Nitramino compounds

These compounds can be rearranged (cfSection 3.2.3.5.l.iv), reduced to hydrazino derivatives or hydrolyzed to pyridones. 

These form derivatives with carbonyl compounds and can be acylated, sulfonylated, eliminated by mild oxidation [e.g. (762 Y = NHNH2) + CuS04 + AcOH — (762 Y = H)]. They are converted by nitrous acid into azides as in benzenoid chemistry. 

Hydrazino groups attached to cationic rings (as 763) undergo oxidative coupling reactions with amines, phenols (to give e.g. 764) and reactive methylene compounds, e.g. (763) + CH2(CN)2 — (765). 

Thermolysis of hydrazine (767) in toluene-methanol catalyzed by TFA led to a translocative rearrangement to give the 2-aminopyridine derivative (768) (88JOC5309). 

---

Amino-3-methylisothiazolehalogenates readily in the 4-position, but nitration leads to the formation of a nitramino compound. Acylaminoisothiazoles nitrate normally. ... 

Nitric acidsulfuric acid gives nitramino compounds 747 which are easily rearranged to C-nitro derivatives 746 (cf. Section 3.2.1.4.4). 

Thermochemical data of explosives will be given in the description of particular compounds. General problems of thermochemistry of nitro compounds was given in the monograph by Lebedev, Miroshnichenko and Knobel [117]. In recent years a considerable number of contributions have been given by Pepekin and co-workers [118] on such problems as the enthalpy of formation of nitro and nitramino compounds and nitrate esters and enthalpy of detonation. Also Pepekin and co-workers [119] contributed considerably to the solution of problems of the energy of dissociation of the bond C-N3. 

Oximes and Related Derivatives.—Beckmann fragmentation of a-hydroxy-ketoximes occurred with dichlorocarbene. For example, a chloroform-ethyl acetate solution of the 5a-hydroxy-6-oximinocholestane (134) gave the keto-nitrile (135) with acqueous NaOH in the presence of benzyltriethylammonium chloride. Improved reduction of nitrimines to nitramines with NaBH4 and acetic acid has been reported and is exemplified by the conversion of the nitrimino-cholestane (136) into the 6 8-nitramino-compound (137). ... 

Taurins reported that nitration of 2-nitramino-5-nitrothiazole yields the fully nitrated 2-imino-4-thiazoline (184) (Scheme 117) (87). This interesting compound should be studied by spectroscopic methods. 

The thermal decomposition of nitramino-1,2,4-triazoles 7 and 8 has been modeled and detailed decomposition pathways proposed for a number of tautomeric forms of these compounds <2006CHE1267, 2006KGS1467>. The chemistry of 4-nitramino-l,2,4-triazole 8 has been studied in depth but no decomposition studies on its derivatives have been documented <2002RJ01343, 2002ZOR1397>. 

Primary nitramines contain an acidic proton which enables them to behave as nucleophiles and undergo addition and condensation reactions. These reactions are extremely useful in two respects. Firstly, these reactions convert primary nitramino functionality into secondary nitramino functionality, which is no longer acidic and much more chemically stable. Secondly, these addition and condensation reactions can be used to prepare functionalized derivatives of polynitramines which can be used to synthesize energetic polymers and other explosive compounds. 

The 7 -substituted-2-nitramino-2-imidazoline derivatives were prepd and investigated by McKay et al (Ref 3). Nitration of these products yielded 1 -substituted-2-nitrimino-3-nitroimidazoli-dines, which proved to be stable at room temperature. As examples of these compounds may be cited ... 

Azido, nitramino, nitro and nitroso derivatives are listed under what may be considered as the parent compound. Thus all the mono-, di-, and trinitrotoluenes will be discussed under toluene. For example, nitraminoterrazoles are discussed under aminotetrazole. With this system the various azido, nitro, etc derivatives included above are kept together and are not scattered throughout the Encyclopedia. Since these derivatives of a given parent compound are usually of some related interest from the point of view of properties, preparation and references, we believe tbat this arrangement is the most convenient... 

One representative of this group of compounds merits attention. This is I-(.V-Ethyl)-nitramino-2-ethanol Nitrate, code name Et-NENA [73]... 

Aminopyridinecarboxylic acids are converted into nitramino derivatives by treating a cold solution of the amino compounds in sulfuric acid with nitric acid. Thus 5-aminonicotinic acid and 5-aminopicolinic acid give 5-nitraminonicotinic and 5-nitraminopicolinic acid, respectively. ... 

---