Diphenyl amine

The nitrosamines are insoluble in water, and the lower members are liquid at ordinary temperatures. The separation of an oily liquid when an aqueous solution of an amine salt is treated with sodium nitrite is therefore strong evidence that the amine is secondary. Diphenylnitrosoamine is selected as a preparation because it is a crystalline substance and is thus easier to manipulate on a small scale than one of the lower liquid members. For this preparation, a fairly pure (and therefore almost colourless) sample of diphenyl-amine should be used. Technical diphenylamine, which is almost black in colour, should not be employed. 

TEST Aniline 0- toluidine m-> toluidine P-. toluidine I- naphthyl- amine 2- naphthyl- amine mono- methyl- aniline diphenyl- amine dimethyl- aniline triphenyl- amine... 

Substances suitable for the estimation acetanilide, sucrose, glucose, cinnamic acid, diphenyl amine, salicylic acid, vanillin, />"bromoacetanilide, toluene p-sul phonamide. 

Diphenyl amine [122-39-4] is produced by heating aniline with aniline hydrochloride at 290°C and 2 MPa (21 atm) in an autoclave (15). 

Diarylamines are compounds that have two aromatic groups and one hydrogen atom attached to nitrogen. Diphenyl amine (DPA), or... 

Stability. In order to have maximum effectiveness over long periods of time, an antioxidant should be stable upon exposure to heat, light, oxygen, water, etc. Many antioxidants, especially in the presence of an impurity when exposed to light and oxygen, are subject to oxidation reactions with the development of colored species. Alkylated diphenyl amines are least susceptible and the -phenylenediamine derivatives the most susceptible to direct oxidation. 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Alkylated diphenyl amines (11) and derivatives of both dihydro quiaoline (12) and polymerized 2,2,4-trimethyl-l,2-dihydroquiQoline [26780-96-1] (13) develop less color than the -phenylenediamiaes and are classified as semistaining antioxidants. Derivatives of dihydro quiaoline are used for the stabilization of animal feed and spices. 

Raw NBR containing 1.5% of the built-in antioxidant retained 92% of its original resistance to oxidation after exhaustive extraction with methanol. NBR containing a conventional aromatic amine antioxidant (octylated diphenyl amine) retained only 4% of its original oxidative stabiUty after similar extraction. 

Condensa.tlon, This term covers all processes, not previously iacluded ia other process definitions, where water or hydrogen chloride is eliminated ia a reaction involving the combination of two or more molecules. The important condensation reactions are nitrogen and sulfur heterocycle formation, amide formation from acid chlorides, formation of substituted diphenyl amines, and misceUaneous cyclizations. 

The reaction of substituted chloronitrobenzenes with arylamines to form substituted diphenyl amines is typified by 4-rutrodiphenylamine-2-sulfoiiic acid where 4-chloronitrobenzene-3-sulfonic acid (PN salt) is condensed with aniline ia an aqueous medium at 120°C and 200 kPa (2 atm) ia the presence of alkaline buffer at low pH to avoid the competing hydrolysis of the PN salt. 

Compound parts polymer, 100 Naugard 445 (substituted diphenyl amine), 2 Armeen 18D (octadecyl amine), 0.5 stearic acid, 2 Vanfre VAM (complex organic alkyl acid), 0.5 SRE Carbon Black (N774), 100 DIAK 1 (hexamethylenediamine), 1.25 and di-o-tolylguanidine, 4. 

Antioxidants. A good antioxidant should be added to CR adhesives to avoid oxidative degradation and acid tendering of substrates. Derivatives of diphenyl amine (octylated diphenyl amine, styrenated diphenyl amine) provide good performance but staining is produced. To avoid staining, hindered phenols or bisphenols can be added. 2 phr antioxidant is sufficient in solvent-borne CR adhesives formulations. 

The progress of the photolysis can be followed either by observing the disappearance of the typical nitrite bands between 1600 and 1680cm (6.25 and 5.95 ju) in the infrared spectrum or by disappearance of the diphenyl-amine-sulfuric acid spot plate test. 

