Interaction between the Cation Radicals and Weak-Nucleophilic Reagent in Photochemical Electron Transfer Systems.

光化学电子转移系统中阳离子自由基与弱亲核试剂之间的相互作用。

• 批准号: 02640400
• 负责人: YASUDA Masahide
• 金额: $ 1.28万
• 依托单位: Miyazaki 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: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640400/
• 关键词: Photochemical Electron Transfer; Photooxygenation; Photoamination; Photophosphonation; Cyanomethylation; 芳香族炭化水素; スチルベン類; 求核付加反応; 1.1ージフェニルアルケン

The interaction between the cation radicals generated by the photochemical electron transfer and various nucleophiles has been investigated.(1)An Interaction with Acetate Anion. The photooxygenation of naphthalene derivatives in the presence of acetate anion gave pothalic acids whereas the photooxygenation in the absence of the salts gave naphthoquinone derivatives. Thus the acetate ion accelerate the reaction of the cation radicals with oxygen molecule.(2)An Interaction with Amines. Regiochemistry on photoamination via the reaction of the cation radical with amines has been investigated for a dozen 1, 2-arylphenylethenes. A regioselective photoamination occurred in the stilbenes having the methoxy group at para position on aryl group. The amine added to 9-alkoxyphenanthrene mainly in trans manner to give cis-9-amino-10-alkoxy-9, 10-dihydrophenanthrene.(3)An Interaction with Trialkylphosphites. The preparation of arene phosphonates was performed by the reaction of the cation radicals of phenanthrene or naphthalene with trialkyl phosphites.(4)An Interaction with Acetonitrile. Cyanomethylation of 1, 1-diphenylalkenes was performed by the photoreaction in the presence of p-dicyanobenzene and t-butylamine in acetonitrile.

研究了光化学电子转移产生的阳离子自由基与各种亲核试剂之间的相互作用。(1)与醋酸阴离子的相互作用。在有乙酸阴离子存在的情况下，萘衍生物的光氧化反应得到邻苯二甲酸，而在没有盐的情况下，光氧化反应得到萘醌衍生物。因此醋酸离子加速了阳离子自由基与氧分子的反应。(2)与胺的相互作用。研究了12种1,2 -芳基苯乙烯阳离子自由基与胺反应的光胺化反应的区域化学。甲氧基与芳基对位的二苯乙烯发生区域选择性光胺化反应。该胺主要以反式方式加入到9-烷氧菲中，得到顺-9-氨基-10-烷氧基- 9,10 -二氢菲。(3)与三烷基亚磷酸酯的相互作用。以菲或萘的阳离子自由基与三烷基亚磷酸酯为原料，制备了芳烃膦酸盐。(4)与乙腈相互作用。在对二苯苯和对丁胺的存在下，在乙腈中进行了1,1-二苯基烯烃的氰甲基化反应。

项目成果

Masahide Yasuda: "Amination of Electron-Rich Substrates via Photoinduced Electron Transfer.Mechanism and Synthetic Application" Reviews on Heteroatom Chemistry. 4. 27-46 (1991)

Masahide Yasuda：“通过光诱导电子转移实现富电子底物的胺化。机理和合成应用”杂原子化学评论。

Toshiaki Yamashita: "Photoーinduced Nucleophilic Addition of Ammonia and AlkylーAmines to ArylーSubstituted Alkenes in the Presence of pーDicyanobenzene." Bull.Chem.Soc.Jpn.,. 64. 366-374 (1991)

Toshiaki Yamashita：“在对二氰基苯存在下，氨和烷基胺与芳基取代的烯烃发生光致亲核加成。”Bull.Chem.Soc.Jpn. 64. 366-374 (1991)

Masahide Yasuda: "Amination of Electron-Rich Substrates via Photoinduced Electron Transfer. Mechanism and Synthetic Application" Reviews on Heteroatom Chemistry. 4. 27 (1991)

Masahide Yasuda：“通过光诱导电子转移实现富电子底物的胺化。机理和合成应用”杂原子化学评论。

Kensuke Shima: "Ring-Splitting Reaction of 2, 2-Diarylthietane by Electron Transfer Photosensitization of 9, 10-Dicyanoanthracene" Bull. Chem. Soc. Jpn.

Kensuke Shima：“通过 9, 10-二氰基蒽的电子转移光敏化实现 2, 2-二芳基硫杂环丁烷的环分裂反应”公牛。

Masahide Yasuda: "Regiochemistry on Photoamination of Stilbene Derivatives with Ammonia via Electron Transfer" J.Org.Chem.57. 1351-1354 (1992)

Masahide Yasuda：“通过电子转移对二苯乙烯衍生物与氨进行光胺化的区域化学”J.Org.Chem.57。