1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde | 50599-08-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde
• 英文别名: 1-Phenyl-3-methylcyclohexen-3-carboxaldehyd；1-methyl-3-phenylcyclohex-2-ene-1-carbaldehyde
• CAS: 50599-08-1
• 化学式: C₁₄H₁₆O
• 分子量: 200.28
• InChiKey: CFNOIRBHNQVONT-UHFFFAOYSA-N

物化性质

• 沸点：
  304.1±42.0 °C(Predicted)
• 密度：
  1.071±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.46
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 生成
  参考文献：
  名称：

  Di-.pi.-methane rearrangement. Stereochemistry

  摘要：

  DOI：

  10.1021/ja00807a028
• 作为产物：
  描述：

  2-苯基环己酮 在 甲醇 、 lithium aluminium tetrahydride 、 potassium tert-butylate 、 sodium 、 对甲苯磺酸 作用下， 以 乙醚 、 叔丁醇 、 苯 为溶剂， 生成 1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde
  参考文献：
  名称：

  Di-.pi.-methane rearrangement. Stereochemistry

  摘要：

  DOI：

  10.1021/ja00807a028

文献信息

• Efficient Access to All‐Carbon Quaternary and Tertiary α‐Functionalized Homoallyl‐type Aldehydes from Ketones
  作者：Vittorio Pace、Laura Castoldi、Eugenia Mazzeo、Marta Rui、Thierry Langer、Wolfgang Holzer

  DOI：10.1002/anie.201706236

  日期：2017.10.2

  β,γ‐Unsaturated aldehydes with all‐carbon quaternary or tertiary α‐centers were rapidly assembled from ketones through a unique synthetic operation consisting of 1) C1 homologation, 2) Lewis acid mediated epoxide–aldehyde isomerization, and 3) electrophilic trapping. The synthetic equivalence of a vinyl oxirane and a β,γ‐unsaturated aldehyde is the key concept of this previously undisclosed tactic

  具有全碳四元或三元α-中心的β，γ-不饱和醛通过一种独特的合成操作由酮快速组装而成，该合成操作包括1）C 1同源，2）Lewis酸介导的环氧-醛异构化和3）亲电捕集。乙烯基环氧乙烷和β，γ-不饱和醛的合成当量是这种以前未公开的策略的关键概念。机理研究和标记实验表明，烯醇醛是重要的中间体。同源类胡萝卜素的形成在确定化学选择性中起关键作用。
• Unexpected Oxadi-π-methane Rearrangement of β,γ-Unsaturated Aldehydes
  作者：Diego Armesto、Maria J. Ortiz、Santiago Romano、Antonia R. Agarrabeitia、Mar G. Gallego、Ana Ramos

  DOI：10.1021/jo951032l

  日期：1996.1.1

  The oxadi-n-methane rearrangement (ODPM) is considered to represent the normal photochemical behavior of beta,gamma-unsaturated ketones in the triplet excited pi,pi* state. However, the usual photoreactivity reported for the majority of beta,gamma-unsaturated aldehydes is decarbonylation. There are only two published reports of beta,gamma-unsaturated aldehydes that undergo the ODPM rearrangement. We now report efficient ODPM rearrangement in the triplet-sensitized irradiation of twelve cyclic and acyclic beta,gamma-unsaturated aldehydes, namely, 2,2-dimethyl-4,4-diphenyl-3-butenal (6), 1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde (7), 1-methyl-3-phenyl-2-cyclopentene-1-carbaldehyde (14a), 1-methyl-3-phenyl-2-cycloheptene-1-carbaldehyde (14b), 2,2-dimethyl-4-phenyl-3-butenal (18), 2-(3,4-dihydro-2-naphthyl)-2-methylpropanal (23), 3-(9-fluorenylidene)-2,2-dimethylpropanal (24), 5-cyclopentylidene-2,2-dimethyl-3-pentenal (27), 2,2,6-trimethyl-3,5-heptadienal (28), 2,2,4,4-tetraphenyl-3-butenal (35), 2-methyl-4,4-diphenyl-2-vinyl-3-butenal (36), and 4-methyl-2,2-diphenyl-3-pentenal (47). All of them afford the corresponding cyclopropyl aldehydes in 8-96% yield. Our results show that the ODPM rearrangement of aldehydes should be considered a normal photoreactivity of this type of compound. In one case (7), the formation of the corresponding 1,3-formyl migrated product was also observed. Aldehydes 35 and 47 undergo, in addition to the ODPM rearrangement, decarbonylation to the alkenes 37 and 51, respectively. The ODPM reaction takes place when the triplet energy from the sensitizer is efficiently transferred to the alkene moiety generating a T-1 ((3) pi,pi*) excited state and, furthermore, when the biradical intermediates are stabilized by phenyl or vinyl substitution. Thus, 2,2,4-trimethyl-3-pentenal (46), in which these two requirements are not met, undergoes decarbonylation exclusively. Some structural factors that influence the efficiency of other di-pi-methane processes, such as the di-pi-methane (DPM) and azadi-pi-methane (ADPM) rearrangements, are also operative in the ODPM rearrangement of aldehydes. Thus, diphenyl substitution on the central carbon of the beta,gamma-unsaturated aldehyde, as in 47, also promotes the ODPM rearrangement. In cases in which the competition between the ODPM and the DPM processes can occur, the selectivity observed depends on the relative stabilities of the 1,4-bridged biradical intermediates. Thus, aldehyde 36 yields the ODPM product exclusively, while 2-(2,2-diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal(43) affords the DPM product 44 only.
• The oxa-di-π-methane rearrangement of β,γ-unsaturated aldehydes
  作者：Diego Armesto、Maria J. Ortiz、Santiago Ramano

  DOI：10.1016/0040-4039(94)02402-w

  日期：1995.2

  As far as we are aware, there are only two examples of oxa-di-pi-methane (ODPM) rearrangement with beta,gamma-unsaturated aldehydes. However, we have discovered four other cases of this reaction, taking place with 1-methyl-3-phenyl-2-cyclohexene-1-carbaldehyde, 1-methyl-3-phenyl-2-cyclopentene-1-carbaldehyde, 2,2-dimethyl-4-phenyl-3-butenal and 2,2-dimethyl-4,4-diphenyl-3-butenal. All of these undergo very efficient ODMP rearrangement affording the corresponding cyclopropyl derivatives in high yield.