Other Nitrocompounds

Pb Lead, and particularly underpotentially deposited Pb, exhibits electrocatalytic properties in numerous electrode processes. The model reaction can be oxygen reduction with slow step of peroxide reduction ]374-376] or reduction of nitrobenzene and other nitrocompounds [377, 378]. In the case of... 

Compounds related to aniline, either directly or by oxidation, and to nitrobenzene by reduction, are numerous and important. When nitrobenzene is reduced in the presence of hydrochloric acid by tin or iron, the product is aniline (colorless liquid in die presence of water by zinc, the product is phenylhydroxylamine (white solid) in the presence of methyl alcohol by sodium alcoholate 01 by magnesium plus ammonium chloride solution, the product is azoxybenzene (pale yellow solid) by sodium stannitc, or by water plus sodium amalgam, the product is azobcnzcnc (red solid) in the presence of sodium hydroxide solution by zinc, the product is hydrazobenzene (pale yellow solid). The behavior of other nitrocompounds is similar to that of nitrobenzene. 

Isolated examples of studies of the decomposition of other nitrocompounds of specialized interest include the thermal decomposition of thin films of nitrocellulose examined by infrared spectroscopy and by a gravimetric technique s . The kinetics are best approximated by a first order curve with two or three branches. Typical values of the activation energy and Arrhenius pre-exponential factor are 45.0 kcal.mole S and 3.54 x 10 sec". ... 

Metallic picrates and oxalates should be absent, and other nitrocompounds should be present only in traces, The melting point or setting point carried out on a well-dried sample should be at least 20. The moisture content is generally limited to o i-o 3S per cent., and the ash to o-oS-o t per cent. this should not be of a gritty nature. Impurities insoluble in water should not exceed the uh content by more than 0 05 per cent. The picric acid should be almost completely soluble in benzene. Sulphates are restricted to 0 05 0 i per cent, as SO,). Chlorides and nitrates are sometimes tested for. Absence of lead in any form which might give rise to the formation of lead picrate is of special importance. Lead sulphate is, however, comparatively harmless. 

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

As stated above under TNMe, in Ger during WWII, the prepn of TeNMe by this process was scaled up for use as an intermediate and as a substitute for nitric acid in the V-2 rocket (Ref 26). A pilot plant was built at Newark, NJ for prodn using this procedure. It was destroyed by an expln in 1953 and not rebuilt (Refs 33 44). Other prepns of lesser importance are by the action of Ag nitrite on iodotrinitro-methane (Ref 3) by the action of 90% nitric acid and 25% oleum on malononitrile, yield 45% (Ref 40) by the action of mixed acid on a number of aromatic nitrocompounds, of which nitrobenzene, dinitrobenzene, and nitronaphtha-lene gave the best yields (Ref 13a) and by the action of nitryl chloride on salts of TNMe. 

Other authors also determined by FTIR that organic nitrocompounds are formed as primary products of the NO CH4-SCR reaction on ZSM-5-based catalysts [121-124], They preadsorbed nitromethane on the sample placed in the IR cell and followed by IR its transformation into other intermediates under 02 and NO versus time at different temperatures. For Cu- and Co-ZSM-5, it was shown that around 300°C adsorbed nitromethane is easily converted into isocyanates and then melamine via polymerization of the former species. Both species easily interact with molecular oxygen, while no reaction with NO is observed and the reactivity depends on the temperature and the nature of the transition metal cation. 

The behaviour of other aromatic nitrocompounds (e.g. m-nitroanisole, 3,5-dimethoxynitrobenzene and 4-nitrobiphenyl) follows the same pattern the same short-lived absorption is produced upon exciting an aromatic compound in the presence of a variety of nucleophilic agents, whereas the lifetime of the species formed depends on the nature of the reagent. 

The presence of N02 and other nitrogen oxides and/or acids in explosives (especially in smokeless powders and dynamites)is very undesirable because they act as catalyzers and promote further, more rapid decomposition. Most of the stabilizers used in smokeless powder, such as diphenylamine, centralites, urethanes etc are really inhibitors because they react with N02 and other nitrogen oxides to form nitroso- and nitrocompounds. 

If nitro compds are absent, the residue is treated with acetic acid to remove NG ("explosive oil ). The grease is then separated from sulfur by creating with acetone. If nitrocompounds are present, only half of the ether-CS2 extract is used for detn of grease and sulfur, while the other half is treated, after evaporation of solvents, with methyl sulfuric acid to remove NG. 

CA 60, 10472(1964) (A waterproof, semi-gelatinous, permissible Dynamite is obtd by incorporating in formulations contg AN, Amm perchlorate, Na nitrate, nitrocompound, etc up to 5% of N,N -methylene-bis-amide or a methylolamide of a C12-15 fatty acid, singly or together with other waterproofing compns)... 

Due to the acute shortage in Germany of TNT and other aromatic nitrocompounds, several substitute explosive mixtures were developed and used during WWII. 

Normally, nitrocompounds resist307 the action of PCC although, on rare occasions, PCC can promote the attack of nucleophiles on nitro groups, in a similar way to the other chromium-based reagents (see pages 10 and 35). 

There are two factors which limit the application of this treatment. For many of the compounds studied (e.g. carbonyl compounds, nitrocompounds etc.), the conjugate acid is so strong that the pK value lies beyond the accessible acidity range. The other limitation is inherent in the assumption that the electrode process (26 b) does not involve any further proton transfer. For numerous systems, in addition to a rapidly established protonation in an acidic grouping placed at some distance from the electroactive group, a further proton transfer to the electroactive group itself occurs at the electrode surface. It is therefore desirable... 

However, owing to the intrinsically high reactivity of aromatic nitrocompounds, a variety of other interactions not involving base addition are also possible. These more general interactions have been reviewed recently (Buncel et al., 1968a) so here it is in place merely to summarize the more important of them. 

Alkylixed Diamines of the Anmolic Series, Nitrocompounds of. Compounds of this type were patented in France (Ref 1) for use in detonators and as HE fillers for shells, mines, torpedoes and bombs. They may be used either alone or mixed with other explosives or with oxidizers, such as nitrates, chlorates or perchlorates... 

Op of these with 100 parts of mixed nitric-sulfuric acid at about 7°(45°F). The resulting products had nitrogen contents about 18.3%, as compared with 18.67% theoretical. They are explosives with properties resembling those of inactive inositol hexanitrate. (The dextro- product is a solid, while the levo- product is a liquid). They are better gelatinizers than NG or NC and have been recommended as ingredients of double-base smokeless powder. They can also be used in dynamites or other commercial explosive mixtures in combination with NG or aromatic nitrocompounds. Crater has also claimed the use of 1H in non-headache dynamites (Ref 5)... 

Olio di sgocciolamento (Drip 03 in the USA and Tropfol in Germany. A crude, commercial, black, oily substance resulting from the two-stage nitration of toluene in the manuf of TNT. Its main constituents are isomers of DNT with small quantities of isomers of TNT and some other aromatic nitrocompounds. It has been used as an antifreeze addn to Dynamites, such as in Dinamiti incongelabili in some AN expls and as a gelatinizer of NC used in some propints. Due to the fact that its composition is variable, and it contains some sulfuric acid derivatives, its use in military expls is not recommended. ... 

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