2-hydroxy-2,5-dimethyltetrahydrofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 英文名称: 2-hydroxy-2,5-dimethyltetrahydrofuran
• 英文别名: 2,5-Dimethyloxolan-2-ol
• 化学式: C₆H₁₂O₂
• 分子量: 116.16
• InChiKey: YDFVTCKSQNCMKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,5-己二酮 在 [Ru(OH₂)₃(di(picolyl)amine)](OTf)₂ 、 氢气 作用下， 以 水 为溶剂， 200.0 ℃ 、5.5 MPa 条件下， 反应 16.0h， 以12%的产率得到2-hydroxy-2,5-dimethyltetrahydrofuran
  参考文献：
  名称：

  In situ generation of water-stable and -soluble ruthenium complexes of pyridine-based chelate-ligands and their use for the hydrodeoxygenation of biomass-related substrates in aqueous acidic medium

  摘要：

  The complexes [Ru(2,2'-dipicolylamine)(OH2)(3)](OTf)(2) and [Ru(6,6'-bis(aminomethyl)-2,2'-bipyridine)(OH2)(2)](OTf)(2) can be prepared by reaction of 2,2'-dipicolylamine or 6,6'-bis(aminomethyl)-2,2'-bipyridine with [Ru-IIIi(DMF)(6)](OTf)(3) in aqueous medium. During the reaction an in situ reduction from a paramagnetic Ru-III to a diamagnetic Ru-II-complexes occurs with one equivalent of DMF acting as the reducing agent for two ruthenium centres by its reaction with water and decomposition to dimethylammonium triflate and CO2 generating an additional equivalent of HOTf in the process. The complex solutions are active as catalysts for the hydrogenation of 2,5-hexanedione and 2,5-dimethylfuran to 2,5-hexanediol and 2,5-dimethyltetrahydrofuran with both complexes realizing very high yields (>95% combined yield of the two products with the selectivity determined as a function of added acid co-catalyst). The 2,2'-dipicolylamine complex is stable to 150 degrees C, while the 6,6'-bis(aminomethyl)-2,2'-bipyridine complex is stable to 200 degrees C allowing the in situ hydrolysis of 2,5-dimethylfuran to the 2,5-hexanedione and thus direct conversion to the same products in up to 78% combined yield. The effects of co-solvents, acid co-catalysts and temperature on catalyst activity, decomposition and stability are explored. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2015.08.026

文献信息

• Nitroalkanes in Aqueous Medium as an Efficient and Eco-Friendly Source for the One-Pot Synthesis of 1,4-Diketones, 1,4-Diols, δ-Nitroalkanols, and Hydroxytetrahydrofurans
  作者：Roberto Ballini、Luciano Barboni、Guido Giarlo

  DOI：10.1021/jo0351163

  日期：2003.11.1

  The Michael addition of primary aliphatic nitro compounds to alpha,beta-unsaturated enones, performed in aqueous media, provides the one-pot synthesis of 1,4-diketones, 1,4-diols, delta-nitroalkanols, and hydroxytetrahydrofurans, respectively, by the appropriate choice of the reaction conditions.

  在水性介质中进行的伯脂肪族硝基化合物向α，β-不饱和烯酮的迈克尔加成反应分别通过以下方法一锅合成1,4-二酮，1,4-二醇，δ-硝基链烷醇和羟基四氢呋喃的反应条件适当选择。
• [Ru(triphos)(CH₃CN)₃](OTf)₂ as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
  作者：Elnaz Latifi、Austin D. Marchese、Margaret C. W. Hulls、Dmitriy V. Soldatov、Marcel Schlaf

  DOI：10.1039/c7gc01956d

  日期：——

  5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium at temperatures between 150 and 200 °C realizing up to 96% combined yields of 2,5-hexanediol and 2,5-dimethyl-tetrahydrofuran with the product distribution being sensitive to the amount of acid co-catalyst (HOTf) present. For the furan, the reaction pathway is through an acid-catalyzed hydrolysis to the dione rather than direct hydrogenation

