methyl 4-O-methyl-α-D-glucopyranosiduronic acid | 73703-00-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-methyl-α-D-glucopyranosiduronic acid
• 英文别名: Methyl 4-O-methyl-α-D-glucopyranosid uronsaeure；(2S,3S,4R,5R,6S)-4,5-dihydroxy-3,6-dimethoxyoxane-2-carboxylic acid
• CAS: 73703-00-1
• 化学式: C₈H₁₄O₇
• 分子量: 222.195
• InChiKey: BMROTMHSIROAJV-WIKBCIAESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 4-O-methyl-α-D-glucopyranosiduronic acid 在 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 sodium hydroxide 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 erythro-3-acetoxy-3-<4-(benzyloxy)-3-methoxyphenyl>-2-(2-methoxyphenoxy)propyl (methyl 2,3-di-O-acetyl-4-O-methyl-α-D-glucopyranosid)uronate
  参考文献：
  名称：

  Synthesis and Rearrangement Reactions of Ester-Linked Lignin-Carbohydrate Model Compounds

  摘要：

  A series of ester-linked lignin-carbohydrate model compounds has been synthesized, which represent possible ester linkages of lignin to hemicellulose in wood through the carboxylic acid group of 4-O-methyl-alpha-D-glucopyranosiduronic acid moieties. The three and erythro isomers of these compounds were prepared through an appropriate combination of protective and stereoselective transformations. Spectroscopic characterization of these esters revealed that the uronosyl group migrated between the primary (gamma) and benzylic (alpha) positions of the lignin side chain in both acidic and neutral conditions. It has been determined that the migration equilibrium favors gamma- over alpha-esters, with the reaction possibly proceeding through a six-membered ring intermediate. That uronosyl migrations occur favoring the gamma-position suggests that the classical view of lignin-xylan ester linkages in wood needs to be reevaluated.

  DOI：

  10.1021/jf00056a026
• 作为产物：
  描述：

  methyl 2,3,6-tri-O-benzoyl-α-D-glucopyranoside 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 2,6-二叔丁基-4-甲基吡啶 、 sodium methylate 、 sodium bromide 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 73.0h， 生成 methyl 4-O-methyl-α-D-glucopyranosiduronic acid
  参考文献：
  名称：

  A practical synthesis of methyl 4-O-methyl-α-d-glucopyranosiduronic acid

  摘要：

  DOI：

  10.1016/0008-6215(95)00087-a

文献信息

• Synthesis and Acid-Catalyzed Hydrolysis of Some 3-(4-Methoxyphenyl)propyl Glucuronates
  作者：Monika Poláková、Dušan Joniak、Miloslav Ďuriš

  DOI：10.1135/cccc20001609

  日期：——

  3-(4-Methoxyphenyl)propyl D-glucuronate, 3-(4-methoxyphenyl)propyl methyl 4-O-methyl-α-Dglucopyranosiduronate, 3-(4-methoxyphenyl)propyl 1,2,3,4-tetra-O-acetyl-α-D-glucopyranuronate and 3-(4-methoxyphenyl)propyl 1,2-(S):3,5-di-O-benzylidene-α-D-glucofuranuronate were prepared as a model substances for the ester lignin-saccharide bonds. Rates of acid-catalyzed hydrolysis of the prepared compounds in 1 M HCl in acetonitrile-water 3 : 1 at 20 °C have been measured by LC-DAD analysis and it showed the low stability of the ester bonds towards acid hydrolysis.

  3-(4-甲氧基苯基)丙基D-葡萄糖醛酸酯、3-(4-甲氧基苯基)丙基甲基4-O-甲基-α-D葡萄糖醛酸酯、3-(4-甲氧基苯基)丙基1,2,3,4-四-O-乙酰基-α-D葡萄糖醛酸酯和3-(4-甲氧基苯基)丙基1,2-(S):3,5-二-O-苯甲醛基-α-D葡萄糖呋喃醛酸酯被制备为酯木质素-糖类键的模型物质。在20℃下，用LC-DAD分析测量了在乙腈-水3:1的1 M HCl中制备的化合物的酸催化水解速率，并表明酯键对酸水解的稳定性较低。
• A practical synthesis of methyl 4-O-methyl-α-d-glucopyranosiduronic acid
  作者：Kaichang Li、Richard F. Helm

  DOI：10.1016/0008-6215(95)00087-a

  日期：1995.8
• Synthesis and Rearrangement Reactions of Ester-Linked Lignin-Carbohydrate Model Compounds
  作者：Kaichang Li、Richard F. Helm

  DOI：10.1021/jf00056a026

  日期：1995.8

  A series of ester-linked lignin-carbohydrate model compounds has been synthesized, which represent possible ester linkages of lignin to hemicellulose in wood through the carboxylic acid group of 4-O-methyl-alpha-D-glucopyranosiduronic acid moieties. The three and erythro isomers of these compounds were prepared through an appropriate combination of protective and stereoselective transformations. Spectroscopic characterization of these esters revealed that the uronosyl group migrated between the primary (gamma) and benzylic (alpha) positions of the lignin side chain in both acidic and neutral conditions. It has been determined that the migration equilibrium favors gamma- over alpha-esters, with the reaction possibly proceeding through a six-membered ring intermediate. That uronosyl migrations occur favoring the gamma-position suggests that the classical view of lignin-xylan ester linkages in wood needs to be reevaluated.