DE963266C - Process for the preparation of anthraquinone dyes - Google Patents

Description

Process for the preparation of anthraquinone dyes The invention relates to a process for the production of, in particular, for dyeing textile materials suitable anthraquinone dyes.

From the British patent 593 955 anthraquinone dyes, such as i, 5, 8-TriOxy-q.-p- [ß- (ßoxy-ethoxy) -ethoxy] -aniline-anthraquinone and i, 5, 8-TriOxy-4.-o- [ß = (ß-oxy -ethoxy) -ethoxy] -aniline-anthraquinone, known.

Anthraquinone dyes, such as i, 5-dioxy-8-nitro-q.-p-ethoxyaniline-anthraquinone, have also become known from British patent specification 646 459. It now appears that anthraquinone compounds of the formula where Z is fluorine, chlorine or bromine, X is a monooxalkyl group with 1 to 3 carbon atoms or a dioxalkyl group with 2 or 3 carbon atoms and Y is hydrogen, chlorine, hydroxyl, methoxy or methyl, are valuable dyes which are the known dyes in are superior in some respects, in particular with regard to their excellent light and gas resistance. The dyes provide deep and bright colors in blue. Since blue dyes with these properties are much rarer than, for example, red dyes, the specified dyes are particularly valuable. The dyes are particularly suitable for dyeing textile materials made from a cellulose alkyl carboxylic acid ester with 2 to 4 carbon atoms in the acid groups, preferably for cellulose acetate textile materials. The person skilled in the art is aware that there are significantly fewer useful dyes available for these textile materials than, for example, for textile materials made from natural fibers or the like.

Among cellulose alkyl carboxylic acid esters with 2 to 4 carbon atoms in the acid groups are, inter alia, both hydrolyzed and non-hydrolyzed Cellulose acetates, cellulose propionates, cellulose butyrates, cellulose acetate propionates and cellulose acetate butyrate. If colorations of the proposed Dyes, for example colorations on cellulose acetate textile materials, according to the American standard test procedure, the so-called AATCC procedure it turns out that the discoloration almost even after six gas treatment show no change in strength and tint.

The AATCC procedure is essentially as follows: The test piece to be tested and a standardized control piece are simultaneously in exposed to nitrogen oxide vapors in a test box. The control piece is made that after a certain treatment time there is a clearly perceptible color change shows. The same color change also occurs when the control piece is 6 months would be exposed to an atmosphere with average nitrogen oxide content. The color change of the control piece is recorded in a comparison color chart. The control piece is now replaced by a new one every time during the test process, when the color change is achieved while the specimen continues in the gas box remain. A six-time gas treatment should mean that in the test six Control pieces have been consumed. A gas treatment six times is therefore equivalent three years of uninterrupted wear of an item of clothing dyed with the dye in areas with average nitrogen oxide content.

In contrast to the proposed dyes, they show many Aminoanthraquinone dyes used for dyeing cellulose acetate textile materials, such as i, 4-dimethylaminoanthraquinone, i-methylamino-4-methoxyethylaminoanthraquinone, i-methylamino-4-ß-oxyäthylaminoanthraquinone, i, 4-diaminoanthraquinone, i, 4, 5, 8-Tetraaminoanthraquinone, i, 4-Di-ß-Oxyäthylarnino-5, 8-dioxyanthraquinone and i-Amino-4-methylaminoanthraquinone-2-carboxamide, a noticeable color change after a single gas treatment in the meaning given above.

The excellent lightfastness of the new anthraquinone dyes on cellulose acetate textile materials shows the fact that only after 40 to 6 hours Exposure in a light resistance measuring device (fade-0-meter) shows a measurable attenuation the color occurs, while cellulose acetate dyeings previously took a 2-hour period Enduring exposure have already been described as good.

The process for the preparation of the new anthraquinone compounds consists in that an anthraquinone compound of the general formula wherein Q is a chlorine or bromine atom and Z is a fluorine, chlorine or bromine atom, with a primary arylamine of the formula wherein X and Y have the meanings given above, preferably condensation in the presence of an inert, organic solvent.

The amine is preferably used in excess. Suitable Solvents or diluents are, for example, nitrobenzene, o-nitrotoluene, n-butyl alcohol, n-amyl alcohol, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide or a glycol such as ethylene glycol, propylene glycol [propanediol- (i, 2)] trimethylene glycol [propanediol- (i, 3)], a-butylene glycol [butanediol- (i, 2)], butanediol- (i, 3), diethylene glycol or an ether glycol such as ethylene glycol monomethyl ether (methyl cellosolve), Ethylene glycol monoethyl ether (cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), Diethylene glycol monobutyl ether (butyl - carbitol), diethylene glycol - m.onoethyl ether (Carbitol) and diethylene glycol - monomethyl ether (methyl carbitol).

