Abstract: A new one-step method for the synthesis of 4-methyl-3(5)-nitropyrazole by nitration of 4-methylpyrazole is developed. Arylation of 4-methyl-3(5)-nitropyrazole with 1,3,5-trinitrobenzene gives 1-(3,5-dinitrophenyl)-4-methyl-3-nitropyrazole, nitration of which leads to 1-(3,5-dinitrophenyl)-4-methyl-3,5-dinitropyrazole. The action of 1 equiv. of an O- or S-nucleophile (phenolate, p-chlorobenzenethiolate and ethoxide ions; anions of glycolanilide and thioglycolanilide) on 1-(3,5-dinitrophenyl)-4-methyl-3,5-dinitropyrazole led to the substitution of the 5-NO2 group of the pyrazole ring; under the action of one more equivalent of a nucleophile the NO2 group of the benzene ring was substituted. The substitution product of the anion of thioglycolanilide for the 5-NO2 group undergoes the intramolecular cyclization — oxidative nucleophilic hydrogen substitution in the benzene ring under the action of K2CO3.

Cite: Zaitsev A.A. , Zaiko D.V. , Dalinger I.L. , Kachala V.V. , Shkineva T.K. , Shevelev S.A.
Nitropyrazoles 17. Synthesis of 1-(3,5-dinitrophenyl)-4-methyl-3,5-dinitropyrazole and the study of its chemical transformations
Russian Chemical Bulletin. 2009. V.58. N10. P.2122-2128. DOI: 10.1007/s11172-009-0290-1 WOS Scopus OpenAlex

Identifiers:

≡ Web of science:	WOS:000280650300017
≡ Scopus:	2-s2.0-77955757731
≡ OpenAlex:	W2027618086

Altmetrics: