2,2-Dimethylspiro[cyclopropane-3,9'-fluorene]-1-carbaldehyde | 169207-86-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,2-Dimethylspiro[cyclopropane-3,9'-fluorene]-1-carbaldehyde
• CAS: 169207-86-7
• 化学式: C₁₈H₁₆O
• 分子量: 248.324
• InChiKey: UCDMQHYMRMCCHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 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-Dimethylspiro[cyclopropane-3,9'-fluorene]-1-carbaldehyde 在 sodium hydroxide 、 silver nitrate 作用下， 以 水 为溶剂， 反应 0.5h， 以71%的产率得到fluorenespiro-2,2-dimethylcyclopropanecarboxylic acid
  参考文献：
  名称：

  通过氮杂-二-π-甲烷重排的拟除虫菊酯中存在的环丙烷羧酸的新光化学合成

  摘要：

  描述了一种新的合成方法，可以合成菊酸，2-环戊二烯基-3,3-二甲基环丙烷羧酸，芴螺-2,2-二甲基环丙烷羧酸和茚螺-2,2-二甲基环丙烷羧酸，它们都存在于已知具有杀虫活性的拟除虫菊酯中。合成中的关键步骤是使用三重态敏化对一些1-aza-1,4,6-三烯和一些1-aza-1,4-二烯进行aza-di-n-乙烷重排。

  DOI：

  10.1016/0040-4020(95)00527-f
• 作为产物：
  描述：

  在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 以80%的产率得到2,2-Dimethylspiro[cyclopropane-3,9'-fluorene]-1-carbaldehyde
  参考文献：
  名称：

  通过氮杂-二-π-甲烷重排的拟除虫菊酯中存在的环丙烷羧酸的新光化学合成

  摘要：

  描述了一种新的合成方法，可以合成菊酸，2-环戊二烯基-3,3-二甲基环丙烷羧酸，芴螺-2,2-二甲基环丙烷羧酸和茚螺-2,2-二甲基环丙烷羧酸，它们都存在于已知具有杀虫活性的拟除虫菊酯中。合成中的关键步骤是使用三重态敏化对一些1-aza-1,4,6-三烯和一些1-aza-1,4-二烯进行aza-di-n-乙烷重排。

  DOI：

  10.1016/0040-4020(95)00527-f

文献信息

• Influence of Electron-Donor Sensitizers on SET-Promoted Photochemical Reactions of β,γ-Unsaturated Aldehydes
  作者：Diego Armesto、Maria J. Ortiz、Antonia R. Agarrabeitia、Mar Martin-Fontecha

  DOI：10.1021/ol049263e

  日期：2004.6.1

  beta,gamma-Unsaturated aldehydes undergo photochemical oxa-di-pi-methane and decarbonylation reactions using DMN as an electron-donor sensitizer, whereas, using DMA, other photoproducts resulting from proton abstraction by ketyl- and alkene-centered radical-anions are also obtained.

  使用DMN作为电子给体敏化剂时，β，γ-不饱和醛会经历光化学的oxa-di-pi-甲烷和脱羰反应，而使用DMA时，酮基和烯烃中心的自由基阴离子质子提取所产生的其他光产物也是获得。
• 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.