Nitrodiphenylamines

Although these are no longer used as explosives, they are formed from diphenylamine that is used as a stabilizer for nitrocellulose explosives. The metabolism of nitrodiphenylamines has been examined under anaerobic conditions, and phenazine and 4-aminoacridine that are cyclization products of the initially formed 2-aminodiphenylamine have been identified (Drzyzga et al. 1996). 

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Abundant ions that are characteristic of the mass spectra of nitrodiphenylamines are m/z 214, 184, and 164. 

Satchell476 also measured the first-order rate coefficients for dedeuteration of [4-3H]-anisole by acetic acid or acetic acid-hydrochloric acid media containing zinc and stannic chlorides (Table 128). The rates here paralleled the indicator ratio of 4-nitrodiphenylamine and 4-chloro-2-nitroaniline, so that the implication is that a linear relationship exists between log k and the unknown H0 values. The results also show the rate-enhancing effect of these Friedel-Crafts catalysts, presumably through additional polarisation of the catalysing acid, for in the absence of them, exchange between acetic acid and anisole would be very slow. Other studies relating to the effect of these catalysts are reported below (p. 238). 

The kinetics of desulphonation of sulphonic acid derivatives of m-cresol, mesitylene, phenol, p-cresol, and p-nitrodiphenylamine by hydrochloric or sulphuric acids in 90 % acetic acid were investigated by Baddeley et a/.701, who reported (without giving any details) that rates were independent of the concentration of sulphuric acid and nature of the catalysing anion, and only proportional to the hydrogen ion concentration. The former observation can only be accounted for if the increased concentration of sulphonic acid anion is compensated by removal of protons from the medium to form the undissociated acid this result implies, therefore, that reaction takes place on the anion and the mechanism was envisaged as rapid protonation of the anion (at ring carbon) followed by a rate-determining reaction with a base. 

Drzyzga O, A Schmidt, K-H Blotevogel (1996) Cometabolic transformation and cleavage of nitrodiphenylamines by three newly isolated sulfate-reducing bacterial strains. Appl Environ Microbiol 62 1710-1716. 

Fig. 1.11 Dissociation ranges of colour indicators for determination of the acidity function H0 in H2S04-H20 mixtures (1) p-nitroaniline, (2) o-nitroaniline, (3) p-chloro-o-nitroaniline, (4) p-nitrodiphenylamine, (5) 2,4-dichloro-6-nitroaniline, (6) p-nitroazobenzene, (7) 2,6-dinitro-4-methylaniline, (8) benzalacetophenone, (9) 6-bromo-2,4-dinitroaniline, (10) anthraquinone, (11) 2,4,6-trinitroaniline. (According to L. P. Hammett and A. J. Deyrup)...

Amination of aromatic nitro compounds is a very important process in both industry and laboratory. A simple synthesis of 4-aminodiphenyl amine (4-ADPA) has been achieved by utilizing a nucleophilic aromatic substitution. 4-ADPA is a key intermediate in the rubber chemical family of antioxidants. By means of a nucleophibc attack of the anilide anion on a nitrobenzene, a o-complex is formed first, which is then converted into 4-nitrosodiphenylamine and 4-nitrodiphenylamine by intra- and intermolecular oxidation. Catalytic hydrogenation finally affords 4-ADPA. Azobenzene, which is formed as a by-product, can be hydrogenated to aniline and thus recycled into the process. Switching this new atom-economy route allows for a dramatic reduction of chemical waste (Scheme 9.9).73 The United States Environmental Protection Agency gave the Green Chemistry Award for this process in 1998.74... 

Fig. 4 Excess acidity plots according to equation (17) for some secondary amines in aqueous sulfuric acid at 25°C. Open circles, A-ethyl-4-chloro-2-nitroaniline closed circles, 4-nitrodiphenylamine open triangles, 2-nitrodiphenylamine closed triangles, N-ethyl-2,4-dinitroaniline open squares, 5-chloro-2-nitrodiphenylamine. Data from ref. 60 numbers to the right of the dashed lines are log/values.

Some time ago, Holliman and co-workers illustrated a method for synthesizing polysubstituted phenazines by reductive cyclization of o-nitrodiphenylamine. However, the yield was poor when competitive cyclizations occurred <70CC1423>. Recently, Kamikawa and co-workers reported a more efficient method to synthesize phenazines using sequential aniline arylation, which was first introduced by Buchwald <97JOC1264>. Regioselective bromination of o-nitrodiphenylamine 226 with bromine in the presence of sodium bicarbonate yielded 227 which was subjected to the Buchwald conditions to provide the desired phenazine 228 and the eliminated product 229 <00TL355>. The former compound is a proposed intermediate for the synthesis of the radical scavenger benthocyanin A. 

Hexanitrodiphenylamin wird durch Nitrierung des durch Kondensation aus Dinitrochlorbenzol und Anilin entstandenen unsymmetrischen Di-nitrodiphenylamins mit konzentrierter Salpetersaure hergestellt. Die Stabilitat und Brisanz ist etwas hoher als die von Pikrinsaure, die Empfindlichkeit ist etwas grolier. 

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