The Synthesis and Reactions of Polyazaaromatics

多氮杂芳烃的合成与反应

• 批准号: 09672158
• 负责人: OHSAWA Akio
• 金额: $ 1.6万
• 依托单位: Showa 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-09672158/
• 关键词: 1,2,3-triazine; 1,2,3,4-tetrazine; polyazaaromatic; aminoazole; oxidation; molecular orbital calculation; nitric oxide; 1,2,3-トリアジン; 1,2,3,4-テトラジン; 含窒素芳香族; トリアジン; テトラジン; N-アミノ化合物

Since last year, we have been investigating the synthetic method for 1,2,3,4-tetrazines and their benzo derivatives. In order to evaluate the scope and limitation of our reaction system. N-aminopyrazoles were oxidized byy various oxidizing agents to give N-nitrene derivatives, which were rearranged to corresponding 1,2,3-triazines. Since this reaction system was revealed to be effective for diverse 1,2,3-triazine derivatives, we applied the reaction to the oxidation of N-amino-l, 2,3-triazole. Thus, the oxidation of 1-amino-triazolotriazole afforded the triazolo-l, 2,3,4-tetrazine, which is the first aromatic tetrazine derivative. The reaction was thought to be of practical use because there are many triazole derivatives which are readily available. The other tetrazine derivatives were, however, not obtained by this procedure. The cause of this failure was studied using the molecular orbital calculations, and the results showed that 1,2,3,4-tetrazine would be decomposed via stepwise radical processes rather than concerted ones, thus the compound would be stable if it was synthesized Thus we decided to study another oxidizing agents to react with N-amino compounds, and found that nitric oxide, which has attracted much attention as a biological radical to act as diverse physiological signal transmitters, reacted with amino compounds in various manners depending upon the amount of molecular oxygen vs. NO.

去年以来，我们一直在研究1,2,3,4-四嗪及其苯并衍生物的合成方法。为了评估我们的反应系统的范围和局限性。 N-氨基吡唑被各种氧化剂氧化得到N-氮宾衍生物，其重排为相应的1,2,3-三嗪。由于该反应体系对多种 1,2,3-三嗪衍生物均有效，因此我们将该反应应用于 N-氨基-1,2,3-三唑的氧化。因此，1-氨基-三唑并三唑的氧化得到三唑-1,2,3,4-四嗪，这是第一个芳香族四嗪衍生物。该反应被认为具有实际用途，因为有许多容易获得的三唑衍生物。然而，其他四嗪衍生物并未通过该程序获得。通过分子轨道计算研究了失败的原因，结果表明1,2,3,4-四嗪的分解是逐步自由基过程而不是协同过程，因此如果合成该化合物将是稳定的。我们决定研究另一种与N-氨基化合物反应的氧化剂，并发现一氧化氮作为一种生物自由基而备受关注，可作为多种生理信号传递者，根据其量的不同，以各种方式与氨基化合物发生反应。分子氧与否。

项目成果

Y.Matsuya, T.Itoh, K.Nagata, and A.Ohsawa: "A Mild Dehydrazination Reaction of Arylhydrazines Using Nitric Oxide in the Presence of Oxygen" Tetrahedron. 53. 15701-15710 (1997)

Y.Matsuya、T.Itoh、K.Nagata 和 A.Ohsawa：“在氧气存在下使用一氧化氮进行芳基肼的温和脱肼反应”四面体。

Y.Matsuya: "A Mild Dehydrazination Reaction of Arylhydrazines Using Nitric Oxide" Tetrahedron. 53. 15701-15710 (1997)

Y.Matsuya：“使用一氧化氮的芳基肼的温和脱肼反应”四面体。

A.Ohsawa 他: "Reaction of Nitric Oxide with Amines" Journal of Organic Chemistry. 62. 3582-3585 (1997)

A. Ohsawa 等人：“一氧化氮与胺的反应”有机化学杂志 62. 3582-3585 (1997)。

A.Ohsawa 他: "Reaction of Nitric Oxide with Amines" Journal of Organic Chemistry. 62. 3582-3585 (1997)

A. Ohsawa 等人：“一氧化氮与胺的反应”有机化学杂志 62. 3582-3585 (1997)。

A.Ohsawa 他: "Deamination of 2-Aminothiazoles and 3-Amino-1,2,4-triazines with Nitric Oxide" Chemical and Pharmaceutical Bulletin. 45. 1547-1549 (1997)

A. Ohsawa 等人：“用一氧化氮脱氨 2-氨基噻唑和 3-氨基-1,2,4-三嗪”《化学和制药公报》45. 1547-1549 (1997)。