Diphenylamine derivatives formed

Chloro-5-nitrobenzaldehyde, -acetophenone, or -benzophenone derivatives treated with 2-aminothiophenol under alkaline conditions provided good yields of the corresponding dibenzo[(3,/][l,4]thiepins. Similar treatment of 2-chloro-3,5-dinitrobenzophenone (318) provided 58% of dibenzo[(3,/][l,4]thiepin 321 and 20% of phenothiazine 323. Its formation can be easily explain by the Smiles rearrangement of the initially formed intermediate 320 into diphenylamine derivative 322, followed by denitrocyclization reaction leading to the corresponding product of denitrocyclization 323 (Scheme 49). When the reaction was done in pyridine, only this product was isolated in 50% yield (57JCS3818). 

High values of the inhibition coefficient (/= 12-28) were detected for the first time in the oxidation of cyclohexanol [1] and butanol [2] inhibited by 1-naphthylamine. For the oxidation of decane under the same conditions, /= 2.5. In the case of oxidation of the decane-cyclohexanol mixtures, the coefficient / increases with an increase in the cyclohexanol concentration from 2.5 (in pure decane) to 28 (in pure alcohol). When the oxidation of cyclohexanol was carried out in the presence of tetraphenylhydrazine, the diphenylaminyl radicals produced from tetraphenylhydrazine were found to be reduced to diphenylamine [3]. This conclusion has been confirmed later in another study [4]. Diphenylamine was formed only in the presence of the initiator, regardless of whether the process was conducted under an oxygen atmosphere or under an inert atmosphere. In the former case, the aminyl radical was reduced by the hydroperoxyl radical derived from the alcohol (see Chapter 6), and in the latter case, it was reduced by the hydroxyalkyl radical. 

Methylnitramine decomposes explosively in contact with concentrated sulphuric acid. It is evolved when aniline reacts with tetryl, a diphenylamine derivative (p. 51) is produced simultaneously. Methylnitramine reacts with picryl chloride to form tetryl. The structure of tetryl (p. 40) was first proved by this synthesis. 

When using method (b) a certain amount of the diphenylamine derivative (II) is also formed as a by-product ... 

This reaction can be extended to almost all non -para substituted hydrazo compounds if one or both para-positions are substituted, either ortAo-benzidine or diphenylamine derivatives known as ortho- or para-semidines are formed. 

Condensation, In a restricted sense, condensation describes those reactions in which a carbon-carbon bond is formed by the elimination of a simple molecule. An example is the condensation of benzanthrone to dibenzanthrone, shown below in Fig. 23.6 and described on page 909. Dye intermediate chemical terminology uses the term condensation more broadly than this to describe a variety of reactions in which molecules are joined the bonds formed are not restricted to carbon-carbon. An example is the formation of the diphenylamine derivative, commonly called Nitro Delta Acid ... 

If aryl azides are irradiated in acidic medium in the presence of arenes, derivatives of diphenylamine are formed." For the diphenylnitrenium ion, G-complexes with benzene have been detected by laser flash photolysis. In reactions with alkenes, nitrenium ions react more rapidly with electron-deficient olefins. Rate constants for the reaction of diphenylnitrenium with electron-rich olefins such as cyclohexanone trimethylsilyl enol ether are of the order of 1.9 x 10 M" s". In the reaction of 2-fluorenylni-trenium with 2 -deoxyguanosine, reaction at C8 of the guanine base takes place. ... 

In explosives, diphenylamine stabilizes cellulose nitrate by reacting with nitrogen oxides (see Explosives and propellants). The products formed include /V-nitrosodiphenylamine and mono andpolynitro derivatives. 

Studies of the hydrogenation of aromatic nitroso compounds have rarely been published. One of the earliest studies is the Pd/C catalyzed hydrogenation of p-nitrosothymol to its corresponding amine (100%) in ethanol at 1 atm hydrogen.289 Useful antioxidants and gasoline stabilizers are made from diamines, which can be produced by hydrogenating their relatively easily formed nitroso derivatives.290 As a result, the hydrogenation of 4-nitroso-diphenylamine has been studied more heavily than others.291-293... 

The oxidation of AT-substituted 5//-dibenz[6,/] azepines with MCPBA is complex and depends upon the nature of the N-substituent. AT-Acyl derivatives do not form the N-oxide but suffer epoxidation of the 10,11-bond. AT-Aryl derivatives undergo hydroxylation of the phenyl ring, whereas N-alkyl congeners, with the exception of the AT-methyl compound, yield mixtures of diphenylamines and acridones. The N-oxide is obtained from the A/-methyl derivative along with ring-opened and ring-contracted products (81CPB1221). 

The bisphenol 3,3-bis(4-hydroxyphenyl)- l-phenyl- l II-indol-2-one was prepared in a single step from /V-phenylisatin and molten phenol and not through the use of a phenolphthalein derivative. Although phenylisatin could have also been prepared through a modified isonitrosoacetanilide isatin process, it was formed in a one-pot process by reacting oxalic acid dichloride and aluminum chloride with diphenylamine. 

T. Urbanski and Rabek-Gawronska [11] found that cyclonite dissolves in molten, highly-nitrated aromatic hydrocarbons, substituted urea derivatives, and camphor to form eutectics of the composition given in Table 18. It is almost insoluble in molten diphenylamine. 

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

PREPARATION OF KETONE DERIVATIVE. For additional evidence of the presence of amphetamine, a ketone derivative is prepared by adding 0.5 cm3 of acetone to the urine extract and evaporating at 60° to a volume of about 50 yl. Some unreacted amphetamine remains. A 5-yl aliquot of the mixture is chromatographed and the relative retention times calculated. The retention time of diphenylamine will not change, as it does not form a ketone derivative. 

Nitrocellulose, pulped and given a preliminary or sour boiling, may be used directly without poaching. Deteriorated smokeless powder, containing nitro derivatives of diphenylamine and acidic decomposition products, may be reduced to a coarse powder under water in a hammer mill, and may then be used. Whichever is used, the first necessity is to stabilize it by complete removal of the acid. For this purpose, the material in the presence of water (which may contain a little chalk in suspension or urea in solution) is introduced into a still where it is dissolved with agitation in ethyl acetate to form a heavy syrup or lacquer, and is treated with some substance which is adsorbed by nitrocellulose more readily than acid is adsorbed. It is a curious fact that nitrocellulose is dissolved or dispersed by ethyl acetate much more readily... 

The only representative of this macrocyclic group of molecules is a hexaaza derivative believed to possess the heavily annulated structure shown in 133 and formed quantitatively on reaction of 2,2 -diaminobi-phenyl with diphenylamine-2,2 -dicarboxyaldehyde.88 From the limited... 

The perchlorates of various secondary amines, such as diphenylamine and indole derivatives, are colorless.64 The similarity of colors produced in the presence of hydrochloric acid also attests to the non-auxochromic character of the perchlorate ion in the production of the colored derivative. Consequently, the only role attributable to the perchloric acid in this test is that with nucleic acids it leads to more effective hydrolysis and releases more 2-desoxyribose for reaction with tryptophan. This reaction leads to the production of a substance of the type represented by XV and XVI (R " = H), and the increase in the number of conjugated double bonds results in the product being colored. With ribose, which has a free hydroxyl group at carbon atom 2, a ketone of the type shown in XVII can be formed, and in this case the net result is no increase in the number of double bonds conjugated with the indole nucleus and no comparable increase in color. Hence the test will distinguish between ribose and 2-desoxyribose. 

---