Polynitro

Yield of crude product, 14 g., the high value being due to traces of polynitro-derivatives. 

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 ... 

This method cannot be applied to polynitro amines, since these are so weakly basic that they can be diazotised only under special conditions in strongly acidic solutions. In such cases use may, however, be made of the mobility oonfared upon halogen atoms by the presence of nitro groups in the orlko and para positions. Thus the valuable reagent 2 4-dinitrophenylhydrazine is readily prepared by the condensation of 2 4-dinitrochlorobenzene with hydrazine ... 

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... 

As well as the cr-complexes discussed above, aromatic molecules combine with such compounds as quinones, polynitro-aromatics and tetra-cyanoethylene to give more loosely bound structures called charge-transfer complexes. Closely related to these, but usually known as Tt-complexes, are the associations formed by aromatic compounds and halogens, hydrogen halides, silver ions and other electrophiles. 

Conjugated nitro olefins can function as the acceptor to which nitroparaffins may add to form polynitro derivatives (50—51). Nitro olefins also... 

The impurities present in aromatic nitro compounds depend on the aromatic portion of the molecule. Thus, benzene, phenols or anilines are probable impurities in nitrobenzene, nitrophenols and nitroanilines, respectively. Purification should be carried out accordingly. Isomeric compounds are likely to remain as impurities after the preliminary purifications to remove basic and acidic contaminants. For example, o-nitrophenol may be found in samples ofp-nitrophenol. Usually, the ri-nitro compounds are more steam volatile than the p-nitro isomers, and can be separated in this way. Polynitro impurities in mononitro compounds can be readily removed because of their relatively lower solubilities in solvents. With acidic or basic nitro compounds which cannot be separated in the above manner, advantage may be taken of their differences in pK values (see Chapter 1). The compounds can thus be purified by preliminary extractions with several sets of aqueous buffers... 

The lack of a uniform order of relative reactivity of the halogens in reactions of certain nucleophiles with nitro- and polynitro-phenyl halides led Parker and Read to propose a one-stage mechanism for some aromatic nucleophilic substitutions. An alternative explanation within the framework of the two-stage S Ar2 mechanism had been proposed earlier. A range of mechanisms has been considered in the past by Chapman, who properly points out that only in a limited number of examples is the evidence for the two-stage mechanism compelling even though the balance of evidence favors it. 

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

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

In Ref 8 are discussed the effects of acid concns on the formn of mono- and polynitro compds by the mixed acid nitration of naphthalene. Other studies on the coml prodn of 1-MNN are in Refs 16, 20,29 30... 

I). These are saturated hydrocarbons having terminal polynitro groups, and may be prepd by treating saturated hydrocarbons, having at feast one terminal nitro group substituted in one terminal Me group, with tetranitromethane... 

Shelegova irradiated nitrobenzene vapor with various light sources. In the 2160—2900A region the products were phenol and N02 in the 1850—2160A region, phenol and polynitro-benzenes (Ref 3) ... 

Polynitroamines. A series of compds developed by Frankel and Klager (Ref) as expls and O donors in proplnt fuels. These compds are prepd by condensing j3-geminal polynitro alcohols with ammonia or polynitro amines. The compds produced are of the type,... 

Polynitro-aromaten werden in erster Stufe mit schwachen Hydrid-Donatoren zu den Meisenhcimer-Komplexen7 hydriert (s. S. 90), die dann durch Natriumboranat zu Polyni-tro-cycloalkanen8 weiterreduziert werden konnen (s. S. 88ff.) (s.a. Bd. X/l, S. 128). Mit Natriumboranat werden direkt die entsprechenden aci- Ni tro-cycloalkene oder -cycloalkane erhalten8 (Die Nitro-Gruppe wird kaum angegriffen). 

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... 

Obviously, polynitro- or polyaminobenzenes other than the meta-conhg-uration may be desirable for one reason or another. This is where the skill and training of organic chemists are required because they have learned to be able to know and use the rules of chemistry to manipulate the shape and composition of carbon-containing molecules. 

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],... 

See 1,1 -DINITRODIFLUORAMINES, See other iv-halogen compounds, polynitro-ALKYL COMPOUNDS... 

A sample of the compound exploded violently after short heating to 100°C. Although this was attributed to presence of polynitro derivatives [1], the thermal decomposition of this type of nitro compound is known [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. 

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