methyl (E)-(2-hydroxy-6-oxo-3,6-dihydro-2H-pyran-3-ylidene)acetate | 81158-22-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: methyl (E)-(2-hydroxy-6-oxo-3,6-dihydro-2H-pyran-3-ylidene)acetate
• 英文别名: (E)-(2-hydroxy-6-oxo-2,3-dihydro-pyran-3-yliden)-acetic acid methyl ester；(E)-(2-Hydroxy-6-oxo-2,3-dihydro-pyran-3-yliden)-essigsaeure-methylester；methyl (2E)-2-(2-hydroxy-6-oxopyran-3-ylidene)acetate
• CAS: 81158-22-7
• 化学式: C₈H₈O₅
• 分子量: 184.149
• InChiKey: HVNYRSVXXUCQRO-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  methyl (E)-(2-hydroxy-6-oxo-3,6-dihydro-2H-pyran-3-ylidene)acetate 在 盐酸 作用下， 反应 1.0h， 以48%的产率得到(E)-2-hydroxy-5-oxo-2,5-dihydro-3-furanpropenoic acid
  参考文献：
  名称：

  Medium effects on formation of cyclic enolates from (2E,4Z)-3-formyl-2,4-hexadienedioates, a novel ring-chain equilibrium: importance of hydrogen bonding, solvent dipolarity/polarizability, and ion-pairing effects. Stereoisomerism of 3-formyl-2,4-hexadienedioates

  摘要：

  DOI：

  10.1021/jo00268a007
• 作为产物：
  描述：

  monomethyl β-formyl-cis,cis-muconate 在 水 作用下， 以99%的产率得到methyl (E)-(2-hydroxy-6-oxo-3,6-dihydro-2H-pyran-3-ylidene)acetate
  参考文献：
  名称：

  The cyanide-catalyzed conversion of β-formylmuconates into triglochinates: A useful biomimetic synthesis

  摘要：

  DOI：

  10.1016/s0040-4039(00)78726-0

文献信息

• STUDIES IN THE POLYOXYPHENOL SERIES: VII. THE OXIDATION OF VANILLIN WITH SODIUM CHLORITE AND CHLORINE DIOXIDE
  作者：R. M. Husband、C. D. Logan、C. B. Purves

  DOI：10.1139/v55-010

  日期：1955.1.1

  Vanillin almost instantly reduced 1.2 to 1.5 moles of aqueous chlorine dioxide at 20 °C. or 5 °C. and any pH between 1.2 and 6.5, and a white crystalline substance with the composition of a dihydroxyvanillin, C₇H₅O₄(OCH₃), was isolated in roughly 25% yield independently of the pH. When oxidized with aqueous sodium chlorite at 20 °C. and pH 0.5, these crystals gave another crystalline substance with the composition of a dihydroxyvanillic acid, C₇H₅O₅(OCH₃). Although both these substances decomposed readily to red oils and then to brown powders free of methoxyl groups, seven well characterized derivatives were prepared. The results showed that the substances were unsaturated, monohydroxy, diketone tautomers of a dihydroxyvanillin and the corresponding dihydroxyvanillic acid, but precise structures could not be assigned. Parallel oxidations of vanillin with aqueous sodium chlorite at 20 °C. and pH 6 proceeded at a negligible rate, but near pH 5 a reaction that often seemed autocatalytic produced about 19% of 5-chlorovanillin. At pH 4 the aldehyde C₇H₅O₄(OCH₃) was isolated in 19% yield; at pH 1 this aldehyde (15%) was mixed with 7.7% of the corresponding acid C₇H₅O₅(OCH₃), but at pH 0.5 the latter alone was produced (28%). Chlorine dioxide and sodium chlorite therefore differed markedly in their oxidizing action and in the effect of pH upon it. When acting on vanillin, both oxidants also produced deep red, unstable oils with quinone-like properties and often containing chlorine.

  香草醛在20°C或5°C的任何pH值下，几乎立即将1.2至1.5摩尔的水溶氯氧化物还原，得到一种白色结晶物质，其组成为双羟基香草醛，C7H5O4(OCH3)，收率约为25％，与pH无关。当在20°C和pH 0.5下用水溶氯酸钠氧化这些晶体时，得到另一种双羟基香草酸的结晶物质，C7H5O5(OCH3)。虽然这两种物质很容易分解为不含甲氧基的红色油和褐色粉末，但已制备出七种经充分表征的衍生物。结果表明，这些物质是双羟基香草醛和相应的双羟基香草酸的不饱和、单羟基、二酮互变异构体，但精确的结构无法确定。在20°C和pH 6下，香草醛与水溶氯酸钠的平行氧化反应几乎不发生，但在接近pH 5时，常常出现一种看似自催化的反应，产生约19％的5-氯香草醛。在pH 4时，醛C7H5O4(OCH3)的收率为19％；在pH 1时，这种醛（15％）与相应的酸C7H5O5(OCH3)（7.7％）混合，但在pH 0.5时仅产生后者（28％）。因此，氯气和氯酸钠在氧化作用和pH影响上有明显的差异。在作用于香草醛时，这两种氧化剂也会产生深红色、不稳定的类醌油，通常含氯。
• Oxidation of some 2-methoxyphenols with chlorous acid
  作者：Jerzy W. Jaroszewski

  DOI：10.1021/jo00132a008

  日期：1982.5
• JAROSZEWSKI, JERZY W.;ETTLINGER, MARTIN G., J. ORG. CHEM., 54,(1989) N, C. 1506-1518
  作者：JAROSZEWSKI, JERZY W.、ETTLINGER, MARTIN G.

  DOI：——

  日期：——
• Medium effects on formation of cyclic enolates from (2E,4Z)-3-formyl-2,4-hexadienedioates, a novel ring-chain equilibrium: importance of hydrogen bonding, solvent dipolarity/polarizability, and ion-pairing effects. Stereoisomerism of 3-formyl-2,4-hexadienedioates
  作者：Jerzy W. Jaroszewski、Martin G. Ettlinger

  DOI：10.1021/jo00268a007

  日期：1989.3
• The cyanide-catalyzed conversion of β-formylmuconates into triglochinates: A useful biomimetic synthesis
  作者：Martin G. Ettlinger、Jerzy W. Jaroszewski

  DOI：10.1016/s0040-4039(00)78726-0

  日期：1980.1