Eletrophilic azidation with azido imidazolinium salt

2019 Fiscal Year Final Research Report

• Project/Area Number: 17K19125
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry and related fields
• Research Institution: Kyushu Institute of Technology
• Principal Investigator: Kitamura Mitsuru 九州工業大学, 大学院工学研究院, 教授 (10313199)
• Project Period (FY): 2017-06-30 – 2020-03-31
• Keywords: アジド / ジアゾ / アジドイミダゾリニウム

Outline of Final Research Achievements

Aryl azides have recently become increasingly important in biological chemistry such as for photoaffinity labeling and drug discovery. There have been reported various synthetic methods of aryl azides from aryl amines and aryl halides which are commonly prepared from arenes. However, direct azidation of arenes have not been developed.
In this Study a new direct azidation of phenols was developed. By treating chloroimidazolium chloride having bulky aryl group on its nitrogen and sodium azide with phenol in the presence of a secondary amine, ortho-azidation of phenol was achieved. In this reaction, choice of solvent was important. When aprotic polar solvent, such as acetonitrile, was used, the yield of azidophenol was low and triazne derivative was formed as by-product. However, the triazne formation was suppressed by using protic solvent and azidophenols were obtained in the highest yields when methoxyethanol was used.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

有機アジド（R-N3）の開発は合成化学に限らずケミカルバイオロジーや高分子・材料分野において重要性が増している。一方,アジドやアジド化剤は爆発性を持つものが多く，爆発性のない安全で簡便なアジド化合物合成法の開発の需要は高い。
本研究では爆発性のない新しいアジド含有化合物を合成し，これを用いた新しいアジド化合物やジアゾ化合物を合成する手法を開発した。