1214-75-1Relevant articles and documents
Nitropyrazoles: XII. Transformations of the 4-methyl group in 1,4-dimethyl-3,5-dinitropyrazole and cyclization of the transformation products
Zaitsev,Dalinger,Starosotnikov,Kachala,Strelenko,Shkineva,Shevelev
, p. 1507 - 1515 (2007/10/03)
A preparative procedure for the synthesis of 1,4-dimethyl-3,5- dinitropyrazole by nitration of 1,4-dimethylpyrazole was developed. The reaction of 1,4-dimethyl-3,5-dinitropyrazole with dimethoxymethyl-(dimethyl)amine (N,N-dimethylformamide dimethyl acetal) gave (E)-N,N-dimethyl-2-(1-methyl-3,5- dinitropyrazol-4-yl)ethenylamine. Acid hydrolysis of the latter afforded (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde, and the reaction with sodium nitrite in hydrochloric acid led to formation of 2-hydroxymino-2-(1-methyl-3,5- dinitropyrazol-4-yl)acetaldehyde. The corresponding O-methyloxime and phenylhydrazone reacted with K2CO3 to give 6-methyl-4-nitropyrazolo[4,3-d]isoxazole-3-carbaldehyde O-methyloxime and 1-methyl-3-nitro-4-(2-phenyl-2H-1,2,3-triazol-4-yl)pyrazol-5-ol, respectively. Treatment of (1-methyl-3,5-dinitropyrazol-4-yl)-acetaldehyde with benzenediazonium chloride gave (1-methyl-3,5-dinitropyrazol-4-yl)acetaldehyde phenylhydrazone which underwent intramolecular cyclization with replacement of the 5-nitro group by the action of K2CO3 in acetonitrile; in the reaction with K2CO3 in ethanol, the 5-nitro group was replaced by ethoxy.