Patent GB-857391-A (GB)
Title: Dyes containing keto groups and their production
Inventor: BRAUN WILLY
IPC: C09B1/00
Filed: 1959-05-22
Abstract: The invention comprises dyes containing at least one group of formula -CO,CH2,CH2,X, directly attached to an aromatic nucleus of the dye molecule, where X is the residue of a secondary or tertiary aliphatic, aromatic or heterocyclic amine attached by way of the amino nitrogen atom which, when it is the radical of a salt of a secondary amine or the radical of a tertiary amine, bears a positive charge.  The dyes are made by reacting a dye which contains, at least once, a methyl ketone group with formaldehyde, or a compound which yields formaldehyde, in the presence of a secondary or tertiary amine, or by combining a compound which contains, at least once, the group CO,CH2, CH2X with a dyestuff intermediate. Dyes of the azomethine, oxazine, triarylmethane, phthalocyanine, anthraquinone and azo series are indicated, those of the last two series being preferred especially azo dyes which do not contain sulphonic acid groups and which are derived from benzenic diazo components and 2-naphthol and its 3- carboxylic acid as coupling components and have X as a radical of a secondary heterocyclic or low molecular weight aliphatic amine or a salt thereof, advantageously a salt of a mineral acid, or a radical of a quaternary ammonium salt of a tertiary aliphatic amine of low molecular weight or of a heterocyclic amine bearing a positive charge on the nitrogen atom.  Indicated as dyes of the anthroquinone series are arylaminoanthraquinones in which an acetyl group is attached to the aryl nucleus, obtainable by reacting halogenanthraquinones with an appropriate arylamine or by reacting an arylaminoanthraquinone with acetyl chloride, or acylaminoanthraquinones of which the acetyl group is attached to the carboxylic acid radical, obtainable by reacting an anthraquinone carboxylic or sulphonic acid chloride with the corresponding amine. Representative of many specified anthraquinone reactants are 1- chlor-, 1, 5- dichlor -4, 8- dihydroxy-, 1-amino -2, 4- dibrom- and 1- cyclohexylamino -4-bromanthraquinones, 4- brom -N- methylanthrapyridone, 1- amino -4- bromanthraquinone -2- carboxylic or sulphonic acids, which may be treated with m- or paminoacetophenone or 1- amino -4- acetylnaphthalene, and 1- amino-, 1, 5- diamino- and 1- amino -4- (41-aminophenyl-amino)- anthraquinones, which may be treated with m- or pacetylbenzoyl chloride, and the acid chlorides of 1- aminoanthraquinone and 1, 4-diaminoanthraquinone -2- carboxylic and -sulphonic acids which may be reacted with m- or p-aminoacetaphenone or with aromatic amines, free from keto groups, the products of the last mentioned reaction being further reacted with acetyl chloride.  Phthalocyanine reactants may be obtained by treating copper phthalocyanine sulphonic acid chlorides with m- or pamino acetophenone or acetyl radicals may be introduced into copper phthalocyanine tetracarboxylic acid anilide or tetraphenyl copper phthalocyanine.  In the azo series the acetyl groups may be introduced into aminoazo dyes by acylating with 1- acetylbenzene -3- or -4- carboxylic acid chloride or methylphenyl or -naphthyl ketones may be diazotised and coupled with such components as 1- and 2- naphthol, 1- naphthol -4-sulphonic acid, 2- naphthol -3- carboxylic acid arylides, acetocetic acid arylides, pyrazolones and aminophenols and -naphthols or by diazotising such compounds as aniline, benzidine, 4- aminodiphenyl, 2- naphthylamine, 4- sulphoaniline, 1- naphthylamine -3- sulphonic acid, 4, 41- diaminodiphenyl -3, 31- disulphonic acid and anthranilic acid and coupling with components containing methyl ketone groups e.g. #s-, m- and phydroxyacetophenone, 1- hydroxy-2, 4- diacetylbenzene, 1- hydroxy -2- acetylnaphthalene or the reaction products of 2-naphthol -3- carboxylic acid chloride with aminoacetophenones. Formaldehyde reagents specified are formaldehyde, paraformaldehyde, polyhydroxymethylene, formaldehyde diethyl acetal, N, N1- dipiperidinomethane, N- methylol -N-methylaniline, N- methylolurea, N- methylolacetamide and the ethyl ether of dimethylmethylolamine. Specified amines include dimethylamine, N- methyl-cyclohexyl- and -benzylamine, N- methylaniline, N, N- dimethylaniline, piperidine, piperazine, morpholine, triethylamine, triethanolamine, pyridine and quinoline.  The reaction may be effected in a variety of solvents, e.g. water, acetic acid, dioxane, nitrobenzene and N- methylpyrrolidine.  The amine itself may be the solvent.  An excess of formaldehyde and amine is usually present.  A temperature of 20 DEG -150 DEG C. is preferred.  From a basic reaction medium the dyes may be isolated as free bases or converted into salts by the addition of such acids as hydrochloric, phosphoric, formic, lactic, oxalic and tartaric acids.  The condensation may take place in an acid medium. Dyes obtained from secondary amines may be quaternated by reaction e.g. with dimethyl sulphate or p-toluene sulphonic acid esters.  The dyes may also be obtained by using components which contain methyl ketone groups and have already been reacted with formaldehyde and amines prior to dye formation.  Thus in the anthraquinone and phthalocyanine series the methyl ketone amine components indicated above may be replaced by their reaction products with formaldehyde and amines and in the azo series diazo components such as omega-dimethylamino-and -piperidylamino -maminopropiophenone and coupling components such as omegadimethylamino- and -piperidylaminoparahydroxypropiophenone may be used.  The dyes dye and print materials such as silk, wool, cellulose acetate, linear polyamides and polyesters, polyacrylonitrile, copolymers of acrylonitrile with other vinyl compounds, leather and paper.  The dyes are especially suitable for native and regenerated cellulose. Examples are provided of the preparation of the dyes and their use in dyeing processes.  Red, yellow and blue shades are obtained.