N- nitramine

M amines competed effectively with 55.5 M H O and 0.1 M OH for the nitrosating agent and suggested that possibly more reactive isomers of N O and N 0. are generated by the gaseous NO and NO components Here, -nltrosamines result from reaction of the unsymmetrical tautomer (ON-NO ), whereas the symmetrical tautomer (O N-NO ) produces an N-nitramine possibly via a four-center transition state. The results for N O may be xplalned similarly in terms of the corresponding ON-nO.ON-ONO tautomers. This conclusion has a prece-... 

Nitrations of aromatic amines often involve the intermediate formation of N-nitramines, although these are rarely seen under the strongly acidic conditions of mixed acid nitration (Section 4.5). N,2,4,6-Tetranitro-N-methylaniline (tetryl) is an important secondary high explosive usually synthesized from the nitration of N,N-dimethylaniline or 2,4-dinitro-N-methylaniline. ° The synthesis of tetryl is discussed in Section 5.14. 

Kubota, N., Nitramine Propellants for Rockets and Guns , Japanese Patent No. 60-177452, Aug. 12th, 1985. 

At an earlier stage Orton [31] found that some aniline derivatives which are difficult to nitrate in the ring, are liable to form N-nitramines when treated with nitric acid and acetic anhydride. For example, he prepared the corresponding nitr-amine from 2,4,6-tribromaniline ... 

TrinitrophenylaminoybiaanoU N-nitramine Nitrate McGill(Ref 4) 2,4.6-Trinitrophenylisobutylolnitramine Nitrate and Blatt(Ref 6) 2l4,6 Trinitropbenyl (l methyloiypTopylnitramme Nitrate. 

Petrosyan VA, Frolovskii VA. 1989. Electrochemical generation of n-nitramine ions upon the reduction of n-nitramines. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science 38 2439. 

Preparation of Acyl N-Nitramine Compounds. Ethyl n-butylcarba-mate (4.0 grams, 0.03 mole) was dissolved in 50 ml. of acetonitrile, cooled to —30°C., and treated with 4.0 grams (0.03 mole) of nitronium tetrafluoroborate. The solution was allowed to warm, with stirring, to 0°C. and quenched into 200 ml. of ice water. A yellow oil separated, which was dissolved in methylene chloride and dried over anhydrous magnesium sulfate. After removing the solvent 5.0 grams (91% yield) of ethyl... 

N-nitro-n-butylcarbamate (b.p. 75°-77°C. at 0.8 mm., n2D41.4476, literature value (17) n2 1.4488) was obtained by fractional distillation under reduced pressure. Other acyl N-nitramine derivatives, with their yields and melting or boiling points are shown in Table II. 

It was shown [108] that the nitration of aromatic amines proceeds differently depending on their basicity. Amines of moderate to low basicity, such as bis(2-cyanoethyl)amine (pATa = 5.25J, bis(2,2,2-trinitroethyI)-amine (p/ a = 0.05) are nitrated by NO2 BF4 to the corresponding N-nitramines in acetonitrile or ethyl acetate in yields of 87-98%. The nitration of highly basic dialkylamines (pK = 8.70-11.15) is accompanied by the partial reduction of NO2 BF4 to nitrosonium tetrafluoroborate and the formation of nitrosamines, The content of nitrosamine in the reaction mixture increases with increase of the reaction temperature. Nitronium hexafluorosilicate proved to be a milder nitrating agent its application makes it possible to reduce greatly the formation of nitroso- derivatives. 

Azo N,N -dioxides Hyponitrous acid esters N-Nitramines N-Nitrosohy droxy lamines... 

Pyridine N-oxide, Pyridazine 1-oxide N-Nitramines Cu, Ag, Ag-Cu, Cu,Mg Copper oxide, CU2O, CuO... 

Nitro compounds, ar. Nitrobenzene, m-Dinitrobenzene o-Nitrophenol N-Nitramines Oxonium fluoroborate Trialky loxonium salt Trialky loxonium fluoroborate Pyrylium fluoroborate Carboxylic acid esters HCOOC Hs, p-Nitro-phenyl formate Isopropenyl acetate Salicylic acid esters Ethyl cyanoacetate Chloroformic acid esters Ethyl chloroformate, ClCOOC Hg-i Methyl trichloroacetate Diethyl oxalate Ethyl malonate... 

Nitro compounds, ar. Nitroarenes Nitrobenzene, m-Dinitrobenzene o-Nitrophenol N-Nitramines Piperidinium chloride,... 

Iodine mercuric oxide j irradiation Remote functionalization with N-nitramines... 

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