1-(3,4-dimethoxyphenyl)propane-1,2-dione | 71367-49-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(3,4-dimethoxyphenyl)propane-1,2-dione
• 英文别名: 1-(3,4-Dimethoxy-phenyl)-propandion-(1,2)
• CAS: 71367-49-2
• 化学式: C₁₁H₁₂O₄
• 分子量: 208.214
• InChiKey: CWGHXUXZAZZJAA-UHFFFAOYSA-N

物化性质

• 熔点：
  67-68 °C
• 沸点：
  329.2±32.0 °C(Predicted)
• 密度：
  1.140±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  1-(3,4-dimethoxyphenyl)propane-1,2-dione 生成 藜芦酸
  参考文献：
  名称：

  GRABKINA, O. A.;BABKIN, V. A.;MEDVEDEVA, S. A.;IVANOVA, S. Z.;PAVLINSKIJ,+, XIMIYA DREVESINY,(1987) N 5, 34-40, 121, 122

  摘要：

  DOI：
• 作为产物：
  描述：

  3-acetoxy-1-(3,4-dimethoxy-phenyl)-propan-1-one 在 氯仿 、 溴 、 potassium acetate 、 potassium carbonate 、 溶剂黄146 、 丙酮 作用下， 生成 1-(3,4-dimethoxyphenyl)propane-1,2-dione
  参考文献：
  名称：

  Lindgren, Acta Chemica Scandinavica (1947), 1950, vol. 4, p. 641,646

  摘要：

  DOI：

文献信息

• [EN] SELECTIVE C-O BOND CLEAVAGE OF OXIDIZED LIGNIN AND LIGNIN-TYPE MATERIALS INTO SIMPLE AROMATIC COMPOUNDS<br/>[FR] COUPURE SÉLECTIVE DE LIAISON C-O DE LIGNINE OXYDÉE ET DE SUBSTANCES DE TYPE LIGNINE EN COMPOSÉS AROMATIQUES SIMPLES
  申请人：WISCONSIN ALUMNI RES FOUND

  公开号：WO2015138563A1

  公开（公告）日：2015-09-17

  A method to cleave C-C and C-0 bonds in β-Ο-4 linkages in lignin or lignin sub-units is described. The method includes oxidizing at least a portion of secondary benzylic alcohol groups in β-Ο-4 linkages in the lignin or lignin sub-unit to corresponding ketones and then leaving C-0 or C-C bonds in the oxidized lignin or lignin sub-unit by reacting it with an organic carboxylic acid, a salt of an organic carboxylic acids, and/or an ester of an organic carboxylic acids. The method may utilize a metal or metal-containing reagent or proceed without the metal or metal-containing reagent.

  描述了一种在木质素或木质素亚单位中裂解β-Ο-4键中的C-C和C-0键的方法。该方法包括氧化木质素或木质素亚单位中β-Ο-4键中至少部分次苯基醇基团，使其转化为相应的酮，然后通过将氧化后的木质素或木质素亚单位与有机羧酸、有机羧酸盐和/或有机羧酸酯反应，使C-0或C-C键保留在氧化后的木质素或木质素亚单位中。该方法可以利用金属或含金属试剂，也可以在没有金属或含金属试剂的情况下进行。
• Cleavage of lignin model compounds and lignin^ox using aqueous oxalic acid
  作者：Ashley C. Lindsay、Shinji Kudo、Jonathan Sperry

  DOI：10.1039/c9ob01452g

  日期：——

  redox neutral cleavage that is analogous to the formic acid-sodium formate mediated lignin cleavage process reported by Stahl. Aqueous oxalic acid also cleaves lignin itself, with oxidised milled wood lignin (MWLox) from Pinus radiata giving a 14% yield of ethyl acetate soluble aromatics with good selectivity for vanillin. Aqueous oxalic acid appears to be a promising lignin cleavage system given the

  草酸水溶液通过两种不同的机理裂解氧化的β-O-4木质素模型化合物，这取决于羟甲基取代基的存在。在空气存在下，暴露于草酸水溶液中时，各种不包含羟甲基取代基的β-O-4苯氧基苯乙酮可能会发生氧化裂解，可能是通过二氧杂环丁烷中间体的一致开环而得到相应的苯甲酸和甲酸苯酯。重要的是，当在空气中进行裂解时，与纯氧相比，由单线态氧和氢过氧自由基（来自O2和草酸）产生的有害副反应极少。当带有羟甲基的氧化的β-O-4木质素模型化合物被草酸水溶液裂解时，生成的二酮和苯酚产物来自氧化还原中性裂解，类似于Stahl报道的甲酸-甲酸钠介导的木质素裂解过程。草酸水溶液还会裂解木质素本身，而辐射松的氧化磨木木质素（MWLox）则可产生14％的乙酸乙酯可溶性芳族化合物，对香兰素具有良好的选择性。鉴于良性的基于生物的试剂，不存在金属和有机溶剂以及简单的提取程序，草酸水溶液似乎是一种有前途的木质素裂解系统。用来自辐射松的氧化
• Formic-acid-induced depolymerization of oxidized lignin to aromatics
  作者：Alireza Rahimi、Arne Ulbrich、Joshua J. Coon、Shannon S. Stahl

