Patent GB-873003-A (GB)
Title: Carboxylic acid amide derivatives of azo-dyestuffs and their manufacture and use
IPC: C09B43/32
Filed: 1958-05-15
Abstract: Lacquers, lacquer-formers, plastic compositions, pigment-printing compositions, masses for spinning artificial filaments, solutions and products of cellulose esters or ethers, viscose, polyamides, polyurethanes, aminoplasts, phenoplasts, polystyrene, polyethylene, polyacrylates, rubber or silicone resins are pigmented by incorporating in them an azo-dyestuff which is free from groups imparting solubility in water and is of the formula: R2-NHCO-B-N=N-A-N=N-B-CONH-R2  in which A is the residue of a coupling component containing two enolizable keto-methylene groups in adjacent positions to the azo groups, the B groups are identical and represent a benzene or diphenyl residue, and R2 is an aryl residue. The residue A may be that of a dipyrazolone compound, e.g. a residue in which two pyrazolone groups are connected through a phenylene or diphenylene group, or it may be a residue containing two aceto-acetyl groups, e.g. the residue:  <FORM:0873003/IV (a)/1> in which R is a benzene or diphenyl residue, preferably a benzene residue bound to the -NH-groups in the 1, 4-positions and containing in the nucleus at least one substituent such as a halogen atom or alkyl or alkoxy group.  In an example, polyvinyl chloride, dioctyl phthalate and dyestuff of the formula:  <FORM:0873003/IV (a)/2> are stirred together, repeatedly rolled in a two-roller callender at 140 DEG C., and then formed into a film having a reddish-yellow colour which is fast to light and migration.  The dyestuff used was obtained by coupling diazotized 4-chloro-3-aminobenzoic acid (2 moles) with 2, 5-bis-(aceto-acetylamino)-1, 4-dimethylbenzene, converting the dicarboxylic acid so obtained into the acid chloride, and forming a diamido compound by reaction with aniline. Many other dyestuffs of the stated general formula are described or indicated by means of listed diazo components, coupling components, and arylamines used in forming the diamido compounds. Pigment printing compositions containing urea-formaldehyde or melamine-formaldehyde condensation products, or polyvinyl chloride or acetate are mentioned.  For the production of water-dispersible preparations, sulphite cellulose waste liquor may be used as medium in which the mechanical dispersion of the pigment is effected, and for the production of cellulose acetate spinning solutions there may be used, as dispersion medium, cellulose acetate containing a salt of dinaphthyl methane disulphonic acid and a small proportion of solvent.ALSO:Bis-acetoacetyl compounds of aromatic diamines are used as coupling components in the production of azo dyes.  They may be obtained by reacting one molecular proportion of the appropriate diamine with two molecular proportions of an acetoacetic ester or of diketene.  The aromatic amine is preferably a 1:4-phenylene diamine having at least one other nuclear substituent, e.g. a halogen atom or an alkyl or alkoxy group. Examples of specified bis-acetoacetyl compounds are those of the following diamines:-1:4-diaminobenzen, 1:4-diamino-2-bromo (or chloro)-benzene, 1:4-diamino-2:5-dichlorobenzene, 1:4-diamino-2:5-dimethylbenzene, 1:4-diamino-2:5-dimethoxybenzene, 4:41-diamino-diphenyl, 4:41-diamino-azobenzene, 3:31:5:51-tetrachloro-4:41-diamino-diphenyl, 4:41-dimethoxy-3:31-diamino-diphenyl-methane, 4:41 - diamino-diphenylamine, 4:41-diamino-diphenyl oxide (or ketone), 2:8-diamino-chrysene, 4:11-diaminofluoranthene, 2:6- or 1:5-diamino-naphthalene, 2-(41-aminophenyl)-6-amino-benzthiazole, and amines of the formulae p  <FORM:0873003/IV (b)/1> and <FORM:0873003/IV (b)/2>ALSO:The invention comprises azo dyestuffs which are free from groups imparting solubility in water and correspond to the general formula:-R2-NHCO-B-N=N-A-N=N-B-CONH-R2 in which A is the residue of a coupling component containing two enolizable keto-methylene groups in an adjacent position to the azo groups, the B groups are identical and represent a benzene or diphenyl residue, and R2 is an aryl residue.  