2-[(2-羟基-3-甲氧基-5-甲基苯基)甲基]-6-甲氧基-4-甲基苯酚 | 1620-70-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-[(2-羟基-3-甲氧基-5-甲基苯基)甲基]-6-甲氧基-4-甲基苯酚
• 英文名称: 2,2'-methylenebis(6-methoxy-4-methylphenol)
• 英文别名: 2-[(2-hydroxy-3-methoxy-5-methylphenyl)methyl]-6-methoxy-4-methylphenol
• CAS: 1620-70-8
• 化学式: C₁₇H₂₀O₄
• 分子量: 288.343
• InChiKey: GOLYEEJKFISPDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[(2-羟基-3-甲氧基-5-甲基苯基)甲基]-6-甲氧基-4-甲基苯酚 在 水 、 氯 作用下， 反应 0.25h， 生成 3,5-dichloro-6-[(2,4-dichloro-3-methyl-5,6-dioxocyclohexa-1,3-dien-1-yl)methyl]-4-methylcyclohexa-3,5-diene-1,2-dione
  参考文献：
  名称：

  木质素模型二聚体依次与氯和氢氧化钠反应。

  摘要：

  Dimer 9, which-is;representative of diaryl methane structures reported present in residual lignin, was reacted with aqueous chlorine at 50 degrees C. The major product was identified as the tetrachloroquinone dimer 13 (x = 2, y 2).; Similar reaction of the tetrachlorocatechol dimer 12 with aqueous chlorine gave a mixture of the tetlachloroquinones 15 and 16. When the mixture of the quinones was reacted with 2.5% sodium hydroxide, an intramolecular oxidation-reduction (Cannizzaro) reaction with the simultaneous loss of two chlorine atoms occurred as the main reaction. The products, 21, were characterized as having a chlorine-free muconic acid lactone group attached to a dichlorocatechol. A third product 17 from the reaction with sodium hydroxide appeared to result from simple displacement of the two chlorine atoms in the quinone ring of 15 by hydroxyl groups. The results provide some clarification of the reactions occurring during classical chlorine bleaching. The results are also in agreement with literature reports concerning some of the-structural characteristics of the high mass material.

  DOI：

  10.1021/es00053a007
• 作为产物：
  描述：

  2-甲氧基-4-甲基苯酚 以97%的产率得到
  参考文献：
  名称：

  McKague Bruce, Reeve Douglas W., Environ. Sci. and Technol, 28 (1994) N 4, S 573-576

  摘要：

  DOI：

文献信息

• Correlation analysis of31P NMR chemical shifts with substituent effects of phenols
  作者：Zhi-Hua Jiang、Dimitris S. Argyropoulos、Alessandro Granata

  DOI：10.1002/mrc.1260330509

  日期：1995.5

  and their 31P chemical shifts were recorded. Excellent resolution between the chemical shifts of phosphitylated carboxylic acids, phenols and aliphatic alcohols was obtained. The correlations of the phosphorus chemical shifts with the chemical environments of lignin‐related phenols using the Hammett principles provided an excellent linear relationship between the resonance substituent constant, σ RO

  超过 60 种木质素相关模型化合物用 2-氯-4,4,5,5-四甲基二氧杂磷杂环戊烷（早期工作中使用的 2-氯-1,3,2-二氧杂环磷烷的空间位阻类似物）及其 31P 化学位移进行亚磷酸化被记录下来。获得了亚磷酸化羧酸、酚类和脂肪醇的化学位移之间的出色分辨率。使用哈米特原理，磷化学位移与木质素相关酚类化学环境的相关性提供了共振取代基常数σ RO 与对位取代木质素相关酚类的相应 31 P NMR 化学位移值之间的极好的线性关系. 此外，获得了邻位和对位取代的亚磷酸化酚的 31P NMR 化学位移之间的相关性。
• Synthesis, Characterization, and Cure Chemistry of Renewable Bis(cyanate) Esters Derived from 2-Methoxy-4-Methylphenol
  作者：Heather A. Meylemans、Benjamin G. Harvey、Josiah T. Reams、Andrew J. Guenthner、Lee R. Cambrea、Thomas J. Groshens、Lawrence C. Baldwin、Michael D. Garrison、Joseph M. Mabry