Methyl Orange.--The first point to notice in this reaction is that the diazonium salt forms no diazoamino-compotind with the dimethylanilinc, but at once pioduces an azo-compound. This is always the case with tertiary amines, some secondary amines like diphenyl.amine and the phenols. The reaction may be regarded as typical of the formation of all azo-colounng m.atters. At least two substances are requisite in this process on the one hand. an aromatic compound containing an amino-groujD in the nucleus, and, on the other, a base or phenol... 

Nucleophilic aromatic substitution of the anthranilic acid derivatives, 72, on ortho-bromonitrobenzene affords the diphenyl-amine, 73. The ester is then saponified and the nitro group reduced to the amine (74). Cyclization of the resulting amino acid by heat affords the lactam (75). Alkylation on the amide nitrogen with 2-dimethylaminoethyl chloride by means of sodium amide affords dibenzepine (76). ... 

PNDA = p-dinitroso diphenyl amine PETA-penta erythritol triacrylate DHBP-peroxy hexane values in parentheses are after aging at 100°C, 72 h. 

Procedure. To obtain experience in the method, the purity of analytical-grade potassium chlorate may be determined. Prepare a 0.02M potassium chlorate solution. Into a 250 mL conical flask, place 25.0 mL of the potassium chlorate solution, 25.0mL of 0.2M ammonium iron(II) sulphate solution in 2M sulphuric acid and add cautiously 12 mL concentrated sulphuric acid. Heat the mixture to boiling (in order to ensure completion of the reduction), and cool to room temperature by placing the flask in running tap water. Add 20 mL 1 1 water/phosphoric(V) acid, followed by 0.5 mL sodium diphenyl-amine-sulphonate indicator. Titrate the excess Fe2+ ion with standard 0.02M potassium dichromate to a first tinge of purple coloration which remains on stirring. 

Reagent 1 Spmy solution 1 Dissolve 1 g iron(III) chloride and 1 g diphenyl-amine in 100 ml cone, sulfuric acid. 

Dimethylaniline (h/ f 5-10), 4-chloroaniline (h/if 10-15), 3-chloroaniline hRf 20-25), 4-chloro-2-nitroaniline (bRf 30-35), 2-chloroaniline (hRf 35-40) and diphenyl-amine (hRf 70-75) appeared as yellow chromatogram zones on a pale yellow background. The detection limits were between 4 ng (4-chloroaniline) and 20 ng (diphenyl-amine) substance per chromatogram zone. 

Thomas JO, Ribelin WE, Woodward JR, Deeds F (1967) The chronic activity of diphenyl-amine for dogs. Toxicol Appl Pharmacol 11 184—194... 

To a solution of oxalic chloride (5 g) in dichloromethane, a solution of diphenyl amine (5 g) in dichloromethane was added dropwise and refluxed for 30 min. The solution was concentrated (50%) and aluminum trichloride (8 g) added in portions. The mixture was refluxed for 45 min and the solvent evaporated. To this residue hydrochloric acid in ice water (1 M) was added and the red-colored precipitate filtered. The precipitate was dissolved in potassium hydroxide (10% in water), refluxed overnight, and poured into hydrochloric acid in ice water (5 M). The yellow acridine-9-carboxylic acid was filtered, washed with water, and dried. 

A new cyclic mechanism of chain termination by nitroxyl radicals, including the formation of aminyl radicals as intermediate species, has been proposed by Korcek and coworkers [42,43]. It was shown that the addition of 4,4 -dioctyldiphenylnitroxyl radical to the hexa-decane that is oxidized (T = 433 K) leads to the formation of the corresponding diphenyl-amine as an intermediate compound during its transformations. The following cyclic mechanism of chain termination was suggested ... 

Most of the early applications of palladium to indole chemistry involved oxidative coupling or cyclization using stoichiometric Pd(II). Akermark first reported the efficient oxidative coupling of diphenyl amines to carbazoles 37 with Pd(OAc)2 in refluxing acetic acid [45]. The reaction is applicable to several ring-substituted carbazoles (Br, Cl, OMe, Me, NO2), and 20 years later Akermark and colleagues made this reaction catalytic in the conversion of arylaminoquinones 38 to carbazole-l,4-quinones 39 [46]. This oxidative cyclization is particularly useful for the synthesis of benzocarbazole-6,11-quinones (e.g., 40). 

Tocopherol acetate 0.3 g Diphenyl amine Each ml of 0.1 N ammonium ceric sulphate = 0.002364 g of C31H5203... 

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