Development of Innovative Synthetic Method of Diazanaphthalene Rings from Hydrazine-Carbonyl Analogs and TCNE

肼羰基类似物和TCNE创新合成二氮杂萘环方法的开发

• 批准号: 09650944
• 负责人: MATSUBARA Yoshio
• 金额: $ 2.05万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650944/
• 关键词: Diazanaphthalenes; Ring formation reaction; New synthetic reaction; Phenylhydrazines; Carbonyl compounds; TCNE; Three components reaction system; カルボニル類

Innovative new synthetic reaction of diazanaphthalenes which are important as key compounds for medicines and functional materials, were found by the reaction of three components system of phenyihydrazines, carbonyls and TONE.The results were noticeable such as showing below.1)Synthesis of diazanaphthalenes was investigated by the various reaction conditions such as reaction media, solvents and reaction temperature. The results were obtained the establishment of new synthetic method and the elucidation for the range of application by substitution and functional group.2)Based on the finding results from the 1 was variously investigated.The results clearly suggest that the reaction proceed initially by the initiation with a charge transfer, via formation of additional intermediate between hydrazone and TONE (1 : 1), elimination of methyl group and finally ring formation by ON of TCNE.

通过苯肼、羰基化合物和TONE三组分体系的反应，发现了作为药物和功能材料关键化合物的二氮杂萘的创新合成新反应，结果引人注目，如下所示：1）通过反应介质、溶剂和反应温度等各种反应条件研究了二氮杂萘的合成。2）在此基础上，对1的结果进行了多方面的研究，结果表明，该反应是通过电荷转移引发，在腙和TONE之间形成额外的中间体（1：1），消除甲基，最后通过TCNE的ON成环。

项目成果

松原凱男: "Synthesis of Novel 2-Substituted-1,3,4-thiadiazoles." Chem.Pharm.Bull.46. 392-331 (1998)

Kaio Matsubara：“新型 2-取代-1,3,4-噻二唑的合成。”Chem.Pharm.Bull.46（1998）。

Y.Matsubara, T.Matsuda, Y.Yamaguchi, Z.Yoshida: "Remarkably Different Behavior of 4-Cyano-3-phenylcinnoline Toward Chemical and Electrochemical Reductions" Tetrahedron Lett.(in press).

Y.Matsubara、T.Matsuda、Y.Yamaguchi、Z.Yoshida：“4-氰基-3-苯基肉啉对化学和电化学还原的显着不同行为”Tetrahedron Lett.（出版中）。

松原凱男: "Reaction of Aromatic Hydrazones with Tetracyano-ethylene Leading to the Formation of Cyanocinnoline"発表予定.

Kaio Matsubara：将介绍“芳香腙与四氰基乙烯的反应导致氰基肉碱的形成”。

Y.Matsubara, A.Horikawa Z.Yoshida,: "A Novel Synthesis of 1, 2-Diazanaphthalenes" Tetrahedron Lett.,. 38. 8199-8202 (1997)

Y.Matsubara、A.Horikawa Z.Yoshida，：“1, 2-二氮杂萘的新颖合成”Tetrahedron Lett.，。

松原凱男: "Synthesis of Novel 2-Substituted-1,3,4-thiadiazoles" Chem.Pharm.Bull.46. 331-392 (1998)

Kaio Matsubara：“新型 2-取代-1,3,4-噻二唑的合成”Chem.Pharm.Bull.46 (1998)。