Patent GB-780031-A (GB)
Title: Acid amide derivatives of azo-dyestuffs and process for making them
IPC: C09B43/38
Filed: 1953-12-16
Abstract: Acid amide derivatives of azo compounds are prepared by a process wherein an amine which is free from groups imparting solubility in water and contains at least two reactive amino and contained at least two reactive amino groups is condensed at each of the amino groups with a carboxylic acid halide free from groups imparting solubility in water, at least one of the amino groups being condensed with a carboxylic acid halide of an azo compound of which at least one azo linkage is bound on one side to an aryl nucleus which contains a carboxylic acid ester group ortho to the azo linkage, and on the other side to the residue containing the carboxylic acid halide group.  Specified amines are mononuclear diamines such as 1:4-diaminobenzene which may be substituted by nitro, alkoxy or alkyl groups or halogen atoms; binuclear amines such as 4:41-diamino-diphenyl and the 3:31-dichloro- or -dimethyl- or -dialkoxy- or 3:5:31:51 - tetramethyl- or -tetrachloro-derivatives thereof; binuclear amines of the benzene series wherein the benzene nuclei are linked by various bridging members, for example by oxygen, or -SO2- as in 4:41-diaminodiphenylsulphone and 3:31 - diamino - 4:41 - dichloro- or -dimethoxy - diphenylsulphone; or -CO- as in 3:31-diaminodiphenyl ketone and 3:31-diamino-4:41-dichloro- or -dimethoxy-diphenyl ketone; or -CH2- as in 3:31-diaminodiphenylmethane, 3:31- or 4:41-diamino-4:41- or 3:31-dichlorodiphenylmethane and 4:41-diamino-3:5:31:51 -tetrachlorodiphenylmethane; or by -NHCO-, -NHCONH-, -SO2NH-, -CH=CH-, -CH2-CH2-, -HNCOC2H4CO-, -NH-or -N=N-; 2:6- or 1:5-diaminonaphthalenes and 2 - (41 - aminophenyl) - 6 - aminobenzthiazole.  The acid halides of the azo dyestuffs are prepared by reacting the azo dyestuff, preferably in the dry state in the presence of an inert solvent such as dimethyl-formamide, chlorobenzenes, toluene, xylene, benzene or nitrobenzene, with an acid halide forming agent such as phosphorus pentabromide, phosphorus tri- or penta-chloride, phosphorus oxyhalides and thionyl chloride. Specified components for use in the preparation of the azo dyestuffs, in addition to those specified in the examples are:-diazo components, 4-chlorophenyl o-aminobenzoate and methyl 2-amino-3-naphthoate; coupling components, N-alkyl derivatives of 2-hydroxycarbazole-3-carboxylic acid, 2-hydroxyanthracene - 3 - carboxylic acid, 3-hydroxy - diphenyl - sulphide - 2 - carboxylic acid, 1 - acetoacetylaminobenzene - 2 - or - 3 - or -4-carboxylic acid and 1-benzoylacetylaminobenzene-3- or -4-carboxylic acid.  The condensation of the carboxylic acid halides with the amines is preferably conducted in an anhydrous medium using solvents such as dimethylformamide, toluene, mono-, di- and tri-chlorobenzenes and nitrobenzene, with removal of the hydrogen halide formed in the condensation by continuous distillation or by the addition of an acid-binding agent such as sodium acetate, pyridine or ammonia. The products of the invention are pigments and may be used in pigment printing and in colouring synthetic resins and cellulose derivatives (see Group IV (a)).  