DE1184438B - Process for the preparation of carboxylic acid and sulfonic acid groups-free mono- and disazo dyes - Google Patents

Description

Process for the preparation of carboxylic acid and sulfonic acid group-free Mono- and disazo dyes It is known that carboxylic acid and sulfonic acid groups-free Mono- and disazo dyes generally have a yellow to red or purple intrinsic color have, while such dyes with a pure blue intrinsic color only in a few cases can be obtained with the combination of certain diazo and coupling components.

It has now been found that new, blue, carboxylic acid and sulfonic acid group-free mono- and disazo dyes are obtained if aromatic or heterocyclic diazo compounds or diazoazo compounds with perimidine derivatives of the general formula are obtained couples, in which R 1 and R 2 - optionally bearing further substituents - are aliphatic or aromatic radicals, where R 1 and R 2 together can belong to an iso- or heterocyclic system and R 2 can also mean a hydrogen atom.

The diazo components used for the production of carboxylic acid and sulfonic acid group-free mono- and disazo diazo compounds which can be used the - benzene, naphthalene and heterocyclic series into consideration. Useful heterocyclic Diazo components are, for example, those produced by diazotization of aminothiophenes, Aminothiazoles, aminobenzothiazoles, aminotriazoles and aminobenzotriazoles can be prepared Diazo compounds and their alkyl, alkoxy, nitro and / or carboxylic acid ester derivatives.

Coupling components of the formula given above are, for. B. 1-methylperimidine, 1-ethylperimidine, 1,2-dimethylperimidine, 1,2-diethylperimidine, 1- ethyl - 2 - methylperimidine, 1- methyl - 2 - phenylperimidine, 1 - methyl - 2 - hydroxymethylperimidine and the following perimidine derivatives: Process for the preparation of such perimidine derivatives are, for. B. in den Annalen der Chemie, Vol. 415 (1918), p. 12, in the Journal of the Chemical Society, Vol. 1955, p. 2396, and in the Journal of Organic Chemistry, Vol. 24 (1959), p 420.

The coupling of the diazo compounds mentioned with the perimidine derivatives mentioned is used in the usual way, e.g. B. in aqueous solution or in organic solvents or in mixtures of water and organic solvents. As organic Examples of suitable solvents are dimethylformamide, pyridine, ethanol and N-methylpyrrolidine or ethylene glycol.

The new dyes have the likely formula in which R3 denotes the remainder of one of the diazo compounds given above and Ri and R2 have the same meaning as above.

With the help of the new process, pure blue mono and disazo dyes can be produced Produce in large numbers, as you especially with regard to the diazo components that can be used has many options for modification.

The new blue carboxylic acid and sulfonic acid group-free mono- and Disazo dyes are suitable, especially in finely divided form, for dyeing and .Printing of textile materials such as fibers, flakes, threads, woven and not woven textiles and films made from linear synthetic polyamides and polyurethanes and linear fiber-forming polyesters, such as cellulose 21/2 acetate, Cellulose triacetate, polyethylene terephthalate and polyhexahydroterephthalyl terephthalate.

In contrast to those already described, made from diazotized 1-amino-4-nitrobenzene and perimidine or 2-methylperimidine available monoazo dyes which are cloudy have their own violet color, are the dyes produced by the new process pure blue.

Compared to the azo dye of the formula known from Annalen der Chemie, Vol. 365 (1909), p.91 The dyes obtainable according to the invention are distinguished by a far better ability to be drawn on textile materials made of polyamides and polyesters.

The parts named in the examples are, unless otherwise specified, Parts by weight. Parts of space relate to parts by weight as liters to kilograms. The percentages relate to percentages by weight.

Example 1 8.6 parts of 1-amino-2-chloro-4-nitrobenzene are rubbed with 20 parts by volume of concentrated hydrochloric acid. After standing for several hours, 100 parts of ice are added to the mixture and it is diazotized by adding 17.5 parts by volume of a 23% aqueous sodium nitrite solution. The diazotization mixture is stirred for 2 hours, filtered and a cooled solution of 14 parts of the hydrochloride of the perimidine derivative of the formula is added to the filtrate in 500 parts of hot water. The coupling is completed by gradually flowing in 100 parts by volume of a 50% aqueous sodium acetate solution. The isolated, water-insoluble dye is obtained after drying in the form of a dark blue powder which dissolves in 50% aqueous acetone with a blue color and dyes cellulose-21, / 2-acetate and polyamides in pure blue shades with very good fastness properties .

