2-(2,2-Diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal | 123003-33-8

• 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: 2-(2,2-Diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal
• 英文别名: 2-methyl-2-(2,2-diphenylvinyl)-4,4-diphenyl-3-butenal；2,2-Bis(2,2-diphenylvinyl)propionaldehyde；2-(2,2-Diphenylethenyl)-2-methyl-4,4-diphenylbut-3-enal
• CAS: 123003-33-8
• 化学式: C₃₁H₂₆O
• 分子量: 414.547
• InChiKey: ZXSURNXHOXIHIE-UHFFFAOYSA-N

物化性质

• 熔点：
  108-109 °C
• 沸点：
  602.9±55.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.06
• 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-(2,2-Diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal 在 吡啶 、 盐酸羟胺 作用下， 以 乙醇 为溶剂， 反应 3.0h， 生成 2-Methyl-4,4-diphenyl-2-vinyl-3-butenal oxime acetate
  参考文献：
  名称：

  A Study of the Competition between the Di-.pi.-methane and the Azadi-.pi.-methane Processes in 2-Vinyl-.beta.,.gamma.-unsaturated Oxime Derivatives. The Novel Azadi-.pi.-methane Reactivity of .beta.,.gamma.-Unsaturated Oximes

  摘要：

  A study aimed at detecting intramolecular competition between the di-pi-methane (DPM) rear-rangement and the azadi-pi-methane (ADPM) process has been carried out. The results show that direct or acetophenone-sensitized irradiation of 2-(2,2-diphenylvinyl)-2-methyl-4,4-diphenyl-3- butenal oxime acetate 3 and the corresponding oxime trifluoroacetate 11 undergo only the DPM process to yield cyclopropanes. Similar DPM rearrangement was observed for 2-methyl-4,4-diphenyl-2-vinyl-3-butenonitrile 22. These are examples of triplet DPM reactivity in acyclic substrates where the central carbon has only one electron-withdrawing group. There is only one case of such reactivity in the aryl di-pi-methane process. However, 2-methyl-4,4-diphenyl-2-vinyl-2-vinyl-3-butenal oxime acetate 26 and the corresponding trifluoroacetate 15 undergo the ADPM rearrangement exclusively on direct or acetophenone-sensitized irradiation. The selectivity observed is interpreted as being dependent on the relative stabilities of the 1,4-bridged biradical intermediates. Based on previous failures to observe the ADPM reactions of beta,gamma-unsaturated oximes, an attempt to suppress the ADPM reactivity in compounds with a substitution pattern such as that present in 15 and 26 was made using the parent oxime 21. Surprisingly this compound reacts efficiently by the ADPM process and affords cyclopropane 30. This is the first example of ADPM reactivity of an acyclic beta,gamma-unsaturated oxime. Ah the rearrangements described are stereoselective. This reaction was extended to other oximes 45, 47a and 47b and also to the oxime ether 36. The photoreaction of 47b shows that the ADPM rearrangement of oximes can be extended to ketone derivatives. Previous studies have shown that such reactivity is uncommon. beta,gamma-Unsaturated oximes are usually considered to be photochemically inert but these results have shown that changes in substitution can promote efficient ADPM reactivity.

  DOI：

  10.1021/jo00105a031
• 作为产物：
  描述：

  ethyl 2-(2,2-diphenylvinyl)-4,4-diphenyl-3-butenoate 在 吡啶 、 chromium(VI) oxide 、 lithium aluminium tetrahydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 2-(2,2-Diphenylvinyl)-2-methyl-4,4-diphenyl-3-butenal
  参考文献：
  名称：

  三-pi-甲烷重排的激发态和基态版本：机械和探索性有机光化学。

  摘要：

  现在已经很好地确定了具有两个连接到单个碳上的可导致pi取代的环丙烷的pi-基的di-pi-甲烷重排。本研究的目标是探索具有三个pi部分与sp（3）杂化原子连接的pi系统的分子系统，以寻求三pi-甲烷重排。实际上，已发现此类系统确实进行了光化学重排以提供环戊烯。然而，还确定了在直接辐射下乙烯基环丙烷环膨胀成环戊烯。由于经常发现同时产生三环和五环光产物，因此重要的是要确定观察到的光化学确实是真正的单步三-pi-甲烷重排的结果，而不是两次连续重排的结果，首先形成乙烯基环丙烷，然后环膨胀成环戊烯。一般情况下，对应于三-pi-甲烷反应物A，乙烯基环丙烷光产物B和环戊烯光产物C的物质分别为A，B和C三种。涉及三个速率常数，即A-> B的k（1），对于A-> C，k（2）；对于B-> C，k（3）。将动力学应用于两个示例，并提供了避免差异光吸收的规定。利用单线敏化。已经确定，环戊烯光产物的直接形成比环扩

