DE1235465B - Process for the preparation of carboxylic acid amide derivatives of azo dyes - Google Patents

Description

Process for the preparation of carboxamide derivatives of azo dyes It has been found that valuable, new carboxamide derivatives of azo dyes are obtained if carboxylic acid halides of the formula which are free from water-solubilizing groups are used in which R 1 denotes a benzene radical which is bonded in the 1-position to the azo group and in the 3-position to the carbonyl group and which has a halogen atom, an alkoxy or phenoxy group in the 6-position, R2 is a naphthalene radical, in which the azo, Oxy and carboxylic acid halide groups are in the 1,2,3-position to one another, means with an amine of the formula in which X and Y are alkyl groups or, in particular, halogen atoms, for example bromine or preferably chlorine, and in which, if X is a halogen atom, Y can also be an alkoxy group, and the benzene nucleus B can be further substituted, for example by halogen , Alkyl or alkoxy.

In the present process, groups of water-solubilizing groups, such as sulfonic acid groups, sulfonamide groups and - COOH groups, free starting materials to use.

The azocarboxylic acids from which the used as starting materials Acid halides of the formula (1) given are produced, if the diazo compound of an m-aminobenzenecarboxylic acid with a 2,3-oxynaphthoic acid clutch.

Preferred m-aminobenzenecarboxylic acids are those of the formula considered in which Z, a halogen atom, an alkoxy or phenoxy group and Z, 2 is a hydrogen or a halogen atom. The aminobenzenecarboxylic acid of the formula is of particular interest The 2,3-oxynaphthoic acid to be used as the coupling component can optionally be substituted in the benzene ring free of the carboxylic acid group, for example by a halogen atom, in particular a bromine atom in the 6-position, an alkoxy or alkyl group. However, thanks to its easy accessibility, the unsubstituted 2,3-oxynaphthoic acid is expediently used.

The azodicarboxylic acids obtained are treated with Niit # eln, the are able to convert carboxylic acids into their halides, e.g. B. the chlorides or bromides, transferred, especially with phosphorus halides, such as phosphorus pentabromide, or phosphorus trichloride or pentachloride, phosphorus oxyhalides and preferably with thionyl chloride.

Treatment with such acid halogenating agents becomes appropriate in indifferent organic Solvents such as chlorobenzenes, z. B. mono- or dichlorobenzene, toluene, xylene or nitrobenzene carried out.

It is usually the case in the production of the carboxylic acid halides expedient to initially add the azodicarboxylic acids prepared in an aqueous medium dry or azeotropic water by boiling in an organic solvent to free. This azeotropic drying can, if desired, immediately before Treatment with the acid-halogenating agents can be carried out.

The new dyes obtainable by the present process correspond to the general formula wherein Ri and R @, X, Y and B have the meaning given. They are valuable red pigments. Dyes of the formula are of particular interest where X and Y are chlorine atoms or methyl groups and Zi, Z.2 and B are as defined. These are distinguished by particularly great color strength and particularly good lightfastness and migrationfastness and also by high temperature resistance and solventfastness.

The pigments obtained by the present process can be used for a wide variety of pigment applications, e.g. B. in finely divided form for dyeing from rayon and viscose or cellulose ethers and esters or from super polyamides or super-polyurethanes or polyesters in the spinning mass and for production of colored lacquers or lacquer formers, solutions and products made from acetyl cellulose, Nitrocellulose, natural resins or synthetic resins such as polymerization or condensation resins, z. B. aminoplasts, alkyd resins, phenolic plastics, polystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyacrylic, rubber, casein, silicone and silicone resins serve well. In addition, they can be advantageous in the production of dyes, cosmetic Use specimens or laminating plates. Compared to comparable dyes the German patent specification 602 064 show the dyes obtainable according to the invention the advantage of better migration authenticity.