Primary arylamines suitable for implementation are as follows: o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, o-aminophenyl ethyl alcohol, m-aminophenyl ethyl alcohol, p-aminophenylethyl alcohol, o-aminophenylmethylcarbinol, p-aminophenylmethylcarbinol, m-aminophenylethylcarbinol, 4-methyl-3-aminophenylmethylcarbinol, 3-chloro-4-aminophenylmethylcarbinol, o- (CHOHCH, CH20H) -aniline, p- (C H O H C HZ C H2 O H) -aniline, o- (C H 0 H C HZ-O H) -aniline, m- (C H 0 H C H2 O H) -aniline, p- (C H O H- CH20H) -aniline, o- (CH2CH2CH20H) -aniline, p- (CH2-CH2CH20H) -aniline, 2-methoxy-5- (CH, CH2CH20H) -aniline, 2-oxy-5- (CH2CH2CH20H) -aniline, 2-chloro-5 - (CH, CH, CH20H) -aniline, 2-methyl-5- (CH2CH2 C H2 0 H) -aniline, 2-methoxy-5- (C H2 C H2 0 H) -aniline, 2-chloro-5- (CH2CH20H) -aniline, 3-chloro-4-aminobenzyl alcohol, 3 - amino - 4 - methoxybenzyl alcohol, 2 - amino - 3 - methylbenzyl alcohol, 6 - amino - 3 - methylbenzyl alcohol, 3-amino-4 - methylbenzyl alcohol, 2-methoxy-5- (CHOHCH3) -aniline, 2-methyl-5- (CH-O H C H3) -aniline, 2-methyl-3- (C H2 C H2 O H) -aniline and 2-oxy-5- (C H2 C H2 O H) aniline.

The following examples explain the preparation of the new anthraquinone compounds.

Example i 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 15 g of p-aminophenylethyl alcohol are heated together to 170 ° for 4 hours. The reaction mixture is then cooled to 50 ° and 50 cc of ethyl alcohol are added. The dye is precipitated by stirring the reaction mixture into zoo cc of cold, 10% aqueous hydrochloric acid, filtered, washed well with water and dried. It has the following formula: After recrystallization from n-amyl alcohol, the dye has a melting point of 24o to 25o °. Example 2 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 15 g of o-aminophenylethyl alcohol are heated together to 170 ° for 4 hours. The reaction mixture is then cooled to 50 ° and 50 cc of ethyl alcohol are added. The dye is precipitated by stirring the reaction mixture into zoo cc of cold, 10% aqueous hydrochloric acid, filtered, washed well with water and dried. After recrystallization from n-amyl alcohol, it has a melting point of 14o to i45 °. Example 3 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone, 2 g of m-aminobenzyl alcohol and 50 cc of n-butyl alcohol are refluxed together for 30 hours in the presence of a small amount of copper sulfate as a catalyst. The dye is precipitated by stirring the reaction mixture into zoo cc of cold water, filtered, washed well with water and dried.

The m-aminobenzyl alcohol used in this example can by 2 g of o-aminobenzyl alcohol or 2 g of p-aminobenzyl alcohol are replaced, whereby also give dyes according to the invention.

