Patent GB-562760-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B23/01
Filed: 1942-07-13
Abstract: Dyes of formula <FORM:0562760/IV/1> (where R1 and R11 are aryl radicals, e.g. of the benzene or naphthalene series, substituted or not and the same or different, R111 is H or a non-reactive substituent, e.g. aryl, alkyl, or acylamino, and X and Y are phenyl radicals, at least one of which is substituted by a dialkylamino group in the 4-position) are prepared by reacting a 2 : 4-diarylpyrrole with a diphenylketone which has at least one of the phenyl groups, a dialkylamino group in the 4-position to the CO group or with a simple functional derivative thereof, e.g. an oxime or anil.  2 : 4-Diarylpyrroles specified are 2 : 4 - diphenylpyrrole, 2-phenyl-4-(p-methoxyphenyl)-pyrrole, 2 - (p - methoxyphenyl) - 4 - phenylpyrrole, 3 - benzoylamino - 2 : 4-diphenylpyrrole, 2 - phenyl - 4 - (o - chlorophenyl) - pyrrole, 2 - (p - acetylaminophenyl) - 4 - phenylpyrrole, 2 - a  - naphthyl - 4 - phenylpyrrole, 2 - phenyl - 4 - b  - naphthylpyrrole, 2 : 3 : 4-triphenylpyrrole, 3 - benzoylamino - 2 : 4-di-p-tolylpyrrole, 3-acetylamino-2 : 4-triphenylpyrrole, and 3-acetoacetylamino-2 : 4-diphenylpyrrole, and the corresponding sulphonic acids. Diphenyl ketones specified are tetramethyldiaminobenzophenone, 4 : 41 - bis - (diethylamino)-benzophenone, 4 - chloro - 41 - dimethylaminobenzophenone, and 4 : 41-bis-benzylethylaminobenzophenone.  The reactants may be heated together, preferably in a mutual solvent, and in presence of a strongly acidic condensing agent, e.g. POCl3, HCl, sulphuric acid, or acetic acid Water-soluble derivatives are obtained by forming the sulphamate, quaternary ammonium compounds, sulphonic acids (e.g. by sulphonating with fuming sulphuric acid or chlorosulphonic acid), or sulphonates.  One or both of the reactants may contain a water-solubilising group, e.g. a sulphonic acid group.  In example 1, a toluene solution of POCl3 is added to a toluene solution of tetramethyldiaminobenzophenone and 2 : 4-diphenylpyrrole at 60 DEG C., and then heating to 100 DEG  C.  The sulphamate may be formed.  A similar dye is obtained from 2 - phenyl - 4 - (o - chlorophenyl) - pyrrole.  In examples 2, 3 and 4, dyes are similarly obtained from 4 : 41 - bis - diethylaminobenzophenone and 2 : 4 - diphenylpyrrole, from 4 - chloro - 41 - di - methylaminobenzophenone and 2 : 4-diphenylpyrrole, and from 4 : 41-bis-benzylethylaminobenzophenone and 2 - phenyl - 4 - (p - methoxy - phenyl)-pyrrole.  In example 5, sodium 2 : 4-diphenylpyrrole monosulphonate and tetramethyldiaminobenzophenone are heated together in 80 per cent H2SO4.  A dye may be similarly obtained from 2 : 4-diphenylpyrrole disulphonic acid trihydrate.  4 : 41 - bis - Diethylamino - benzophenone is prepared by the action of phosgene on diethylaniline. 4 : 41 - bis - Benzylethylaminobenzophenone is similarly obtained from benzylethylaniline.  Specifications 554,102 and 556,156 are referred to.  According to the Provisional Specification, diarylketones in general may be used, e.g. 2 - hydroxy - 3 - methyl - 5 - (4 - chlorobenzoyl) - benzoic acid (made by hydrolyzing the methyl ester obtained by reacting methyl 2-hydroxy-3-methylbenzoate with p-chlorobenzoyl chloride in presence of AlCl3.  Dyes of the general formula in which R111 is a benzylideneamino or alkylamino radical are also referred to.