1 Classification reactions Nitro compounds

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

The nature of the azo bond is such that only a very limited number of possible functional groups can be considered to have the necessary features to serve as starting materials for reductive methods of preparation. In a sense, the Bogo-slovskii reaction [17, 18] may be considered a reduction of a diazonium salt by copper(I) ions. However, because the reaction resembles the other condensations of diazonium salts, its classification among the condensation reactions seems appropriate. The direct reduction of azoxy compounds as such is of minor preparative importance except as a method of identification of an azoxy compound. However, in the various bimolecular reduction procedures of aromatic nitro compounds, it has been postulated that an azoxy intermediate forms in the course of the reaction. This intermediate azoxy compound is ultimately reduced to an azo compound. 

DOT CLASSIFICATION Forbidden SAFETY PROFILE A powerful oxidant which explodes above 140°C. Explosive reaction with boron. Hypergolic reaction with dimethyl hydrazine or other strong organic bases. Forms powerfully explosive mixtures with nitrogen containing organic compounds (e.g., 2-nitroaniline). Upon decomposition it emits toxic fumes of NOx. See also NITRO COMPOUNDS. 

DOT CLASSIFICATION 6.1 Label Poison SAFETY PROFILE Poison by ingestion, intravenous, and intraperitoneal routes. Moderately toxic by intramuscular route. Mutation data reported. Acute symptoms of exposure are headache, nausea, vomiting, weakness and stupor, cyanosis and methemoglobinemia. Chronic exposure can cause liver damage. Experimental reproductive effects. Combustible when exposed to heat or flame. See NITRATES for explosion and disaster hazards. To fight fire, use water spray or mist, foam, dry chemical, CO2. Vigorous reaction with sulfuric acid above 200°C. Reaction with sodium hydroxide at 130°C under pressure may produce the explosive sodium-4-nitrophenoxide. When heated to decomposition it emits toxic fumes of NOx. See also m-NITROANILINE, o-NITROANILINE, NITRO COMPOUNDS OF AROMATIC HYDROCARBONS, and ANILINE DYES. 

DOT CLASSIFICATION 6.1 Label Poison SAFETY PROFILE Confirmed carcinogen with experimental carcinogenic data. A poison by ingestion. Experimental reproductive effects. Mutation data reported. Flammable liquid when exposed to heat, sparks, or flame. May explode on heating. Potentially violent reaction with sodium methoxide. When heated to decomposition it emits very toxic fiimes of NOx and CL. See also other chloronitrobenzene entries and NITRO COMPOUNDS OF vkROMATIC HYDROCARBONS. 

Various secondary sources of safety data are now listing this as an explosive. I can find no primaiy source for this classification, which seems very improbable. Simple minded use of many computational hazard prediction procedures would show thermodynamically that this compound, like most lower amines, could hypothetically convert to alkane, ammonia and nitrogen with sufficient energy (about 3 kJ/g) to count as an explosion hazard. This reaction is not known to happen. (Simple minded thermodynamicists would rate this book, or computer, and its reader as a severe hazard in an air environment.) Like other bases, iminobispropylamine certainly sensitises many nitro-explosives to detonation. It is used experimentally to study the effect, which may have found technical exploitation and, garbled, could have led to description of the amine as itself an explosive. 

The same classification is found in presence of photosensitizers. Poly-1 insolubilization above 290 nm is accelerated by nitro-2 fluorene, Michler s ketone and especially by xanthone. On the other hand when irradiation is carried out on films with additional 253.7 nm ray, nitrofluorene only gave an effect. The results obtained with the same sensitizers were similar in the case of Poly-3. The observations are quite different with Poly-2, the photochemical reaction of which is very sligthly improved by the presence of xanthone and greatly reduced by the two other compounds perhaps because of quenching effect. 

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