SYNTHESIS AND REACTIVITY OF 4-NITRO-3-(TETRAZOL-5-YL) FURAZAN WITH N- AND O-NUCLEOPHILES

Abstract

A rational four-stages scheme for the synthesis of 4-nitro-3-(tetrazol-5-yl)furazane is proposed. The synthesis starts from the stage of 3-amino-4-(1,2,4-oxadiazol-3-yl)-furazan preparation by condensation of amidoxime of 4-aminofurazan-3-carboxylic acid with triethyl orthoformate, further reductive ring opening of 1,2,4-oxadiazole cycle. The action of hydrazine results in amidrazone of 4-aminofurazan-3-carboxylic acid formation. On the next step the diazotization of the resulting compound with sodium nitrite in acetic acid gives 3-amino-4-(tetrazol-5-yl)furazane. At last stage the titled 4-nitro-3-(tetrazol-5-yl)furazan was synthesized by oxidation of the amino group of 3-amino-4-(tetrazol-5-yl)furazan by a solution of 30% hydrogen peroxide in concentrated sulfuric acid with 85% yield. The increase in the oxidative activity of the H2O2/H2SO4 system by carrying out the oxidation stage at an elevated temperature made possible to substantially reduce the consumption of hydrogen peroxide and sulfuric acid. The desired 4-nitro-3-(tetrazol-5-yl)furazan was isolated by partial neutralization of the reaction mixture with sodium orthophosphate, followed by extraction with ethyl acetate. The total yield of 4-nitro-3-(tetrazol-5-yl)furazane in terms of the starting amidoxime of 4-aminofurazan-3-carboxylic acid was 42-48%. It was shown that the reaction of 4-nitro-3-(tetrazol-5-yl)furazan with a number of N- and O-nucleophilic agents (sodium azide, high-basic amines, hydrazine, sodium hydroxide, methanol in the presence of potassium carbonate) resulted in the substitution of the nitro group of the selected compound by a nucleophile and formation of corresponding 4-R-3-(tetrazol-5-yl)furazane derivatives (R = N3, substituted amino group, NHNH2, OH, OMe). Some chemical properties of thereby obtained compounds are considered. Thus [3 + 2] cycloaddition reaction of 4-azido-3-(tetrazol-5-yl)furazane (R = N3) with propargyl alcohol was used at the synthesis of 4- (4-hydroxy-methyl-1,2,3-triazol-1-yl)-3-(tetrazol-5-yl)furazane. The condensation of 3-hydrazino-4-(tetrazol-5-yl)furazane (R = NHNH2) with carbonyl compounds in the case of reaction with benzaldehyde leads to the corresponding hydrazone, with β-dicarbonyl compounds (malonaldehyde, acetylacetone) pyrazole derivatives were obtained. The synthesized compounds are characterized by 1H and 13C nuclear magnetic resonance spectra, by IR and mass spectroscopy. For citation:Stepanova E.V., Stepanov A.I. Obtaining and Reactivity of 4-nitro-3-(tetrazol-5-yl) furazan with N- and O-nucleophiles. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 5. P. 21-29