Non-conventional Aromatic Electrophilic Reactions Occurring via "ipso" Arenium Ion Intermediates

通过“ipso”芳烃离子中间体发生的非常规芳香亲电反应

• 批准号: 60470024
• 负责人: SUZUKI Hitomi
• 金额: $ 4.93万
• 依托单位: Ehime University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60470024/
• 关键词: Aromatics; Nitration; Electrophilic Reaction; 反応機構

Non-conventional reactions of benzenoid compounds which occur as a consequence of "ipso" attack of electrophiles have been investigated, with a special emphasis on the elucidation of the anomalies observed during the side-chain nitration of polysubstituted arenes; nitrooxylation with <HNO_3> / <CH_2> <Cl_2> and nitration with <HNO_3> / <(CH_3CO)_2> O. Based on the evidence obtained from product variations with substituents, electrochemical nitrodecarboxylation of arylacetates, and ESR examination of the initial stage of the side-chain reactions, a proposal is made that the side-chain substitution of polysubstituted arenes occurs via heterolytic path with <HNO_3> / <CH_2> <Cl_2> and via a homolytic path with <HNO_3> / <(CH_3CO)_2> O. The first isolation of a proposed methylenecyclohexadiene intermediate for the side-chain substitution of arenes under heterolytic conditions is also included.

已经研究了由于亲电试剂“原位”攻击而发生的苯环化合物的非常规反应，特别强调了多取代芳烃侧链硝化过程中观察到的异常现象的阐明； <HNO_3> / <CH_2> <Cl_2>硝化和<HNO_3> / <(CH_3CO)_2> O硝化。基于取代基产物变化、芳基乙酸酯的电化学硝基脱羧和侧链反应初始阶段的ESR检查获得的证据，提出侧链反应 多取代芳烃的取代通过 <HNO_3> / <CH_2> <Cl_2> 的杂解路径以及通过 <HNO_3> / <(CH_3CO)_2> O 的均解路径发生。还包括在杂解条件下用于芳烃侧链取代的所提出的亚甲基环己二烯中间体的首次分离。

项目成果

H.Suzuki;H.Koide;Y.Taki;E.Ohbayashi;T.Ogawa: Chem.Lett.1987. (1987)

H.Suzuki；H.Koide；Y.Taki；E.Ohbayashi；T.Okawa：Chem.Lett.1987。

H.Suziki;T.Ogawa: Seventh IUPAC Conference on Physical Organic Chemistry;Conference Abstracts. (1985)

H.Suziki；T.Okawa：第七届 IUPAC 物理有机化学会议；会议摘要。

H. Suzuki, H. Koide, Y. Taki, E. Ohbayashi, and T. Ogawa: "An Interpretation of the Puzzling Dichotomy of the Reaction Modes Observed during the Side-chain Nitration of Alkylaromatics with <HNO_3> / <CH_2> <Cl_2> and <HNO_3> / <(CH_3CO)_2> O" Chem. Lett.,

H. Suzuki、H. Koide、Y. Taki、E. Ohbayashi 和 T. Okawa：“对使用 <HNO_3> / <CH_2> 进行烷基芳烃侧链硝化过程中观察到的令人困惑的反应模式二分法的解释 <

H.Suzuki;E.Kimura;T.Katayama;T.Ogawa: Chem.Lett.1987. (1987)

H.Suzuki；E.Kimura；T.Katayama；T.Okawa：Chem.Lett.1987。

H. Suzuki, E. Kimura, T. Katayama, and T. Ogawa: "9-Methyl-9-nitro-10-nitromethylene-9,10-dihydroanthracene. The First Isolation of a Proposed Intermediate for the Side-chain Nitration of Arenes under Heterolytic Conditions" Chem. Lett., 1987.

H. Suzuki、E. Kimura、T. Katayama 和 T. Okawa：“9-甲基-9-硝基-10-硝基亚甲基-9,10-二氢蒽。首次分离出用于侧链硝化的拟议中间体