3-(9-fluorenylidene)-2,2-dimethylpropanal | 169207-61-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 3-(9-fluorenylidene)-2,2-dimethylpropanal
• 英文别名: 3-Fluoren-9-ylidene-2,2-dimethylpropanal
• CAS: 169207-61-8
• 化学式: C₁₈H₁₆O
• 分子量: 248.324
• InChiKey: WEJUQMOJSBWPQB-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：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  3-(9-fluorenylidene)-2,2-dimethylpropanal 在 吡啶 、 盐酸羟胺 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以72%的产率得到3-Fluoren-9-ylidene-2,2-dimethyl-propionaldehyde oxime
  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：

  ethylene acetal of 3-(9-fluorenylidene)-2,2,-dimethylpropanal 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以62%的产率得到3-(9-fluorenylidene)-2,2-dimethylpropanal
  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

• SmI₂-Mediated 3-<i>exo-trig</i> Cyclization of β,γ-Unsaturated Carbonyl Compounds: Diastereoselective Synthesis of Cyclopropanols
  作者：Mar Martin-Fontecha、Antonia R. Agarrabeitia、Maria J. Ortiz、Diego Armesto

  DOI：10.1021/ol101666m

  日期：2010.9.17

  SmI2-mediated 3-exo-trig cyclizations of β,γ-unsaturated carbonyl compounds to generate cyclopropanols are not generally observed processes. The reported examples are limited to β,γ-unsaturated carbonyl compounds that possess ester groups conjugated with the alkene unit. The results of the current study show that this cyclization also occurs when other substitution patterns are present on the alkene

  通常没有观察到SmI 2介导的β，γ-不饱和羰基化合物的3- exo - trig环化反应生成环丙醇。报告的实例限于具有与烯烃单元共轭的酯基的β，γ-不饱和羰基化合物。当前研究的结果表明，当在烯烃部分上存在其他取代模式时，也会发生这种环化反应，从而以良好至极好的收率提供（E）-环丙醇，并且在大多数情况下具有很高的非对映选择性。
• 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.
• A new photochemical synthesis of cyclopropanecarboxylic acids present in pyrethroids by the aza-di-π-methane rearrangement
  作者：Diego Armesto、Mar G. Gallego、William M. Horspool、Antonia R. Agarrabeitia

  DOI：10.1016/0040-4020(95)00527-f

  日期：1995.8

  A novel synthetic route to chrysanthemic acid, 2-cyclopentylidenmethyl-3,3-dimethylcyclopropanecarboxylic acid, fluorenespiro-2,2-dimethylcyclopropanecarboxylic acid and indenespiro-2,2-dimethylcyclopropanecarboxylic acid, all of them present in pyrethroids of known insecticidal activity, is described. The key step in the synthesis is the aza-di-n-rnethane rearrangement of some 1-aza-1,4,6-trienes

  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。