Nitramino

When 2-amino-4-methylthiazole is nitrated under mild conditions, 2-nitramino-4-methylthiazole (180) is isolated (Scheme 114) (16, 194. 374). 

Experimental requirements for the isolation of these nitramino derivatives are developed in Ref. 87. They rearrange easily to ring nitro-substituted isomers (see Section V.6). In the 2-aminothiazole series, nitration may proceed through direct electrophilic substitution competing with rearrangement of nitramino derivatives. Dickey et al. have shown that the rearrangement proceeds rapidly in 96% sulfuric acid at 2(fC, but in 85% sulfuric add it is very slow so. according the concentration of add various mechanisms can participate in the formation of the 5-nitro derivative. 

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. 

Amino-4-phenyl-5-benzoylthiazole is reported to react with nitric acid to give the 2-nitramino derivative (89). 

Pyridines, [(l-methyl-2-indoloyl)amino]-photocyclization, 4, 204 Pyridines, [(l-methyl-2-pyrroloyl)amino]-photocyclization, 4, 204 Pyridines, nitramino-synthesis, 2, 343 Pyridines, nitro-N-oxides... 

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

A low-temperature nitration of 2-amino-l,8-naphthyridine (59a) and 2-amino-l,5-naphthyridine (59b) yielded the 2-nitramino-l,8-naphthyridine (60a, 65%) (98MI3) and 2-nitramino-l,5-naphthyridine (60b, 70%) (63RTC988) respectively. Attempts to rearrange (60a) and (60b) to 2-amino-3- (or 6-) nitro-l,8-(or -1,5-) naphthyridines failed. 

NENA, Code name for N-(j3-Nitroxyethyl) nitramine. It is described as l-Nitramino-2-ethanol Nitrate in Vol 1, A201-L. See also... 

Nitramino- -triazine-2,4-diol. See under Am-melide and Derivatives in Vol 1, A273... 

PETX. Code name for Tetrakis(nitramino-methyl)-methane or Pentaerythrityltetrakis(nitra-mine) (qv in this Vol)... 

Sayles (Ref 82) also found that bis N-(trinitroethyl) nitramino ethane can be used as an oxidizer in EA/AA proplnts to produce smokeless propints. 

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>. 

Methyl 3,3-diazido-2-cyanoacrylate, 1824 Methylenebis(3 -nitramino-4-methylfurazan), 2805 1-Methyl-1,2,3-triazole, 1189 Nitrosyl azide, 4766 3-Nitro-l,2,4-triazolone, 0716 Pentazole, 4443... 

Hydroxy-4,6-bis(nitroamino)-l,3,5-triazine, 1122 Lead methylenebis(nitramide), 4882 Methylenebis(nitramine), 0483 Methylenebis(3-nitramino-4-methylfurazan), 2805... 

A number of important explosives contain nitramino functionality in conjunction with nitrate ester or C-nitro functionality. A-Nitrodiethanolamine dinitrate (DINA) (7) is a powerful explosive which can be melt-cast into charges. A,2,4,6-Tetranitro-A-methylaniline (tetryl) (8) exhibits high brisance (VOD 7920 m/s, d = 1.73 g/cm ) and has found application in both detonators and boosters, in addition to being a component of some composite high explosives. 

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. 

G. F. Wright, in The Chemistry of the Nitro and Nitroso Groups, Part 1, Organic Nitro Chemistry Series, Ed. H. Feuer, Wiley-Interscience, New York, Methods of Formation of the Nitramino Group, its Properties and Reactions , Chapter 10, 614-684 (1969). 

The incorporation of the nitramino group into the core of cubane has not yet been achieved. However, a number of cubane-based energetic nitramines and nitramides have been synthesized. 

Unsymmetrical arylnitramines with two nitro groups positioned ortho to the nitramino functionality can yield two isomeric diazophenol products. The diazophenols (76) and (77) were isolated in a 4 1 ratio from the nitration of 3-amino-2,6-dinitrotoluene (74) with mixed acid, the reaction proceeding via the intermediate nitramine (75). ... 

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