Acetylation of 5-amino-1H-[1,2,4]triazole revisited.
The products of the acetylation reactions of the common herbicide 5-amino-1H-[1,2,4]triazole were investigated using HPLC, GC-MS, 1H NMR, and FTIR spectroscopy. The conventional annular monoacetylation procedures with acetyl chloride are not regioselective and furnish a mixture of isomers. Traditional diacetylation in neat acetic anhydride under reflux produces a mixture of di-, mono-, and triacetylated derivatives. By using equivalent amounts of acetic anhydride in a dimethylformamide solution, a rapid and selective annular monoacetylation of 5-amino-1H-[1,2,4]triazole was achieved. The monoacetylation proceeds via the formation of the intermediate, 1-acetyl-3-amino-1H-[1,2,4]triazole, which had not been observed previously and which undergoes transformation into the known 1-acetyl-5-amino-1H-[1,2,4]triazole. Neat acetic anhydride at room temperature affords the diacetylated derivative, 1-acetyl-3-(acetylamino)-1H-[1,2,4]triazole both from 5-amino-1H-[1,2,4]triazole itself and from either 1-acetyl-5-amino-1H-[1,2,4]triazole or 5-(acetylamino)-1H-[1,2,4]triazole. The atypical product of the second acetylation, 1-acetyl-5-(acetylamino)-1H-[1,2,4]triazole, has been identified. These results may be useful in the development of effective and selective preparative procedures for the acetylation of 5-amino-1H-[1,2,4]triazole.
Dzygiel
Anetta
A
Institute of Chemistry, University of Opole, 48 Oleska Street, 45-052 Opole, Poland.
Masiukiewicz
Elzbieta
E
Rzeszotarska
Barbara
B
D000107:Acetylation; D000640:Amitrole / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D017550:Spectroscopy, Fourier Transform Infrared
D000640:Amitrole