Patent GB-562758-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B23/16
Filed: 1942-07-13
Abstract: Dyes of the formula <FORM:0562758/IV/1> (where R1 and R11 stand for aryl radicals, e.g. of the benzene or naphthalene series, substituted or not and the same or different, and where R111 stands for H or for a non-reactive substituent, e.g. an aryl, alkyl, or acylamino radical) are prepared by condensing a 2 : 4-diarylpyrrole with one or more nitroso compounds chosen from (a) 1-aryl-4-nitroso-5-pyrazolones which may carry alkyl or aryl radicals in the 3-position; (b) 3-nitrosoindoles which may carry alkyl or aryl radicals in the 1 and/or 2 positions and may also be substituted in the benzene nucleus; and (c) 1-dialkylamino-4-nitrosobenzenes which may be substituted in the 3-position and in the alkyl groups.  2 : 4-Diarylpyrroles specified are 2 : 4 - diphenylpyrrole, 2-phenyl-4-(p-methoxyphenyl)-pyrrole, 2 - (p - methoxyphenyl) - 4 - phenylpyrrole, 2 - (m - hydroxyphenyl) - 4 - phenylpyrrole, 2 - (o - chlorophenyl)-4-phenylpyrrole, 2-phenyl-4-(o-chlorophenyl) - pyrrole, 2 - (p - acetylaminophenyl) - 4 - phenylpyrrole 2 - a  - naphthyl - 4 - phenyl - pyrrole, 2-phenyl-4-b -naphthylpyrrole, 2 : 3 : 4-triphenylpyrrole, 3-benzoylamino-2 : 4-diphenylpyrrole, 3 - acetylamino - 2 : 4 - diphenylpyrrole, 3-benzoylamino-2 : 4-di-p-tolylpyrrole, and 3-acetoacetylamino - 2 : 4 - diphenylpyrrole, and the sulphonic acids made by sulphonating the above compounds.  Nitroso compounds specified are p - nitrosodimethylaniline, 1 - (3 - sulpho - benzoylethylamino) - 4 - nitrosobenzene, 1-(b -hydroxyethylethylamino) - 4 - nitrosobenzene, 1 - di - (b  - hydroxyethyl) - amino - 4 - nitrosobenzene, 1 - diethylamino - 3 - hydroxy - 4 - nitrosobenzene, 3-nitroso-2-phenylindole, 1-methyl-2-phenyl-3-nitrosoindole, and 1-phenyl-3-methyl-4-nitroso-5-pyrazolone.  The reactants may be heated together, preferably in a mutual solvent, and in the presence of an acidic condensing agent, e.g. acetic anhydride, acetic acid, or HCl.  Water-soluble derivatives may be obtained by forming the sulphamates, the quaternary ammonium compounds, sulphonic acids, or sulphonates, e.g. by sulphonating the dyes with fuming sulphuric acid or chlorosulphonic acid.  One or both of the reactants may contain water-solubilising groups, e.g. sulphonic acid groups.  In example 1, 2 : 4-diphenylpyrrole or 2-phenyl-4-(p-methoxyphenyl) - pyrrole are reacted with p  p-nitrosodimethylaniline in presence of acetic anhydride.  In example 2, sodium 2 : 4-diphenylpyrrole disulphonate is reacted with p - nitrosodimethylaniline hydrochloride.  In example 3, 2-phenyl-4-(o-chlorophenyl)-pyrrole and 1 - phenyl - 3 - methyl - 4 - nitroso - 5 - pyrazolone are refluxed together in acetic anhydride.  In example 4, 1 - methyl - 2 - phenyl - 3 - nitrosoindole and 2-phenyl-4-(p-methoxyphenyl)-pyrrole are refluxed together in acetic acid and acetic anhydride.  In example 5, 1-di-(b -hydroxyethyl)-amino-4-nitrosobenzene is reacted with 2 : 4-diphenylpyrrole or with 2-phenyl-4-(o-chlorophenyl)-pyrrole in presence of acetic anhydride.  In example 6, p-nitrosodimethylaniline, 2 - phenyl - 4 - (o - chlorophenyl) - pyrrole, anhydrous sodium acetate, and acetic anhydride are heated together.  In example 7, 4-nitroso-3-hydroxydiethylaniline and 2 - (p - methoxy - phenyl) - 4 - phenylpyrrole are refluxed together in acetic anhydride.  In example 8, acetic anhydride is added to p-nitroso-N-benzylethylaniline sulphonic acid and 2 : 4-diphenylpyrrole dissolved together in pyridine.  b -Benzoyl-a  : b -diphenylpropionitrile is prepared by the action of HCN on benzylidenedesoxybenzoin.  2 : 3 : 4-Triphenylpyrroline is prepared by reducing b  - benzoyl - a  : b  - diphenylpropionitrile. 3-Sulphobenzylethylaniline is prepared by sulphonating benzylethylaniline with oleum at a temperature not higher than 60 DEG C.  1 - (3 - Sulphobenzylethylamino) - 4 - nitroso - benzene is prepared by the action of nitrous acid on 3-sulphobenzylethylaniline. 1-Phenyl-3-methyl-4-nitroso - 5 - pyrazolone is made by the action of nitrous acid on 1-phenyl-3-methyl-5-pyrazolone.  1 - (b  - Hydroxyethylethylamino) - 4 - nitroso - benzene is made by the action of nitrous acid on b -hydroxyethylethylaniline.  3 - Nitroso - N - ethylcarbazole is made by the action of nitrous acid on N-ethylcarbazole.  According to the Provisional Specification, dyes may be prepared using as the nitroso compound p-nitrosophenol, 1-nitroso-2-naphthol, 1-nitroso-4-naphthol, 1 : 3 : 3-trimethyl-2-nitroso-methylene-dihydroindole, and 3-nitroso-N-ethylcarbazole.  3-Nitroso-N-ethylcarbazole is made by the action of nitrous acid on N-ethylcarbazole.  Specifications 554,102 and 556,156 are referred to.  The Provisional Specification refers also to dyes of the general formula in which R111 stands for a benzylideneamino or alkylamino radical.