Formyl diphenylamine

During World War II N-arylurethanes were extensively used for the manufacture of nitroglycerine powder, e.g. ethylphenylurethane, diphenylurethane, otolylure-thane, also, to a lesser extent, N-arylsubstituted amides of aliphatic acids, e.g. formyl-diphenylamine were used. The latter was used in Japan [33] as gelatinizer and stabilizer. 

N-Formylation. Diphenylamine, carbazoles, 3-alkylindoles, and moderately weakly nucleophilic anilines are formylated in neat formic acid. 

The major product isolated from the reaction of secondary amines with dichloro-carbene the reaction under phase-transfer conditions is the A-formylamine [12-14], The isolated yields are considerably higher (Table 7.14) than those recorded for classical procedures and are not inhibited by steric effects [15]. Diphenylamine is converted into its A-formyl derivative in low yield by conventional procedures and, although application of the phase-transfer catalysed procedure increases the yields, the E- and Z-l,2-bis(diphenylamino)-l,2-dichloroethenes are also obtained as byproducts of the reaction [13],... 

Photochemical formylation of carbazole,methyl-carbazoles,and diphenylamine has been observed when they are illuminated with ultra-violet light or sunlight in chloroform solution, while chlorination products of pyrene and perylene have been observed when these arenas are irradiated in carbon tetrachloride.A report of the light induced chlorination of pyridine by chlorine in the gas phase has also appeared. 

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). 

Limitations of the reaction include de-halogenation and halogen exchange in substituted pyrroles, while condensation products are obtained from the formylation of aniline, dimethylaniline and diphenylamine. °... 

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