Nitroamino compounds

Arylamino-3-nitroamino-l,2,4-thiadiazoles are crystalline solids which explode at their melting points. They are monobasic acids, remarkably stable to alkalis and to the action of boiling sodium plumbite. Mild reduction by sulfur dioxide reconverts 5-anilino-3-nitroamino-l,2,4-thiadiazole into its parent amidinothiourea from which it arises by oxidation. Attempts to reduce 3-nitroamino compounds to the corresponding 3-hydrazines were not successful.141... 

These acids occupy an intermediate position between the monoamino-arylarsinic acids on the one hand and the di- and tri-aminoarylarsinic acids on the other, since the latter are the reduction products of the nitroamino compounds. Where the amino-group is not substituted, the acids have been prepared by four methods (1) By direct arsenation of nitroarylaniincs. (2) The aminoarylarsinic add is converted to its... 

A lot of work has been done for the synthesis of azido nitroamino compounds, their properties and applications [32]. Reed and Dolah first started the study of this kind of compounds. Rosher, Morton, and Eimslic synthesized series of azido nitroamino compounds, and applied them as the composition of propellants. They notably rise the combustion/buming rate and specific impulse without influencing the pressure index. Their energy approximately equals that of HMX. Their detonation sensitivity is relatively low. They are widely applied in smoke-free propellants with low sensitivity to replace HMX. 

Azido nitroamino compounds and azido compounds have been synthesized large quantitatively. They are used in energetic plasticizers and energetic oxidants [34] according their properties. 

The synthesis of methyl azido nitroamino compounds (1) is based on the preparation of primary nitramine, then introducing a chloride atom using chlo-romethylation, followed by azidization, the schematics are below. 

Some of the internal salts derived from /V-hcterocycles are dangerously explosive solids, sensitive to modest heating and to impact, also liable to violent spontaneous decomposition, even in solution. A related A-nitroimide (hetero-N—NH—NO2) was also explosive. It is possible the benzotriazolium imidates were also, in fact, the tautomeric nitroaminobenzotriazoles. None of their potassium salts exploded [1]. Related chemistry has been examined with a view to new explosives, in particular l,4-bis(nitroamino)-l,4-diazabicyclo[2.2.2]octane, said to be surprisingly stable.The individually indexed unstable compounds are ... 

The reaction of the diamino compound (107) under several different nitration conditions led to the formation of 5-nitroamino-8-aminopyrazino[2,3-d]pyridazine exclusively (68JHC53). 5,8-Dimorpholino substituted pyrazino[2,3-d]pyridazines are known to react with Grignard reagents to give 3-substituted 3,4-dihydro derivatives (75CPB1488). The dimorpholino heterocycles are also known to react photochemically with alcohols and cyclic ethers in the presence of photosensitizers to give 3-substituted 3,4-dihydro derivatives (Scheme 3) (75CPB1500). 

Azines. Two or more electron-releasing substituents make 5-nitration in pyrimidines relatively easy 2,4-diamino-6-chloropyrimidine yields the 5-nitro compound via a nitroamino intermediate. Similarly, 4-amino-3,6-dimethoxypyridazine undergoes easy nitration to the corresponding 5-nitro compound. The less activated 3-meth-oxy-5-methylpyridazine requires more vigorous conditions, yielding 4-, 6-, and 4,6-di-nitro derivatives. 

Amino-4-phenyl-5-benzoylthiazole is nitrated by nitric acid with the formation of the 2-nitroamino derivative [235], During the nitration of 5-acetamidothia-zole a compound melting at 197-198°C was obtained. It was assigned the structure of 2,4-dinitro-5-acetamidothiazole [221], In fact, it was the mononitration product 4-nitro-5-acetamidothiazole [201] (Scheme 29). 

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