Example 4 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 25 g of m-aminophenylmethylcarbinol are heated together for 4 hours at from 170 to 175 ° and treated further according to the process described in example i. The resulting dye has the following formula: The m-aminophenylmethylcarbinol used according to this example can be replaced by 25 g of o-aminophenylmethylcarbinol or 25 g of p-aminophenylmethylcarbinol, which also results in dyes according to the invention. Example 5 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 30 g of p- (CHOHCH2CH20H) -aniline are refluxed together for 4 hours and further treated according to the method described in Example i, a dye being as follows Formula: results. Example 6 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 30 g of o- (CHOHCH, CH2OH) -aniline are heated together at 160 ° for 5 hours. The resulting dye is separated off by further treatment of the reaction mixture according to the method described in Example i. Example 7 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 30 g of p- (CH 0 HC H2 0 H) -aniline are heated to 160 ° for 6 hours. The resulting dye is separated off by working up the reaction mixture according to the method described in Example i. Example 8 3 g of 1,5-dioxy-4-chloro-8-fluoroanthraquinone and 25 g of o-aminophenylethyl alcohol are heated together to 160 ° to 170 ° for 4 hours. After working up the reaction mixture by the method described in Example i, a dye of the following formula is obtained: Example 9 5 g of 1,5-dioxy-4, 8-dibromoanthraquinone and 25 g of p-aminophenylethyl alcohol are refluxed together for 4 hours. After working up the reaction mixture by the process described in Example i, a dye of the formula is obtained 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 25 g of 2-methoxy-5- (CH, CH 2 O H) -aniline are refluxed together for 5 hours. The resulting dye is obtained after working up the reaction mixture by the method described in Example i. Example ii 5 g of 1,5-dioxy-4, 8-dibromoanthraquinone and 25 g of 2-chloro-5- (CH, CH 2 O H) -aniline are refluxed together for 5 hours. After working up the reaction mixture by the method described in Example i, a dye is obtained Example i2 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 25 g of 2-methyl-5- (CHOHCH3) -aniline are refluxed together for 5 hours. The resulting dye is obtained after working up the reaction mixture according to the method described in Example i. Example 13 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 25 g of 2-oxy-5- (CHZCH, OH) -aniline are refluxed together for 6 hours. The resulting dye is obtained after working up the reaction mixture according to the method described in Example i. Example 14 5 g of 1,5-dioxy-4, 8-dibromoanthraquinone and 25 g of 6-amino-3-methylbenzyl alcohol are refluxed together for 6 hours. The resulting dye is obtained after working up the reaction mixture by the method described in Example i. Example 15 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 15 g of 3-amino-4-methoxybenzyl alcohol are refluxed together for 4 hours. The resulting dye is obtained by working up the reaction mixture according to the method described in Example i. Example 16 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 20 g of 3-chloro-4-aminophenylmethylcarbinol are refluxed together for 5 hours. The resulting dye is obtained by working up the reaction mixture according to the method described in Example i. Example 17 5-g 1,5-dioxy-4, 8-dibromoanthraquinone and 18 g 4-methyl-3-aminophenylmethylcarbinol are refluxed together for 4 hours. The resulting dye is obtained by working up the reaction mixture according to the method described in Example i. Example 18 3.09 g of 1,5-dioxy-4, 8-dichloroanthraquinone and 20 g of m-aminophenylethylcarbinol are refluxed together for 5 hours. The resulting dye is obtained by working up the reaction mixture according to the method described in Example i.

m-Aminophenylethyl alcohol is prepared as follows: m-Nitrophenyl acetic acid becomes m-aminophenylacetic acid in ethyl alcohol over Raney nickel at 5o to 55 ° reduced. The ethyl alcohol is evaporated under vacuum and the essentially residue consisting of m-aminophenylacetic acid in a Soxhlet device in the presence a boiling ethyl ether solution with a large excess of lithium aluminum hydride reduced to m-aminophenylethyl alcohol. After working up the reaction mixture one m-aminophenylethyl alcohol, which boils at 135 to 138 ° J2 mm. That p- (CHOHCH, CH2 0 H) -aniline used in Example 5 was in the form of a viscous Oil by nitrating the acetic diester of 3- (phenyl) I, 3-propanediol with fuming Nitric acid and acetic anhydride obtained at 20 to 30 °. The acetic acid diester of 3- (p-Nitrophenyl) -i, 3-propanediol separates out as a solid mass when the The nitration mixture is poured into ice water and can be filtered off. By reducing the nitro group with hydrogen in the presence of a Raney nickel catalyst and Subsequent hydrolysis of the ethyl acetate groups gives p- (C H O H C H2 C HZ O H) -aniline.

The isomer o- (C H O H C H2 C H2 O H) -aniline is obtained by extracting the nitriding mixture obtained with -ether. The acetic acid diester of 3- (o-nitrophenyl) -I, 3-propanediol is separated from the ether extract and converted to o- (C H 0 H C H2 C H2 O H) -aniline reduced and hydrolyzed. o- (C H O H C H2 C H2 O H) -aniline can also by reducing 3- (o-nitrophenyl) -I, 3-propanediol (reports from Deutsche Chemischen Gesellschaft, Vol. 15, p. 286) with hydrogen in the presence of a Raney nickel catalyst be won.

