Patent GB-562759-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B23/04
Filed: 1942-07-13
Abstract: Dyes of formula <FORM:0562759/IV/1> (wherein R1 and R11 are aryl radicals, e.g. of the benzene or naphthalene series, substituted or not and the same or different and R111 is H or a non-reactive substituent, e.g. aryl, alkyl or acylamino) are prepared by reacting a 2 : 4-diarylpyrrole with an aldehyde XCHO in which the CHO group is attached, either directly or through a methylene group, to a carbon atom of a beterocyclic ring containing nitrogen, other than a 5 - formyl - 2 : 4 - diarylpyrrole.  2 : 4 - Diarylpyrroles specified are 2 : 4 - diphenyl - pyrrole, 2-phenyl-4-(p-methoxyphenyl)-pyrrole, 2 - (p - methoxyphenyl) - 4 - phenylpyrrole, 2 - (m - hydroxyphenyl) - 4 - phenylpyrrole, 2 - (o - chloro - phenyl) - 4 - phenylpyrrole, 2 - (p - acetylamino - phenyl) - 4 - phenylpyrrole, 2 - a  - naphthyl - 4 - phenylpyrrole, 2-phenyl-4-b -naphthyl-pyrrole, 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 obtained by sulphonating the above compounds.  Aldehydes specified are 1 : 3 : 3 - trimethyl - 2 - formylmethylenedihydroindole, 4 - formyl - 1 - phenyl - 3 - methyl - 5 - pyrazolone 4 - formyl - 1 - (p - benzoylamino - phenyl) - 3 - methyl - 5 - pyrazolone, 4 - formyl - 1 - (symm.-tribomophenyl)-3-methyl-5-pyrazolone, 4-formyl-1-(symm.-trichlorphenyl)-3-methyl-5-pyrazolone, 1 - ethyl - 2 - formylmethylenebenzthiazole, and N - methyl - 2 - formylmethylenequinoline.  Simple functional derivatives, e.g. oximes and anils, may be used.  The reactants may be heated together in a mutual solvent, preferably in presence of an acidic condensing agent. Water-soluble derivatives may be obtained by forming the sulphamates, quaternary ammonium compounds, sulphonic acids (e.g. with fuming sulphuric acid or chlorosulphonic acid), and sulphonates.  One or both of the reactants may contain water-solubilising groups, e.g. sulphonic acid groups.  In example 1, HCl is passed into a boiling suspension of sodium 2 : 4-diphenylpyrrole monosulphonate in glacial acetic acid until no more is absorbed, 1 : 3 : 3-trimethyl - 2 - formylmethylene - dihydroindole and acetic acid is added, and the mixture refluxed.  In example 2, 2 : 4-diphenylpyrroledisulphonic acid, the anil of 4-formyl-1-phenyl-3-methyl-5-pyrazolone, methanol, and concentrated hydrochloric acid are boiled together.  In example 3, 2 - N - acetylanilinovinylbenzthiazole ethiodide, 2 : 4-diphenylpyrrole, glacial acetic acid, and aqueous Hl are refluxed together.  In example 4, 2-anilinovinylquinoline ethiodide, 2 - phenyl - 4 - (p - methoxyphenyl) - pyrrole, glacial acetic acid, and aqueous Hl are refluxed together.  In example 5, 1 : 3 : 3-trimethyl - 2 - formylmethylene indoline, 2 - phenyl - 4 - (p - methoxyphenyl) - pyrrole, glacial acetic acid and aqueous Hl are refluxed together. 1 : 3 : 3 - Trimethyl - 2 - formylmethylenedi - hydroindole is prepared by reacting 1 : 3 : 3-trimethyldihydroindole with POCl3 and N-methylformanilide.  4-Formyl-1-phenyl - 3 - methyl - 5 - pyrazolone anil is prepared by reacting 1-phenyl-3-methyl-5-pyrazolone with diphenylformamidine.  4 - Formyl - 1 - (p - benzoylaminophenyl) - 3 - methyl-5-pyrazolone is prepared by reacting 1-(p-benzoylaminophenyl) - 3 - methyl - 5 - pyrazolone with methyldiphenylformamidine and decomposing the product by distilling in steam.  4 - Formyl - 1 - (symm. - tribromophenyl) - 3 - methyl - 5 - pyrazolone and 4-formyl-1-(symm.-trichlorophenyl) - 3 - methyl - 5 - pyrazolone are similarly prepared.  Specifications 554,102 and 556,156 are referred to.  According to the Provisional Specification, aldehydes in general (other than a 5-formyl-2 : 4-diarylpyrrole) may be used. Additional aldehydes specified are benzaldehyde, 4-dimethylaminobenzaldehyde, 4 - (ethyl - b  - chloroethyl - amino) - benzaldehyde, 2 - hydroxy - 5 - formyl - 3 - methylbenzoic acid, 2 - chlorobenzaldehyde, 4 - chlorobenzaldehyde, benzaldehyde - 4 - sulphonic acid, 4 - formyldiphenylamine, 4 - methoxybenzaldehyde, salicylaldehyde, cinnamaldehyde, and N - formyldihydroindole.  4 - (Ethyl - b  - chloroethylamino) - benzaldehyde is prepared by reacting N-ethyl : N-b -chloroethylaniline with POCl3 and N-methylformanilide.  2 - Hydroxy - 5 - formyl - 3 - methylbenzoic acid is prepared by reacting 2-hydroxy-5-chloromethyl-3-methylbenzoic acid and hexamethylenetetramine.  4-Formaldiphenylamine is prepared by reacting diphenylamine with POCl3 and N - methylformanilide. Dyes of the general formula in which R111 is a benzylideneamino or alkylamino substitute are also referred to. Specification 5533/13, [Class 2 (iii)], is referred to.