Synthesis of Nitro‐Octaaza Derivatives of Reduced Anthracene

Abstract

Nitro compounds of octaaza derivatives of reduced anthracene were synthesized for the first time by reaction of 2,3,4a,6,7,8a,9,10‐octaaza‐4,8‐dioxo‐3,4,4a,7,8,8a,9,9a,10,10a‐decahydroanthracene with nitric acid, mixed nitric acid/sulfuric acid, and nitric acid/acetic anhydride at between –20 and –30 °C. In addition, 1,2,4,5‐tetrazine azido derivatives were obtained by hydrolytic decomposition of the starting compound by nitrous acid. All the resultant compounds exhibit high thermal stability.

A New Approach for the Synthesis of 2,3,4а,6,7,8а,9,10-Octaaza-4,8-dioxo-3,4,4a,7,8,8а,9,9a,10,10а-decahydroanthracene and High-Energy Performance Characterization of Its Dinitramide Salt

“…It is seen in Figure 2 that the 1 H NMR spectrum of the obtained sample of compound 3 has no singlet protons of the NH 2 group of the starting bis(hydrazone)glyoxal at 6.59 ppm, while the characteristic signal for the double-bond proton shifts to 5.76 ppm due to the impact of the dinitrourea anion, in which case a characteristic triplet corresponding to the NH 3 + cation protons shows up at 6.96-7.22 ppm [25]. The splitting of the signal into a few equivalent peaks suggests an interaction between the proton in question and the other non-equivalent protons.…”

“…The free protons on the nitrogen atoms at positions 3, 7 (the amide ones) and 9, 10 (the amine ones) were theoretically capable of being protonated with acid to generate the respective di-or tetranitro derivatives or salts. However, the previous studies showed that the basicity of the amide nitrogen was lowered by the impact of the electron-withdrawing carbonyl, and the amine protons of the central ring were involved in salt formation (Scheme 4) [25]. A similar reaction using dinitramic acid afforded 2,3,4а,6,7,8а,9,10-octaaza-4,8-dioxo-3,4,4a,7,8,8а,9a,10а-octohydroanthracene-9,10-ion-bis (dinitramide) (4), a high-melting crystalline compound in a 53% yield (Scheme 5).…”

“…The functionalization of the tricyclic compound using various nitrating agents allows the diversity-oriented synthesis of both the acid salts and di-and tetranitro derivatives of the reduced anthracene. In contrast, the corresponding diazide was isolated via nitrosation [25]. However, the synthesis problems of the starting 2, particularly the multistage process and low yields (at most 16% calculated on a starting urea basis), heavily hinder further research on expanding the compound's practical application.…”

New Reaction Products of Acetylacetone with Semicarbazide Derivatives

“…4,5 4-Nitrosemicarbazide reacts with glyoxal (dialdehyde) and diacetyl (diacetone) to yield the respective linear glyoxal bis(nitrosemicarbazone) and diacetyl bis(nitrosemicarbazone). 5 The resultant compounds can be used in further synthesis of novel cyclic nitro compounds 6,7 and bioactive substances. 8 In light of the aforesaid background, a logical question arises as to which compounds will be formed by the reaction between 4-nitrosemicarbazide and 1,3-dicarbonyl compounds since it is well known that the reaction of carbonic acid hydrazide derivatives (semicarbazide, 1,3-diaminourea, etc.)…”

“…Despite a few binding sites, the molecule of 4-nitrosemicarbazide exhibits regioselectivity toward monoaldehydes to yield the respective nitrosemicarbazones. , 4-Nitrosemicarbazide reacts with glyoxal (dialdehyde) and diacetyl (diacetone) to yield the respective linear glyoxal bis (nitrosemicarbazone) and diacetyl bis (nitrosemicarbazone) . The resultant compounds can be used in further synthesis of novel cyclic nitro compounds , and bioactive substances …”