DE1120041B - Process for the production of azo dyes - Google Patents

Description

Process for the preparation of azo dyes The invention relates to a process for the preparation of azo dyes which are free from solubilizing groups, such as sulfonic and carboxylic acid groups, and of the formula correspond. In this formula, R, an amino, acylamino, alkylsulfonylamino or arylsulfonylamino group, R2 an amino, acylamino, alkylsulfonylamino or arylsulfonylamino group, R3 and R4 hydrogen, a low molecular weight alkyl or oxyalkyl group or together part of a heterocyclic ring and X. Hydrogen, chlorine or bromine. The metal complex compounds of such dyes are also included.

Azo dyes that differ from known azo components and diazo components derive and contain sulfonic acid amino substituents are already known. Such Dyes are usually used in metallized form and generally contain free sulfonic acid groups, which mainly cause a certain water solubility should be used when dyeing wool, polyamides and similar fiber materials. the However, most dyes that contain free sulfonic acid groups have the Disadvantage that they do not exhaust neutral dye baths. When they come out of a weak acidic dye baths are used to produce the sulfonated, metallized monoazo dyes often uneven colorations. Furthermore, the washing and lightfastness of the means of this Colorings obtained by dyes are not entirely satisfactory. The present Invention is based on the finding that dyes that are free of carbon and sulfonic acid groups and correspond to the above formula, surprisingly have improved properties that make them very useful for technical applications do. The dyes are characterized by excellent lightfastness and washfastness Wool and polyamides are characterized and also have a superior quality Leveling ability. You can easily choose from neutral or wool and polyamides weakly acidic baths. Dyes of the above formula result from the so far known monoazo dyes the greenest blue tones on wool and Polyamides, these tones also having a superior lightfastness and / or washfastness own. Such green-blue tones cannot be obtained by mixing.

The process according to the invention for the preparation of azo dyes is now characterized in that an aminohydroxybenzene of the general formula wherein X is hydrogen, chlorine or bromine, diazotized and with an azo component of the formula couples, in which R3 and R4 are hydrogen, a low molecular weight alkyl or oxyalkyl group or together are a heterocyclic radical and R5 is an acylamino, alkylsulfonylamino or arylsulfonylamino group, the nitro group is reduced to the amino group and the amino group is then optionally acylated or reacted with an alkyl or arylsulfonyl chloride and / or hydrolyzed the radical R5 to the free amino group.

It has been found that azo components in which RS is an NH2 group means not delivering the results you want. Probably kick it Couplings in the 0 position to the amino group, resulting in dye mixtures. Dyes of the above formula in which R2 is an NHZ group are identified by Hydrolysis of the RS residue obtained after coupling. Dyes of the above formula, in which R1 is an acylamino, alkylsulfonylamino and arylsulfonylamino group, by subsequent acylation or reaction with an alkyl or aryl sulfonyl chloride obtain.

Azo components useful for the present invention can e.g. B. be prepared in that 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonyl chloride are reacted with ammonia or a suitable primary or secondary base, such as dimethylamine, ethylamine, isopropylamine, ethanolamine, diethanolamine, butylamine, Morpholine, piperidine. Other 1-acylamino, 1-alky1-sulfonylamino- and 1-arylsulfonylamino-8-hydroxynapthalene-3,5-disulfonic acid amides are used in a similar manner Way made. So RS can be an acetylamino, propionylamino, butyrylamino, Benzoylamino, substituted benzoylamino, methylsulfonylamino, ethylsulfonylamino, Benzenesulfonylamino, or substituted benzenesulfonylamino group mean. In of the above formula, R3 and R4 can be the same or different and, for. B. for hydrogen, low molecular weight alkyl groups, such as methyl, ethyl, propyl, isopropyl or Butyl group, oxyalkyl groups, such as the oxyethyl, oxypropyl or oxybutyl group, or together represent the morpholine or piperidine residue. The Rl residue in the invention produced dyes can be used for the same or different acylamino, alkylsulfonylamino or arylsulfonylamino groups such as RS.

