6-氧代吡喃-2,4-二甲酸 | 72698-24-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 中文名称: 6-氧代吡喃-2,4-二甲酸
• 中文别名: 9-O-乙酰基-2-酮-3-脱氧甘油-半乳-九酸
• 英文名称: 2-pyrone-4,6-dicarboxylic acid
• 英文别名: 2-oxo-2H-pyran-4,6-dicarboxylic acid；6-oxopyran-2,4-dicarboxylic acid
• CAS: 72698-24-9
• 化学式: C₇H₄O₆
• 分子量: 184.105
• InChiKey: VRMXCPVFSJVVCA-UHFFFAOYSA-N

物化性质

• 沸点：
  355.5±42.0 °C(Predicted)
• 密度：
  1.821±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  101
• 氢给体数：
  2
• 氢受体数：
  6

安全信息

• 海关编码：
  2932209090

反应信息

• 作为反应物：
  描述：

  6-氧代吡喃-2,4-二甲酸 在 sodium hydroxide 作用下， 以 水 为溶剂， 反应 1.0h， 生成 4-oxalomesaconate
  参考文献：
  名称：

  半胱氨酸残基在och草假单胞菌NGJ1的4-草酸酯中的水合酶的作用。

  摘要：

  在没有还原剂（如二硫苏糖醇）的情况下，来自草假单胞菌NGJ1的4-氧杂草酸水合酶不稳定，并被5,5'-二硫代双（2-硝基苯甲酸）（DTNB）强烈抑制。为了研究半胱氨酸残基在酶催化中的作用，通过定点诱变将酶的八个单独的半胱氨酸残基替换为丝氨酸残基。DTNB对野生型和突变型酶的催化性质和化学修饰表明：（i）8个半胱氨酸残基都不是酶催化所必需的；（ii）DTNB的抑制作用主要是由于Cys-186的修饰；（iii）Cys-96可能是与DTNB发生反应的另一个残基，其修饰导致4-草酸酯的K（m）值增加；（iv）DTNB无法接近其他六个半胱氨酸残基，但易受HgCl（2）影响；（v）在没有还原剂的情况下，仅置换Cys-186可显着提高酶的稳定性。

  DOI：

  10.1271/bbb.60503
• 作为产物：
  描述：

  PDC sodium salt 在 盐酸 作用下， 以 水 为溶剂， 以88%的产率得到6-氧代吡喃-2,4-二甲酸
  参考文献：
  名称：

  LARGE-SCALE PURIFICATION OF 2-PYRONE-4,6-DICARBOXYLIC ACID

  摘要：

  提供一种通过发酵生产获得的PDC的工业纯化方法。一种纯化2-吡喃-4,6-二羧酸的方法，包括将一价到四价阳离子的盐加入含有微生物产生的2-吡喃-4,6-二羧酸的发酵液中；以及一种纯化2-吡喃-4,6-二羧酸的方法，包括从含有微生物产生的2-吡喃-4,6-二羧酸的发酵液中提取2-吡喃-4,6-二羧酸，而不形成2-吡喃-4,6-二羧酸盐。

  公开号：

  US20110319640A1

文献信息

• A Novel Biomass-based Polymer Prepared from Lignin-derived Stable Metabolic Intermediate by Copper(I)-catalyzed Azide–Alkyne Click Reaction
  作者：Tsuyoshi Michinobu、Yasunori Inazawa、Kenta Hiraki、Yoshihiro Katayama、Eiji Masai、Masaya Nakamura、Seiji Ohara、Kiyotaka Shigehara

  DOI：10.1246/cl.2008.154

  日期：2008.2.5

  The Cu I -catalyzed, but ligand-free azide-alkyne cycloaddition reaction was applied to the polymerization of the newly synthesized diethynyl-functionalized 2-pyrone monomer originally isolated from lignin via metabolic pathway. The polymerization was monitored by GPC and IR spectra and the resulting high molecular weight polymer was unambiguously characterized by 1 H NMR, thermal analysis, and optical