Preparations of the pigments capable of water-dispersion may be made using sulphite cellulose waste liquor or salts of naphthyl-methane disulphonic acid.  In examples and a Table the acid chlorides of the azo dyestuffs specified below are condensed with the amines specified below. Azo dyestuffs specified are:-methyl or ethyl or phenyl o-aminobenzoate --> 2-hydroxy-3-naphthoic acid; 4- or 5-chloro- or 4:6 - dichloro - 1 - aminobenzene - 2 - carboxylic acid methyl ester --> 2-hydroxy-3-naphthoic acid; methyl o-aminobenzoate --> 1-(21-chlorophenyl)- or -phenyl-5-pyrazolone-3-carboxylic acid; ethyl 2-amino-3-naphthoate --> 2-hydroxy-3-naphthoic acid; ethyl or n-butyl o-aminobenzoate or 4- or 5-chloro- or 4:6-dichloro - 1 - aminobenzene - 2 - carboxylic acid methyl ester --> 1-phenyl-3-methyl-5-pyrazolone-41-carboxylic acid; methyl o-aminobenzoate --> 2-hydroxy-carbazole-3-carboxylic acid or 2-hydroxy-11-benzo[a]carbazole-3-carboxylic acid or 3-hydroxydiphenylene-oxide-2-carboxylic acid or 3-acetoacetylamino-4-chlorobenzene-1-carboxylic acid; 4-chloro-1-aminobenzene-2-carboxylic acid methyl ester --> 3-acetoacetylamino - 4 - methoxybenzene - 1 - carboxylic acid; and 1-amino-2-nitro-4-chlorobenzene --> 5 - ethoxy - 1 - aminobenzene - 2 - carboxylic acid methyl ester --> 2-hydroxy-3-naphthoic acid (the first coupling in the preparation of this dyestuff is carried out in aqueous methanol).  Amines specified are:-1:4- or 1:3-diaminobenzene, 3:31-dichloro- or -dimethyl- or -dimethoxy - 4:41 - diaminodiphenyl, 4:41 - diaminodiphenyl, 1:5-diaminonaphthalene, di-(p-aminobenzenesulpho) - imine, 1:3 - diamino - 4:6 - dimethylbenzene, 1:4 - diamino - 2:5 - dichloro- or -diethoxy-benzene, 1:6-di(p-aminobenzoylamino) - n - hexane, 3:31 - dimethoxy-4:41 - diamino - 6:61 - dimethyl - 1:11 - azobenzene, 4:11-diaminofluoranthene, 3:6:31:61-tetrachloro - 4:41 - diaminodiphenylmethane, 2:21 - dichloro - 4:41 - diamino - diphenylmethane, 3:8 - diaminopyrene, 4:41 - diamino-1:11 - azobenzene, 4:41 - diaminodiphenylurea, 4:41-diaminodiphenylsulphone, 2:8-diaminochrysene, 4 - aminobenzene - 1 - carboxylic acid - 41 - aminophenyl ester, 1 - methyl - 2:4 - diaminobenzene, 4:41 - diaminodiphenyl ether and 2:4:41-triaminodiphenyl.  Specification 528,268, [Group IV], is referred to.  Reference has been directed by the Comptroller to Specification 427,208, [Group IV].ALSO:Acid amide derivatives of azo compounds (see Group IV (c)) are used as pigments in colouring synthetic resins and cellulose derivatives.  They are particularly used in colouring polyvinyl compounds, for example, by incorporation into polyvinyl foils during rolling.  The pigments are also used in a finely dispersed form for colouring artificial silk or viscose or cellulose ethers or esters or superpolyamides or superpolyurethanes in the spinning mass and also in colouring lacquers and lacquer formers, solutions and products from acetylcellulose, nitrocellulose, aminoplasts, phenoplasts, polystyrene, polyethylene and silicones.  In an example, the pigment obtained by the condensation of 2 mols. of the acid chloride of the monoazo dyestuff, methyl o-aminobenzoate --> 2-hydroxy-3-naphthoic acid, with 1 mol. of 1 : 4-diaminobenzene is mixed with polyvinyl chloride and dioctyl phthalate and rolled to a reddish-brown foil. Specifications 427,208 and 528,268, [both in Group IV], are referred to.