Nitro diphenylamine

Amines have been used for the following purposes related to expls,propellants, pyrotechnic compositions and fuels a)Stabilizers for NC propellants(eg, diphenylamine, nitro-diphenylamine and phenyl-/l-naphthylamine, the last examined in Ftance(Ref 3) b)Sensi-tizers for some expl and propellent compns (Ref 4 and addnl ref d) c)Smoke-producing compds (Addnl Ref d) d)Liquid fuels for rockets in conjunction with strong oxidizers, such as nitric acid(some of these are hyper-golic) (Refs 6 8 and addnl refs e,g,i,k8fl)... 

Nitro derivatives of aniUne (Vol, I, p. 556). With the exception ofhexanitro- diphenylamine nitro derivatives of aniline are not in use as explosives. Some of them are intermediates of reactions leading to higltly nitrated compounds by oxidation NH, — NOj according to the method of Nielsen. Coon et al. [10. 16]. See also (38). 

Notes (i) Feebly basic solid amines, e.g. diphenylamines, nitro-amines, polyhalogeno-amines and nitro-arylhydrazines dissolve appreciably only in concentrated acids. Some liquid amines form hydrochlorides sparingly soluble in dilute add. 

Various basic substances, such as aromatic amines (naphthyl-amines dissolve with difficulty in dil. HCl, diphenylamine only in cone. HCl, triphenylamine insoluble) nitro-anilines some amino-carboxylic acids. 

In the Colour Index both conventional sulphur dyes and their leuco counterparts are allocated the same Cl constitution number a different number is given to the related solubilised version. Thus, for example, Cl Sulphur Black 1 and Cl Leuco Sulphur Black 1 have the reference Cl 53185 whereas Cl Solubilised Sulphur Black 1 appears under Cl 53186. Because of the complexity of the final products, sulphur dyes are classified according to the chemical structure of the organic starting material that predominates in the manufacturing process. Typical intermediates include aromatic amines, with or without nitro and phenolic groups, and diphenylamine derivatives. 

Amino groups may act not only as proton acceptor, but also as proton donor. Acidic N—H protons interact with basic solvents. In these cases an ortho-nitro group in an aniline system competes with the solvent by an internal hydrogen bond66, as depicted in 12. The stretching frequencies (by IR spectra in carbon tetrachloride) of vnh of complexes between A-methylaniline or diphenylamine (and some nitro-anilines66) and solvents depend on the proton accepting ability of the solvent (which is a moderate base)67. The frequency shifts are linearly related to the solvent s donor number (DN)3. 

Lin and Zhang reported the synthesis of l-hydroxy-3-methylcarbazole (23) starting from the nitro derivative 625 (578). This synthesis uses a Buchwald-Hartwig amination for the synthesis of the diphenylamine 628. After protection of the hydroxy group in the nitrophenol 625 as a benzyl ether, the nitro group was reduced to the corresponding amino derivative 627. Amination of 627 with iodobenzene under Buchwald-Hartwig conditions afforded the diarylamine 628. Palladium(ll)-mediated cyclization of 628 led to the carbazole derivative 629, albeit in low... 

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>. 

An efficient chemical process for closing a diphenylamine is that using palladium(II) acetate (2 mol for substrates carrying electron-withdrawing groups) in acetic acid-methanesulfonic acid. Carbazole formation has been achieved with alkyl-, halo-, nitro-, and carboxyl-substituted diphenylamines. 1-Chlorocarbazole and carbazol-l-yl carboxylic acid as examples were efficiently prepared. - This is probably the best method now available for cyclizing diphenylamines. 

Pristera has developed an IR method for determining a, (3 y TNT as well as 2,4-DNT in mixtures such as found in exudates (Ref 1) Castelli et al (Ref 3) worked out a rapid IR method for determining NG, TA 2-Nitro-diphenylamine in Casting Solvent... 

Determination of Concentration of 2-Nitro-diphenylamine (2-NDPA) in EGDN and in Liquid Propellant... 

