Kitamura Mitsuru
Department Applied Chemistry, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550, Japan.
Chem Rec. 2017 Jul;17(7):653-666. doi: 10.1002/tcr.201600118. Epub 2016 Dec 21.
2-Azido-1,3-dimethylimidazolinium chloride (ADMC) and its corresponding hexafluorophosphate (ADMP) were found to be efficient diazo-transfer reagents to various organic compounds. ADMC was prepared by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. ADMP was isolated as a crystal having good thermal stability and low explosibility. ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild basic conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which were easily isolated in virtue of the high water solubility of the by-products. ADMP showed high diazo-transfer ability to primary amines even in the absence of metal salt such as Cu(II). Using this diazotization approach, various alkyl/aryl azides were directly obtained from their corresponding primary amines in high yields. Furthermore, naphthols reacted with ADMC to give the corresponding diazonaphthoquinones in good to high yields. In addition, 2-azido-1,3-dimethylimidazolinium salts were employed as azide-transfer and migratory amidation reagents.
发现2-叠氮基-1,3-二甲基咪唑啉氯化物（ADMC）及其相应的六氟磷酸盐（ADMP）是对各种有机化合物有效的重氮转移试剂。ADMC由2-氯-1,3-二甲基咪唑啉氯化物（DMC）与叠氮化钠反应制备。ADMP被分离为具有良好热稳定性和低爆炸性的晶体。ADMC和ADMP在温和的碱性条件下与1,3-二羰基化合物反应，以高收率得到2-重氮基-1,3-二羰基化合物，由于副产物的高水溶性，这些化合物易于分离。即使在没有诸如Cu（II）等金属盐的情况下，ADMP对伯胺也显示出高重氮转移能力。使用这种重氮化方法，可以从相应的伯胺中直接以高收率获得各种烷基/芳基叠氮化物。此外，萘酚与ADMC反应，以良好至高的收率得到相应的重氮萘醌。此外，2-叠氮基-1,3-二甲基咪唑啉盐被用作叠氮转移和迁移酰胺化试剂。