  将 Cu I 催化但无配体的叠氮化物-炔环加成反应应用于新合成的二乙炔官能化 2-吡喃酮单体的聚合反应，该单体最初是通过代谢途径从木质素中分离出来的。聚合反应通过 GPC 和 IR 光谱监测，所得高分子量聚合物通过 1 H NMR、热分析和光吸收和发射光谱明确表征。
• Liquid Crystallinity and Organogelation Behavior of Lignin-Derived Metabolic Intermediate Bearing Cholesterol Groups
  作者：Tsuyoshi Michinobu、Kenta Hiraki、Nozomu Fujii、Kazuhiro Shikinaka、Yoshihiro Katayama、Eiji Masai、Masaya Nakamura、Yuichiro Otsuka、Seiji Ohara、Kiyotaka Shigehara

  DOI：10.1246/bcsj.20110055

  日期：2011.6.15

  Two cholesterol groups were for the first time attached to a lignin-derived metabolic intermediate, 2-pyrone-4,6-dicarboxylic acid (PDC). This PDC molecule showed a liquid crystalline mesophase and interesting organogelation behavior. The relationship between molecular structure and assembly properties was investigated by modifying the PDC core and a spacer group between the PDC and cholesterol moieties. Although all derivatives displayed similar phase transition behavior with a SmA phase, only a few of them could form organogels. Detailed morphology investigations of the xerogels by X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggested that both the PDC moiety and a carbamate spacer are essential for the occurrence of organogelation. Hydrogen bonds of the carbamate spacers and van der Waals interactions of the cholesterol moieties lead to a dipolar-induced interaction of the pyrone rings. The physical gels were probably stabilized by these cooperative interactions. The IR and 1H NMR spectroscopies clearly revealed the presence of weak intermolecular interactions, such as hydrogen bonds and dipolar-type interactions, for efficient gelator molecules.

  在木质素衍生的代谢中间体 2-吡喃酮-4,6-二羧酸（PDC）上首次连接了两个胆固醇基团。这种 PDC 分子显示出液晶介相和有趣的有机凝胶行为。通过改变 PDC 核心和 PDC 与胆固醇分子之间的间隔基团，研究了分子结构与组装特性之间的关系。尽管所有衍生物都显示出与 SmA 相类似的相变行为，但只有少数衍生物能形成有机凝胶。通过 X 射线衍射（XRD）和扫描电子显微镜（SEM）对这些异构凝胶进行的详细形貌研究表明，PDC 分子和氨基甲酸酯间隔基对发生有机凝胶化至关重要。氨基甲酸酯间隔物的氢键和胆固醇分子的范德华相互作用导致了吡喃酮环的双极性相互作用。物理凝胶可能是通过这些协同作用稳定下来的。红外光谱和 1H NMR 光谱清楚地揭示了高效凝胶剂分子中存在着微弱的分子间相互作用，如氢键和双极型相互作用。
• Molecular Properties of 2-Pyrone-4,6-dicarboxylic Acid (PDC) as a Stable Metabolic Intermediate of Lignin Isolated by Fractional Precipitation with Na⁺Ion
  作者：Tsuyoshi Michinobu、Masami Bito、Yoshiko Yamada、Yoshihiro Katayama、Keiichi Noguchi、Eiji Masai、Masaya Nakamura、Seiji Ohara、Kiyotaka Shigehara

  DOI：10.1246/bcsj.80.2436

  日期：2007.12.15

  A chemically stable metabolic intermediate of lignin, 2-pyrone-4,6-dicarboxylic acid (PDC), was isolated, and the molecular properties were comprehensively investigated by using thermal analysis, optical spectroscopy, potentiometric titration, and X-ray crystallography. UV absorption spectra of PDC did not show any solvent effects, whereas the fluorescence spectra displayed distinct solvatochromism. Despite the fairly good planarity of the PDC geometry, dual fluorescence was observed in some small donor number solvents. The emission behaviors are thought to be due to the significant twist between the pyrone ring and carboxylate substituents, found in the X-ray crystal structures of the Na+ complex. The crystal structure also showed the intermolecular, centrosymmetric short hydrogen bonding of the carboxylate moieties with an O···H···O distance of 0.2452 nm, which made it possible to assign the pKa values to the molecular structure. PDC was thermally stable and could be sublimed even at atmospheric pressure, offering the preparation possibility of ultra-thin films by vapor-deposition techniques. The fact that the chemically and thermally stable compound possessing many attractive functions, such as unique emission, facile sublimation, and strong acidity, resulting in exceptionally short intermolecular contacts, can be obtained from biomass on a large quantity will lead to establishment of carbon neutral system in future industry.