The 3-amino-4-methoxybenzyl alcohol used in Example 15 is prepared as follows: 71.5 g of 4-methoxy-3-nitrobenzaldehyde in 500 cc of ethyl alcohol are placed in a suitable pressure flask and hydrogenated over Raney nickel at about 98 to 112 kg / cm2 and a temperature of 85 to 100 ° hydrogenated. The reaction mixture is then evaporated to dryness and the residue is recrystallized from benzene. 32 g of 3-amino-4-methoxybenzyl alcohol with a melting point of 95 ° to 97 ° are obtained.

The 3-chloro-4-aminophenylmethylcarbinol used in Example 16 is prepared as follows: 6o, g 3,4-dichloroacetophenone, 2ooccm 29% ammonia water and i g CuO are heated to 25o to 26o ° for 8 hours in an autoclave. The reaction product is filtered off, washed with water until neutral and dried. You get so 48 g of a product that melts at 118 to 122 °. This is made with hydrogen hydrogenated over Raney nickel at 100 to 105 ° and about 84 kg / cm2 in dioxane. Thereafter the dioxane is evaporated, 42 g of 3-chloro-4-aminophenylmethylcarbinol with a Melting point of gi to 94 ° remain behind.

The 4-Methy1-3-amino- used in Example 17. phenylmethylcarbinol is prepared as follows: 40 g of p-methylacetophenone are dissolved in 18o ccm 96% H 2 SO and the resulting solution is frozen to -2o °. A mixture of 36 cc of 96% H 2 SO 4 and 28 cc of nitric acid (specific weight 1.5) is stirred into this solution within 1/2 hour while maintaining a temperature of -2o °. After stirring for a further 15 minutes, the reaction mixture is poured onto ice and filtered. The filter residue is washed acid-free with water and dried. After recrystallization from dilute acetic acid, 21 g of a compound with a melting point of 52 to 56 ° are obtained, which is dissolved in 50 cc of ethyl alcohol and hydrogenated with hydrogen over Raney nickel at 100 ° and approximately 70 kg / cm2. The ethyl alcohol is then evaporated off and the residue is recrystallized from toluene. This gives 13 g of 4-methyl-3-aminophenyhnethylcarbinol with a melting point of 61 to 65 °.

The m-aminophenylethylcarbinol used in Example 18 is prepared as follows: 40 g of propiophenone are dissolved in 180 ccm of 96% sulfuric acid at 0 ° and 28 ccm of nitric acid (specific weight 1.5) are stirred in at -2o ° within 1/2 hour. After a further 1/2 hour, the mixture is allowed to warm to -io °, poured onto ice and filtered. The filter residue is recrystallized from dilute acetic acid. 26 g of a compound with a melting point of 94 to 96 ° are obtained. This is hydrogenated with hydrogen over Raney nickel in 50 cc of ethyl alcohol at 100 ° and a pressure of about 84 kg / cm2. Then the ethyl alcohol is evaporated and the residue is recrystallized from toluene. This gives ig g of m-aminophenylethylcarbinol which melts at 65 to 68 °.

1, 5-Dioxy-4-chloro-8-fluoroanthraquinone is prepared by 1, 5-Dioxy-8-fluoroanthraquinone chlorinated, according to that in the German patent 167 743 described chlorination process. Similarly, 1, 5-Dioxy-4-bromo-8-fluoroanthraquinone by brominating i, 5-dioxy-8-fluoroanthraquinone using the usual Bromination process produced.

The new anthraquinone dyes can be applied directly to the material by immersing it in an aqueous suspension. This can can be made by treating the dye with a sulfonated oil, a soap, Sodium lignosulfonate or other suitable dispersing agent to form a paste grinds that is dispersed in water.

The dye bath advantageously has temperatures of about 7o to go °. However, any other suitable temperature is also permissible. The one to be colored Textile material, e.g. B. cellulose acetate, is preferably the dye bath at a Temperature, for example from 45 to 55 ° added, which then depends on the, the The material to be colored is brought to a slightly different dyeing temperature. The amount of the dye to be used depends on the desired intensity of the coloration for example 1/3 to 3% by weight of the textile material.

Claims (1)

PATENT CLAIM: Process for the preparation of anthraquinone dyes, characterized in that an anthraquinone compound of the formula wherein Q is a chlorine or bromine atom and Z is a fluorine, chlorine or bromine atom, with a primary axylamine of the formula wherein X is a monooxyalkyl group with z to 3 carbon atoms or a dioxyalkyl group with 2 or 3 carbon atoms and Y is hydrogen, chlorine, a hydroxyl, methoxy or a methyl group, to a dye of the formula is condensed. References considered: British Patent Nos. 593 955, 646 459.