Diphenylamines 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). 

Arylbenzotriazoles (797) are prepared via 2-nitro- and 2-amino-diphenylamines (Scheme 161). The 2-nitrodiphenylamines (796) are prepared from the appropriate aniline by reaction with 2-fluoronitrobenzene in the presence of KF <808215,85JCS(Pl)2725>. Azo-coupling of 2-amino-1-cyano-azulene (798) with p-tolyldiazonium chloride gives (799) (Scheme 162). Catalytic reduction of (799) quantitatively yields the diamino derivative (800), which on diazotization affords 9-cyano-azuleno[l,2-J]triazole (801) in 77% yield <85TL335>. 

Key DBP, dibutylphthalate DNT, dinitrotoluene DPA, diphenylamine EC, ethylcentralite MC, methylcentralite MEDPA, methylethyldiphenylamine NC, nitrocellulose NDPA, a nitrodiphenylamine NG, nitroglycerine TNT, trinitrotoluene V, delected —, not detected. 

Substituted diphenylamines react in the same way, and the formation of small amounts of 4-substituted phenothiazines is observed, a feature also encountered in other thionation reactions. Phenothiazine could be obtained neither from nitrodiphenylamines nor, surprisingly, from A -phenyltoluidines. Also surprising is the... 

The composite proplnts are not the only ones subject to degradation processes which affect shelf-life, although they are relative newcomers to proplnt history. In NC-based proplnts, NC decomposes slowly to release NO2 which reacts catalytically to hasten the degradation in physical and ballistic properties. To slow the process, stabilizing agents such as diphenylamine or 2-nitrodiphenylamine are added to react w ith the NO2. The first reaction product is diphenyl-nitrosoamine, followed by ring nitration. When the stabilizer is used up, for all purposes the shelf-life of the proplnt is ended... 

Diphenylamine-p-arsinic acid inay be produced by the hydrolysis of p-phenylacetylaminophenylarsinic acid or by the direct arsenation of diphenylamine. The nitrodiphenylamine-p-arsinic acids may also be formed by the direct arsenation of nitrodiphenylamines. Direct arsenation of diphenylamine leads to the formation of two by-products, diphenylamine-p-p -diarsinic acid and iisdiphenylaminearsinic acid, the fonner yielding an arseno-compound on reduction. 

Nitrodiphenylamine-4 -arsinic acid, obtained from w-nitro-diphenylamine, crystallises in yellow needles, and yields a disodiwn salt containing 8 molecules of water. 

Continuing examples of ring closure of diphenylamine arsinic, acids and their derivatives, 2-nitrodiphenylamine-6 -dichloroarsine when boiled in acetic acid solution for three hours is transformed into 10-chloro-4i-nitro-5 lO-dihydropkenarsazine (XIII), and reduction of... 

Diphenylamine Ardnic Acids. 2-Nitrodiphenylamine-4-arsinic acid, ... 

Beilstein Handbook Reference) AI3-02915 Amine, diphenyl, 4-nitro- Benzenamine, 4-nitro-N-phenyl- BRN 2051910 CCRIS 5174 Diphenylamine, 4-nitro- EINECS 212-646-2 HSDB 5763 4-Ndpa 4-Nitro-N-phenylanlline 4-Nitrodlfenylamin 4-Nitrodiphenylamine p-Nitrodiphenylamine N-(4-Nitro-... 

The stabilizers in cunent use in the US are diphenylamine (see Vol5, D1416-R to D1426-R), 2-nitrodiphenylamine (see Vol 5, D1427-R to... 

Nitrodiphenylamines and, surprisingly, Al-phenyltoluidines, did not react in this way to yield phenothiazines (57MI393). Also surprising is the failure of thionation in the case of 2-chlorodiphenylamine, compared to the normal behavior of 4-chloro-diphenylamine (59BCJ294). 

There are other stabilisers of a similar nature, which are 4-nitrodiphenylamine, 2-nitrodiphenylamine, N-methyl-p-nitroaniline and diphenylamine. 