In the following example, unless otherwise stated, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius. EXAMPLE 20.3 parts of the dye obtained by coupling diazotized 5-amino-2,4-dichlorobenzoic acid with 2,3-oxynaphthoic acid are mixed with 250 parts of o-dichlorobenzene, 0.5 parts of dimethylformamide and 12 parts of thionyl chloride heated with stirring to 115 to 120 ° for 3 hours. After the reaction mixture has cooled, the uniformly crystalline dicarboxylic acid chloride of the dye is isolated by filtration and dried in vacuo at 55 to 60 minutes. 22 parts of this diacid chloride are placed in 1000 parts of o-dichlorobenzene with stirring at 100 °. A warm solution of 28.5 parts of 2,5-dichloro-4-benzoylaminoaniline in 300 parts of o-dichlorobenzene is poured into this. The mixture is stirred at 140 to 145 ° for 16 hours. The pigment formed is then filtered at 120 ", washed with hot o-dichlorobenzene, hot benzene and methanol and dried in vacuo at 70 to 80 ' real migration, scarlet tones.

The product thus obtained has the following formula The following table describes further pigment dyes which were obtained in the specified route and which likewise have very good fastness properties. Column I indicates the diazo component, column II the coupling component, column III the condensation base and column IV the color of the polyvinyl chloride film colored with the pigment. No. 1 il 111 IV 1 5-Amino-2,4-dichloro-2,3-oxynaphthoe-2,5-dimethyl-4-benzoylaminoaniline scarlet benzoic acid 2 same. Same. 5-chloro-4-benzoylamino-2-methoxy-scarlet red aniline 3 The same. The same 2,5-dichloro-4- (4'-chloro) -benzoylamino-scarlet red aniline 4 Same. Same. 2,5-dichloro-4- (2 ', 4'-dichloro) -benzoyl- scarlet red aminoaniline 5 The same. The same 2,5-dimethyl-4- (2 ', 5'-dichloro) -benzoyl-scarlet red aminoaniline 6 The same. The same 2,5-dichloro-4- (2 ', 5'-dichloro) -benzoyl-bordo aminoaniline 7 the same. Likewise 2,5-dimethyl-4- (4'-chlorobenzoylamino red aniline 8 Lik. Likewise 2,5-dimethyl-4- (2 ', 4'-dichloro) -benzoyl-scarlet red aminoaniline 9 Lik. Likewise 2-methoxy-4- (4'-chloro) -benzoylamino-scarlet red 5-chloroaniline 10 as well as 2-methoxy-4, a-naphthoylamino-scarlet red 5-chloroaniline 11 5-Amino-4-methoxy- like 2-methoxy-4-benzoylamino-5-chloro-bluish red 2-chlorobenzoic acid aniline 12 as well as 2,5-dichloro-4-benzoylaminoaniline Bordo 13 The same. The same 2,5-dimethyl-4-benzoylaminoaniline bluish-tinted red 14 5-Amino-4-methoxy- like 2,5-dichloro-4- (4'-chloro) -benzoylamino-red 2-chlorobenzoic acid aniline 15 3-Amino-4- (4'-chloro) - likewise. 2-Methoxy-4-benzoylamino-5-chloro-red phenoxybenzoaniline acid 16 Lik. Likewise 2-chloro-4-benzoylamino-5-methoxy-scarlet red aniline 17 the same. The same 2,5-dichloro-4-benzoylaminoaniline red 18 the same. Likewise 2,5-dimethyl-4-benzoylaminoaniline scarlet red - Continuation No. 1 11 111 IV 19 4-Methoxy-3-amino-2,3-oxynaphthoe-2-methoxy-4-benzoylamino-5-chloro-Bordo benzoic acid aniline 20 the same. The same. 2-Chloro-4-benzoylamino-5-methoxy-red aniline 21 The same. The same 2,5-dichloro-4-benzoylaminoaniline Bordo 22 Lik. Likewise 2,5-dimethyl-4-benzoylaminoaniline - ruby 23 The same. The same 2,5-dichloro-4- (4'-chloro) -benzoylamino-red aniline 24 the same. The same 2,5-dichloro-4- (2 ', 5'-dichloro) -benzoyl-Bordo aminoaniline 25 