We have developed the diazo-transfer of 2-azido-1,3-dimethylimidazolinium salts to 1,3-dicarbonyl compounds. 2-Azido-1,3-dimethylimidazolinium chloride (ADMC) was prepared by N-nitrosation of N-aminoguanidine or by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. The corresponding phosphate, ADMP, was isolated as a crystal, and was found to be a stable and safe reagent. Both ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water.

Organic azides were prepared from primary amines in high yields by metal-free diazo transfer with 2-azido-1,3-dimeth-

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.

An efficient synthetic method for the synthesis of diazonaphthoquinones from naphthols is described. A variety of diazonaphthoquinones were synthesized from the corresponding naphthols by the diazo transfer with 2-azido-1,3-dimethylimidazolinium chloride prepared by the reaction of 2-chloro-1,3-dimethylimidazorinium chloride and sodium azide.

Diazo transfer from 2-azido-1,3-dimethylimidazolinium chloride to 1,3-dicarbonyl compounds has been developed. The reaction proceeds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water.