1-(4-羟基-3,5-二甲氧基-苯基)-丙烷-1,2-二酮 | 6925-65-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: 1-(4-羟基-3,5-二甲氧基-苯基)-丙烷-1,2-二酮
• 英文名称: Syringoyl-methyl-keton
• 英文别名: 1-(4-Hydroxy-3,5-dimethoxy-phenyl)-propane-1,2-dione；1-(4-hydroxy-3,5-dimethoxyphenyl)propane-1,2-dione
• CAS: 6925-65-1
• 化学式: C₁₁H₁₂O₅
• 分子量: 224.213
• InChiKey: HULVQYKNRRMOBW-UHFFFAOYSA-N

物化性质

• 熔点：
  80-81 °C
• 沸点：
  400.6±45.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)
• 保留指数：
  1859.5

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 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：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  对硝基甲苯 、 1-(4-羟基-3,5-二甲氧基-苯基)-丙烷-1,2-二酮 生成 丁香酸
  参考文献：
  名称：

  Studies on Lignin and Related Compounds. XLIV. The Ethanolysis of Maple Wood; Separation and Identification of the Water-Soluble Aldehyde Constituents

  摘要：

  DOI：

  10.1021/ja01877a066
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 吡啶 、 copper(II) sulfate 作用下， 生成 1-(4-羟基-3,5-二甲氧基-苯基)-丙烷-1,2-二酮
  参考文献：
  名称：

  Studies on Lignin and Related Compounds. LIII. Isolation of Vanilloyl and Syringoyl Methyl Ketones from Ethanolysis Products of Maple Wood

  摘要：

  DOI：

  10.1021/ja01854a017

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。
• 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。
• Microorganisms and methods for producing 2-pyrone-4,6-dicarboxylic acid and other compounds
  申请人：WISCONSIN ALUMNI RESEARCH FOUNDATION

  公开号：US11028418B2

  公开（公告）日：2021-06-08

  Recombinant microorganisms configured for enhanced production of compounds such as 2-pyrone-4,6-dicarboxylic acid (PDC) and methods of using the recombinant microorganisms for the production of these compounds. The recombinant microorganisms include one or more modifications that reduce 2-pyrone-4,6-dicarboxylic acid (PDC) hydrolase activity, 4-carboxy-2-hydroxy-6-methoxy-6-oxohexa-2,4-dienoate (CHMOD) cis-trans isomerase activity, 4-carboxy-2-hydroxy-6-methoxy-6-oxohexa-2,4-dienoate (CHMOD) methyl esterase activity, and/or vanillate/3-O-methylgallate O-demethylase activity. The recombinant microorganisms can be used to generate PDC from media comprising plant-derived phenolics, such as syringyl phenolics, guaiacyl phenolics, and p-hydroxyphenyl phenolics. The plant-derived phenolics can be derived from pretreated lignin, including depolymerized lignin or other chemically altered lignin.

  用于提高 2-吡喃酮-4,6-二羧酸（PDC）等化合物生产的重组微生物以及使用重组微生物生产这些化合物的方法。重组微生物包括一种或多种可降低 2-吡喃酮-4,6-二羧酸（PDC）水解酶活性的修饰物、4-羧基-2-羟基-6-甲氧基-6-氧代己-2、4-羧基-2-羟基-6-甲氧基-6-氧代六氢-2,4-二烯酸酯（CHMOD）顺反异构酶活性、4-羧基-2-羟基-6-甲氧基-6-氧代六氢-2,4-二烯酸酯（CHMOD）甲酯酶活性和/或香草酸酯/3-O-甲基没食子酸酯 O-脱甲基酶活性。重组微生物可用于从含有植物源酚类（如丁香基酚类、愈创木酰基酚类和对羟基苯基酚类）的培养基中生成 PDC。植物源酚类可以来自预处理过的木质素，包括解聚木质素或其他化学变化的木质素。
• SELECTIVE C-O BOND CLEAVAGE OF OXIDIZED LIGNIN AND LIGNIN-TYPE MATERIALS INTO SIMPLE AROMATIC COMPOUNDS
  申请人：Wisconsin Alumni Research Foundation

  公开号：US20150259368A1

  公开（公告）日：2015-09-17

  A method to cleave C—C and C—O bonds in β-O-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-O-4 linkages in the lignin or lignin sub-unit to corresponding ketones and then leaving C—O 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.
• METHODS OF DEPOLYMERIZING LIGNIN
  申请人：Wisconsin Alumni Research Foundation

  公开号：US20220127217A1

  公开（公告）日：2022-04-28

  Methods of depolymerizing lignin and products obtained therefrom. The methods include reacting lignin in a liquid solvent comprising an oxidation catalyst with the solvent being in contact with 02 gas. The solvent can include aprotic polar solvents. The oxidation catalyst can include heterogeneous catalysts. The methods can be used in the oxidative catalytic fractionation of raw biomass to generate soluble aromatic monomers and a solid carbohydrate residue. Depolymerized lignin products include phenolic and benzoquinone monomers, such as p-hydroxybenzoic acid, vanillin, syringaldehyde, vanillic acid, and/or syringic acid.