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Nitropyrazoles: XII. Transformations of the 4-Methyl Group in 1,4-Dimethyl-3,5-dinitropyrazole and Cyclization of the Transformation Products

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Abstract

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.

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Authors and Affiliations

  1. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991, Russia

    A. A. Zaitsev, I. L. Dalinger, A. M. Starosotnikov, V. V. Kachala, Yu. A. Strelenko, T. K. Shkineva & S. A. Shevelev

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  1. A. A. Zaitsev
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  2. I. L. Dalinger
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  3. A. M. Starosotnikov
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  4. V. V. Kachala
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  5. Yu. A. Strelenko
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  6. T. K. Shkineva
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  7. S. A. Shevelev
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Dedicated to Full Member of the Russian Academy of Sciences N.S. Zefirov on His 70th Anniversary

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Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 10, 2005, pp. 1538–1546.

Original Russian Text Copyright © 2005 by Zaitsev, Dalinger, Starosotnikov, Kachala, Strelenko, Shkineva, Shevelev.

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Zaitsev, A.A., Dalinger, I.L., Starosotnikov, A.M. et al. Nitropyrazoles: XII. Transformations of the 4-Methyl Group in 1,4-Dimethyl-3,5-dinitropyrazole and Cyclization of the Transformation Products. Russ J Org Chem 41, 1507–1515 (2005). https://doi.org/10.1007/s11178-005-0374-9

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  • DOI: https://doi.org/10.1007/s11178-005-0374-9

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