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

• Project/Area Number: 03555175
• Research Category: Grant-in-Aid for Developmental Scientific Research (B)
• Allocation Type: Single-year Grants
• Research Field: 有機工業化学
• Research Institution: University of Tokyo
• Principal Investigator: SHIRAISHI Shinsaku University of Tokyo, Institute of Industrial Science, Professor, 生産技術研究所, 教授 (30013163)
• Co-Investigator(Kenkyū-buntansha): NAKAYAMA Yoshiki Ihara Chemical Ind.Incorp., Shizuoka Plants, Director, 静岡工場, 工場長 ; YASHIRO Morio University of Tokyo, Faculty of Engineering, Lecturer, 工学部, 講師 (30192785)
• Project Period (FY): 1991 – 1993
• Project Status: Completed (Fiscal Year 1993)
• Budget Amount: ¥8,400,000 (Direct Cost: ¥8,400,000); Fiscal Year 1993: ¥1,100,000 (Direct Cost: ¥1,100,000); Fiscal Year 1992: ¥3,300,000 (Direct Cost: ¥3,300,000); Fiscal Year 1991: ¥4,000,000 (Direct Cost: ¥4,000,000)
• Keywords: 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

Research Abstract

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.

Research Products

• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 井上 幸彦,荒木 孝二,白石 振作: "Unusual Solvent Effect on the Cycloadditiones of Aromatic Nitrile N-Oxide with Alkyl Substituted P-Benzoquinones in Ethanol-Water Systems" Bull.Chem.Soc.Jpn.64. 3079-3083 (1991)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 白石 振作,B.S.Itolla,今村 清,井上 幸彦: "The Reactions of Nitrile-Oxide-Quinone Cycloodducts I.Base-Induced Rearrangement of the 1:1-C=C-Adducts of Aromatic Nitrile Oxider with Dialkyl Substituted P-Benzoquinones" Bull.Chem.Soc.Jpn.65. 2480-2483 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 井上 幸彦,S.Y.Ambekar,許 暁紅,白石 振作: "The Reactions of Nitrile Oxide-Quinone Cycloadducts,II.The Reactions of 2,5-D_1-t-butyl-P-benzoquinone with Nitrile Oxides:1:2 Cycloaddition and Base Induced Ring Transformation of the Cycloadducts" Bull.Chem.Soc.Jpn.65. 2484-2489 (1992)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Shinsaku SHIRAISHI, Yukihiko INOUE, Kiyoshi IMAMURA: "The Cycloaddition of N, alpha-Diarylnitrones and Substituted p-Benzoquinones" Bull.Chem.Soc.Jpn.64. 2388-2392 (1991)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 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)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Shinsaku SHIRAISHI, B.Shivarama HOLLA, Kiyoshi IMAMURA, Yukihiko INOUE: "The Reactions of Nitrile Oxide-Quinone Cycloadducts. I.Base-Induced Rearragement of the 1 : 1-C=C-Adducts of Aromatic Nitrile Oxides with Dialky-Substituted p-Benzoquinones" Bull.Chem.Soc.Jpn.65. 2480-2483 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Yukihiko INOUE, Salvottam Y.AMBEKAR, Xiao-Hong XU, Shinsaku SHIRAISHI: "The Reactions of Nitrile Oxide-Quinone Cycloadducts. II.The Reactions of 2, 5-Di-t-butyl-p-benzoquinone with Nitrile Oxides : 1 : 2 Cycloaddition and Base Induced Ring Transformation of the Cycloadducts" Bull.Chem.Soc.Jpn.65. 2484-2489 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 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)
• [Publications] Y.INOUE,S.Y.AMBEKAR Xiao-Hong Xu,S.SHIRAISHI: "The Reactions of Nitrile Oxide-Quinone Cycloadducts.II.The Reactions of 2,5-Di-t-butyl-p-benzoquinone with Nitrile Oxides 1:2 Cycloaddition and Base Induced Ring Transformation of the Cycloadducts" Bull.Chem.Soc.Jpn.65. 2484-2489 (1992)
• [Publications] 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)
• [Publications] S.Shiraishi,Y.Inoue,and K.Imamura: "The Cycloaddition of N,α-Diarylnitrones and Substituted p-Benzoquinones" Bull.Chem.Soc.Jpn.64. 2388-2392 (1991)