Fig. 18. Differential pulse polarograms from the determination of selected nitroso and nitro diphenylamine derivatives, a 2-nitrodiphenylamine b 4-nitrodiphenylamine c 4-nitrosodiphenylamine d N-nitrosodiphenylamine e 2,4-dinitrodiphenylamine f 2,4-dinitro-4-hydroxi-diphenylamine g N-nitroso-4-nitro-diphenylamine h 2,2 ,4-trinitrodiphenylamine i 2,4,4 ,6-tetranitrodiphenylamine...

Fig.20 shows a chromatogram from the determination of 4-nitroso-2-nitrodiphenyl-amine, 4-nitrodiphenylamine and 2-nitrodiphenylamine in the presence of a high diphenylamine concentration. The method can also be used for a selective determination of nitroso and nitro diphenylamine derivatives when high concentrations of nitrate esters are present. 

Diphenylamine, 4,4 -dioctyl-. See p,p -Dioctyldiphenylamine Diphenylamine, 4-isopropoxy-. See p-Isopropoxy diphenylamine Diphenylamine, a-methylstyrenated. See 4,4 -Dicumyl diphenylamine Diphenylamine, 2-nitro-. See 2-Nitrodiphenylamine Diphenylamine, 4-nitroso-. See p-Nitrosodiphenylamine Diphenylamine, N-nitroso-. See... 

Nitrodiphenyl o-Nitrodiphenyl. See2-Nitro-1,r-bi phenyl 2-Nitrodiphenylamine CAS 119-75-5 EINECS/ELINCS 204-348-6 Synonyms Benzenamne, 2-nitro-N-pheyl- Cl 10335 Diphenylamine, 2-nitro- o-Nitrodiphenylamine o-Nitro-N-phenylaniline 2-Nitro-n-phenylbenzeneamine o-(Phenylamino) nitrobenzene N-Phenyl-o-nitroaniline Phenyl 2-nitrophenylamine Sudan yellow 1339 Empin cal C12H10N2O2 Properties Reddish-brn. cryst. powd. sol. in DMSO, acetone, alcohol sol. 1-10 mg/ml in 95% ethanol sol. < 1 mg/ml in water m.w. 214.22 m.p. 74-76 C... 

BusP as ligand.Poor yields in the reductive cyclization method—when competitive cyclization is possible—and also the need for milder reaction conditions in the cyclization step urged Emoto et al. to report an alternative method based on sequential palladium-catalyzed aryl amination (Scheme 10). The substrate for the cyclization was 2-amino-2 -bromo-diphenylamine, obtained by selective bromination and reduction of the well-known 2-nitrodiphenyl-amines or by coupling of 2-bromoaniline with a l-bromo-2-nitrobenzene and subsequent reduction. Treatment of 2-bromo-2 -nitrodiphenylamine with catalytic amounts of palladium(II) and BINAP as ligand afforded the desired phenazines in good yields. ... 

Of the derivatives of p-phenylenediamine, the most effective are the N, N -di-alkyl derivatives, in which the alltyl possesses a branched hydrocarbon chain on the carbon closest to the nitrogen atom [235]. They are usually produced by reductive allq lation of p-nitroaniline, p-phenyl-enediamine, p-nitrodiphenylamine, p-nitrosodiphenylamine, or p-amino-diphenylamine with aldehydes and ketones [236-252] with hydrogen at a temperature of 100-250°C and a pressure from 5 to 200 atm in the presence of catalysts. Copper-chromium catalysts (mixtures of oxides of the metals chromium, copper, barium, etc.) [241, 242, 245-247, 249, 250], iodine in the presence of HCl, HBr, or HI [253, 254], Pt/C [245, 252], and Raney nickel [244] are most often used as the catalysts. 

In diphenylamine the benzene ring is still very strongly activated. Thus nitration in acetic anhydride (Table 22), gives a mixture of 2-and 4-nitrodiphenylamine as the main nitration product . 

NitrodiphenyIamine 4-Nitrodiphenylamine Benzenediazosulphonylbenzene Benzenediazothiobenzene trans-2-StyryIfuran Diphenylamine trans-2-StyrylpyrroIe 1,2-Dimethylnaphthalene Dodeca-2,8,10-triene-4,6-diyne... 

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