(dimethyl 2-benzoylmalonate) | 24821-06-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (dimethyl 2-benzoylmalonate)
• 英文别名: Dimethyl benzoylmalonate；dimethyl 2-benzoylpropanedioate
• CAS: 24821-06-5
• 化学式: C₁₂H₁₂O₅
• 分子量: 236.224
• InChiKey: MSPBDOIUNJDTJR-UHFFFAOYSA-N

物化性质

• 熔点：
  36.5 °C
• 沸点：
  168-171 °C(Press: 2 Torr)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (dimethyl 2-benzoylmalonate) 生成 2-(Hydroxy-phenyl-methylene)-malonic acid dimethyl ester
  参考文献：
  名称：

  ROMAS, A. D.;PETROV, A. A.;ERSHOV, B. A., ZH. ORGAN. XIMII, 1985, 21, N 7, 1372-1377

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(Hydroxy-phenyl-methylene)-malonic acid dimethyl ester 生成 (dimethyl 2-benzoylmalonate)
  参考文献：
  名称：

  ROMAS, A. D.;PETROV, A. A.;ERSHOV, B. A., ZH. ORGAN. XIMII, 1985, 21, N 7, 1372-1377

  摘要：

  DOI：

文献信息

• Dimethyl malonate/LHMDS system as a new protocol for generating methyl formate anion (−COOMe) in the condensed-phase
  作者：Valeria Di Bussolo、Salvatore Princiotto、Elisa Martinelli、Vittorio Bordoni、Paolo Crotti

  DOI：10.1016/j.tetlet.2016.02.090

  日期：2016.4

  The treatment of dimethyl malonate with LHMDS in anhydrous THF (condensed-phase) generates, in addition to the expected corresponding lithium enolate, methyl formate anion (or methoxycarbonyl anion, −COOMe) which can react with several electrophiles to give corresponding methoxycarbonyl derivatives by nucleophilic substitution reaction.

  用LHMDS在无水THF（凝聚相）丙二酸二甲酯的治疗产生，除了预期的相应的烯醇化锂，甲酸甲酯阴离子（或甲氧基羰基阴离子，- COOMe），它可以与多个亲电反应，得到通过亲核对应甲氧基羰基衍生物取代反应。
• Photo-oxidative Cross-Dehydrogenative Coupling-Type Reaction of Thiophenes with α-Position of Carbonyls Using a Catalytic Amount of Molecular Iodine
  作者：Yusuke Sudo、Eiji Yamaguchi、Akichika Itoh

  DOI：10.1021/acs.orglett.7b00428

  日期：2017.4.7

  A metal-free photo-oxidative intermolecular C–H/C–H coupling reaction of thiophenes is demonstrated with carbonyls using a catalytic amount of molecular iodine. In this system, molecular oxygen in the air acted as a terminal oxidant to regenerate molecular iodine. A mechanistic study was also performed.

  使用催化量的分子碘，证明了羰基化合物与噻吩的无金属光氧化分子间C–H / C–H偶联反应。在该系统中，空气中的分子氧充当终端氧化剂，以再生分子碘。还进行了机理研究。
• Pd-catalyzed carbonylation for the construction of tertiary and quaternary carbon centers with sp3 carbon partners
  作者：Wei Lu、Yang Li、Chao Wang、Dong Xue、Jian-Gang Chen、Jianliang Xiao

  DOI：10.1039/c4ob00568f

  日期：——

  The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp3 carbon partners are presented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structurally unique carbonyl compounds. By employing 2-substituted 1,3-diesters, synthetically-challenging quaternary carbon centres were accessed. In total, 42 examples of aryl carbonyl compounds were prepared in moderate to good yields. The catalytic system features the use of a bidentated phosphine ligand and a relatively low CO pressure (5 atm), providing an easy, alternative method for the preparation of triketones.

  展示了使用Pd催化的芳基硼酸与sp3碳伙伴进行羰基化的首个示例。各种硼酸与1,3-二酯和1,3-二酮反应，生成了结构独特的羰基化合物。通过使用2-取代的1,3-二酯，成功获得了合成上具有挑战性的四级碳中心。总共合成了42种芳基羰基化合物，产率中等到良好。该催化系统采用了双联磷配体和相对较低的CO压力（5个大气压），为合成三酮提供了一种简单的替代方法。
• An unexpected formation of benzoyl benzoin from benzil during the attempted Knoevenagel type condensation with dimethylmalonate (or malononitrile)
  作者：M. Shyam Sundar、Ashutosh V. Bedekar

  DOI：10.1016/j.tetlet.2012.03.084

  日期：2012.5

  An unexpected product, 2-oxo-1,2-diphenylethyl benzoate (benzoyl benzoin), was isolated during the attempted Knoevenagel reaction of benzil and dimethylmalonate (or malononitrile) in the presence of potassium carbonate. The product was confirmed by spectral analysis as well as by single crystal studies and a mechanism is proposed to explain its formation.

  在苯甲酸和丙二酸二甲酯（或丙二腈）存在碳酸钾的情况下，在尝试的Knoevenagel反应过程中，分离出了意外的产物2-氧代-1,2-二苯乙基苯甲酸酯（苯甲酰基安息香）。通过光谱分析以及单晶研究证实了该产物，并提出了解释其形成的机理。
• Molecular structure and OH⋯O hydrogen bond in 1-aryl-1,3-diketone malonates
  作者：Federico Jiménez-Cruz、Lubanski Fragoza Mar、Jose Luis García-Gutierrez

  DOI：10.1016/j.molstruc.2012.09.010

  日期：2013.2

  almost in a planar conformation. These results are well-supported by DFT B3LYP/6-31++G(d,p) calculations and MO analysis. These compounds are in the enol–keto (EK) tautomer. In comparison with a full π delocalized enolone (λQ = 0.5), diketones 1–4 have a EK π-delocalization in the O H⋯O moiety because of the λQ values are between 0.283 and 0.321 A and showing values of O⋯O length between 2.488 and 2.567 A

  摘要 通过分析在 293 K 下单晶 X 射线衍射实验获得的几何参数，研究了四种 1,3-二酮丙二酸酯 1-4 的分子结构，显示三个部分：芳环（4-取代苯基或萘基环） , H1O1C1C2C3O3 烯醇-酮 (EK) 系统和带有丙二酸二甲酯的线性链。在涉及 C6 的丙二酸部分中，未观察到可烯醇化的片段。两个第一部分（芳香环和烯醇酮系统）几乎处于平面构象。这些结果得到了 DFT B3LYP/6-31++G(d,p) 计算和 MO 分析的充分支持。这些化合物处于烯醇-酮 (EK) 互变异构体中。与完整的 π 离域烯醇酮 (λQ = 0.5) 相比，二酮 1-4 在 OH⋯O 部分具有 EK π-离域，因为 λQ 值介于 0.283 和 0 之间。