With 12 parts of 2-methyl-5-methoxy-4-aminoazobenzene as the diazo component a disazo dye is obtained, the polyamides in blue shades of excellent Dyes fastness properties.

If 10 parts are used instead of the coupling component mentioned above 1,2-Dimethylperimidine, dissolved in 250 parts by volume of dimethylformamide, is obtained a dye with similar properties.

Example 2 17 parts of 1-amino-2-methoxy-4-nitrobenzene are rubbed with 25 parts by volume of concentrated hydrochloric acid and, after standing for several hours, this mixture is suspended in a mixture of 250 parts of water and 150 parts of ice. 30 parts by volume of a 23% aqueous sodium nitrite solution are added to this suspension, the whole is stirred for 2 hours at 0 to 5 ° C. and a solution of 21 parts of the compound of the formula is then added to this mixture in a mixture of 20 parts of concentrated hydrochloric acid and 400 parts of water. In the course of one hour, 70 parts by volume of a 50% strength aqueous sodium acetate solution are stirred into this reaction mixture and the resulting dye is then worked up as described in Example 1. It is obtained in the form of a dark blue powder which dissolves easily in dimethylformamide and dyes polyethylene terephthalate in genuine blue-gray shades and cellulose 21/2 acetate in blue shades of similar fastness properties.

If 17 parts of 1-amino-2-chloro-4-nitrobenzene are used as the diazo component in the same way, so becomes a dye of similar properties; obtain.

Example 3 10 parts of 2-aminothiazole are 100% in 40 parts Dissolved sulfuric acid; the temperature should not rise above + 5 ° C. In the course of 60 minutes, the solution is set from 0 to + 5 ° C. with a solution of 10.4 parts Potassium nitrate in 45 parts of concentrated sulfuric acid, then stir the reaction mixture 60 minutes at room temperature, it is heated again to 90 ° C. and allowed to cool.

The resulting sulfuric acid solution of 2-amino-5-nitrothiazole is treated with a mixture of 125 parts of anhydrous acetic acid and 25 parts of anhydrous; Diluted propionic acid. The resulting mixture is allowed to flow into a nitrosylsulfuric acid solution prepared from 100 parts of concentrated sulfuric acid, 8.5 parts of sodium nitrite, 125 parts of anhydrous acetic acid and 25 parts of anhydrous propionic acid, with cooling and vigorous stirring, 'where: a temperature of 0 to + 5 ° C holds .. Then the mixture is stirred for 3 hours at this temperature; give 20 parts of urea to destroy excess nitrosylsulfuric acid and then a solution of 22 parts of the compound of the formula in a mixture of 125 parts of anhydrous acetic acid and 25 parts of anhydrous propionic acid. 400 parts of anhydrous sodium acetate are added to the mixture and a temperature of at most + 5 ° C. is maintained during the diazotization and coupling. After 2 hours, the reaction mixture is poured into ice water, stirred for a further 12 hours and the azo dye formed is filtered off. Wash it thoroughly with water and dry it at about 60 ° C. The dye is obtained in the form of a dark blue powder which dissolves in 80% strength aqueous acetone with a blue-green color and dyes polyamides in blue-green shades with excellent fastness properties. If 21 parts of the compound of the formula are used instead of the abovementioned azo component or 20 parts of 1,2-dimethylperimidine, the result is dyes with similar properties. All these dyes color cellulose 21/2 acetate in blue-green tones which are extremely lightfast and fume-proof.

Claims (1)

Claim: Process for the preparation of carboxylic acid and sulfonic acid group-free mono- and disazo dyes, characterized in that aromatic or heterocyclic diazo compounds or diazoazo compounds with perimidine derivatives of the general formula are used couples, in which R1 and R2 - optionally carrying further substituents - denote aliphatic or aromatic radicals, where R1 and R2 together can belong to an iso- or heterocyclic system and R2 can also denote a hydrogen atom. Considered publications Annalen der Chemie, Vol. 365 (1909), p. 91. When the application was announced, a coloring table was laid out with explanations.