  DOI：10.1038/nature13867

  日期：2014.11

  A method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid is described that results in more than 60 wt% yield of low-molecular-mass aromatics. The aromatic biopolymer lignin, a major component of plant cell walls and generally obtained from wood, is a valuable and renewable source of aromatic chemicals. Considerable progress has been made in the conversion of cellulose and hemicellulose to fuels and chemicals, but lignin has proved more recalcitrant. In this manuscript, the authors report a high-yield method for conversion of lignin to low molecular mass aromatics. The C–O cleavage reaction proceeds under mild conditions in aqueous formic acid. It produces small number of well-defined aromatic products, providing raw materials well suited for targeted conversion to a variety of valuable chemicals. Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth1 and is one of the few renewable sources of aromatic chemicals2. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin)3, lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills4. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries5,6. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing7. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products8,9, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10–20wt%)2,10,11. Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C–O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  一种在温和条件下使用水合甲酸对氧化木质素进行解聚的方法被描述，该方法的产物中低分子量芳烃的收率超过60wt%。木质素是植物细胞壁的主要成分，通常来自木材，是一种宝贵且可再生的芳烃化学品来源。在将纤维素和半纤维素转化为燃料和化学品方面已经取得了显著进展，但木质素的转化则证明更为困难。在本文中，作者报告了一种将木质素转化为低分子量芳烃的高产率方法。C–O断裂反应在水合甲酸的温和条件下进行，生成少量界定良好的芳香产物，为针对性转化为多种有价值化学品提供了合适的原材料。木质素是一种异质芳香生物聚合物，约占地球有机碳的30%1，也是少数可再生的芳香化学品来源之一2。由于木质素是木质纤维素生物质（纤维素、半纤维素和木质素）3中最难处理的成分，木质素在纸浆和造纸工业中被视为废弃物，通常燃烧以提供能量和回收造纸化学品4。从木质素中提取更高价值的产品越来越被认为对综合生物精炼厂的经济可行性至关重要5,6。解聚是许多木质素增值策略的重要起点，因为它能够产生有价值的芳香化学品和/或提供适合下游处理的低分子量原料7。商业先例表明，某些类型的木质素（木素磺酸盐）可以转化为香草醛和其他可销售产品8,9，但需要新技术来增强木质素的价值链。木质素复杂、不规律的结构使得化学转化工作变得复杂，已知的解聚方法通常导致低产率（即低于10–20wt%）的定义不清的产物2,10,11。在这里，我们描述了一种在温和条件下使用水合甲酸对氧化木质素进行解聚的方法，其低分子量芳烃的产率超过60wt%。我们展示了这种简便的C–O断裂方法的发现，及其在白杨木质素解聚中的应用，以及对反应机制的深入理解。这些结果对木质素转化和生物质精炼的更广泛影响也进行了探讨。
• N-Heterocyclic Carbene-Catalyzed Umpolung of β,γ-Unsaturated 1,2-Diketones
  作者：Jian Liu、Deb Kumar Das、Guoxiang Zhang、Shuang Yang、Hao Zhang、Xinqiang Fang

  DOI：10.1021/acs.orglett.7b03358

  日期：2018.1.5

  The umpolung of β,γ-unsaturated diketones through N-heterocyclic carbene catalysis is described, which allows access to a variety of highly functionalized bicyclic cyclohexene-β-lactones and 1,3,4-triaryl benzenes. An unprecedented reaction pattern involving the catalytic formation of nucleophilic O-acylated homoenolate intermediate is proposed. A diverse set of transformations on the product further

  描述了通过N-杂环卡宾催化的β，γ-不饱和二酮的溶剂化反应，它允许使用各种高度官能化的双环环己烯-β-内酯和1,3,4-三芳基苯。提出了涉及催化形成亲核O-酰化均烯酸酯中间体的前所未有的反应模式。产品上的各种转化进一步显示了该方案的合成潜力。
• Iron-catalysed oxidative cleavage of lignin and β-O-4 lignin model compounds with peroxides in DMSO
  作者：Jakob Mottweiler、Torsten Rinesch、Claire Besson、Julien Buendia、Carsten Bolm

  DOI：10.1039/c5gc01306b

  日期：——

  Simple FeCl3-derived iron catalysts are used for the cleavage of [small beta]-O-4 linkages in lignin and lignin model compounds. The degradation of the [small beta]-O-4 linkages and the resinol structures in both...

  简单的FeCl 3衍生的铁催化剂用于裂解木质素和木质素模型化合物中的β-O-4小键。两种化合物中小β-O-4键和树脂结构的降解