  络合物[Ru（triphos）（CH 3 CN）3 ]（OTf）2是一种有效的催化剂，可在150至200°C的温度下，在含水酸性介质中将2,5-己二酮和2,5-二甲基呋喃加氢，实现2,96-己二醇和2,5的合计产率高达96％ -二甲基-四氢呋喃，产物分布对存在的酸助催化剂（HOTf）的数量敏感。对于呋喃，反应途径是通过酸催化的水解成二酮，而不是环的直接氢化。对二酮的氢化反应显示出对氢压力的一级依赖性，这是通过在温度和压力下（150°C下为1.38–6.90 MPa）直接测量氢的吸收率来确定的，并且假定该氢可通过[Ru]的氢杂化活化作用进行操作。 （H）x（triphos）（Y）y ] n+（Y =溶剂，水，抗衡离子）物种通过腈配体的损失和氢化原位形成。在水中，催化剂通过二聚反应失活为[Ru 2（μ-OH） 3（triphos） 2 ]（OTf）。
• Hydrodeoxygenation of 2,5-Hexanedione and 2,5-Dimethylfuran by Water-, Air-, and Acid-Stable Homogeneous Ruthenium and Iridium Catalysts
  作者：Ryan J. Sullivan、Elnaz Latifi、Benjamin K.-M. Chung、Dmitriy V. Soldatov、Marcel Schlaf

  DOI：10.1021/cs501202t

  日期：2014.11.7

  The complexes [(4'-Ph-terpy)Ru(H2O)(3)](OTf)(2) and [(4'-Ph-terpy)Ir(OTf)(3)] have been evaluated as catalysts for the conversion of 2,5-hexanedione and 2,5-dimethylfuran to hydrodeoxygenated products in aqueous acidic medium at elevated temperature (150-225 degrees C) under hydrogen gas (5.5 MPa). These two substrates form part of a value chain leading from C6 sugars to 2,5-hexanediol, 2,5-dimethyltetrahydrofuran, and hexane, which can be generated by the homogeneously acting ruthenium catalyst in up to 69%, 80%, and 10% yield, respectively, while at T > 175 degrees C the iridium system decomposes to a highly active but heterogeneously acting coating in the reactor defeating the premise of a homogeneous catalyst system. The deactivation and decomposition pathway of both catalysts leads to the formation of a series of isostructural complexes [M(4'-Ph-terpy)2](n)+ (M = Fe, Ni, Ru, Ir; n = 2, 3) characterized by ESI-MS and single crystal X-ray crystallography, in which the source of the Fe and Ni is the 316SS reactor body.
• KUPCHIK, I. P.;KORYAK, EH. B.;GEVAZA, YU. I.;STANINETS, V. I., YKP. XIM. ZH., 54,(1988) N 11, S. 1180-1183
  作者：KUPCHIK, I. P.、KORYAK, EH. B.、GEVAZA, YU. I.、STANINETS, V. I.

  DOI：——

  日期：——
• In situ generation of water-stable and -soluble ruthenium complexes of pyridine-based chelate-ligands and their use for the hydrodeoxygenation of biomass-related substrates in aqueous acidic medium
  作者：Thomas A. Minard、Christopher T. Oswin、Fraser D.C. Waldie、Jennifer K. Howell、Benjamin M.T. Scott、Domenico Di Mondo、Ryan J. Sullivan、Benjamin Stein、Michael Jennings、Marcel Schlaf

  DOI：10.1016/j.molcata.2015.08.026

  日期：2016.10

  The complexes [Ru(2,2'-dipicolylamine)(OH2)(3)](OTf)(2) and [Ru(6,6'-bis(aminomethyl)-2,2'-bipyridine)(OH2)(2)](OTf)(2) can be prepared by reaction of 2,2'-dipicolylamine or 6,6'-bis(aminomethyl)-2,2'-bipyridine with [Ru-IIIi(DMF)(6)](OTf)(3) in aqueous medium. During the reaction an in situ reduction from a paramagnetic Ru-III to a diamagnetic Ru-II-complexes occurs with one equivalent of DMF acting as the reducing agent for two ruthenium centres by its reaction with water and decomposition to dimethylammonium triflate and CO2 generating an additional equivalent of HOTf in the process. The complex solutions are active as catalysts for the hydrogenation of 2,5-hexanedione and 2,5-dimethylfuran to 2,5-hexanediol and 2,5-dimethyltetrahydrofuran with both complexes realizing very high yields (>95% combined yield of the two products with the selectivity determined as a function of added acid co-catalyst). The 2,2'-dipicolylamine complex is stable to 150 degrees C, while the 6,6'-bis(aminomethyl)-2,2'-bipyridine complex is stable to 200 degrees C allowing the in situ hydrolysis of 2,5-dimethylfuran to the 2,5-hexanedione and thus direct conversion to the same products in up to 78% combined yield. The effects of co-solvents, acid co-catalysts and temperature on catalyst activity, decomposition and stability are explored. (C) 2015 Elsevier B.V. All rights reserved.