3-(1,3-dimethoxy-1,3-dioxopropan-2-yl)-1,3-dihydro-2-benzofuran-1-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 3-(1,3-dimethoxy-1,3-dioxopropan-2-yl)-1,3-dihydro-2-benzofuran-1-one
• 英文别名: dimethyl 2-(1,3-dihydro-1-oxoisobenzofuran-3-yl)malonate；dimethyl 2-(3-oxo-1H-2-benzofuran-1-yl)propanedioate
• 化学式: C₁₃H₁₂O₆
• 分子量: 264.235
• InChiKey: LDNCPEJSHAVIFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-醛基苯甲酸甲酯 、 丙二酸二甲酯 在 三乙胺 作用下， 以99%的产率得到3-(1,3-dimethoxy-1,3-dioxopropan-2-yl)-1,3-dihydro-2-benzofuran-1-one
  参考文献：
  名称：

  基于 β-二酮酸酯-3-取代苯酞（异苯并呋喃酮）和异吲哚啉酮的新型 Cu(II)、Fe(III)、Al(III) 和 Zn(II) 螯合剂

  摘要：

  紫外-可见光谱研究强调了β-二酮-3-取代的苯酞（异苯并呋喃酮）或异吲哚啉酮对Cu（II）、Fe（III）、Al（III）和Zn（II）盐的络合能力。相反，用丙二酸二甲酯取代的杂环类似物没有表现出络合能力。平衡常数和分布图的确定提供了进一步的见解，而 Cu(II)-β-二酮酸-异吲哚啉酮复合物的合成、分离和表征已通过标准程序的方便修改实现。此外，还讨论了配体生物利用度的计算机模拟评估，以用于潜在的药理学应用。图形概要

  DOI：

  10.1080/00958972.2014.939075

文献信息

• Oxidative cyclization of dialdehydes with alcohols and 1,3-dicarbonyl compounds under Rh(III)/Cu(II) conditions
  作者：Takanori Matsuda、Kentaro Suzuki、Shinya Abe、Haruki Kirikae、Noboru Okada

  DOI：10.1016/j.tet.2015.10.034

  日期：2015.12

  For the preparation of 3-alkoxyphthalides from phthalaldehydes and alcohols, a cyclization reaction in the presence of a rhodium(III) catalyst and copper(II) salt is reported. Cyclization of phthalaldehydes also occurs with 1,3-dicarbonyl compounds under similar conditions to produce 3-substituted phthalides in good yields. An acylrhodium(III) species might be a key intermediate in these cyclization

  对于从phthalaldehydes和醇3- alkoxyphthalides制备，则报告在铑（III）催化剂和铜的存在下进行环化反应（II）盐。phthalaldehydes的环化也会发生与在类似条件下的1,3-二羰基化合物，以良好的产率生产3-取代的苯酞。酰基铑（III）可能是这些环化反应中的关键中间体。
• Ring-Chain Tautomerism in 2-(2,2-Dicyano-1-methylethenyl)benzoic Acid and Related Compounds.
  作者：Per Kolsaker、Joe Arukwe、József Barcóczy、Are Wiberg、Anne Kristine Fagerli、Ole Hammerich、Inger Søtofte、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0490

  日期：——

  Ring-chain tautomerism with slow interconversion (compared with the NMR timescale) was observed in solutions of 2-(2,2-dicyano-1-methylethenyl)benzoic acid (3e), obtained by Knoevenagel condensation of 2-acetylbenzoic acid with malononitrile, forming the ring tautomer 3-dicyanomethyl-3-methylphthalide (4e) in admixture with 3e. Similar condensations of 2-formylbenzoic acid with methyl cyanoacetate or malononitrile give 2-(2-cyano-2-methoxycarbonyl-ethenyl)benzoic acid (3b) and 2-(2,2-dicyanoethenyl)benzoic acid (3d), respectively, which in solution also exhibit the same tautomerism to give the ring tautomers, 3-(cyanomethoxycarbonylmethyl)phthalide (4d) and 3-(dicyanomethyl)phthalide (4d), respectively. Condensation of 2-formylbenzoic acid with dimethyl malonate gave only the ring compound, 3-(dimethoxycarbonylmethyl)phthalide (4a). Attempts to synthezise 2-(2-cyano-2-methoxycarbonyl-1-methylethenyl)benzoic acid (3c) by methylation of the trimethyl silylester of 3b with diazomethane led to the ring form of 3c, viz. 3-cyanomethoxycarbonylmethyl-3-methylphthalide (4c) as an equimolar mixture of two diastereomers. No tautomerism was observed when the benzene ring was replaced by a thiophene ring (7a, 7b and 8) or an aliphatic double bond (9). Solid state spectra (IR and NMR) indicated that all compounds carrying two cyano groups at the double bond, except the aliphatic compound 9, were in the open-chain form, while all the others were in the ring form. Equilibrium studies for compound (3e reversible arrow 4e) indicated increased stability for the chain form 4e with increasing solvent polarity. Determination of the free energy change, Delta G degrees, and of the free energy of activation, Delta G(double dagger), for the tautomerization in deuteriochloroform (using H-1 NMR spectroscopy) indicated that, in this solvent, a concerted process from the starting material 3e to the anion of 4e is taking place. It is also postulated that a similar reaction path is followed in the other solvents used in this investigation, all belonging to the solvent class 'protophobic dipolar aprotic solvents'.
• Active methylene compounds in a very effective approach to 3-substituted isobenzofuranones through tandem aldol/lactonization reactions
  作者：Antonia Di Mola、Gianluca Croce、Vijaykumar More、Paolo De Caprariis、Rosanna Filosa、Antonio Massa

  DOI：10.1016/j.tet.2012.05.079

  日期：2012.8

  In this article we describe a new accessible methodology for the synthesis of isobenzofuran-1(3H)-ones. In this process we exploited an effective, economic, useful and environmentally benign K2CO3 catalyzed, solvent-free one-pot tandem aldol-lactonization reaction between active methylene compounds and methyl 2-carboxy benzaldehyde. A particularly simple work-up and purification procedure are additional advantages addressed to a general green chemistry approach to this important class of heterocyclic compounds. (C) 2012 Elsevier Ltd. All rights reserved.
• New chelating agents for Cu(II), Fe(III), Al(III), and Zn(II) based on β-diketonate-3-substituted phthalide (isobenzofuranone) and isoindolinone
  作者：Luana Di Matteo、Olga Christodoulakis、Rosanna Filosa、Paolo De Caprariis、Antonia Di Mola、Ermanno Vasca、Antonio Massa

  DOI：10.1080/00958972.2014.939075

  日期：2014.7.3

  isoindolinones toward Cu(II), Fe(III), Al(III), and Zn(II) salts has been highlighted by UV–vis spectroscopic studies. Conversely, heterocyclic analogs substituted with dimethyl malonate showed no complexing ability. Further insights have been given by the determination of equilibrium constants and distribution diagram, while the synthesis, isolation, and characterization of Cu(II)-β-diketonate-isoindolinone

  紫外-可见光谱研究强调了β-二酮-3-取代的苯酞（异苯并呋喃酮）或异吲哚啉酮对Cu（II）、Fe（III）、Al（III）和Zn（II）盐的络合能力。相反，用丙二酸二甲酯取代的杂环类似物没有表现出络合能力。平衡常数和分布图的确定提供了进一步的见解，而 Cu(II)-β-二酮酸-异吲哚啉酮复合物的合成、分离和表征已通过标准程序的方便修改实现。此外，还讨论了配体生物利用度的计算机模拟评估，以用于潜在的药理学应用。图形概要