The azo dyes of the above formula can optionally be used in a known manner With an agent that donates metal in an acidic, neutral or alkaline medium are treated, where appropriate, increased pressure and / or increased temperatures can be applied. The metallizing agents can be used as metal-releasing compounds containing metals with an atomic weight of 52 to 66, e.g. B. copper, nickel, iron, cobalt and especially chromium. These funds can be used in Form of their oxides, hydroxides or salts z. B. of inorganic or organic Acids such as hydrochloric acid, sulfuric acid, hydrofluoric acid, formic acid, acetic acid, Tartaric acid or acetylic acid can be used. The metallizing agents can alone or in the presence of other compounds, which optionally with these metallizing agents enter into a complex compound, can be used, e.g. B. ammonia, pyridine, ethylenediamine, Ethanolamine, formamide, formic acid, acetic acid, oxalic acid, aliphatic and aromatic compounds containing oxy groups, such as alcohol, glycerine, aliphatic oxycarboxylic acids, such as tartaric, lactic and citric acid, aromatic oxycarboxylic acids, such as saccylic acid, Sugar, cellulose derivatives, phenols, tannins and lignins, soluble salts of sulfonic and carboxylic acids of the aliphatic, aromatic and hydroaromatic series, inorganic Metal, alkali metal and alkaline earth metal salts, oxides and hydroxides. Likewise can Dispersants, solvents and other auxiliaries are used in metallization will.

The metallization can be carried out with one or more metallizing agents Metallizing means are carried out simultaneously or in succession, wherein mixed metal complex compounds of the azo compounds can be obtained. The metallizing agent can be applied so that the compound obtained is a complex compound or a mixture of complex compounds of the azo dye represents the less contain than 1 atom, 1 atom, or more than 1 atom of the metal. So can the received Metal complex compound a complex compound of a metal atom of 1/2 to 1 or Represent 2 or more molecules of the azo dye, depending on the valency and the complex-forming properties of the metal and the reaction relationships.

The dyes of the invention can be prepared by the diazotization and / or coupling and / or metallization in bulk, on one Substrate or in situ. The dyes can be used for dyeing (dyeing, Pigmentation) can be used in one piece or on the fiber. It'll be excellent Results obtained when these dyes are from neutral or slightly acidic aqueous Bath can be dyed on wool or polyamides. The dyes can also be used for dyeing other materials can be used, e.g. B. for silk, leather, mixed fibers, natural and synthetic materials in bulk, film or fiber form, such as cellulose esters or ethers, polyesters, copolymers or proteins. You can also go for coloring or pigmentation of natural or artificial resins and plastics in substance, organic solvents, stains, varnishes and lacquers.

The process according to the invention is described in more detail by the following examples. Unless otherwise stated, parts stand for parts by weight; the ratio of parts by weight to parts by volume corresponds to the ratio of grams to cubic centimeters. 1. The preparation of the azo component 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid-N, N'-dimethylamide was carried out in a manner similar to that described in the introduction.

2. Diazotization of the amine: 10.95 g of 4-chloro-5-nitro-2-anino-1-hydroxybenzene were obtained (= 4.0 / 69 mol, 90.5 ° / 0, MW = 188.6) in 40.0 cc of water and 6.5 cc of sodium hydroxide solution (40% w / v) dissolved and 13.5 ccm sodium nitrite solution (30% w / v) admitted. The mixture was cooled to 13 ° C. and within 45 minutes in 60 cc ice water, 11.3 cc concentrated hydrochloric acid (38%) together with 4.0 cc glacial acetic acid dripped in. The mixture was back titrated with 3.4 cc sulfamic acid to remove excess Destroying nitrite. 3.85 / 69 mol of diazo compound were obtained in this way.

3: Coupling: 26.5 g of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid were obtained N, N-dimethylamide (4.81 / 69 mol, MW = 415.5) by heating to 60 ° C in 100 cc of pyridine dissolved, whereupon cooled to 15 ° C and the slurry of the diazo compound at 15 to 20 ° C of the azo component was added. The reaction mixture became thick, (pH value 5.9), but again a little thinner after stirring for 10 minutes. At this time a test for free diazo compound (resorcinol) was positive. There were 25 cc Glacial acetic acid was added, heated to 40 ° C on a steam bath, whereupon the test for a coupling with resorcinol was negative. The pH was 5.5 and the volume was 280 ccm. The compound was stirred for an additional half hour and the temperature increased Reduced 25 ° C, whereupon 280 ccm of water were added. The slurry turned 15 Stirred for minutes, filtered and the filter cake washed with 250 cc of water. Of the The press cake containing the unmetallized dye weighed 98.6 g.