The dyestuffs may be obtained by condensing two moles of a primary aryl monoamine, free from groups imparting solubility in water, with one mole of a dihalide of a dicarboxylic acid of the formula:-HOOC-B-N=N-A-N=N-B-COOH which contains, apart from the two carboxylic groups, no groups imparting solubility in water.  The dicarboxylic acid may contain as the group A the residue of a dipyrazolone compound, e.g. a residue in which two pyrazolone groups are connected through a phenylene or diphenylylene group, or the acid may be of the formula:-  <FORM:0873003/IV(c)/1> in which R and B are benzene or diphenyl residues; B is preferably a benzene residue, and R is a benzene residue bound to the -NH-groups in the 1, 4-positions, and containing in the nucleus at least one substituent such as a halogen atom or alkyl or alkoxy group.  The dicarboxylic acid may be obtained by coupling two moles of a diazotized benzene or diphenyl monoamino-monocarboxylic acid with one mole of a coupling component containing two enolizable keto-methylene groups, e.g. a compound of formula:-CH3 CO CH2 CO-NH-R-NH-CO CH CO2 CH3 which itself may be obtained by the reaction of diketene or acetoacetic acid ester with an aromatic diamine.  Many bis-acetoacetyl compounds of diamines are listed including those of 1, 4-diaminobenzene, 1, 3-diamino-4-methoxy-benzene, 1, 4-diamino-2, 5-dichlorobenzene, 4, 41-diamino-diphenyl, 4 : 41-diamino-azobenzene, 4, 41-diamino-diphenylamine, 2, 8-diamino-chrysene, 4, 11-diamino-fluoranthene, 2, 6-diaminonaphthalene, and 2-(41-aminophenyl)-6-aminobenzthiazole.  Among listed diazo components are 1-aminobenzene-3-carboxylic acid, 1-amino-2-chlorobenzene- 4-carboxylic acid, 1-amino- 2-chloro- 5-methoxybenzene- 4-carboxylic acid, 1-amino- 2-nitrobenzene- 5-carboxylic acid, and 41-aminodiphenyl- 4-carboxylic acid.  The azo-dicarboxylic acids may be converted into their bromides or chlorides by treatment with a phosphorous halide, preferably in presence of an organic solvent.  Many primary aromatic amines, which may be used for forming the amides of the azo-dicarboxylic acids, are mentioned, including aniline, toluidines, xylidines, chlor-, brom-, and nitro-anilines and alkylate anilines, 3-trifluoro-methyl aniline, 3-cyanoaniline, 2- chloro- 5-methylaniline, 2- chloro- 5- trifluoromethylaniline, 4-chloro-2-methoxyaniline, anilines containing carboxylic ester groups, aminonaphthalenes, aminoanthraquinones, and aminopyrenes. Formation of the carboxylic acid amides is preferably carried out in an inert organic solvent at a raised temperature.  The dyestuffs obtained may be used as pigments for dyeing plastic materials, particularly polyvinyl compounds.  They may be used for pigment printing of textile fibres, paper, glass fabrics, and other materials, by methods in which the pigment is fixed by means of an adhesive.  The pigments may be incorporated in spinning masses from which are obtained filaments of regenerated cellulose, cellulose esters or ethers, polyamides, or polyurethanes. They may be incorporated in lacquers, or plastics of cellulose acetate or nitrate, natural or synthetic resins, e.g. aminoplasts, phenoplasts, polystyrene, polyethylene, polyacrylates, rubber, casein, or silicone resins.  They may be used in the preparation of pencils, cosmetics, and laminated sheets.