DNB — Dinitrobenzene DNCB — Dinitrochlorobenzene DNCr — Dinitiocresole DNPh — Dinitro-phenol DNT — 2,4, Dinitrotoluene EtN — Erythritol Tetranitrate HNDPhA — Hexanitio-diphenylamine MHeN — Mannitol Hexanitrace MNPh — Mononitrophenol MNT — Mononitrotoluene PA — Picric Acid PETN — Pentaerythritol Tetranitrate TNAn — Trinitroaniline TNAns — Tri-nitroanisole TNB — Trinitrobenzene TNCr — Trinitrocresole TNPh — Tri nitro phenol TNT —... 

It is generally agreed that powder in which diphenylamine is completely converted into N-nitrosodiphenylamine is suitable for storage. However, on the disappearance of N-nitrosodiphenylamine and its conversion into nitro compounds, the powder should be considered unsuitable for storage since it then lacks a stabilizer. 

Powder in which nitro derivatives of diphenylamine have been formed is coloured reddish-yellow or brown. 

According to Schroeder et al. [72] the chromatographic analysis on silica of the conversion products of diphenylamine in nitrocellulose powder indicates that diphenylamine may be converted into hexanitrodiphenylamine. From to f of diphenylamine is converted into nitro derivatives if the powder is kept at a temperature of 71°C for 258 days. 

CA 60, 14325(1964) (Identification of N-nitroso- and nitro- diphenylamine by two-dimensional tbin-layer chromatography on silica gel contg Zn dust) 34) J. Cure, MP 46-47, 59-76(1964-1965) (Detn of DPhA... 

Dinttro-N-nitroso-diphenylamine [called Bis-(2-nitrophenyl)-nitrosamin in Gef], 03N.C6H4.N.N0.C(iH.4.N02 not obtd in pure state dec in ale to 2,2l-Dinitro-DPhA obtd with the 2,4l-Dinitro-N-nitroso deriv by nitrating 2-nitro-N-nitroso-diphenylamine in glac acet ac with nitric acid below 10° (Ref 1) 2,4>-Dinitro N-nitroso-diphenylamine,... 

N- Phenyl-N picry l-4-nitro-l, 2-phenylene-diamineot 5,2, 4, 6 -Tetranitro-2-anilino-diphenylamine,... 

Mononitroaminodtphenylamines, HaN(OaN) -CeHs-NH-C6Hs, mw 229-23, N 18.33%. The isomers 4-nitro-2-amino- and 6-nitro-2-amino-diphenylamine, are described in Beil 13,29,(10) [21]... 

Tetranitro-3 methylnitramino-di phenyl-amine, also called in Beil N-Nitro-N-methyl-N -[2-nitro-phenyl)-2,4.6 trinitropbenylendia-min-( 1.3), 0JN-CiH4.NH-C6H(N0a)J-N(N02).CHs. Yel crysts (from AcOH), mp 200°(dec). Was prepd by treating 2,4,6-tr ini tro-3-me th y Ini tramino-diphenylamine with HNO,(d 1.49) at RT. Its expl props were not examined... 

Pentanitro- 3- meth/In itramni nodi phenyiamine, also called in Beil, Af-Nitro-Ai-metbyl-N -(2.4 dinitrophenyl)-2.4 6 trinitro-phenylendi3ntitiw( 1.3), (0,N), C6H3 NH C6H(NO,)3- N(NO, )-CHs. Crysts(from AcOH), mp 224—5 Can be prepd by nitrating 2,4,6,2-or 2,4,6,4 -tetranitro-3-methylmtramino-diphenylamine with cold HNO, (d 1.52) or by nitr ati ng 4, D di nitro - 3 -me th y Initr aini no -diphenyl amine with mixed HNOs-H, S04 at RT... 

Trinitro-3-methyl-diphenylamine or N-(2, 4 -DinitrophenylJ-4-nitro-m-toluidine, (0aN)aC6H3.NH.C8H3(CH3).N02 red prisms mp l7l-2c(from AcOH). Was obtained after a mixt of l-chloro-2,4-dinitrobenzene, 6-nitro-m-col ui dine and anhydrous AcONa had been heated for an hr at 190°... 

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