3-hydroxy-3,5,5-trimethylcyclohexanone | 89768-14-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-hydroxy-3,5,5-trimethylcyclohexanone
• 英文别名: Cyclohexanone, 3-hydroxy-3,5,5-trimethyl-；3-hydroxy-3,5,5-trimethylcyclohexan-1-one
• CAS: 89768-14-9
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: ZFBPQXPBBSXEQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  氧化异佛尔酮 在 naphthalen-1-yl-lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以78%的产率得到3-hydroxy-3,5,5-trimethylcyclohexanone
  参考文献：
  名称：

  Lithium naphthalenide induced reductive cleavage of α,β-epoxy ketones: an efficient procedure for the preparation of β-hydroxy ketones

  摘要：

  萘基锂化合物作为一种温和且高效的试剂，能够有效地切割α,β-环氧酮，从而以良好的产率生成相应的β-羟基酮。

  DOI：

  10.1039/a904646a

文献信息

• Aryl-substituted dimethylbenzimidazolines as effective reductants of photoinduced electron transfer reactions
  作者：Eietsu Hasegawa、Taku Ohta、Shiori Tsuji、Kazuma Mori、Ken Uchida、Tomoaki Miura、Tadaaki Ikoma、Eiji Tayama、Hajime Iwamoto、Shin-ya Takizawa、Shigeru Murata

  DOI：10.1016/j.tet.2015.06.071

  日期：2015.8

  Photoinduced electron transfer (PET) reactions promoted by 2-aryl substituted 1,3-dimethylbenzimidazolines (Ar-DMBIH) were investigated. Excited states of Ar-DMBIH, formed by irradiation using light above 360 nm, initiate PET reductions of various organic substrates, including transformations of epoxy ketones to aldols, free radical rearrangements such as the Dowd-Beckwith ring-expansion and 5-exo

  研究了由2-芳基取代的1,3-二甲基苯并咪唑啉（Ar-DMBIH）促进的光诱导电子转移（PET）反应。通过使用360 nm以上的光进行辐照而形成的Ar-DMBIH激发态，可引发PET还原各种有机底物，包括将环氧酮转变为羟醛，自由基重排（如Dowd-Beckwith环扩环和5-外己烯基环化） ，对N脱保护-磺酰基吲哚和酰基甲酸酯的烯丙基化。在这些方法中，具有1-萘基，2-萘基，1-吡啶基和9-蒽取代基的Ar-DMBIH在形式上起两个电子和一个质子供体的作用，而被羟基萘基取代的衍生物充当两个电子和两个质子的供体。根据吸收光谱研究，循环伏安法和DFT计算的结果，提出了这些还原反应的机理顺序，包括对Ar-DMBIH的芳基发色团进行初始光激发，然后单电子转移（SET）到有机物底物产生苯并咪唑啉的自由基阳离子和底物的自由基阴离子。
• CHEMO- AND REGIOSELECTIVE REDUCTION OF α,β-EPOXY KETONES TO β-HYDROXY KETONES BY SODIUM HYDROGENTELLURIDE
  作者：Atsuhiro Osuka、Koji Taka-Oka、Hitomi Suzuki

  DOI：10.1246/cl.1984.271

  日期：1984.2.5

  α,β-Epoxy ketones were chemo- and regioselectively reduced to β-hydroxy ketones by sodium hydrogenteiiuride in good yields.

  α,β-环氧酮通过氢化钠选择性地还原为β-羟基酮，产率良好。
• 1,3-Dimethyl-2-phenylbenzimidazoline (DMPBI)-Acetic Acid: An Effective Reagent System for Photoinduced Reductive Transformation of α,β-Epoxy Ketones to β-Hydroxy Ketones
  作者：Eietsu Hasegawa、Naoki Chiba、Aiko Nakajima、Kumiko Suzuki、Akira Yoneoka、Kazuki Iwaya

  DOI：10.1055/s-2001-15055

  日期：——

  aqueous solvents. When THF solutions containing aryl carbonyl possessing α,β-epoxy ketones and DMPBI and acetic acid were irradiated (λ > 280 nm), β-hydroxy ketones were isolated in good to excellent yields. Photosensitized conditions (λ > 340 nm) were employed for the reactions of alkyl carbonyl possessing α,β-epoxy ketones.

