2-(4-hydroxy-3-methoxyphenyl)butanal | 40275-46-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-(4-hydroxy-3-methoxyphenyl)butanal
• 英文别名: 2-(p-Hydroxy-m-methoxyphenyl)-butanal-1；α-ethyl-4-hydroxy-3-methoxy-benzeneacetaldehyde；2-ethyl-2-(3-methoxy-4-hydroxy-phenyl)-acetaldehyde；2-(4-Hydroxy-3-methoxyphenyl)butanal
• CAS: 40275-46-5
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: MREREEWFAZGGMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  一氧化碳 、 异丁香酚 在 methoxy(cyclooctadiene)rhodium(I) dimer 、 trisodium tris(3-sulfophenyl)phosphine 、 氢气 、 十六烷基三甲基溴化铵 作用下， 以 水 为溶剂， 100.0 ℃ 、2.0 MPa 条件下， 反应 1.0h， 生成 2-(4-hydroxy-3-methoxyphenyl)butanal 、 3-(4-hydroxy-3-methoxyphenyl)-2-methylpropanal
  参考文献：
  名称：

  Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands

  摘要：

  The rhodium-catalyzed hydroformylation of eugenol was performed in aqueous biphasic systems using various water soluble phosphines: TPPTS (triphenylphosphinetrisulphonated); BDPPETS (bisdiphenylphosphinoethanetetrasulphonated), BDPPPTS (bisdiphenylphosphinopropanetetrasulphonated) and BISBIS (diphosphane 2,2'-bis(diphenylphosphinomethyl)-1,1'-biphenyl disuphonated). The addition of the cationic surfactant CTAB (cetyltrimethylammonium bromide) increased the reaction rate; however, high surfactant concentrations unfavorably affected the reaction selectivity. The regio-selectivity of the hydroformylation was strongly depended on the ligand nature. The procedure was successfully extended to other allylbenzenes, i.e., estragole and safrole, producing several fragrance compounds starting from the substrates easily available from natural bio-renewable resources. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.apcata.2014.11.028

文献信息

• Hydroformylation of natural olefins with the [Rh(COD)(μ-OMe)]2/TPPTS complex in BMI-BF4/toluene biphasic medium: Observations on the interfacial role of CTAB in reactive systems
  作者：Pablo J. Baricelli、Mariandry Rodríguez、Luis G. Melean、Margarita Borusiak、Isis Crespo、Juan C. Pereira、Merlín Rosales

  DOI：10.1016/j.mcat.2020.111189

  日期：2020.12

  The complex [Rh(COD)(μ-OMe)]2 in presence of TPPTS (TPPTS = triphenylphosphinetrisulfonate) was evaluated as catalyst precursor for the in situ hydroformylation of natural olefins (eugenol, estragole and safrole) in biphasic media BMIm-BF4/toluene. Under moderate reaction conditions, the substrates showed the following reactivity order: eugenol > estragole > safrole. The rhodium system showed a high

  在TPPTS（TPPTS =三苯基膦三磺酸盐）存在下，络合物[Rh（COD）（μ-OMe）] 2被评估为在双相介质BMIm-BF 4中天然烯烃（丁香酚，雌蕊和黄樟素）原位加氢甲酰化的催化剂前体/甲苯。在适度的反应条件下，底物显示出以下反应顺序：丁子香酚>雌蕊>丁香酚。铑体系显示出对所需醛的高活性和选择性。发现使用十六烷基三甲基溴化铵（CTAB）作为相转移剂会抑制加氢甲酰化反应。催化相最多可循环使用四次，而活性或选择性没有明显损失。在这项工作中，我们报告了使用具有亲水特性的离子液体，而不在反应介质中使用水。
• Verfahren zur Hydroformylierung von substituierten Allylbenzolen
  申请人：Celanese Chemicals Europe GmbH

  公开号：EP1719752A1

  公开（公告）日：2006-11-08

  Die vorliegende Erfindung betrifft ein Verfahren zur Hydroformylierung von substituierten Allylbenzolen, insbesondere von Eugenol, Estragol, Eugenolmethylether und Safrol in Gegenwart einer wässrigen Katalysatorlösung, enthaltend wasserlösliche Rhodiumverbindungen, die sulfonierte Arylphosphine in komplexer Bindung enthalten.

