytic activity for the synthesis of β-amino carbonyls in excellent yields via aza-Michael addition of amines to electron deficient alkenes. A remarkable enhancement in the reaction rates was observed with the prepared bifunctional organocatalyst in comparison to the either starch grafted sulfonic acid or the corresponding homogeneous pyridinium p-toluenesulfonate.

  一种由化学改性的含磺酸基团的膨胀玉米淀粉与吡啶反应合成的生物材料负载型有机催化剂，在胺与缺电子烯烃的aza-Michael加成反应中，表现出优异的催化活性，可高效合成β-氨基羰基化合物。与淀粉接枝磺酸酸或相应的均相吡啶盐-对甲苯磺酸盐相比，所制备的双功能有机催化剂显著提高了反应速率。
• Functionalized Cyclobutenes via Multicomponent Thermal [2 + 2] Cycloaddition Reactions
  作者：Helen M. Sheldrake、Timothy W. Wallace、Craig P. Wilson

  DOI：10.1021/ol051675f

  日期：2005.9.1

  [reaction: see text] Enamine [2 + 2] cycloadditions can be achieved in useful yields simply by stirring a mixture of an aldehyde, diethylamine, a dialkyl fumarate, and potassium carbonate in acetonitrile at 25 degrees C, conditions that are compatible with the presence of a potential leaving group on the beta-position of the intermediate enamine. Methylation and elimination of the product cyclobutanes

  [反应：见正文]烯胺[2 + 2]的环加成反应可通过在25°C下在与乙腈相容的条件下搅拌乙醛，二乙胺，富马酸二烷基酯和碳酸钾在乙腈中的混合物来实现在中间体烯胺的β位上存在潜在的离去基团。甲基化和产物环丁烷的消除完成了温和的非光化学路线，从而实现了官能化的环丁烯。
• Insights into post-polymerisation modification of bio-based unsaturated itaconate and fumarate polyesters via aza-michael addition: Understanding the effects of CC isomerisation
  作者：T. J. Farmer、D. J. Macquarrie、J. W. Comerford、A. Pellis、J. H. Clark

  DOI：10.1002/pola.29079

  日期：2018.9.1

  renewable bio‐based unsaturated polyesters is undergoing a renaissance, typified by the use of itaconate and fumarate monomers. The electron‐deficient CC bond found on the corresponding polyesters allows convenient post‐polymerisation modification to give a wide range of polymer properties; this is notably effective for the addition of nucleophilic pendants. However, preservation of unsaturated functionality

  可再生生物基不饱和聚酯的开发正在经历复兴，以衣康酸酯和富马酸酯单体的使用为代表。相应聚酯上的缺电子 C-C 键可以方便地进行聚合后改性，从而获得广泛的聚合物性能；这对于添加亲核侧链特别有效。然而，不饱和官能团的保留受到两种不良副反应的影响，即支化/交联和 C-C 异构化。在此，对衣康酸和富马酸二酯模型中二乙胺加成的初步动力学研究强调了不良 C-C 异构化的重要性。特别是，它表明从衣康酸酯到中康酸酯（一种较差的迈克尔受体）的可逆异构化与氮杂迈克尔加成直接竞争，其中胺迈克尔供体充当异构化催化剂。我们假设中康酸酯的不良形成是导致先前报道的衣康酸酯聚酯聚合后改性反应时间长的原因。这项研究表明迫切需要克服 C-C 异构化问题，以增强生物基不饱和聚酯的聚合后改性。© 2018 Wiley periodicals, Inc. J. Polym。科学，A 部分：聚合物。化学。2018 , 56 , 1935–1945
• Pfau,M., Bulletin de la Societe Chimique de France, 1967, p. 1117 - 1125
  作者：Pfau,M.

  DOI：——

  日期：——