4-[3-Hydroxy-2-(2-methoxy-phenoxy)-prop-(Z)-ylidene]-2-methoxy-cyclohexa-2,5-dienone | 86370-40-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-[3-Hydroxy-2-(2-methoxy-phenoxy)-prop-(Z)-ylidene]-2-methoxy-cyclohexa-2,5-dienone
• 英文别名: (4Z)-4-[3-hydroxy-2-(2-methoxyphenoxy)propylidene]-2-methoxycyclohexa-2,5-dien-1-one
• CAS: 86370-40-3
• 化学式: C₁₇H₁₈O₅
• 分子量: 302.327
• InChiKey: HGZZEYVOKAAJOS-XFXZXTDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-[3-Hydroxy-2-(2-methoxy-phenoxy)-prop-(Z)-ylidene]-2-methoxy-cyclohexa-2,5-dienone 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 生成 4-[3-hydroxy-2-(2-methoxyphenoxy)-propyl]-2-methoxyphenol
  参考文献：
  名称：

  Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins

  摘要：

  据信，木质素是由 4-羟基苯丙烷氧化偶联合成的。在原生木质素中，有一些类型的还原结构不能完全用氧化偶联来解释。在本研究中，我们通过仿生模型实验表明，烟酰胺腺嘌呤二核苷酸（NADH）在未催化的情况下，可将β-芳基醚醌甲苷还原为其苄基衍生物。其他一些具有重要生物意义的还原剂，包括纤维素生物糖脱氢酶，都未能产生还原结构。在还原剂 NADH 的存在下合成的针叶醇脱氢聚合物（在氧化条件下）产生了与模型实验中相同的还原结构，这表明氧化和还原过程可以在同一环境中发生，而且原位生成的醌甲醚的还原与加水具有充分的竞争性。本研究未实现原位还原 β-β-醌甲苷。因此，木质素中外消旋苄基结构的来源仍然未知，但本文展示了简单化学还原的潜力。

  DOI：

  10.1039/b606369a
• 作为产物：
  描述：

  4-苄氧基-3-甲氧基苯乙酮 在 sodium tetrahydroborate 、 三甲基溴硅烷 、 氢气 、 溴 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.07h， 生成 4-[3-Hydroxy-2-(2-methoxy-phenoxy)-prop-(Z)-ylidene]-2-methoxy-cyclohexa-2,5-dienone
  参考文献：
  名称：

  The Incorporation of 3,4-Dichloroaniline, a Pesticide Metabolite, into Dehydrogenation Polymers of Coniferyl Alcohol (DHPs).

  摘要：

  A mechanism by which pesticide metabolites may become incorporated into plant lignins has been studied with the aid of 3,4-dichloroaniline (DCA) and lignin model compounds. DCA was found to react rapidly with a quinone methide representing an intermediate in lignin biosynthesis. The resulting benzyl-amine group was stable to mild acidolysis under simulated stomach conditions. Addition of DCA to dehydrogenative polymerizations of coniferyl alcohol yielded DHPs containing covalently bended DCA. NMR spectroscopy showed that the DCA had become bonded to the benzylic position in arylglycerol-beta-guaiacyl ether structures. The majority of these structures were phenolic. This observation and the fact that the DCA accumulates in the low molecular weight fraction of the DHP indicates that the DCA functions as a trap for quinone methides and stops the further growth of the polymer.

  DOI：

  10.3891/acta.chem.scand.52-1338

文献信息

• METHOD OF SELECTIVELY OXIDIZING LIGNIN
  申请人：Wisconsin Alumni Research Foundation

  公开号：US20190177259A1

  公开（公告）日：2019-06-13

  A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product. The method includes the step of reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst, in a solvent, and optionally in the presence of an oxidant, for a time and a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product, preferably coniferaldehyde and/or sinapaldehyde.

  一种选择性地将木质素或木质素衍生反应物反应以产生芳香产物的方法。该方法包括以下步骤：将木质素或木质素衍生反应物与含钼催化剂在溶剂中反应，可选地在氧化剂的存在下，在一定时间和温度下，使至少部分木质素或木质素衍生反应物选择性地转化为芳香产物，最好是对香豆醛和/或丁香豆醛。
• The Incorporation of 3,4-Dichloroaniline, a Pesticide Metabolite, into Dehydrogenation Polymers of Coniferyl Alcohol (DHPs).
  作者：Gösta Brunow、Sanni Raiskila、Jussi Sipilä、Gerhard Erkel、Olov Sterner

  DOI：10.3891/acta.chem.scand.52-1338

  日期：——

  A mechanism by which pesticide metabolites may become incorporated into plant lignins has been studied with the aid of 3,4-dichloroaniline (DCA) and lignin model compounds. DCA was found to react rapidly with a quinone methide representing an intermediate in lignin biosynthesis. The resulting benzyl-amine group was stable to mild acidolysis under simulated stomach conditions. Addition of DCA to dehydrogenative polymerizations of coniferyl alcohol yielded DHPs containing covalently bended DCA. NMR spectroscopy showed that the DCA had become bonded to the benzylic position in arylglycerol-beta-guaiacyl ether structures. The majority of these structures were phenolic. This observation and the fact that the DCA accumulates in the low molecular weight fraction of the DHP indicates that the DCA functions as a trap for quinone methides and stops the further growth of the polymer.
• Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins
  作者：Anders Holmgren、G?sta Brunow、Gunnar Henriksson、Liming Zhang、John Ralph

  DOI：10.1039/b606369a

  日期：——

  Lignin is believed to be synthesized by oxidative coupling of 4-hydroxyphenylpropanoids. In native lignin there are some types of reduced structures that cannot be explained solely by oxidative coupling. In the present work we showed via biomimetic model experiments that nicotinamide adenine dinucleotide (NADH), in an uncatalyzed process, reduced a β-aryl ether quinone methide to its benzyl derivative. A number of other biologically significant reductants, including the enzyme cellobiose dehydrogenase, failed to produce the reduced structures. Synthetic dehydrogenation polymers of coniferyl alcohol synthesized (under oxidative conditions) in the presence of the reductant NADH produced the same kind of reduced structures as in the model experiment, demonstrating that oxidative and reductive processes can occur in the same environment, and that reduction of the in situ-generated quinone methides was sufficiently competitive with water addition. In situ reduction of β–β-quinone methides was not achieved in this study. The origin of racemic benzyl structures in lignins therefore remains unknown, but the potential for simple chemical reduction is demonstrated here.

  据信，木质素是由 4-羟基苯丙烷氧化偶联合成的。在原生木质素中，有一些类型的还原结构不能完全用氧化偶联来解释。在本研究中，我们通过仿生模型实验表明，烟酰胺腺嘌呤二核苷酸（NADH）在未催化的情况下，可将β-芳基醚醌甲苷还原为其苄基衍生物。其他一些具有重要生物意义的还原剂，包括纤维素生物糖脱氢酶，都未能产生还原结构。在还原剂 NADH 的存在下合成的针叶醇脱氢聚合物（在氧化条件下）产生了与模型实验中相同的还原结构，这表明氧化和还原过程可以在同一环境中发生，而且原位生成的醌甲醚的还原与加水具有充分的竞争性。本研究未实现原位还原 β-β-醌甲苷。因此，木质素中外消旋苄基结构的来源仍然未知，但本文展示了简单化学还原的潜力。