Development of New Photochemical Reactions of Phenols Promoted by Lewis Acid and its Synthetic Application

路易斯酸促进酚类新光化学反应的进展及其合成应用

• 批准号: 03805077
• 负责人: TOBE Yoshito
• 金额: $ 1.02万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03805077/
• 关键词: Phenol; Lewis Acid; Photochemical Reaction; Isomerization Reaction; Addition Reaction; フェノ-ル

We have found new photochemical reactions of phenol derivatives promoted by Lewis acid and have developed new method for carbocyclic ring construction starting from readily available aromatic compounds.1. We found that irradiation of 3-methoxyphenol (1) in the presence of aluminum bromide gave 4-methoxybicyclo [3.1.0] hexenone (2) in a good yield.2. We found that irradiation of 1-naphthol (3) in the presence of aluminum halides afforded ringcontracted halomethylindanone (4) in a good yield. indanone 4 was converted to the cyclopropane-containing compound 5 quantitatively by treatment with a base.3. We have already reported that 2-naphthol (6) produced the [2+2] cycloadduct with ethylene by irradiation in the presence of Lewis acid. In order to clarify the mechanism of this novel reaction, we investigated the effect of olefins and Lewis acids in this reaction.4. We found that the reactivity of 1-naphthol (3) and its derivatives was divergent and it was critically dependent on the position of the substituent. Thus 3 and its 3-methyl derivative gave [2+2] cycloadducts 7 in good yields. On the other hand, 2-alkyl and 6-methoxy derivatives yielded ringcontracted adducts 8 having an indenone core as the major products.

我们发现了苯酚衍生物在刘易斯酸促进下的新的光化学反应，并开发了从易得的芳香族化合物出发构建碳环的新方法.我们发现，在溴化铝存在下，3-甲氧基苯酚（1）经辐射得到4-甲氧基双环[3.1.0]己烯酮（2），产率较高.我们发现，在卤化铝存在下，1-萘酚（3）的辐射以良好的产率得到缩环的卤甲基茚酮（4）。通过用碱处理将茚满酮4定量转化为含环丙烷的化合物5。我们已经报道了在刘易斯酸存在下，2-萘酚（6）与乙烯经辐照生成[2+2]环加合物。为了阐明该反应的机理，我们考察了烯烃和刘易斯酸对反应的影响.我们发现1-萘酚（3）及其衍生物的反应活性是不同的，它是关键取决于取代基的位置。因此，3及其3-甲基衍生物以良好的产率得到[2+2]环加合物7。另一方面，2-烷基和6-甲氧基衍生物产生具有茚酮核的缩环加合物8作为主要产物。

项目成果

Kiyomi Kakiuchi: "Novel Photochemical Reactions of 1- and 2-Naphthols with Ethylene Promoted by Aluminum Halides" Journal of Organic Chemistry. 58. (1993)

Kiyomi Kakiuchi：“卤化铝促进的 1- 和 2-萘酚与乙烯的新型光化学反应”有机化学杂志。

Kiyomi Kakiuchi: "Novel Photochemical Ring Contraction of 1-Naphthols Promoted by Aliminum Halides" Journal of Organic Chemistry. 56. 5745-5747 (1991)

Kiyomi Kakiuchi：“由卤化铝促进的 1-萘酚的新型光化学环收缩”有机化学杂志。

Kiyomi Kakiuchi: "Novel Photochemical Ring Contraction of 1-Naphthols Promoted by Aluminum Halides" Journal of Organic Chemistry. 56. 5745-5747 (1991)

Kiyomi Kakiuchi：“卤化铝促进的 1-萘酚的新型光化学环收缩”有机化学杂志。

K.Kakiuchi: "Photochemical LumiketoneーType Rearrangement of 3ーMethoxyphenol Promoted by AlBr_3" Bull.Chem.Soc.Jpn.64. 3468-3470 (1991)

K.Kakiuchi：“光化学Lumiketone－AlBr_3促进的3－甲氧基苯酚型重排”Bull.Chem.Soc.Jpn.64（1991）。

Kiyomi Kakiuchi: "Photochemical Lumiketone-Type Rearrangement of 3-Methoxyphenol Promoted by AIBr_3" Bulletin of the Chemical Society of Japan. 64. 3468-3470 (1991)

Kiyomi Kakiuchi：“AIBr_3 促进的 3-甲氧基苯酚的光化学 Lumiketone 型重排”日本化学会会刊。