  本发明涉及一种在含有水溶性铑化合物的水催化剂溶液存在下，对取代烯丙基苯酚进行氢甲酰化的方法，特别是对丁香酚、茴香醛、丁香酚甲醚和樟脑进行氢甲酰化的方法，所述水催化剂溶液中包含含有磺化芳基膦的复合配位的铑化合物。
• Production of diacetates from propenylphenols: A one-pot two-step approach involving hydroformylation/hydrogenation/O-acylation
  作者：Adelson de O. Dias、Fábio G. Delolo、Jesus A. Avendaño-Villarreal、Eduardo N. dos Santos、Elena V. Gusevskaya

  DOI：10.1016/j.apcata.2023.119369

  日期：2023.9

  A one-pot two-step approach for the synthesis of diacetate esters from propenylphenols was developed. This protocol involves the functionalization of the propenylphenol in two remote sites, performing multiple consecutive and parallel reactions: hydroformylation of the C-C double bond, hydrogenation of the formed aldehyde, and the O-acylation of both phenolic and hydroxy groups of the resulting alcohol

  开发了一种由丙烯基酚合成二乙酸酯的一锅两步法。该方案涉及丙烯基苯酚在两个远程位点的官能化，执行多个连续且平行的反应：CC双键的加氢甲酰化、形成的醛的氢化以及所得醇的酚基和羟基的O-酰化。对于这样一个具有挑战性的转化，必须开发特定的催化系统，包括用于串联加氢甲酰化/氢化的Rh络合物和磷(III)配体，以及4-二甲基氨基吡啶（有机催化剂）以促进Ac 2 O的酰化步骤。 Ac 2的存在在氢化步骤导致不希望的副反应之前，开发了一锅两步方案以提高选择性。最终，该方法能够从丙烯基酚中以良好到优异的收率（82-96％）获得二乙酸酯，二乙酸酯作为香料和香料成分具有潜在的价值。
• Hydroaminomethylation of eugenol with di-n-butylamine catalyzed by rhodium complexes: Bringing light on the promoting effect of Brönsted acids
  作者：Kelley C.B. Oliveira、Alexandra G. Santos、E.N. dos Santos

  DOI：10.1016/j.apcata.2012.08.033

  日期：2012.11

  The hydroaminomethylation of eugenol with di-n-butylamine was performed employing a bis[(1,5-ciclooctadiene)(mu-methoxy)rhodium(1)] as pre-catalyst. In the absence of phosphines, the catalyst was efficient in the process, but the regioselectivity for amines was poor. For phosphine-promoted catalyst, the chemoselectivity at the hydroformylation step improved, but the hydrogenation of enamine intermediates was hampered. The regioselectivity within the class of amines was surprisingly high (>96%) for the linear product. The addition of triflic acid (10-20 mol%) improved significantly the efficiency of HAM. Employing the 22'-bis((diphenylphosphino)methyl)-1,1'-binaphthyl as ancillary and triflic acid as a promoter, the linear product was obtained in up to 93% yield. (C) 2012 Elsevier B.V. All rights reserved.
• Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands
  作者：Pablo J. Baricelli、Mariandry Rodriguez、Luis G. Melean、Maria Modroño Alonso、Margarita Borusiak、Merlin Rosales、Beatriz Gonzalez、Kelley C.B. de Oliveira、Elena V. Gusevskaya、Eduardo N. dos Santos

  DOI：10.1016/j.apcata.2014.11.028

  日期：2015.1

  The rhodium-catalyzed hydroformylation of eugenol was performed in aqueous biphasic systems using various water soluble phosphines: TPPTS (triphenylphosphinetrisulphonated); BDPPETS (bisdiphenylphosphinoethanetetrasulphonated), BDPPPTS (bisdiphenylphosphinopropanetetrasulphonated) and BISBIS (diphosphane 2,2'-bis(diphenylphosphinomethyl)-1,1'-biphenyl disuphonated). The addition of the cationic surfactant CTAB (cetyltrimethylammonium bromide) increased the reaction rate; however, high surfactant concentrations unfavorably affected the reaction selectivity. The regio-selectivity of the hydroformylation was strongly depended on the ligand nature. The procedure was successfully extended to other allylbenzenes, i.e., estragole and safrole, producing several fragrance compounds starting from the substrates easily available from natural bio-renewable resources. (C) 2014 Elsevier B.V. All rights reserved.