4. Chroming: The wet color cake was placed in a 400 cc beaker fitted with a thermometer and stirrer and located in a steam bath. 150 cc of formamide was added and heated to 95 ° C to complete the dissolution. 11.6 g of chloroformate paste (13.02% Cr = 2.0 / 69 g atoms of Cr) were then added, the mixture was stirred at 95 to 98 ° C. for 3 hours and then allowed to cool overnight. The mixture was then heated again to 98 ° C., poured into 750 ccm of water, 96 g of sodium chloride were added, the slurry was stirred for 4 hours and then filtered. The cake was washed with 100 cc of aqueous saline solution (5% w / v) to obtain the ammonium salt of the chromium complex compound of the dye of the following formula: 5. Reduction of the nitro group: The press cake was slurried again in water to a volume of 800 ccm, the mixture was heated to 95 ° C. and then 11.6 ccm of potassium hydroxide solution (56% w / v) and 160 ccm of pyridine were added . The mixture completely dissolved when the pyridine was added. Then 32.0 g of sodium sulfide monohydrate (9.24 / 69 mol), dissolved in 60 cc of water, were added at 95 ° C., and the mixture was then allowed to cool. 47 g of sodium bicarbonate were then added to the slurry, as a result of which the pH fell from 12.3 to 9.0 and the dye precipitated. It was then stirred for 4 hours, filtered, washed with water and dried. The dry weight of the obtained sodium salt of the desired chromium complex dye was 24.1 g.

6. Dispersion: A 10.0 g sample of the above dry dye was 3 hours in a paddle mixer with 10.0 g of the condensation product Formaldehyde and sodium naphthalene-2-sulfonic acid kneaded in the form of a thick paste, small amounts of water were added at intervals. After kneading it was the dye is dried by applying steam to the mixer, whereupon the dry powder was removed and processed in a hammer mill.

7. Dyeing: 0.4 g of the dispersed powder was dissolved in 300 cc of water and a woolen fabric weighing 10 g was added. The dye bath was heated to 100 ° C. within 45 minutes, the fabric being agitated in the liquid and the temperature of the bath being kept at 100 ° C. for a further hour while the fabric was continuously agitated. Then this was removed, rinsed and dried. A very level dyeing was obtained with very good exhaustion of the dye bath. The fabric was dyed greenish blue and the dye was excellent in light and water fastness. Example 2 Preparation of the dye This dye was prepared from the acetylated dye according to Example 1 by splitting off the acetyl group using sodium hydroxide as follows: 10 g (1.29 / 2-69 mol) of the acetylated dye according to Example 1 were added together with 13 cc of pyridine and 11.5 g of sodium hydroxide added to 200 cc of water. The mixture was stirred for a total of 9 hours at 95 ° C., after which it was diluted to 600 ccm, filtered and dried. Dry weight 6.3 g. The dispersion of this dye was carried out as in Example 1. The dyeing of the dye on wool was carried out in the same manner as in Example 1. A greenish-blue dyeing was obtained which was very lightfast and exhibited excellent washfastness. Example 3 Preparation of the dye The azo component 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid amide was prepared as follows: 942 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (150/69 mol, 73.7 ° / y, MW = 319 ) were dissolved in 850 cc of water and 244 cc of sodium hydroxide solution (40 ° / jg w / v) at 40 to 50 ° C. Then 253 g of sodium carbonate (2.38 mol) dissolved in 2300 cc of water were added and then 335 g of benzoyl chloride (2.38 mol) were added over 3 hours with rapid stirring while maintaining a temperature of 20 ° C. 200 cc of sodium hydroxide solution (40% w / v) were then added and then a further 60 g of benzoyl chloride (0.43 mol) were added dropwise at 20 ° C. with vigorous stirring over the course of one hour. The test for free amine by diazotization and self-coupling was very weak. The mixture was stirred for a further 2 hours, then the p $ value was adjusted to 11.5 by adding sodium hydroxide, and the mixture was heated to 80 ° C. for 2 hours in order to hydrolyze all of the O-acylated compound to the free hydroxynaphthalene. The mixture was then cooled to 20 ° C., 200 g of salt were added, the mixture was filtered, pressed off and dried. The dry weight of the 1-benzoylamino-8-hydroxynaphthalene -3,6-disulfonic acid obtained was 13 g (85% pure). The formula of the compound is This compound was in the disulfonyl chloride converted using equimolecular amounts. Equivalent amounts were also used in converting the disulfonyl chloride to the disulfonic acid amide.

