diethyl 2-(amino(phenyl)methylene)malonate | 97652-62-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: diethyl 2-(amino(phenyl)methylene)malonate
• 英文别名: diethyl 2-[amino(phenyl)methylene]malonate；diethyl aminophenylmethylidenemalonate；diethyl phenylaminomethylenemalonate；Diethyl [amino(phenyl)methylidene]propanedioate；diethyl 2-[amino(phenyl)methylidene]propanedioate
• CAS: 97652-62-5
• 化学式: C₁₄H₁₇NO₄
• 分子量: 263.293
• InChiKey: VMYREASMFNIMEB-UHFFFAOYSA-N

物化性质

• 沸点：
  382.0±42.0 °C(Predicted)
• 密度：
  1.161±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  78.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-(amino(phenyl)methylene)malonate 在 (二氯碘)-苯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 以89%的产率得到diethyl (E)-2-chloro-2-[(chloroimino)(phenyl)methyl]malonate
  参考文献：
  名称：

  PhICl2-Mediated Conversion of Enamines into α,N-Dichloroimines and Their Reverse Conversion Mediated by Zinc in Methanol

  摘要：

  Treatment of enamine compounds with iodobenzene dichloride (PhICl2) conveniently gives a variety of alpha,N-dichloroimines in high yields. This approach allows the double insertion of the chloro moiety, which is postulated to take place via the iodobenzene dichloride mediated oxidative alpha-chlorination of the enamine substrates followed by further N-chlorination of the imine intermediates. Furthermore, the obtained alpha,N-dichloroimines could be converted reversely into the original enamines under reductive conditions using zinc in methanol.

  DOI：

  10.1055/s-0033-1341067
• 作为产物：
  描述：

  乙氧基甲叉丙二酸二乙酯 在 苯胺 作用下， 生成 diethyl 2-(amino(phenyl)methylene)malonate
  参考文献：
  名称：

  Pyrazoloquinolines

  摘要：

  2-芳基吡唑并[4-3-c]喹啉-3-酮，例如式##STR1##及其药用可接受的酰基衍生物或盐，是用于治疗焦虑或抑郁的精神活性剂。

  公开号：

  US04312870A1

文献信息

• Expanding Blaise-Type Reactions towards Indium-Mediated Transformations of α-Bromo-β-keto Esters with Nitriles
  作者：Luomo Li、Emre Babaoglu、Klaus Harms、Gerhard Hilt

  DOI：10.1002/ejoc.201700868

  日期：2017.8.24

  brominated β-keto esters with nitriles to generate enamino-substituted keto esters. The best results were obtained when a combination of indium metal (0.7 equiv.) with indium trichloride (1.6 equiv.) were applied at 60 °C for 20 to 72 hours, and these conditions could be applied to a broad range of nitriles and a significant number of different β-keto esters. The transformation of aliphatic nitriles proved

  这项工作的目的是确定溴化 β-酮酯与腈的 Blaise 型转化以生成烯氨基取代的酮酯的温和反应条件。将铟金属（0.7 当量）与三氯化铟（1.6 当量）的组合在 60 °C 下应用 20 到 72 小时可获得最佳结果，并且这些条件可应用于广泛的腈类和大量不同的β-酮酯。脂肪腈的转化被证明是困难的并且仅产生中等的产率。然而，在许多情况下，芳香腈的产率很高。β-酮酯的适用范围是可以接受的，而酮酯上的一些缺电子芳基取代基是具有挑战性的底物。尽管如此，
• Synthesis of β-enaminodicarbonyl derivatives in the titanium(<scp>iv</scp>) chloride-promoted reactions of β-dicarbonyl compounds with nitriles
  作者：Shuchen Pei、Chenchen Xue、Li Hai、Yong Wu

  DOI：10.1039/c4ra05100a

  日期：——

  Titanium(IV) chloride selectively promoted the nucleophilic attack of ethyl acetoacetate with nitriles to give enaminoketoesters, which were valuable intermediates for the syntheses of 2,3,4-substituted heterocyclics. Moreover a plausible mechanism for this transformation was given.

  氯化钛（IV）选择性地促进了乙腈对乙酰乙酸乙酯的亲核攻击，生成了烯氨基酮酸酯，这是合成2,3,4-取代杂环的有价值的中间体。此外，给出了这种转化的合理机制。
• Indium-Mediated Blaise-Type Reaction of Bromomalonates with Nitriles and Isocyanates
  作者：Gerhard Hilt、Emre Babaoglu、Klaus Harms

  DOI：10.1055/s-0035-1561973

  日期：——

  The indium-mediated Blaise-type reaction of bromomalonates with nitriles and isocyanates is described. The choice of the solvent is crucial for the successful reaction; the dependency on dichloromethane proved to be nonplussed. The reaction with nitriles led to the corresponding β-enamino diesters in moderate to good yields. The conversion with isocyanates generated carbamoyl malonates in good to excellent

  描述了溴丙二酸酯与腈和异氰酸酯的铟介导的 Blaise 型反应。溶剂的选择是反应成功的关键；事实证明，对二氯甲烷的依赖是无法理解的。与腈的反应以中等至良好的产率产生相应的 β-烯氨基二酯。与异氰酸酯的转化以良好到极好的产率生成氨基甲酰基丙二酸酯。两种反应都耐受有关电子性质的各种官能团。此外，由异氰酸异氰酸甲酯或异氰酸二异丙基苯酯引起的起始材料中的空间位阻也能很好地耐受。此外，还描述了一个连续的三组分一锅反应序列，用于形成 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates，使该领域的未来研究成为可能。
• Preparation of α,β-dehydro-β-amino acid derivatives by tin-promoted addition of malonates to simple nitriles
  作者：Frank Scavo、Paul Helquist

  DOI：10.1016/s0040-4039(00)98113-9

  日期：1985.1

  Simple aliphatic and aromatic nitriles undergo reaction with malonate esters in the presence of tin(IV) chloride to give derivatives of α,β-dehydro-β-amino acids. The same products are obtained through use of bromomalonate esters.

  简单的脂族和芳族腈在氯化锡（IV）的存在下与丙二酸酯反应，得到α，β-脱氢-β-氨基酸的衍生物。通过使用溴代丙二酸酯可以得到相同的产物。
• Ultrasound-Assisted Synthesis of β-enaminone Derivatives via Tin(IV)- Catalyzed Addition Reaction from β-dicarbonyl Compounds with Nitriles
  作者：Ziqiang Li、Shuchen Pei、Jinhua Yang、Jieyu Wang、Kangyao Yuan

  DOI：10.2174/1570178619666211221141854

  日期：2022.6

  An efficient and eco-friendly approach for the synthesis of β-enaminone derivatives is described by adding nitriles with β-dicarbonyl compounds under ultrasound irradiation conditions at room temperature. The scope and limitation of this strategy are also discussed. A variety of substituted amides can be obtained in moderate to good yields. We hope that this protocol for the efficient synthesis of β-enaminones will offer insights into further investigations.

  摘要：本文描述了一种高效、环保的方法，用于在室温下，通过超声辐射条件下将腈与β-二羰基化合物添加，合成β-烯酰胺衍生物。还讨论了这种策略的范围和限制。可以获得多种取代酰胺，收率中等到良好。我们希望这种β-烯酰胺高效合成方案能为进一步研究提供启示。