From Diphenylamines

Condensation of l-bromo-2-methoxy-4-methyl benzene (64) with 5,6-dimethoxyaniline acetate (65) in pyridine in the presence of Cu and K2CO3 and subsequent hydrolysis with 20% KOH furnished the di-phenylamine derivative (66) which on treatment with palladium acetate in DMF afforded murrayastine (13). Condensation of l-bromo-3-methoxy-4-methylbenzene (67) with the dimethyl acetal of 6-formyl-5-methoxyaniline acetate (68) furnished the diphenylamine derivative (69) which on hydrolysis and on subsequent cyclisation furnished murray-aline (14). 

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The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

This work supports the suggestion that sulfur dyes are complex thiamines derived generally from diphenylamine units (22). Depending on the conditions of the thionation, two or more thiamine units could be linked by sulfur to produce a typical sulfur blue (17, R = OH or NH2). 

BERNTHSEN Acndine synthesis Acndine synthesis from diphenylamine and cartxixylic acids... 

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). 

The dye which is formed here is identical with that which is produced from diphenylamine in the well-known test for nitric acid (and other oxidising agents), namely, diphenyldipkenoquinone - dhmonium sulphate) (Kehrmann). 

Dihydro-2-quinazolinones are available from diphenylamine-2-acetic acids via isocyanate intermediates, and thus the nonsteroidal anti-inflammatory agent diclofenac 745 gave the dihydro derivative 746 in 63% yield on treatment with diphenylphosphoryl azide <2004BML357>. 

Oxidation of the anion from diphenylamine apparently involves attack of oxygen at carbon rather than nitrogen. ... 

Apart from diphenylamine a number of other organic bases were tested for use as stabilizers. Some of them, e.g. aniline, were used only temporarily, chiefly during World War I when diphenylamine was in short supply. The basic properties of aniline are too marked and this is detrimental to stability. On the other hand, relatively good results have been obtained with carbazole which resembles diphenylamine in its structure ... 

Diphenylnitrosamine, which is always present in powders made from diphenylamine, is decomposed at 110°, and that temperature therefore is not a suitable one for a study of the stability of smokeless powder. At 75° diphenylnitrosamine attacks nitrocellulose less rapidly than diphenylamine itself, but this is not true at lower temperatures (40° and 60°) at which there is no appreciable difference between the two substances. Carbazol at 110° is an excellent stabilizer but at 60° and 75° is so poor as to... 

Mittal et al. investigated the electron transfer from diphenylamine (DPA) or triphenylamine (TPA) to two pentaphenylated fullerene derivatives (PPF). The... 

Grellmann, K.-H., Kiihnle, W., Weller, H., and Wolff, T. (1981) Photochemical formation of dihydrocarbazoles from diphenylamines and their thermal rearrangement and disproportionation reactions. Journal of the American Chemical Society, 103, 6889-6893. 

Dipheny[amine (7) is prepared industrially either by heating aniline with aniline hydrochloride at 140 °C under pressure, or by heating aniline with phenol at 260 °C in the presence of zinc chloride. The most convenient laboratory synthesis uses the Ullmann reaction (Scheme 8.9) (see Chapter 10), in which acetanilide is refluxed with bromobenzene in the presence of potassium carbonate and copper powder in nitrobenzene solvent. Triphenylamine is similarly prepared from diphenylamine and iodobenzene. 

Dicyclopentadiene was used as another difunctional agent for the synthesis of an oligomeric AO from 4-methylphenol [120] (after tert-butylation, AO 99 was obtained) or diphenylamine [121]. Polymeric aromatic amines for application in rubber stabilization were obtained in the presence of acid catalysts from diphenylamine and l,4-bis(l-hydroxy-l-methylethyl)benzene or 1,4-diisopropylbenzene [122] or from iV,A -diphenyl-l,4-phenylenediamine and a,to-p-xylylenedi-chloride [123]. Polymerization of 2,2,4-trimethyl-1,2-dihydroquinoline in the presence of protic or Lewis adds [1] is very important commerdally. Oligomeric product 100 is an effective AO and AF agent for rubbers. 

This compound is prepared from diphenylamine-p-p -diarsinic acid by the method of reduction previously used, the solution being allowed to stand for fifteen to twenty hours after reduction. The acid is very... 

This is produced by the action of alkali upon an acetone solution of phenarsazine chloride, or by hydrolysis of the cyanide. It may also be obtained from diphenylamine by heating with arsenious oxide and phosphorus pentoxide at 160° to 170° C. for one hour, the mixture being mechanically stirred. When aniline and arsenious chloride are condensed in n-heptane solution, trianilinoarsine hydrochloride is formed, and this, when heated alone or in the presence of aniline, yields phenarsazine chloride, treatment of which with sodium hydroxide gives the oxide. The reaction may be represented as foUo-ws ... 

Phenotellurazine was obtained in 7% yield starting from diphenylamine. ... 

Anodic oxidation of 4-aminobiphenyl (68f, X = Ph) in mixtures of hydrochloric acid and ACN results in the same polymer (38) as that obtained from diphenylamine, suggesting68 the conventional head-to-tail coupling, as for other para-substituted anilines. 

Dlphenylhydrazlne, (CeH5>2NNH2. Mol. wt. 184.24, m.p. 34.5°. Supplied as the hydrochloride by Eastman. Preparation from diphenylamine by conversion to the N-nitrosoamine and reduction with zinc dust and acetic acid in ethanol. - ... 

BERNTHSEN Acridine Synthesis Acridine synthesis from diphenylamine and carboxylic acids (see 1st edition). 

Phenoselenazines can be synthesized from diarylamines by direct reaction with diselenium dichloride in chloroform <70CCA6i > phenoselenazine itself (176) is obtained in this way from diphenylamine <59JOC37>. Y-Alkyl phenoselenazines can be prepared in a similar way from 7V-alkyldiphenylamines, or by A-alkylation of phenoselenazine (see Section 6.24.7.2.1). 

The pyrochemical conversion of diphenylmethane into fluorene and of bibenzyl into phenanthrene, first effected by Graebe,264 is fully analogous to that of biphenyl from benzene. These reactions, as well as the preparation of carbazole from diphenylamine, were carried out by Zelinsky and his co-wor-... 

Describe how would you synthesize ethopropazine hydrochioride—a phenothiazine analogue from diphenylamine. 

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