  1,3-二甲基-2-苯基苯并咪唑啉 (DMPBI) 和乙酸的组合已用于将 α,β-环氧酮光诱导还原转化为 β-羟基酮。使用几种质子供体进行的光反应研究表明，乙酸优于其他质子供体，例如 HCl、p-TsOH、MeOH 和水。1,3-二甲基-2-苯基苯并咪唑鎓在与乙酸的反应中生成，而 N-苯甲酰基-N,N'-二甲基-邻苯二胺在水性溶剂中生成。当辐照含有具有 α,β-环氧酮和 DMPBI 和乙酸的芳基羰基的 THF 溶液时（λ > 280 nm），β-羟基酮以良好至优异的收率分离。光敏条件（λ > 340 nm）用于具有α，β-环氧酮的烷基羰基的反应。
• 2-Hydroxyphenyl-1,3-dimethylbenzimidazolines. Formal Two Hydrogen Atom-donors for Photoinduced Electron Transfer Reactions
  作者：Eietsu Hasegawa、Naoki Chiba、Tomoya Takahashi、Shinya Takizawa、Takashi Kitayama、Toshio Suzuki

  DOI：10.1246/cl.2004.18

  日期：2004.1

  Both 2-(2′-hydroxyphenyl)-1,3-dimethylbenzimidazoline and 2-(4′-hydroxyphenyl)-1,3-dimethylbenzimidazoline were found to act as formal two hydrogen atom-donors for photoinduced electron transfer reactions of epoxy ketones and other carbonyl compounds.

  研究发现，2-(2′-羟基苯基)-1,3-二甲基苯并咪唑啉和 2-(4′-羟基苯基)-1,3-二甲基苯并咪唑啉在环氧酮和其他羰基化合物的光诱导电子转移反应中均可作为正式的两个氢原子供体。
• Electrolysis in the presence of ultrasound: cell geometries for the application of extreme rates of mass transfer in electrosynthesis
  作者：Frank Marken,、Richard G. Compton,、Stephen G. Davies、Steven D. Bull、Thies Thiemann、M. Luisa Sá e Melo、André Campos Neves、José Castillo、C. Gisèle Jung、André Fontana

  DOI：10.1039/a701004d

  日期：——

  Two types of sonoelectrochemical reactors for preparative synthetic work are suggested and characterized by their performance in the reversible one electron reduction of cobalticenium cations in acetonitrile solution. The dominant effect of ultrasound is to strongly agitate the liquid phase and the corresponding parameters (mass transport coefficients) for the transport at the electrode surface are reported. An upper limit for ultrasound induced mass transport at macroelectrodes an order of magnitude beyond that achieved in conventional electrolysis is described. Further, for a synthetic scale reaction, the reductive ring opening of the α,β-epoxyketone isophorone oxide to yield the corresponding β-hydroxyketone, an improved current efficiency (3 F for a direct two electron reduction) and a clean conversion (yields up to 80% isolated) are demonstrated. The extremely high rates of mass transport achieved in the presence of ultrasound considerably enhance the performance and current efficiency in electrosynthesis by selectively increasing the rates of the mass transport controlled processes.

  本文介绍了两种用于制备合成工作的超声电化学反应器，并描述了其在乙腈溶液中可逆性一电子还原钴离子阳离子的性能。超声波的主要作用是强烈搅拌液相，并报告了电极表面传输的相应参数（质量传递系数）。本文描述了超声波在宏观电极上引起的质量传递的上限，其数值级超过了常规电解中达到的上限。此外，对于合成规模反应，本文还展示了α，β-环氧酮异佛尔酮的还原开环反应，以产生相应的β-羟基酮，并提高了电流效率（3 F用于直接二电子还原）和清洁转化（分离率高达80%）。超声波的存在下实现了极高的质量传递速率，通过选择性提高质量传递速率控制过程，大大提高了电合成中的性能和电流效率。