2,2,4,4-四苯基-3-丁烯醛 | 41326-74-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 中文名称: 2,2,4,4-四苯基-3-丁烯醛
• 英文名称: 2,2,4,4-Tetraphenyl-3-butenaldehyde
• 英文别名: 2,2,4,4-tetraphenyl-3-butenal；2,2,4,4-tetraphenylbut-3-enal
• CAS: 41326-74-3
• 化学式: C₂₈H₂₂O
• 分子量: 374.482
• InChiKey: QUMSRAMJWZJFGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 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：

  2,2,4,4-四苯基-3-丁烯醛 以 叔丁醇 为溶剂， 生成 1,2,2,3-Tetraphenylcyclopropancarboxaldehyd
  参考文献：
  名称：

  Accentuation of di-.pi.-methane reactivity by central carbon substitution. Mechanistic and exploratory organic photochemistry. LXXV

  摘要：

  DOI：

  10.1021/ja00788a013
• 作为产物：
  描述：

  2,2,4,4-Tetraphenyl-3-butensaeure 在 lithium aluminium tetrahydride 、 乙酸酐 作用下， 生成 2,2,4,4-四苯基-3-丁烯醛
  参考文献：
  名称：

  Accentuation of di-.pi.-methane reactivity by central carbon substitution. Mechanistic and exploratory organic photochemistry. LXXV

  摘要：

  DOI：

  10.1021/ja00788a013

文献信息

• Photochemistry in a box. Photochemical reactions of molecules entrapped in crystal lattices: mechanistic and exploratory organic photochemistry
  作者：Howard E. Zimmerman、Michael J. Zuraw

  DOI：10.1021/ja00202a044

  日期：1989.9

  intramolecular 2sub pi}} + 2sub pi}} cycloaddition between a dicyanovinyl and a phenyl group, (2) di-pi}-methane reactivity but with reversed regioselectivity, and (3) cyclopentene formation where the reactant has an additional vinyl group on the methane carbon. Finally, 1,1,5,5-tetraphenyl-3,3-dimethyl-1-penten-5-ol afforded five- and six-membered ring ethers rather that the solution phenyl migration. Solid-state

  对我们之前在溶液中研究过的一系列分子在结晶状态下的光化学行为进行了探索。所研究的反应分为环己烯酮重排、二-π}-甲烷体系的反应以及在溶液中产生长距离苯基迁移的分子行为。4,4-二芳基环己烯酮与溶液行为的不同之处在于产生不含顺式异构体和 3,4-二芳基环己烯酮的反式双环光产物。在 4,5,5-三苯基环己烯酮的情况下，双环光产物与溶液相比具有倒立的立体化学，否则显示出与通常溶液环丁酮形成完全不同的光化学。二-pi}-甲烷系统产生了三种类型的行为：(1) 双氰基乙烯基和苯基之间的分子内 2sub pi}} + 2sub pi}} 环加成，(2) 二-pi}-甲烷反应性但具有反向区域选择性，以及 (3) 环戊烯反应物在甲烷碳上有一个额外的乙烯基。最后，1,1,5,5-四苯基-3,3-二甲基-1-戊烯-5-醇提供了五元和六元环醚，而不是溶液中的苯基迁移。固态量子产率是通过使用新设计的设
• Unusual organic photochemistry effected by cyano and methoxy substitution. Exploratory and mechanistic organic photochemistry
  作者：Howard E. Zimmerman、Diego Armesto、Mercedes G. Amezua、Thomas P. Gannett、Richard P. Johnson

  DOI：10.1021/ja00515a035

  日期：1979.10
• The photochemistry of bis(2,2-diphenylvinyl) ether: a search for the 3-oxadi-.pi.-methane rearrangement
  作者：Waldemar Adam、Albrecht Berkessel、Knut Hildenbrand、Eva Maria Peters、Karl Peters、Hans Georg Von Schnering

  DOI：10.1021/jo00224a050

  日期：1985.11
• Armesto, Diego; Langa, Fernando; Martin, Juan-Antonio Fernandez, Journal of the Chemical Society. Perkin transactions I, 1987, p. 743 - 746
  作者：Armesto, Diego、Langa, Fernando、Martin, Juan-Antonio Fernandez、Perez-Ossorio, Rafael、Horspool, William M.

  DOI：——

  日期：——
• 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.