Search for Antifouling Sobstances Derived from Ring-Trans-formation of p-Benzoquinone Cycloadducts with 1, 3-Dipoles

寻找1, 3-偶极子对苯醌环负载管环化衍生的防污物质

• 批准号: 03555175
• 负责人: SHIRAISHI Shinsaku
• 金额: $ 5.38万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03555175/
• 关键词: Cycloaddition; Nitrile N-oxides; p-Benzoquinones; Isoxazolines; Catechols; Hydroquinones; Antifoulant; Barnaclicide; 防活剤; 成環付加反応; p-ベンゾキノン; イソキサゾリン; 水中生物防汚剤; カテコ-ル; ニトロン

Cycloaddition of p-benzoquinones with 1, 3-Dipoles such as nitrile N-oxides and nitrones has been investigated and site- and regio-selectivity has been shown to be governed by the substituents and substitution pattern of the quinone moieties. The C=C cycloadducts of the quinones with nitrile oxides, 9-aryl-7-oxa-8-azabicyclo[4.3.0]nona-3, 8-diene-2, 5-diones, were shown to undergo base-induced reactions in different patterns also depending on the substituents and substitution pattern of the starting quinones.Some of the cycloadducts underwent isomerization on treatment with a base to give isoxazole-fused cyclohexadienones, which were transformed to isoxazole-fused catechol diacetates by the reaction with acetic anhydride-sulfuric acid.Direct treatment of the cycloadducts with acetic anhydride-sulfuric acid gave isoxazole-fused hydroquinone diacetates.The transformation of the adducts to the catechol or hydroquinone derivative was investigated mainly in terms of substituent effects.The catechol and hydroquinone derivatives obtained were screened for barnaclicidal activity against cypris larva of Balanus amphitrite amphitrite.

对苯醌与1，3-偶极分子如腈氮氧化物和硝酮的环加成反应进行了研究，发现醌的取代基和取代方式决定了环加成反应的位置和区域选择性。醌与腈氧化物的C=C环加合物9-芳基-7-氧杂-8-氮杂双环[4.3.0]壬-3，8-二烯-2，5-二酮在碱诱导下发生了不同的反应，这些反应也取决于起始醌的取代基和取代模式，有些环加合物在碱处理下发生异构化，得到了异恶唑稠合的环己二烯酮，与乙酸酐-硫酸反应生成邻苯二酚二乙酸异恶唑稠合物，再与乙酸酐-硫酸反应生成邻苯二酚二乙酸异恶唑稠合物稠合的对苯二酚二乙酸酯。主要根据取代基效应研究了加合物向邻苯二酚或对苯二酚衍生物的转化。得到的邻苯二酚和对苯二酚衍生物对藤壶（Balanus amphitrite amphitrite）的鲤幼虫进行杀藤壶活性筛选。

项目成果

Y.Inoue,K.Araki,and S.Shiraishi: "Unusual Solvens Effect on the Cycloadditions of Aromatic Nitrile N-Oxide with Alkyl Substituted p-Benzoquinones in Ethanol-Water Systems" Bull.Chem.Soc.Jpn.64. 3079-3083 (1991)

Y.Inoue、K.Araki 和 S.Shiraishi：“乙醇-水体系中芳族腈 N-氧化物与烷基取代的对苯醌环加成的异常溶剂效应”Bull.Chem.Soc.Jpn.64。

Yukihiko INOUE, Koji ARAKI, Shinsaku SHIRAISHI: "Unusual Solvent Effect on the Cycloadditions of Aromatic Nitrile N-Oxide with Alkyl Substituted p-Benzoquinones in Ethanol-Water Systems" Bull.Chem.Soc.Jpn.64. 3079-3083 (1991)

Yukihiko INOUE、Koji ARAKI、Shinsaku Shiraishi：“乙醇-水体系中芳香族腈 N-氧化物与烷基取代的对苯醌环加成的异常溶剂效应”Bull.Chem.Soc.Jpn.64。

白石 振作,井上 幸彦,今村 清: "The Cycloaddition of N,α-Diarylnitrones and Substituted P-Benzoquinones" Bull.Chem.Soc.Jpn.64. 2388-2392 (1991)

Shinsaku Shiraishi、Yukihiko Inoue、Kiyoshi Imamura：“N,α-二芳基硝酮和取代的对苯醌的环加成”Bull.Chem.Soc.Jpn.64 (1991)。

Shinsaku SHIRAISHI, Yukihiko INOUE, Kiyoshi IMAMURA: "The Cycloaddition of N, alpha-Diarylnitrones and Substituted p-Benzoquinones" Bull.Chem.Soc.Jpn.64. 2388-2392 (1991)

Shinsaku SHIRAISHI、Yukihiko INOUE、Kiyoshi IMAMURA：“N，α-二芳基硝酮和取代的对苯醌的环加成”Bull.Chem.Soc.Jpn.64。

S.SHIRAISHI,B.S.Holla,K.IMAMURA,Y.INOUE: "The Reactions of Nitrile Oxide-Quinone Cycloadducts,I.Base-Induced Rearrangement of the 1:1-C=C-Adducts of Aromatic Nitrile Oxides with Dialkyl-Substituted p-Benzoquinones" Bull.Chem.Soc.Jpn.65. 2480-2483 (1992)

S.SHIRAISHI，B.S.Holla，K.IMAMURA，Y.INOUE：“氧化腈-醌环加合物的反应，I.二烷基取代的芳香族腈氧化物的 1:1-C=C-加合物的碱诱导重排