Polynitro-compounds

It is known that the application of N NMR chemical shifts to the study of chemical micro-mechanism of initiation of nitramines by heat [77], impact 

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The method depends for its success on the quantitative liberation of the nitrogen content of substances as molecular nitrogen this can be rather difficult in certain cases [e.g., polynitro compounds) but satisfactory determinations can be carried out by slight modification of the experimental conditions. 

It is convenient to include under Aromatic Amines the preparation of m-nitroaniline as an example of the selective reduction of one group in a polynitro compound. When wt-dinitrobenzene is allowed to react with sodium polysulphide (or ammonium sulphide) solution, only one of the nitro groups is reduced and m-nitroanUine results. Some sulphur separates, but the main reaction is represented by ... 

The Lassaigne procedure for detecting nitrogen in organic compounds frequently gives unsatisfactory results with explosive compounds (diazonium salts, polynitro compounds and the like) and with certain volatile nitrogenous substances, such as bases, their acyl derivatives or their salts. These difficulties... 

Energedcdlly rich polynitro compounds hjve been prepared from polycyclic kelones by the nitro compounds, as shown In Table 2.6. 

Complexes in Which the Acceptor Is an Organic Molecule. Picric acid, 1,3,5-trinitrobenzene, and similar polynitro compounds are the most important of these. Picric acid forms addition compounds with many aromatic hydro... 

Explosions occurred dining distillation of this polynitro compound [1]. Though not an endothermic compound, it is of positive oxygen balance and the heat of decomposition (2.80 kJ/g) would give an adiabatic decomposition temperature exceeding 2200°C and a 40-fold increase in pressure [2],... 

Use of the mixed cone, acids to dissolve an organic residue caused a violent explosion. Nitric acid is a very powerful and rapid oxidant and may form unstable fulminic acid or polynitro compounds under these conditions. 

Distillation behind safety glass in a nitrogen atmosphere appears advisable in view of the nature of polynitro compounds although the submitters have not had an explosion in the preparation of 3,4-dinitro-3-hexene. 

Here, the term polynitro compounds refers to AN in which the a-C atom contains at least two nitro groups. Scheme 3.8 presents data on their successful O -alkylation. 

Anions of polynitro compounds (21) or neutral nitrodiazo compounds (22) can be considered as possible precursors of nitrocarbenes (A B) by analogy with other functionalized carbenes. Nitrocarbenes can react with a double bond... 

However, in our opinion, the rigorous assignment of products to covalent nitronic esters rather than to their structural isomers, which are true nitro compounds or ionic salts, is a more important and complex problem This problem involves difficulties, because ambident anions of nitro compounds (which are evident precursors of nitronates) have comparable O- and C-nucleophilicities and, therefore, the resulting substrates can belong to any of the above mentioned series. Incorrect structure assignments of derivatives of polynitro compounds prepared from tetranitromethane were made in former studies. In addition, the structures of nitronates assigned to some products in early studies, should not have been accepted without the use of modem spectral methods. 

A review appeared on the determination of nitroalkanes, polynitroalkanes, nitroalkenes, aromatic nitro and polynitro compounds, heterocyclic nitro derivatives and inactive compounds after nitration, by polarography, voltammetry and HPLC with electrochemical detection441. 

On treatment of certain other tertiary aromatic amines with nitrous acid, it has been found that either C-nitroso compounds, nuclear nitro compounds, or jV-nitrosoamines are formed with loss of an alkyl group. In the case of the nitrodimethylanilines, the latter two types of reaction may occur. The formation of nitro-jV-nitrosomethylanilines predominate at room temperature, whereas the formation of polynitro compounds predominates at more elevated temperatures. The formation of nitrosoamines from iVW-dimethylanilines appears to be particularly favored when both ortho positions are occupied by nitro groups, although /V-nitroso compounds were also obtainable from other nitrodimethylanilines. The product of the reaction, of course, is an /V-nitroso secondary amine. 

ZIMMERMANN REACTION. The reaction that occurs between methylene ketones and aromatic polynitro compounds in the presence of alkali. When applied to 17-oxosleroids, the colored compounds formed can be used for the quantitative determination of 17-oxosteroids. 

Aromatic nitro compounds are generally stable but are frequently reactive, especially if they contain groups other than nitro groups in the meta position with respect to one another. As a class they constitute the most important of the military high explosives. They are also used as components of smokeless powder, in compound detonators, and in primer compositions. Liquid nitro compounds, and the mixtures which are produced as by-products from the manufacture of pure nitro compounds for military purposes, are used in non-freezing dynamite and other commercial explosives. The polynitro compounds are solvents for nitrocellulose. 

W.L. Glen, Polynitro Compounds Allied to TNT , Glasgow Rept No 116 (1942)... 

Polynitro compounds, e.g. picric acid (and heavy metal picrates), trinitrobenzene (TNB), trinitrotoluene (TNT) all these substances are safe when damp with water. 

Ammonium or alkali metal sulphides or polysulphides exhibit a useful selective reducing action in that they smoothly reduce one nitro group in a polynitro compound to yield the corresponding nitroamine (e.g. m-nitroariiline, Expt 6.51). 

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