Abstract
A method for the synthesis of 1-methyl-3,5-dinitropyrazole-4-carbonitrile from 1,4-dimethyl-3,5-dinitropyrazole was developed. Nucleophilic substitution in 1,4-dimethyl-3,5-dinitropyrazole, 1-methyl-3,5-dinitropyrazole-4-carboxamide, and 1-methyl-3,5-dinitropyrazole-4-carbonitrile involves solely the 5-NO2-group in the ring. 1-Methyl-3,5-dinitropyrazole-4-carbonitrile reacts with thioglycolic acid phenylamide and potassium carbonate to give 4-amino-1-methyl-3-nitro-N-phenyl-1H-thieno[2,3-c]pyrazole-5-carboxamide. The use of glycolic acid phenylamide instead of thioglycolic acid N-phenylamide under analogous conditions resulted in 5-anilino-1-methyl-3-nitro-1H-pyrazole-4-carbonitrile. An explanation for the regiospecificity of the nucleophilic substitution of the 5-NO2 group in 4-R-1-methyl-3,5-dinitropyrazoles is given.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2004–2014, October, 2007.
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Zaitsev, A.A., Cherkasova, T.I., Dalinger, I.L. et al. Nitropyrazoles. Russ Chem Bull 56, 2074–2084 (2007). https://doi.org/10.1007/s11172-007-0323-6
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DOI: https://doi.org/10.1007/s11172-007-0323-6