the same. Likewise 2,5-dichloro-4- (2 ', 4'-dichloro) -benzoyl-scarlet red aminoaniline 26 4-Ethoxy-3-amino-like 2,5-dichloro-4-benzoylaminoaniline Bordo benzoic acid 27 the same. Likewise, 2,5-dimethyl-4-benzoylaminoaniline ruby 28 same. Same. 2,5-dichloro-4- (2 ', 4'-dichloro) -benzoyl- red aminoaniline 29 the same. Likewise 2,5-dimethyl-4- (4'-chloro) -benzoyl-ruby aminoaniline 30 Same. Same. 2,5-Dimethyl-4- (2 ', 4'-dichloro) -benzoyl- red aminoaniline 31 4-fluoro-3-amino-like. 2-methoxy-4-benzoylamino-5-chloro-scarlet red benzoic acid aniline 32 the same. Likewise 2-chloro-4-benzoylamino-5-methoxy-scarlet red aniline 33 Lik. Likewise 2,5-dichloro-4-benzoylaminoaniline scarlet red 34 the same. Likewise 2,5-dimethyl-4-benzoylaminoaniline scarlet red 35 4-chloro-3-amino-like. 2-methoxy-4-beiiioylamino-5-chloro-scarlet red benzoic acid 36 Lik. Likewise 2-chloro-4-benzoylamino-5-methoxy-scarlet red aniline 37 the same. Likewise 2,5-dichloro-4-benzoylaminoaniline scarlet red 38 The same. The same 2,5-dimethyl-4-benzoylaminoaniline scarlet red 39 Lik. Likewise 2,5-dichloro-4- (4'-chloro) -benzoylamino-orange aniline 40 Same. Same. 2,5-dichloro-4- (2 ', 4'-dichloro) benzoyl orange aminoaniline 41 the same. Likewise 2,5-dimethyl-4- (4'-chloro) -benzoyl-scarlet red aminoaniline 42 same. Same. 2,5-dimethyl-4- (2 ', 5'-dichloro) -benzoyl- red aminoaniline 43 4-Bromo-3-amino-like 2,5-dichloro-4-benzoylaminoaniline scarlet red benzoic acid 44 the same. The same. 2-Methoxy-4-benzoylamino-5-chloro-red aniline 45 Same as 2.5-dichloro-4-benzoylaminoaniline orange 46 the same. Likewise 2,5-dimethyl-4-benzoylaminoaniline scarlet red 47 4-Methoxy-3-amino-6-bromo-2-oxy-2,5-dimethyl-4-benzoylaminoaniline ruby benzoic acid 3-naphthoic acid 48 Lik. Likewise 2,5-dichloro-4-benzoylaminoaniline ruby 49 Same. Same. 2,5-dichloro-4- (2 ', 4'-dichloro) benzoyl violet aminoaniline 50 the same. Likewise 2,5-dimethyl-4- (4'-chloro) -benzoyl-ruby aminoaniline 51 the same. Likewise 2,5-dimethyl-4- (2 ', 5'-dichloro) -benzoyl-Bordo aminoaniline 52 4-Amino-3-nitro-2,3-oxynaphthoe-2,5-dichloro-4-benzoylaminoaniline Orange benzoic acid 53 Likewise. Likewise 2,5-dichloro-4- (4'-chloro) -benzoylamino-orange aniline 54 Same as 2,5-dimethyl-4- (2 ', 5'-dichloro) benzoyl orange aminoaniline 55 Likewise, 2,5-dimethyl-4-benzoylaminoaniline brown 56 the same. Likewise 2,5-dimethyl-4- (4'-chloro) -benzoyl-red-orange aminoaniline

Claims (1)

Claim: Process for the preparation of carboxamide derivatives of azo dyes, characterized in that 1 mol of a carboxylic acid halide of the formula which is free from water-solubilizing groups is used in which R 1 denotes a benzene radical which is bonded in the 1-position to the azo group, in the 3-position to the carbonyl group and in the 6-position has a halogen atom, an alkoxy or phenoxy group and R2 is a naphthalene radical in which the azo, oxy - and carboxylic acid halide group are in the 1,2,3-position, means with 2 moles of an amine of the formula condensed, in which X and Y denote alkyl groups or halogen atoms and in which, if X denotes a halogen atom, Y can also represent an alkoxy group and the benzene nucleus B can be further substituted. Considered publications German patent specification No. 602 064. When the application was published, a coloring table with explanations was laid out.