4-methyl-4-n-propylcyclohexenone | 35161-15-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methyl-4-n-propylcyclohexenone
• 英文别名: 4-ethyl-4-methylcyclohexa-2,5-dien-1-one；DL-4-Methyl-4-propyl-2-cyclohexenon；4-Methyl-4-n-propylcyclohex-2-enon；2-Cyclohexen-1-one, 4-methyl-4-propyl-；4-methyl-4-propylcyclohex-2-en-1-one
• CAS: 35161-15-0
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: WZPGBIYWYMLIEU-UHFFFAOYSA-N

物化性质

• 沸点：
  221.5±10.0 °C(Predicted)
• 密度：
  0.902±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  4-methyl-4-n-propylcyclohexenone 在 palladium on activated charcoal 氢气 作用下， 生成 1,1-Dimethoxy-4-methyl-4-propyl-cyclohexane
  参考文献：
  名称：

  Vandenbroucke,W.; Anteunis,M., Journal of the Chemical Society. Perkin transactions II, 1972, p. 123 - 127

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲基戊醛 、 丁烯酮 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 生成 4-methyl-4-n-propylcyclohexenone
  参考文献：
  名称：

  环己二烯与环戊二烯的不对称催化狄尔斯-阿尔德-反应中的斯塔克和斯特里施控制

  摘要：

  摘要Wir stellen eine hochenantioselektiven Diels-Alder-Reaktion zwischen kreuzkonjugierten Cyclohexadienonen 和 Cyclopentadien vor, in der fünf Stereozentren durch den stark sauren und sterisch eingeschränkten 亚胺二磷酰亚胺-催化剂控制控制器。方法是通过方法进行的，它是中级技术中的产品，是一个量子化学研究，是一种反应机制和立体选择性的最佳工具埃格伦登。

  DOI：

  10.1002/ange.202000307

文献信息

• Oxidation of enones to α′-acetoxyenones using manganese triacetate
  作者：Norma K. Dunlap、Mark R. Sabol、David S. Watt

  DOI：10.1016/s0040-4039(01)81699-3

  日期：1984.1

  The oxidation of α,β-unsaturated ketones with manganese (III) triacetate in benzene furnishes α'-acetoxyenones in good yields.

  用三乙酸锰（III）在苯中氧化α，β-不饱和酮可提供高产量的α'-乙酰氧烯酮。
• Stereochemical Studies. XXVI. Asymmetric Synthesis using Proline Derivatives of optically Active Various 4, 4-Disubstituted 2-Cyclohexenones with Enamine Alkylation
  作者：GENJI OTANI、SHUNICHI YAMADA

  DOI：10.1248/cpb.21.2125

  日期：——

  Enamines III, prepared from some disubstituted acetaldehydes I and L-proline pyrrolidide (II), were alkylated with methyl vinyl ketone to generally afford optically active 4, 4-disubstituted 2-cyclohexenones V. This asymmetric synthesis is found to be widely applicable, their absolute configurations could be deduced by a comparison of the two substituents.

  由一些二取代乙醛 I 和 L-脯氨酸吡咯烷酮 (II) 制备的烯胺 III 经甲基乙烯酮烷基化后，一般可得到具有光学活性的 4，4-二取代 2-环己烯酮 V。
• Demethylaromatization of cyclohexadienones by iodotriphenylphosphonium iodide
  作者：Guanghui Chen、Yong Shi、Weisheng Tian、Hongyan Xie、Zhaohua Yan、Junmin Yu

  DOI：10.1016/j.tetlet.2023.154365

  日期：2023.3

  A highly efficient and metal-free demethylation and concomitant aromatization of cyclohexadienones using iodotriphenylphosphonium iodide was developed. A variety of steroidal and non-steroidal substrates smoothly underwent demethylaromatization reaction generating the corresponding phenolic products in good yields. This approach exhibits broad functional group tolerance. An ionic mechanism of synergistic

  开发了使用碘化三苯基磷碘化物对环己二烯酮进行高效且无金属的去甲基化和伴随的芳构化。多种甾体和非甾体底物顺利进行去甲基芳构化反应，以良好的收率生成相应的酚类产物。这种方法表现出广泛的功能组耐受性。提出了协同作用的离子机制。该方法在 1,4-androstadiene-3,17-dione 一步转化为 3-hydroxy-1,3,5(10)-estratrien-17-one 过程中显示出潜在的工业价值一系列甾体避孕药。
• Ruthenium‐Catalyzed Activation of Nonpolar C−C Bonds via π‐Coordination‐Enabled Aromatization
  作者：Lun Xu、Hang Shi

  DOI：10.1002/anie.202307285

  日期：2023.8.21

  Activation of C−C bonds allows editing of molecular skeletons, but methods for selective activation of nonpolar C−C bonds in the absence of a chelation effect or a driving force derived from opening of a strained ring are scarce. Herein, we report a method for ruthenium‐catalyzed activation of nonpolar C−C bonds of pro‐aromatic compounds by means of π‐coordination‐enabled aromatization. This method was effective for cleavage of C−C(alkyl) and C−C(aryl) bonds and for ring‐opening of spirocyclic compounds, providing an array of benzene‐ring‐containing products. The isolation of a methyl ruthenium complex intermediate supports a mechanism involving ruthenium‐mediated C−C bond cleavage.

  摘要 C-C 键的活化可以编辑分子骨架，但在没有螯合效应或打开应变环产生的驱动力的情况下，选择性活化非极性 C-C 键的方法却很少。在此，我们报告了一种通过 π 配位促成的芳香化作用，在钌催化下活化原芳香族化合物非极性 C-C 键的方法。这种方法对 C-C（烷基）键和 C-C（芳基）键的裂解以及螺环化合物的开环非常有效，可提供一系列含苯环的产物。甲基钌络合物中间体的分离支持了钌介导的 C-C 键裂解机制。
• Pichia stipitis OYE 2.6 variants with improved catalytic efficiencies from site-saturation mutagenesis libraries
  作者：Athéna Patterson-Orazem、Bradford Sullivan、Jon D. Stewart

  DOI：10.1016/j.bmc.2014.07.001

  日期：2014.10

  An earlier directed evolution project using alkene reductase OYE 2.6 from Pichia stipitis yielded 13 active site variants with improved properties toward three homologous Baylis-Hillman adducts. Here, we probed the generality of these improvements by testing the wild-type and all 13 variants against a panel of 16 structurally-diverse electron-deficient alkenes. Several substrates were sterically demanding, and as hoped, creating additional active site volume yielded better conversions for these alkenes. The most impressive improvement was found for 2-butylidenecyclohexanone. The wild-type provided less than 20% conversion after 24 h; a triple mutant afforded more than 60% conversion in the same time period. Moreover, even wild-type OYE 2.6 can reduce cyclohexenones with very bulky 4-substituents efficiently. (C) 2014 Elsevier Ltd. All rights reserved.