Organic azides were prepared from primary amines in high yields by a metal free diazo-transfer reaction using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP), which is safe and stable crystalline. The choice of base was important in the diazo-transfer reaction. In general, 4-(N,N-dimethyl)aminopyridine (DMAP) was efficient, but a stronger base such as alkylamine or DBU was more appropriate for the reaction of nucleophilic primary amines. X-ray single crystal structural analysis and geometry optimization using density functional theory (B3LYP/6-31G**) were conducted to study the ADMP structure, and the diazo-transfer reaction mechanism was explained with the help of the results of these analyses.

A Reagent for Safe and Efficient Diazo-Transfer to Primary Amines: 2-Azido--1,3-dimethylimidazolinium Hexafluorophosphate. -The title compound, a safe, crystalline, and commercially available substance, is found to be an efficient diazo--transfer reagent for primary amines, even without the aid of a metal salt such as Cu(II). Various alkyl and aryl azides (II), (IV), and (VI) are obtained directly from the corresponding amines (I), (III), and (V). The choice of base is important in the diazo-transfer reaction. In general DMAP is efficient, but stronger bases such as alkylamine of DBU are more appropriate for the reaction of nucleophilic primary amines. -(KITAMURA*, M.; KATO, S.; YANO, M.; TASHIRO, N.; SHIRATAKE, Y.; SANDO, M.; OKAUCHI, T.; Org. Biomol. Chem. 12 (2014) 25, 4397-4406, http://dx.doi.org/10.1039/c4ob00515e ; Dep. Appl. Chem., Fac. Eng., Kyushu Inst. Technol., Tobata, Kitakyushu 804, Japan; Eng.) -M. Paetzel 48-039

Die Dithiosäuren (I) reagieren mit sekundären und tertiären Aminen in hohen Ausbeuten zu den Salzen (II) bzw. (III).