Dinitraminic acid

The nitration of nitramine (153) with nitronium tetrafluoroborate, followed by neutralization of the resulting dinitraminic acid with ammonia, also generates ammonium dinitramide (152). Neutralization of this reaction with alkylamines, instead of ammonia, yields the corresponding alkylammonium salts of dinitramide. The nitration of ammonia with dinitrogen pentoxide (15 %) or nitronium salts like the tetrafluoroborate (25 %) yield ammonium dinitramide (152) through the initial formation of nitramine. 

Ammonium dinitramide has been synthesized from the nitration of ammonium sulfamate with strong mixed acid at -35 to -45 °C followedby neutralization of the resulting dinitraminic acid with ammonia. The yield is 45 % when the mole ratios of sulfuric acid to nitric acid is 2 1 and ammonium sulfamate to total acid is 1 6. The nitration of other sulfonamide derivatives, followed by hydrolysis with metal hydroxides, also yields dinitramide salts. ... 

Computational Study of the Structure of Dinitraminic acid, HN(NC>2)2, and the Energetics of Some Possible Decomposition Steps, Chem. Phys. Let. 216 (1993) 348. 

The existence and preparation of stable dinitramides was disclosed publicly in two patent applications filed by the US military contractor SRI [1,2]. They cover a series of dinitramide salts, including ADN. The anion, N(N02)2", was named here for the first time as dinitramide, in contrast to the covalent alkyl compounds called dinitramines. The protonated form of the dinitramide anion was named dinitraminic acid, HN(N02)2. 

The dinitraminic acid is converted in a subsequent step by a cation exchange with a salt MX, where X could, for example, be a halide. 

The stability of the anion is reflected in the strength of the corresponding acid, dinitraminic acid. The pKa is -5.6, which means it is stronger than nitric acid and similar to sulfuric acid. 

The decomposition of ADN can follow at least two different routes. One involves the formation, at 127°C, of ammonium nitrate and N20 [10], followed by a second step, with onset above 200°C, in which the AN decomposes to N02 and water. Potassium dinitramide decomposes with an analogous initial step, forming KNO3. A second route for ADN begins with dissociation of the salt into ammonia and dinitraminic acid, HN(N02)2. This can be viewed as an acid/base equilibrium ... 

Compared to any of its salts, dinitraminic acid is extremely thermally unstable, and cannot be isolated at room temperature. The decay... 

A. Langlet, H. Ostmark and N. Wingborg, Method of Preparing Dinitraminic Acid Salts Thereof, Int. App. No. PCT/SE96/00976. 

Note Free dinitraminic acid is a very strong acid with a pKA value of -5.6. It is unstable however and decomposes quickly to N20 and HN03. 

Salts of the acidic dinitramine find use as oxidants in propellant formulations. The dinitramine itself is explosively unstable, though more stable than nitramide [1], Although described as relatively stable the sodium salt has an autoignition temperature of 123°C, the potassium 140°C [2],... 

The condensation of a primary nitramine with formaldehyde in the presence of concentrated sulfuric acid is a useful route to 1,3-dinitramines. A number of linear dinitramines have been prepared via this route including 2,4-dinitro-2,4-diazapentane (212), 3,5-dinitro-3,5-diazaheptane (213), and 5,7-dinitro-5,7-diazaundecane (214). ... 

The dinitramide ion is stable in both acidic and basic solutions between pH 1-15 at room temperature but is slowly decomposed in the presence of strong concentrated acid. In contrast to alkyl V,V-dinitramines (Section 6.11.2) where the central nitrogen atom is highly electron deficient, the dinitramide anion has its negative charge delocalized over both nitrogen and oxygen atoms with the consequence that the N-N bonds are less susceptible to rupture. However, the dinitramide anion is not as stable as the nitrate anion ammonium dinitramide melts at 92 °C and decomposition starts at 130 °C. 

Alkyl lV,lV-dinitramines (154) have been prepared from the reaction of the tetraalkylam-monium salts (155) of primary nitramines with nitryl fluoride in acetonitrile at subambient temperature. The same reaction with the primary nitramine or its alkali metal salts yields the corresponding nitrate ester. Treatment of the ammonium, potassium, or lithium salts of primary nitramines (156) with a solution of nitronium tetrafluoroborate in acetonitrile at subambient temperature yield alkyl iV,iV-dinitramines. ° The same reactions in ether or ester solvents enables the free nitramine to be used. The nitrolysis of A-alkylnitramides (157) and N,N-diacylamines with nitronium tetrafluoroborate in acetonitrile, and the nitration of aliphatic isocyanates with nitronium tetrafluoroborate and nitric acid in acetonitrile, also yield alkyl A,A-dinitramines (154). 

Mercury azide Mercury fulminate Mercury fulminate Mercury nitride Methylene dinitramine Methylpicric acid MGP MNA... 

This substance was isolated in the form of its barium salt by Hirst et al. [12] when investigating the nitration of hexamethylenetetramine to cyclonite. They found that hexamethylenetetramine, when dissolved in nitric acid at 40°C, yields the product (II) which is hydrolysed by barium hydroxide to form the barium salt of methylene-dinitramine. From this the free nitramine may be obtained ... 

Salts of this diamine (which probably does not exist as free base) with nitric and perchloric acids, dinitramine and trinitromethane were prepared, they were isolable, but far too unstable to consider as propellant explosive components. Many were too sensitive to consider handling on large scale. 

Dimethomorph heterocyclic nitrogen, morpholine Dimethylarsinic acid see Cacodylic acid Dimethylvinphos see Tetrachlorvinphos Diniconazole heterocyclic nitrogen, triazole Dinitramine dinitroaniline Dinobuton dinitrophenol derivate Dinocap dinitrophenol derivate Dinoseb dinitrophenol Dinoseb acetate dinitrophenol derivate... 

Methyl picric acid Methylamine dinitramine Methylene glycol dinitrate... 

---