  DOI：10.1021/bm3018438

  日期：2013.3.11

  materials. In some cases, post-cure of the resins at 350 °C resulted in significant decomposition and off-gassing, but cure protocols that terminated at 250–300 °C generated void-free resin pucks without degradation. Thermogravimetric analysis revealed that cured resins were stable up to 400 °C and then rapidly degraded. TGA/FTIR and mass spectrometry results showed that the resins decomposed to phenols

  由双酚制备了一系列可再生的双（氰酸酯）酯，该双酚是通过2-甲氧基-4-甲基苯酚（甲酚）与甲醛，乙醛和丙醛缩合而合成的。1 H和13红外光谱已充分表征了氰酸酯1 H NMR光谱和单晶X射线衍射。这些化合物的熔化温度为88至143°C，而固化树脂的玻璃化转变温度为219至248°C，吸水率（96 h，85°C浸入）为2.05-3.21％，湿玻璃化温度为90-120°C。 174至193°C。这些性质表明，由creosol衍生的氰酸酯可用于多种军事和商业应用。已经用FTIR光谱和差示扫描量热法研究了氰酸酯的固化化学。结果表明，具有更高空间要求的桥连基团的氰酸酯与具有桥连亚甲基的那些相比，固化更慢，但也更完全。除了结构上的差异外，氰酸酯的纯度对固化化学和最终产品都有重要影响。T g的材料。在某些情况下，树脂在350°C下进行后固化会导致明显的分解和放气，但是在250–300°C下终止的固化方案会产
• Renewable polyphenols, thermoplastics, and resins
  申请人：THE UNITED STATES OF AMERICA AS REPRESENTED BY THE SECRETARY OF THE NAVY

  公开号：US10252966B1

  公开（公告）日：2019-04-09

  A series of renewable bisphenols has been synthesized from creosol (2-methoxy-4-methylphenol) through stoichiometric condensation with short chain aldehydes. Creosol can be readily produced from lignin, potentially allowing for the large scale synthesis of bisphenol A replacements from abundant waste biomass. The renewable bisphenols were isolated in good yield and purity without resorting to solvent intense purification methods. Zinc acetate was shown to be selective catalyst for ortho-coupling of formaldehyde but was unreactive with more sterically demanding aldehydes. Dilute HCl and HBr solutions were shown to be effective catalysts for the selective coupling of aldehydes in the position meta to the phenol. Acid solutions could be recycled and used multiple times without decreases in activity or yield.

  一系列可再生的双酚类化合物已经从甲酚（2-甲氧基-4-甲基苯酚）通过与短链醛的化学计量缩合合成。甲酚可以从木质素中轻松生产，潜在地允许从丰富的废弃生物质中大规模合成双酚A替代品。这些可再生的双酚类化合物以良好的产率和纯度分离出来，而无需使用溶剂密集的纯化方法。已经证明乙酸锌是甲醛的邻位偶联的选择性催化剂，但对于更具立体位阻的醛类不具有反应性。稀盐酸和溴化氢溶液被证明是对苯酚的间位选择性偶联的有效催化剂。酸性溶液可以回收并多次使用，而不会降低活性或产率。
• The effect of metal ions on the reaction of hydrogen peroxide with Kraft lignin model compounds
  作者：Yujun Sun、Michael Fenster、Annie Yu、Richard M Berry、Dimitris S Argyropoulos

