Nitrodiphenylamine

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). 

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.

This transformation avoids problems with the change of polarity during the reaction, which occurred in the telomerization, because two aromatic compounds react with each other to form a new aromatic product. The synthesis of 4-nitrodiphenylamine via a Pd-catalyzed Buchwald-Hartwig-type amina-tion from 4-chloronitrobenzene and aniline was chosen as the next test reaction in a cooperation with Lanxess as industrial partner of the network (Scheme 5). 

Water was used as the catalyst phase for the palladiiun complex of TPPTS and toluene or an excess of the substrate anihne served as the non-polar product phase. To determine an appropriate solvent system cloud titrations were performed at 90 °C, 60 °C, 40 °C and 25 °C. A solution of 4-chloro-nitroben-zene in aniline and water were mixed in a weight ratio of 1 1 and semi-polar solvents were added as a mediator until a homogeneous solution was formed. As the mediator the following solvents were apphed methanol, ethanol, isopropyl alcohol, n-butanol, DMF, DMSO, ethylene glycol, N-methylpyrrohdone (NMP), 1.4-dioxane and acetonitrile. The cloud titrations were repeated whereby the substrate 4-chloro-nitrobenzene was replaced with the product 4-nitrodiphenylamine. In all cases more of the semi-polar mediator is required for the product mixture at 25 °C than for the reaction mixture at 60 °C to obtain a clear solution. 

Suitable thermomorphic solvent systems were appUed to the telomeriza-tion of butadiene with ethylene glycol or with carbon dioxide, to the isomer-izing hydroformylation of trans-4-octene and to the hydroaminomethylation of 1-octene with morpholine. Further investigations for the carboxytelomer-ization and for the synthesis of 4-nitrodiphenylamine were also carried out. In addition to common Ugands, PEG-modified ligands and fiuorous Ugands were used for the telomerization and the carboxytelomerization. 

N-Ethyl-4-nitrodiphenylamine, mw 242.18, yel, mp 87—88°. It is prepd from 4-nitrodipbenyl-amine, ethyl iodide and base Refs 1) Beil, not found 2) K.A. Nuridzhanyan V.A. Izmail skii, ZhurVsesoyuzKhimObsh-cbestva Im D.I. Mendeleeva 5,237-8(1960) 81 CA 54, 20927(1960)... 

Ethyldiphenylamine and derivs 6 E227 N-ethyl-2,4-dinitrodiphenylamine 6 E227 N-ethyl-hexanitrodiphenylamine 6 E227 N-ethyl-1 (or 4) -nitrodiphenylamine 6 E227 N-ethyl-2,4,6-trinitrodiphenylamine 6 E227... 

Nitrodiphenylamine-6 -arsinic acid, obtained when p-bromo-nitrobenzene is used in the foregoing, crystallises from acetic acid or ethyl alcohol in yellow prisms, possessing similar properties to the preceding acids. 

Nitrodiphenylamine-4 -arsinic acid, obtained from -nitro-diphenvlaniine, sei arates in fine, yellow needles, decomposing above 820 C. ... 

Nitrodiphenylamine-6 -arsinic acid behaves like the 8-nitro-compouncl, and produces 10-chloro-2-nitro-5 10-dihydrophenarsazine (XV) ... 

The reaction of 4-chloronitrobenzenes 299 with anilines 300 in the presence of DBU, copper(I) oxide, and potassium carbonate in refluxing xylene gave 4-nitrodiphenylamines 301 (83GEP3137041). 

T>iazo-4 -nitrodiphenylamine, red crysts having a Cu luster, mp - explodes when heated to 60-65° or by friction was prepd by diazo-lizing 4 -nitro-4-aminodiphenylamine and treating the diazonium salt with NH3 (Refs 1 2, p 11)... 

Direct coupling to 4-nitrosodiphenylamine and 4-nitrodiphenylamine. Addition to tctramethylammonium hydroxide dihydrate, (CH,)4NOH 2H206 to a mixture of aniline and nitrobenzene results in a a-complcx 1, which is then converted to a mixture of 4-nitrosodiphcnylaminc (2) and 4-nitrodiphenylaminc (3). The ratio of 2 and 3... 

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-... 

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