The diazotization of 4-chloro-5-nitro-2-amino-1-hydroxybenzene was carried out in the same way as described in Example 1. An equimolecular amount of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid amide was used as the azo component in place of the 1-acetylamino-8-hydroxynaphthalene- 3,6 -disulfonic acid-N, N-dimethyl amide used in Example 1. The coupling was carried out as described in Example 1; likewise the chromation and reduction of the nitro dye to the free amino dye. The finally obtained dye of the above formula is water-soluble and therefore does not require dispersion.

0.2 g of this undispersed dye was dissolved together with 0.3 g of ammonium sulfate in 300 cc of water. A piece of woolen fabric weighing 10.0 g was added and the temperature of the dye bath was increased to 100 ° C. within 45 minutes, the fabric being agitated in the liquid. The temperature of the dye bath was kept at 100 ° C. for a further hour while the piece of wool was kept moving, after which it was removed, rinsed and dried. A very level greenish-blue dyeing was obtained which had excellent lightfastness and good washfastness. Example 4 Preparation of the dye The azo component 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acidoxyethylamide was prepared in the same way as 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid-N, N-dimethylamide; an equimolecular amount of ethanolamine was used in place of the dimethylamine.

The diazotization of the 5-nitro-2-amino-1-hydroxybenzene was carried out using equimolecular amounts in the same manner as the diazotization of the 5-nitro-4-chloro-2-amino-1-hydroxybenzene. The coupling was carried out in the same manner as in Example 1, an equimolecular amount of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid-oxyethylamide instead of the 1-acetylamino-8-hydroxynaphthalene used in Example 1 - 3.6 - Disulfonsäuredimethylamids was used. The chromation of the dye and the reduction of the nitro group to the amino group were carried out as in Example l. The finally obtained dye of the above formula was water-soluble and was dyed on polyamides and wool in the same manner as the dye of Example 3. Blue dyeings with excellent lightfastness and good washfastness on wool were obtained. 10.0 g of the dye according to Example 4 were suspended in 150 cc of glacial acetic acid, and the mixture was heated to 94 ° C., most of which dissolved. Then 9.2 cc of acetic anhydride were added, the mixture was heated to 95 ° C. for 8 hours and then cooled to room temperature. It was then diluted to 400 cc with water, then 50 cc of sodium hydroxide solution (40% w / v) was added in a thin stream together with about ice so that the temperature does not rise above 30 ° C. The mixture was heated for 2 hours then filtered and the press cake dried in a vacuum oven at 75 ° C. Dry weight = 9.55 g.

The dyeing of the dye on wool was carried out in exactly the same way as in Example 4. A reddish-blue dyeing of good fastness to light and washing was obtained. Example 6 Preparation of the dye This dye was obtained in the form of the sodium salt by deacetylating the dye according to Example 4 as in Example 2. The dyeing of the water-soluble dye obtained on wool or polyamides was carried out in the same way as in Example 4. Greenish-blue dyeings of excellent lightfastness and very good washfastness were obtained.

Example 7 Preparation of the free acid of the dye according to Example 6 The sodium salt of the dye according to Example 6 was treated with 5% acetic acid slurried, the NHZ group in the above dye being converted into the ammonium ion became. The dye precipitated in the form of the ammonium salt or zwitterion. The received Precipitate was filtered off, dried and mixed with the dispersant described above dispersed. The dyeing was carried out as in the previous examples. The results were similar to those of Example 6.

Claims (3)

PATENT CLAIMS: 1. Process for the preparation of azo dyes, characterized in that an aminohydroxybenzene of the general formula wherein X is hydrogen, chlorine or bromine, diazotized and with an azo component of the formula couples, in which R3 and R4 are hydrogen, a low molecular weight alkyl or oxyalkyl group or together are a heterocyclic radical and R5 is an acylamino, alkylsulfonylamino or arylsulfonylamino group, the nitro group is reduced to the amino group and the amino group is then optionally acylated or with an alkyl or arylsulfonyl chloride converts and / or hydrolyzes the residue RS to the free amino group. 2. Procedure according to Claim 1, characterized in that before or after the reduction of the nitro group is metallized in a known manner, the preferred metallizing agent a chromium, iron, nickel, cobalt or copper releasing agent is used. 3. The method according to claim 1 and 2, characterized in that the metal complex compound contains less than 1 metal atom, 1 or more than 1 metal atom per molecule of the azo dye. Documents considered: German Patent No. 921 224. A coloring table was laid out when the application was published.