GB738013A - New nitrogen containing heterocyclic compounds - Google Patents

Abstract

The invention comprises compounds of the formula <FORM:0738013/IV (b)/1> and their production from 2-acylamino-diphenylamines of the formula <FORM:0738013/IV (b)/2> by heating with a phosphorus oxide, halide or oxyhalide; R is hydrogen or an alkyl, aryl, aralkyl or heterocyclic radical, R1 is alkyl, aryl or aralkyl and R2 is hydrogen, lower alkyl or aralkyl; and nuclei X and Y may carry substituents which are not affected by the reaction conditions, e.g. alkylsulphonyl, halogen, nitro or alkoxy. The reaction may be carried out in an inert solvent such as nitrobenzene, but this is unnecessary if R2 is hydrogen. Examples show the production of the following substituted 2 : 3 : 6 : 7 - dibenz - 1 : 4 - diazepines (the nature of the Group R2 in the starting material being indicated):-1 - methyl - 31 - nitro - 5 - phenyl (R2=methyl), 1 - methyl - 31 - nitro - 5 - p - nitrophenyl (R2=methyl), 1 - methyl - 211 : 31 - dinitro - 5 - phenyl (R2=H and methyl), 211 : 31-dibromo - 1 - methyl - 5 - phenyl (R2=H and methyl), 211 - methoxy - 1 - methyl - 31 - nitro - 5 - phenyl (R2=H), 211 - methoxy - 1 : 5 - dimethyl-31-nitro (R2=H, acylamino compound prepared in situ), 211-methoxy-1-methyl-31-nitro (R2=H, acylamino compound prepared in situ), 1 - methyl - 5 - phenyl (R2=H), and 1 : 5-diphenyl (R2=H). Diphenylamines.-The following are made by direct acylation:- 2-benzoylamino-N-methyldiphenylamine, 2 - benzoylamino - 4 : 41 - dibromo-diphenylamine, 2-benzoylamino-4 : 41-dibromo - N - methyl - diphenylamine, 2 - benzoylamino - 41 - methoxy - N - methyl - 4 - nitro - diphenylamine, 4 - nitro - 2 - (p - nitrobenzoylamino) - diphenylamine, 2 - benzoylamino - 4 : 41 - dinitro - diphenylamine, 2 - benzoylamino - 4 : 41 - dinitro - N - methyl - diphenylamine and 2 - benzoylamino - triphenylamine. The following are made by N-methylation:-N - methyl - 2 - nitro - diphenylamine, 2 - amino - 41 - methoxy - N - methyl - 4 - nitro - diphenylamine, 2 - amino - 4 : 41 - dinitro - N - methyl - diphenylamine, 2 - benzomethylamino - 4 : 41 - dibromo - N - methyl - diphenylamine, 4 : 41 - dibromo - N - methyl - 2 - nitro - diphenylamine, 2 - benzomethylamino - N - methyl - 4 - nitro - diphenylamine, 2 - benzomethylamino - 4 : 41 - dinitro - N - methyl - diphenylamine and N - methyl - 4 - nitro - 2 - (p - nitrobenzomethylamino) - diphenylamine. The following are made by reduction of the corresponding nitro compounds:- 2 - amino - N - methyl - diphenylamine, 2 - amino - 4 : 41 - dinitro - diphenylamine, 2 - amino - 41 - methoxy-4 - nitro - diphenylamine, 2 - amino - 4 : 41 - dibromo - diphenylamine and 2 - amino - 4 : 41 - dibromo - N - methyl - diphenylamine. 4 : 41 - Dibromo - 2 - nitro - diphenylamine is made by condensing aniline with 2 : 5-dibromonitrobenzene and brominating the product.