The syntheses and properties of the cycloadducts of p-benzoquinones with 1,3-dipoes

对苯醌与1,3-二聚物环加合物的合成及性质

基本信息

  • 批准号:
    07455353
  • 负责人:
  • 金额:
    $ 4.74万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
  • 财政年份:
    1995
  • 资助国家:
    日本
  • 起止时间:
    1995 至 1997
  • 项目状态:
    已结题

项目摘要

1.Some of the 1,3-dipolar cycloadducts of aromatic nitrile oxides with 2,5- and 2,6-dialkyl-p-benzoquinones undrgo base-induced isomerization. We have proposed the structure of the isomerized products as isoxazole-fused derivatives which were formed by ring-opening and recyclization with a base from spectroscopic data. However the X-ray structure determination of the isomerized product from 2,5-di-tert-butyl-p-benzoquinone (25DBQ) with 2,6-dichlorobenzonitrile oxide (CNO) showed that one of the tert-butyl group migrated from the bridgehead poositon to neighboring carbonyl carbon atom. The cycloadducts which have a methyl group at the bridgehead position did not undergo isomerization. We investigate the mechanism of rearrangement in detail.Also we investigate the reaction of some novel 1,3-dipolar cycloadducts with base. The cycloadduct of 25DBQ with N-phenyl-alpha-p-nitrophenylnitrone yields no isomerized product by the reaction with base. The reaction of 25DBQ with trimethylsilyldiazo … More methane generates pyrazoline derivative instead of simple 1,3-dipolar cycloadduct. This compound reacts with NaOH and isomerize to pyrazole derivative with the migration of the bridgehead tert-butylgroup. Also in the case of the cycloadduct of 2-tet-butylnaphthoquinone with CNO,the bridgehead trt-butyl group moves to neighboring carbonyl carbon to form isoxazole derivative. It is seemed that such a very unusual alkylmigration results from the aromatization of heterocyclic moieties of cycloadducts.2.Treatment of the cycloadducts with acetic anhydride-sulkfuric acid caused elimination of the bridgehead t-Bugroup to afford the isoxazole-fused hydroquinone diacetate derivatives. The rearranged products were also susceptible to the similar acetylation, but the resulting products were isoxazole-fused catechol derivatives and/or hydroquinone diacetate derivatives.3.The reaction of 2-tert-butyl-5-methyl-p-benzoquinone with a large excess of the nitrile oxide gave the 1 : 3 cycloadduct instead of the 1 : 2 cycloadduct. The cycloaddition occurred at two C=C bonds and one C=O bond.4.The cycloaddition of trimethylenemethane with p-benzoquinones gave the 1 : 1 cycloadduct at the C=C bond. The other alkyl-substituted benzoquinones also gave the corresponding cycloadducts. Less
1.芳香腈氧化物与2,5-和2,6-二烷基-对苯二酚的部分1,3-偶极环加成产物发生碱诱导的异构化反应。根据波谱数据,我们提出了异构化产物的结构为异恶唑稠合衍生物,这些异构化产物是以碱为碱基通过开环和环合形成的。而2,5-二叔丁基-对苯二酚(25DBQ)与2,6-二氯苯腈(CNO)异构化产物的X-射线结构测定表明,其中一个叔丁基团从桥头基团迁移到邻近的羰基碳原子上。桥头位置有甲基的环加合物没有发生异构化反应。我们详细研究了重排反应的机理,并考察了一些新型的1,3-偶极环加合物与碱的反应。25DBQ与N-苯基-α-对硝基苯基硝酮的环加成反应不生成异构化产物。25DBQ与三甲基硅基重氮…的反应更多的甲烷生成吡唑啉衍生物,而不是简单的1,3-偶极环加合物。该化合物与氢氧化钠反应,在桥头叔丁基团迁移的情况下异构化为吡唑衍生物。另外,在2-叔丁基萘酚与CNO的环加成反应中,桥头TRT-丁基转移到邻近的羰基上形成异恶唑衍生物。这种异常的烷基迁移似乎是环加合物杂环部分芳构化的结果。2.用乙酸酐-硫酸处理环加合物,消除桥头t-丁基,得到异恶唑稠合对苯二酚二乙酸酯衍生物。重排产物也易发生类似的乙酰化反应,但产物为异恶唑稠合邻苯二酚衍生物和/或对苯二酚二乙酸酯衍生物。3.2-叔丁基-5-甲基-对苯二酚与过量的氧化腈反应生成1:3的环加成产物,而不是1:2的环加成产物。环加成反应发生在两个C=C键和一个C=O键上。4.三亚甲基甲烷与对苯二酚的环加成反应在C=C键处形成1:1的环加成产物。其他烷基取代的苯二酚也给出了相应的环加成产物。较少

项目成果

期刊论文数量(2)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
務川高志: "p-ベンゾキノン類とニトリルオキシドとの成環付加体の反応" 第27回複素環化学討論会講演要旨集. 382-385 (1996)
Takashi Mukawa:“对苯醌和氧化腈的环加合物的反应”第 27 届杂环化学研讨会摘要 382-385(1996)。
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    0
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  • 通讯作者:
務川高志: "p-ベンゾキノン類とトリメチレンメタンとの反応" 日本化学会第70春季年会講演予稿集. II. 1212-1212 (1996)
Takashi Mukawa:“对苯醌与三亚甲基甲烷的反应”日本化学会第 70 届春季年会论文集 II 1212-1212(1996 年)。
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    0
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SHIRAISHI Shinsaku其他文献

SHIRAISHI Shinsaku的其他文献

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{{ truncateString('SHIRAISHI Shinsaku', 18)}}的其他基金

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
  • 财政年份:
    1991
  • 资助金额:
    $ 4.74万
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research (B)

相似海外基金

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
  • 财政年份:
    1991
  • 资助金额:
    $ 4.74万
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research (B)
SOLUTION CHEMISTRY OF N-ACETYL-P-BENZOQUINONE IMINE
N-乙酰基-对苯醌亚胺的溶液化学
  • 批准号:
    3438538
  • 财政年份:
    1987
  • 资助金额:
    $ 4.74万
  • 项目类别:
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