  DOI：

  10.1021/jo001601b

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
• 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.
• A ground state tri-π-methane rearrangement
  作者：Howard E Zimmerman、Vladimı́r Cı́rkva、Lei Jiang

  DOI：10.1016/s0040-4039(00)01705-6

  日期：2000.12

  An example of a ground state tri-pi -methane rearrangement is described. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Excited- and Ground-State Versions of the Tri-π-methane Rearrangement: Mechanistic and Exploratory Organic Photochemistry¹
  作者：Howard E. Zimmerman、Vladimír Církva

  DOI：10.1021/jo001601b

  日期：2001.3.1

  Since both three-ring and five-ring photoproducts often are found to be produced, it was important to establish that the observed photochemistry was really the result of a true single-step tri-pi-methane rearrangement and not the consequence of two sequential rearrangements, first to form a vinyl cyclopropane which subsequently ring expanded to the cyclopentene. The general situation has three species-A

  现在已经很好地确定了具有两个连接到单个碳上的可导致pi取代的环丙烷的pi-基的di-pi-甲烷重排。本研究的目标是探索具有三个pi部分与sp（3）杂化原子连接的pi系统的分子系统，以寻求三pi-甲烷重排。实际上，已发现此类系统确实进行了光化学重排以提供环戊烯。然而，还确定了在直接辐射下乙烯基环丙烷环膨胀成环戊烯。由于经常发现同时产生三环和五环光产物，因此重要的是要确定观察到的光化学确实是真正的单步三-pi-甲烷重排的结果，而不是两次连续重排的结果，首先形成乙烯基环丙烷，然后环膨胀成环戊烯。一般情况下，对应于三-pi-甲烷反应物A，乙烯基环丙烷光产物B和环戊烯光产物C的物质分别为A，B和C三种。涉及三个速率常数，即A-> B的k（1），对于A-> C，k（2）；对于B-> C，k（3）。将动力学应用于两个示例，并提供了避免差异光吸收的规定。利用单线敏化。已经确定，环戊烯光产物的直接形成比环扩
• A Study of the Competition between the Di-.pi.-methane and the Azadi-.pi.-methane Processes in 2-Vinyl-.beta.,.gamma.-unsaturated Oxime Derivatives. The Novel Azadi-.pi.-methane Reactivity of .beta.,.gamma.-Unsaturated Oximes
  作者：Diego Armesto、Maria J. Ortiz、Ana Ramos、William M. Horspool、Elena P. Mayoral

  DOI：10.1021/jo00105a031

  日期：1994.12

  A study aimed at detecting intramolecular competition between the di-pi-methane (DPM) rear-rangement and the azadi-pi-methane (ADPM) process has been carried out. The results show that direct or acetophenone-sensitized irradiation of 2-(2,2-diphenylvinyl)-2-methyl-4,4-diphenyl-3- butenal oxime acetate 3 and the corresponding oxime trifluoroacetate 11 undergo only the DPM process to yield cyclopropanes. Similar DPM rearrangement was observed for 2-methyl-4,4-diphenyl-2-vinyl-3-butenonitrile 22. These are examples of triplet DPM reactivity in acyclic substrates where the central carbon has only one electron-withdrawing group. There is only one case of such reactivity in the aryl di-pi-methane process. However, 2-methyl-4,4-diphenyl-2-vinyl-2-vinyl-3-butenal oxime acetate 26 and the corresponding trifluoroacetate 15 undergo the ADPM rearrangement exclusively on direct or acetophenone-sensitized irradiation. The selectivity observed is interpreted as being dependent on the relative stabilities of the 1,4-bridged biradical intermediates. Based on previous failures to observe the ADPM reactions of beta,gamma-unsaturated oximes, an attempt to suppress the ADPM reactivity in compounds with a substitution pattern such as that present in 15 and 26 was made using the parent oxime 21. Surprisingly this compound reacts efficiently by the ADPM process and affords cyclopropane 30. This is the first example of ADPM reactivity of an acyclic beta,gamma-unsaturated oxime. Ah the rearrangements described are stereoselective. This reaction was extended to other oximes 45, 47a and 47b and also to the oxime ether 36. The photoreaction of 47b shows that the ADPM rearrangement of oximes can be extended to ketone derivatives. Previous studies have shown that such reactivity is uncommon. beta,gamma-Unsaturated oximes are usually considered to be photochemically inert but these results have shown that changes in substitution can promote efficient ADPM reactivity.