Reactivity of imidazole moiety of fused aromatic ring for ionic and radical reaction species : Molecular stady for DNA damage

稠合芳环的咪唑部分对离子和自由基反应物种的反应性：DNA损伤的分子研究

• 批准号: 05671763
• 负责人: KOHDA Kohfuku
• 金额: $ 1.41万
• 依托单位: Nagoya City 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: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05671763/
• 关键词: q-ethylguanine; l-methylbenzimidazole; electrophilic amination; N-aminoguanine; N-amino-l-methylbenzimidazole; guanine; benzimidazole; amination; carcinogenesis

Electrophilic amination of four 9-ethylguanine derivatives (1a-d) and seven 1-methylbenzimidazole derivatives (4a-g) with 2,4-dinitrophenoxyamine (DNPA) was carried out in DMF.N-amination proceeded at the imidazole moiety of these compounds with pKa's of more than 3.2 (1a, 1b, 4a, 4b, 4c, 4d). Treatment of these N-aminated derivatives (2a-b, 5a-d) with 0.1 N NaOH gave different results depending on their structures. In the guanine series, 9-ethyl-8-oxoguanine derivatives (3a, 3b)were obtained from N-aminated compounds (2a, 2b). In the benzimidazole series, no reaction proceeded with N-aminated compounds of 5a and 5b, whereas the benzo [1,2,4] triazine derivatives (6c, 6d) were obtained from N-aminated compounds (5c, 5d) , respectivery. It is not clear why the reactivity was different between purines (2a, 2b) and benzimidazoles (5c, 5d) although these have similar pKa values.

在DMF中，4个9-乙基鸟嘌呤衍生物（1a-d）和7个1-甲基苯并咪唑衍生物（4a-g）与2，4-二硝基苯氧基胺（DNPA）进行了亲电胺化反应，这些化合物的咪唑部分发生了N-胺化反应，其pKa均大于3.2（1a，1b，4a，4 b，4c，4d）。用0.1N NaOH处理这些N-胺化衍生物（2a-b，5a-d），根据它们的结构得到不同的结果。在鸟嘌呤系列中，9-乙基-8-氧代鸟嘌呤衍生物（3a，3b）由N-胺化化合物（2a，2b）得到。在苯并咪唑系列中，不与N-胺化化合物5a和5 b进行反应，而苯并[1，2，4]三嗪衍生物（6c，6d）分别由N-胺化化合物（5c，5d）得到。目前尚不清楚为什么嘌呤（2a，2b）和苯并咪唑（5c，5d）之间的反应性不同，尽管它们具有相似的pKa值。

项目成果

T.Kaiya: "Electrophilic amination of imidazole moieties of 9-ethylguanine and 1-methylbenzimidazole derivatives of N-aminated Products" Tetrahedron. 49. 8795-8804 (1993)

T.Kaiya：“N-胺化产物的 9-乙基鸟嘌呤和 1-甲基苯并咪唑衍生物的咪唑部分的亲电胺化”四面体。

Toyo Kaiya, Masahiro Ohta and Kohfuku Kohda: "Electrophilic amination of imidazole moieties of q-ethylguanine and l-methylbenzimidazole deriuatiues and reactivities of N-aminated Products" Tetrahedron. 49. 8795-8804 (1993)

Toyo Kaiya、Masahiro Ohta 和 Kohfuku Kohda：“q-乙基鸟嘌呤和 L-甲基苯并咪唑衍生物的咪唑部分的亲电胺化和 N-胺化产物的反应性”四面体。

T.Kaiya: "Electrophilic amination of imidazole moieties of 9-ethylgunine and 1-methylbenzimidazole derivatives of N-aminated products" Tetrahedron. 49. 8795-8804 (1993)

T.Kaiya：“N-胺化产物的 9-乙基鸟嘌呤和 1-甲基苯并咪唑衍生物的咪唑部分的亲电胺化”四面体。

Toyo Kaiya,Masahiro Ohta,Kohfuku Kohda: "Electrophilic amination of imidazolemoieties of 9-ethylguanine and 1-methylbenzimidazole derivatives and reactivities of N-amineted Products" Tetrahedron. 49. 8795-8804 (1993)

Toyo Kaiya、Masahiro Ohta、Kohfuku Kohda：“9-乙基鸟嘌呤和 1-甲基苯并咪唑衍生物的咪唑部分的亲电胺化和 N-胺化产物的反应性”四面体。