Reactions of 3-amino-4-methylfurazan with nitrating agents

Abstract

Depending on the type of nitrating agent and the reaction temperature, nitration of 3 amino 4 methylfurazan 1 gives either nitramine or the products of formal oxidation of the amino group, namely, nitroso , nitro , azo , and azoxyfurazans. The methyl group of compound 1 is resistant against all the nitrating agents studied.

Nitration of primary aminofurazans with aqueous nitric acid

“…The yield of nitramine 1b (93%) significantly exceeds that attained in the nitration of amine 2b with 100% HNO 3 (22%) and is close to that with the use of N 2 O 5 or an HNO 3 -P 2 O 5 system (96%) (see Ref. 3).…”

“…They can be obtained by either direct nitration of primary aminofurazans 2a-с (see Refs 5-7, 10, 12 and Scheme 1) or nitration of aminofurazan derivative 3 with replacement of the leaving group R (see Ref. 3 and scheme 2), or destructive nitrolysis. 4 3 Amino 4 R furazans 2 are weak bases, e.g., 3 ami no 4 nitrofurazan (pK BH + = -4.4 (see Ref.…”

“…Therefore, in the nitration of aminofurazans 2 with nitric acid or its mixtures the extent of protonation of the amino group is low, which allows one to relatively easily obtain 3 nitramino 4 R furazans 1 using the majority of nitra tion systems including acidic. Fuming nitric acid (d 20 = = 1.5 g cm -3 ), its solutions in organic solvents, mixtures with H 2 SO 4 or oleum, as well as mixtures of H 2 SO 4 with NaNO 3 or KNO 3 , and mixtures of HNO 3 with P 2 O 5 , NO 2 BF 4 , N 2 O 5 (see 11) are employed for N nitra tion of primary aminofurazans. In most cases, nitramino furazans 1 are isolated in yields not exceeding 70-80%.…”

“…2, 3 In some cases, 3 preliminary pro tection of the primary amino group (silylation, boryla tion) followed by substitutive nitration of compound 3 with NO 2 BF 4 affords ultimately the target product 1b in 85-93% yield (see Scheme 2). In the present work, we studied nitration of primary aminofurazans with nitric acid with different concentra tions.…”

Combination of 1,2,4‐Oxadiazole and 1,2,5‐Oxadiazole Moieties for the Generation of High‐Performance Energetic Materials

“…[4] 1,2,5-Oxadiazole (furazan) is highly energetic and has potential use in both propellant and explosive formulations. [3a-e] A large number of nitro-, amino-, and nitramine-functionalized monofurazan compounds, [5] macrocyclic furazans, [6] linked furazans, [7] and ring-fused furazans bridged by azo,o xy,a nd azoxy groups have been reported. [8] However,1 ,2,4-oxadia-zoles [3f-l] and 1,3,4-oxadiazoles [3n-q] have been studied only rarely as energetic materials.…”