Anthraquinone azo dyes

Abstract

Provided are anthraquinone azo dyes and dye mixtures which are distinguished by a very good build-up capacity and which also yield tinctorially strong dyeings or prints in a golden-yellow to orange shade having all around good properties, especially high temperature light fastness properties. ##STR00001##

Claims

1. An azo dye of the formula ##STR00032## wherein R.sub.1 is hydrogen, R.sub.2 is hydroxy, R.sub.3 is hydrogen, R.sub.4 is hydrogen, and D represents a radical of the formula ##STR00033## wherein R.sub.5 denotes C.sub.4H.sub.9 .

2. A process for the dyeing or printing of polyester material, wherein an azo dye of formula (1) according to claim 1 is applied to the polyester material or is incorporated into the polyester material.

3. A polyester material dyed or printed by the process according to claim 2.

Description

I. SYNTHESIS EXAMPLES

I.1 Preparation of 1-hydroxy-5-amino-6,8-dichloroanthraquinone

(1) 28.7 g 1-hydroxy-5-aminoanthraquinone are dissolved in 128.5 g N-methylpyrrolidone (NMP). Chlorine gas is passed through the solution for three hours at a temperature of 0-5 C. The reaction mixture is stirred over night at room temperature. Afterwards the resulting solution is filtered off and the filter cake is recrystallized in NMP.

(2) .sup.1H NMR (250 MHz, CDCl.sub.3) =12.32 (s, 1H), 7.97 (s, 1H), 7.80 (t, 1H), 7.71 (dd, 1H), 7.35 (dd, 1H)

(3) I.2 Preparation of 1-hydroxy-5,7-dichloro-8-aminoanthraquinone

(4) 28.7 g 1-hydroxy-8-aminoanthraquinone are dissolved in 177 g NMP. Chlorine gas is passed through the solution for three hours at a temperature of 0-5 C. The reaction mixture is stirred over night at room temperature. Afterwards the resulting solution is filtered off and the filter cake is recrystallized in NMP.

(5) .sup.1H NMR (250 MHz, CDCl.sub.3) =12.42 (s, 1H), 7.89 (s, 1H), 7.56 (t, 1H), 7.56 (dd, 1H), 7.30 (dd, 1H)

(6) I.3 Preparation of 1,4-dihydroxy-5-nitro-8-aminoanthraquinone

(7) 5.0 g of boric acid is dissolved in 150 g of sulfuric acid. Subsequently, 1,4-dihydroxy-5-aminoanthraquinone is added at room temperature. Thereafter, 13.0 g of nitration acid (52% nitric acid in sulfuric acid) and, afterwards, 50 g of sulfuric acid is added dropwise at a temperature of 6-10 C. After 8 d stirring at room temperature the reaction mixture is given to 500 g of ice, 200 g of water and 10 g of sulfamic acid. The resulting suspension is filtered off and washed with acetic acid and water.

(8) .sup.1H NMR (250 MHz, CDCl.sub.3) =12.83 (s, 1H), 8.60 (d, 1H), 7.68 (d, 1H), 7.36 (d, 1H), 7.31 (d, 1H)

Example I.4

Compound of Formula (101)

(9) ##STR00008##

(10) 2.4 g 5-amino-1-hydroxy anthraquinone are reacted with 3.2 g nitrosyl sulfuric acid (40%) in 18 g concentrated sulfuric acid at a temperature from 18 to 20 C. The diazotation is finished after 18 h. The resulting solution is dropped into a solution of 2.1 g 1-butyl-3-cyano-6-hydroxy-2-pyridone in 4 g of 10% aqueous NaOH which is cooled with an ice bath to keep the temperature at 10-20 C. The pH value is held between 1 and 2 by adding 37 g of 30% aqueous NaOH. After the reaction is completed, the mixture is filtered off. The residue is washed with an ethanol/water mixture and dried in vacuum.

(11) .sup.1H NMR (250 MHz, CDCl.sub.3) =16.4 (s, 1H), 12.50 (s, 1H), 8.40 (dd, 1H), 8.28 (dd, 1H), 8.02 (dd, 1H), 7.90 (t, 1H), 7.74 (t, 1H), 7.36 (dd, 1H), 4.09 (t, 2H), 2.68 (s, 3H), 1.67 (m, 2H), 1.44 (m, 1H) 0.98 (t, 3H).

Examples I.2-I.93

(12) In general accordance with the procedure described in Example 1.1, the following dyes can be prepared, which dye PES with good allround fastness properties.

(13) ##STR00009## ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##

II. APPLICATION EXAMPLES

II.1 Exhaust Dyeing of Polyester

(14) 100 g of polyester fabric is immersed at room temperature, at a liquor ratio of 1:20, in a liquor containing 0.5 g of the azo dye of formula (101), 1 g/l of ammonium sulfate and 0.5 g/l of a commercial levelling agent,

(15) the liquor having been adjusted to a pH value of from 4.5 to 5 using 80% formic acid. The liquor is then heated first at a heating rate of 3 C./minute to 60 C. and then at a heating rate of 2 C./minute to 135 C.

(16) At 135 C., dyeing is carried out for 60 minutes. The liquor is then cooled to 40 C., and the dyed polyester fabric is washed with water and cleaned reductively at from 70 to 80 C., for 20 minutes, in a bath containing 5 ml/l of 30% sodium hydroxide solution, 2 g/l of 85% sodium dithionite solution and 1 g/l of a commercial detergent. The finished dyeing is then washed with water and dried.

(17) A tinctorially strong orange (?) dyeing having good allround fastness properties, especially high-temperature light fastness properties that are excellent, is obtained.