2-(cyclohexylmethylidene)cyclohexanone | 24195-40-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(cyclohexylmethylidene)cyclohexanone
• 英文别名: 2-Hexahydrobenzyliden-cyclohexanon；2-(Cyclohexylmethylidene)cyclohexan-1-one
• CAS: 24195-40-2
• 化学式: C₁₃H₂₀O
• 分子量: 192.301
• InChiKey: JFFUVFUXWNKVNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(cyclohexylmethylidene)cyclohexanone 在 镍 乙醇 、 氢气 、 sodium 作用下， 生成 trans-2-Hexahydro-benzyl-cyclohexanol
  参考文献：
  名称：

  Moreau,M. et al., Bulletin de la Societe Chimique de France, 1969, p. 1362 - 1367

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(cyclohexylhydroxymethyl)cyclohexanone 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 0.5h， 以95%的产率得到2-(cyclohexylmethylidene)cyclohexanone
  参考文献：
  名称：

  通过烯丙基邻锡烷基酮基的分子间羟醛反应

  摘要：

  α，β-不饱和酮与三丁基锡自由基的温和中性自由基反应产生了共振稳定的烯丙基O-锡烷基酮基中间体。接下来，通过随后的氢原子转移生成的锡（IV）烯醇锡，再用各种醛淬灭，生成羟醛产物，可以很容易地用对甲苯磺酸消除，得到新的α/β-不饱和酮，其E / Z比最高为> 100：1。

  DOI：

  10.1016/0040-4039(95)01999-x

文献信息

• Facile alkylation of o-hydroxyarylaldehydes and α-formylketones with trialkylboranes
  作者：Keiji Okada、Yasushi Hosoda、Masaji Oda

  DOI：10.1016/s0040-4039(00)85435-0

  日期：1986.1

  Trialkylboranes readily undergo alkylation reactions with o-hydroxyarylaldehydes and α-formylketones via the dialkylboryl complexes.

  三烷基硼烷容易通过二烷基硼基络合物与邻-羟基芳基醛和α-甲酰基酮发生烷基化反应。
• Reversal of Enantioselectivity in Aldol Reaction: New Data on Proline/γ-Alumina Organic–Inorganic Hybrid Catalysts
  作者：György Szőllősi、Mónika Fekete、András A. Gurka、Mihály Bartók

  DOI：10.1007/s10562-013-1177-1

  日期：2014.3

  We report new results on the aldol reactions between aldehydes of three different types (aromatic, aliphatic and cycloaliphatic) and acetone/cycloalkanones as reaction partners, driven by organic-inorganic hybrid catalyst Pro/gamma-Al2O3. In contrast to the homogeneous liquid-phase reaction, over Pro/gamma-Al2O3 reversal of the enantioselection in up to 20-40 % ee depending on the structure of the aldehyde was observed in reactions of acetone. Reversal of the ee in the presence of gamma-Al2O3 cannot be generalized, as it has only been observed for acetone among the ketones studied by us. It was proven using methods of a great variety such as ultrasonic irradiation, reuse measurements on used catalyst and the filtrate of the first reaction, measurements on the l-Pro-l-Pro(OH) dipeptide, studies using mixtures of l-Pro and d-Pro that the organic-inorganic hybrid catalyst Pro/gamma-Al2O3 formed in situ is responsible for reversal of the ee. In the reactions of cycloalkanones there is presumably competition between the liquid-phase and the surface reaction over Pro/gamma-Al2O3 with preference for the former. Based on these results a surface reaction pathway was proposed. Although, the ees obtained under heterogeneous catalytic conditions are low, further studies may lead to application of this unusual phenomenon for obtaining chiral heterogeneous catalysts suitable for the preparation of the desired enantiomer of a chiral compound using the same chiral source.
• Reactions of Tin(IV) Enolates Obtained from <i>O</i>-Stannyl Ketyls under Neutral Free Radical Conditions
  作者：Eric J. Enholm、Paul E. Whitley、Yongping Xie

  DOI：10.1021/jo960639e

  日期：1996.1.1

  Under mild and neutral free radical conditions, an alpha,beta-unsaturated ketone reacted with tributyltin hydride to produce an intermediate resonance-stabilized allylic O-stannyl ketyl. Upon subsequent hydrogen atom abstraction, a tin(IV) enolate was afforded which could be quenched with a variety of electrophiles and form new carbon-carbon bonds. Aldehydes react to produce aldol-type products and both intramolecular and intermolecular carbonyl addition reactions were investigated using this strategy. Using similar methodology, the tin(TV) enolate could be quenched in the presence of HMPA with various alkyl halides and alpha,beta-unsaturated carbonyl compounds (Michael accepters) to yield alkylated products in good yields. These reactions represent a very mild regioselective alternative to metal enolate formation which usually requires strong bases such as LDA or strongly reductive dissolving metal conditions to achieve success. New carbon skeletons for natural product synthesis can be readily constructed using this chemically neutral approach.