  通过热分析、光学光谱、电位滴定和 X 射线晶体学等方法，对木质素的化学性质稳定的代谢中间体--2-吡喃酮-4,6-二羧酸（PDC）进行了全面研究。PDC 的紫外吸收光谱没有显示出任何溶剂效应，而荧光光谱则显示出明显的溶解色。尽管 PDC 的几何形状具有相当好的平面性，但在一些供体数目较少的溶剂中仍能观察到双重荧光。这种发射行为被认为是由于在 Na+ 复合物的 X 射线晶体结构中发现吡酮环和羧酸取代基之间存在明显的扭曲。晶体结构还显示了羧酸基分子间的中心对称短氢键，O--H--O 间距为 0.2452 nm，这使得将 pKa 值赋予分子结构成为可能。PDC 具有热稳定性，即使在常压下也能升华，这为利用气相沉积技术制备超薄薄膜提供了可能。这种化学性质和热稳定性都很稳定的化合物具有许多吸引人的功能，如独特的发射、易于升华和强酸性，导致分子间接触特别短，可以从生物质中大量获得，这将有助于在未来的工业中建立碳中和系统。
• Organogels of Lignin-derived Stable Metabolic Intermediate, 2-Pyrone-4,6-dicarboxylic Acid (PDC), Bearing Cholesteryl Groups
  作者：Tsuyoshi Michinobu、Kenta Hiraki、Nozomu Fujii、Kazuhiro Shikinaka、Yoshihiro Katayama、Eiji Masai、Masaya Nakamura、Yuichiro Otsuka、Seiji Ohara、Kiyotaka Shigehara

  DOI：10.1246/cl.2010.400

  日期：2010.4.5

  The organogelation behavior of a lignin-derived stable metabolic intermediate bearing two cholesteryl groups was examined for the first time, and it was found that the carbamate spacers possessing a hydrogen-bonding ability are essential for gelation of aliphatic or aromatic organic solvents.

  首次对木质素衍生的稳定代谢中间体（带有两个胆固醇基团）的有机凝胶化行为进行了研究，发现具有氢键能力的氨基甲酸酯间隔物对于脂肪族或芳香族有机溶剂的凝胶化至关重要。
• USEFUL MICROORGANISM AND METHOD FOR PRODUCING SUBSTANCE OF INTEREST
  申请人：GENARIS, INC.

  公开号：US20150197775A1

  公开（公告）日：2015-07-16

  It is an object of the present invention to provide a bacterial strain that can decrease the amount of an intermediate Compound P converted into Metabolite M and efficiently accumulate Compound P in a medium that is not supplemented with Metabolite M or the final product generated from Metabolite M. The present invention provides a prokaryotic organism having all features (a) to (d) as defined in the specification so as to accumulate Compound P by regulating expression level of Enzyme X that converts Compound P as an intermediate metabolite into Metabolite M in a biosynthetic pathway in which Metabolite M indispensable for the growth is produced from a carbon source.

  本发明的目的是提供一种细菌菌株，该菌株能够降低中间产物P转化为代谢物M的数量，并在不添加代谢物M或从代谢物M生成的最终产物的培养基中高效地积累化合物P。本发明提供了一种原核生物，具有规定在生产必需的代谢物M的生物合成途径中将化合物P转化为中间代谢物M的酶X的表达水平，以通过所有在说明书中定义的特征（a）至（d）来积累化合物P。

表征谱图