  DOI：10.1139/v99-036

  日期：1999.6.1

  Peroxide bleaching is significantly affected by transition and alkaline earth metals. Isolating the effects of different transition and alkaline earth metals on the reactions of peroxide with different representative lignin structures allows the separation of the positive from the negative contributions of these metal ions. In this work, five monomeric or dimeric phenolic lignin model compounds were treated with alkaline hydrogen peroxide in the absence or presence of Mn²⁺, Cu²⁺, Fe³⁺, and Mg²⁺. We followed the disappearance of the starting material and the progress of demethylation, radical coupling and oxalic acid formation were followed. Transition metals increased the reactivities of all the lignin model compounds with hydrogen peroxide in the order Mn²⁺ > Cu²⁺ > Fe³⁺, which is the same as the order of activity toward peroxide decomposition while Mg²⁺ stabilized the system. Demethylation, radical coupling, and oxalic acid formation were all increased by the presence of transition metals in the system and decreased by the addition of Mg²⁺. The acceleration of the total degree of reaction and of the demethoxylation reactions improves peroxide bleaching, but the increase in the radical coupling reactions can affect the further bleachability of pulp while the increase in the formation of oxalic acid could lead to a greater probability of scaling.Key words: lignins, hydrogen peroxide, peroxide bleaching, reactivity, chemical pulps, metal compounds, alkali treatment, transition metals, delignification.

  过氧化物漂白受过渡金属和碱土金属的显着影响。隔离不同过渡金属和碱土金属对过氧化物与不同典型木质素结构反应的影响，可以将这些金属离子的正面和负面贡献分开。在这项工作中，五种单体或二聚酚酚木质素模型化合物在缺乏或存在Mn²⁺、Cu²⁺、Fe³⁺和Mg²⁺的碱性过氧化氢中处理。我们跟踪了起始物质的消失以及去甲基化、自由基偶联和草酸形成的进展。过渡金属按Mn²⁺ > Cu²⁺ > Fe³⁺的顺序增加了所有木质素模型化合物与过氧化氢的反应性，这与对过氧化物分解活性的顺序相同，而Mg²⁺稳定了系统。过渡金属的存在增加了体系中所有木质素模型化合物的去甲基化、自由基偶联和草酸形成，并且Mg²⁺的加入则减少了这些反应。总反应程度和去甲氧基化反应的加速改善了过氧化物漂白，但自由基偶联反应的增加可能会影响纸浆的进一步漂白性，而草酸形成的增加可能会导致更大的结垢概率。关键词：木质素、过氧化氢、过氧化物漂白、反应性、化学纸浆、金属化合物、碱处理、过渡金属、脱木质素。
• Selective C–C Bond Cleavage of Methylene-Linked Lignin Models and Kraft Lignin
  作者：Li Shuai、Jake Sitison、Sunitha Sadula、Junhuan Ding、Mark C. Thies、Basudeb Saha

  DOI：10.1021/acscatal.8b00200

  日期：2018.7.6

  Biorefinery and paper pulping lignins, referred hereto as technical lignins, contain condensed C–C interunit linkages. These robust C–C linkages with higher bond dissociation energies are difficult to disrupt under hydrogenolysis conditions, which are generally used for cleaving C–O bonds of native lignin in biomass or model C–O linked compounds. Thus, selective interunit C–C cleavage to release aromatic monomers

  生物炼油厂和纸浆造纸业的木质素（以下称为工业木质素）包含稠密的C-C单元间键。这些具有较高键解离能的健壮的C–C键在氢解条件下很难被破坏，这些条件通常用于裂解生物质或模型C–O连接的化合物中天然木质素的C–O键。因此，选择性的单元间C–C裂解以释放用于高价值应用的芳族单体是一个挑战。我们报告了一种有效的催化体系，可在温和条件下选择性裂解此类C–C键。代表性的亚甲基连接的CC模型二聚体使用商业CoS 2在合理的低温（250°C）下1.5 h内即可获得主要两种芳香族单体的88％收率。催化剂。长时间反应后，芳族单体转化为非芳族产物。芳香环脱羟基后，二聚体的单元间C–C键对裂解变得不活泼，而甲氧基对裂解的影响很小。β-1和5-5 C–C连接的模型二聚体形成脱甲氧基化的羟基二聚体为主要产物。纯化的硫酸盐木质素馏分的解聚产生五个芳族单体和较低分子量的可溶性产物。这项研究开辟了使用廉价催化剂对工业木质素进行增值的可能性。