5,5′-(propane-1,1-diyl)bis(2-methoxy-4-methylphenol) | 102430-93-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,5′-(propane-1,1-diyl)bis(2-methoxy-4-methylphenol)
• 英文别名: 5,5-(propane-1,1-diyl)bis(2-methoxy-4-methylphenol)；5-[1-(5-Hydroxy-4-methoxy-2-methylphenyl)propyl]-2-methoxy-4-methylphenol
• CAS: 102430-93-3
• 化学式: C₁₉H₂₄O₄
• 分子量: 316.397
• InChiKey: MXEMWQSWIMIPSZ-UHFFFAOYSA-N

物化性质

• 沸点：
  499.7±45.0 °C(Predicted)
• 密度：
  1.129±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  5,5′-(propane-1,1-diyl)bis(2-methoxy-4-methylphenol) 在 吡啶 、 1,1'-双(二苯基膦)二茂铁 、 甲酸 、 palladium diacetate 、 三溴化硼 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.33h， 生成 4,4′-(propane-1,1′-diyl)bis(1-cyanato-3-methylbenzene)
  参考文献：
  名称：

  Effects of o-Methoxy Groups on the Properties and Thermal Stability of Renewable High-Temperature Cyanate Ester Resins

  摘要：

  Renewable phenols derived from biomass sources often contain methoxy groups that alter the properties of derivative polymers. To evaluate the impact of o-methoxy groups on the performance characteristics of cyanate ester resins, three bisphenols derived from the renewable phenol creosol were deoxygenated by conversion to ditriflates followed by palladium-catalyzed elimination and hydrolysis of the methoxy groups. The deoxygenated bisphenols were then converted to the following cyanate ester resins: bis(4-cyanato-2-methylphenyl)methane (16), 4,4'-(ethane-1,1'-diy1)bis-(1-cyanato-3-methylbenzene) (17), and 4,4'-(propane-1,1'-diy1)bis(1-cyanato-3-methylbenzene) (18). The physical properties, cure chemistry, and thermal stability of these resins were evaluated and compared to those of cyanate esters derived from the oxygenated bisphenols. 16 and 18 had melting points 37 and >95 degrees C lower, respectively, than the oxygenated versions, while 17 had a melting point 14 degrees C higher. The T-g's of thermosets generated from the deoxygenated resins ranged from 267 to 283 degrees C, up to 30 degrees C higher than the oxygenated resins, while the onset of thermal degradation was 50-80 degrees C higher. The deoxygenated resins also exhibited water uptakes up to 43% lower and wet T(g)s up to 37 degrees C higher than the oxygenated resins. TGA-FTIR of thermoset networks derived from 16-18 revealed a different decomposition mechanism compared to the oxygenated resins. Instead of a low-temperature pathway that resulted in the evolution of phenolic compounds, 16-18 had significantly higher char yields and decomposed via evolution of small molecules including isocyanic acid, CH4, CO2, and NH3.

  DOI：

  10.1021/acs.macromol.5b00496
• 作为产物：
  描述：

  2-甲氧基-4-甲基苯酚 、 丙醛 在 氢溴酸 作用下， 以 水 为溶剂， 反应 16.0h， 以67%的产率得到5,5′-(propane-1,1-diyl)bis(2-methoxy-4-methylphenol)
  参考文献：
  名称：

  由甲酚合成可再生双酚

  摘要：

  甲酚（2-甲氧基-4-甲基苯酚）通过化学计量与短链醛缩合而合成了一系列可再生双酚。木质素可轻松生产甲酚，潜在地允许从丰富的废物生物质中大规模合成双酚A替代品。可分离的可再生双酚具有良好的收率和纯度，无需借助溶剂密集型纯化方法。醋酸锌被证明是甲醛邻位偶联的选择性催化剂，但是当使用空间上要求更高的醛时，醋酸锌不具有反应性。稀HCl和HBr溶液被证明是在位间醛选择性偶联的有效催化剂羟基。酸溶液可以循环使用多次，而不会降低活性或收率。

  DOI：

  10.1002/cssc.201100402

文献信息

• 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。
• [EN] PRODUCTION OF HIGHLY PURE META,META-COUPLED BIS(4-ALKYLPHENOL) DERIVATIVES AND USES THEREOF<br/>[FR] PRODUCTION DE DÉRIVÉS DE BIS(4-ALKYLPHÉNOL) MÉTA,MÉTA-COUPLÉS TRÈS PURS ET LEURS UTILISATIONS
  申请人：UNIV LEUVEN KATH

  公开号：WO2018134427A1

  公开（公告）日：2018-07-26

  In general the present invention concerns a method for production of highly pure m,m'- coupled bis(4-alkylphenol) derivatives from particular lignin-derived 4-alkylphenol derivatives. More specifically this invention relates to a process for the selective purification of m,m'- coupled bis(4-alkylphenol) derivatives by selective crystallization in the presence of residual substrate and isomeric and/or oligomeric by-products/impurities. This new class of bis(4-alkylphenol)s are valuable precursors for renewable thermoplastics, (high temperature) resins/thermosets, bio-derived C15-C19 fuel additives, antioxidants, UV-stabilizers, plasticizers, soluble n-type perylene copolymers and/or positive working photoresists.

  总的来说，本发明涉及一种从特定木质素衍生的4-烷基酚衍生物生产高纯度m，m'-偶联的双(4-烷基酚)衍生物的方法。更具体地说，本发明涉及一种通过在残留底物和同分异构体和/或寡聚体副产物/杂质存在下进行选择性结晶实现对m，m'-偶联的双(4-烷基酚)衍生物的选择性纯化的方法。这种新类别的双(4-烷基酚)是可再生热塑性塑料、(高温)树脂/热固性塑料、生物衍生的C15-C19燃料添加剂、抗氧化剂、紫外线稳定剂、增塑剂、可溶性n-型苝共聚物和/或正向光刻胶的有价值前体。
• PRODUCTION OF HIGHLY PURE META,META-COUPLED BIS(4-ALKYLPHENOL) DERIVATIVES AND USES THEREOF
  申请人：Katholieke Universiteit Leuven

  公开号：EP3571180A1

  公开（公告）日：2019-11-27
• US9315623B1
  申请人：——

  公开号：US9315623B1

  公开（公告）日：2016-04-19