DE2132681A1 - Quinophthalone dyes - esp for polyester fibres - Google Patents

Abstract

Dyes are of formula (where R1 may be H, Cl, CH3, CH3O, C2H5O, C6H5, C6H5O or OH; R2 may be H, Cl or CH3, R1 and R2 may together form a fused benzene ring, X1 may be H, F, Cl, OH, CH3O, C2H5O, C6H5O, 1-4C alkyl, phenyl, (opt. substd) benzoyl, (opt. substd) acylamine, alkylaminocarbonylamino or alkylaminosulphonylamino, X2 may be H, Cl or CH3 and n is 1-4).

Description

Quinophthalone Dye Mixtures The invention relates to dye mixtures of the formula I in which n is> 1 to 4. The new dye mixtures are yellow and, depending on the bromine content, are suitable for dyeing textile material made of synthetic polyesters, such as polyethylene glycol terephthalate, or plastics, such as polystyrene, polyethylene or polyesters, in bulk.

Yellow, very strong dyeings with good all-round fastness properties are obtained. Particularly noteworthy are the good thermosetting and light fastness properties.

Compared to that known from German Patent 1,619,348 Dye 3'-hydroxy-4'-bromo-quinophthalone are the new dye mixtures Surprisingly, it is characterized by increased heat-setting fastness and color strength.

Compounds of the formula II can be used to prepare the new dye mixtures in which m - is 0 to 2, in solvents or melts which are inert under the reaction conditions with the amount of bromine required to achieve the total bromine content of m> 2, optionally in the presence of a catalyst.

Compounds of the formula II are in particular 3'-hydroxy- and 3'-hydroxy-4'-bromo-quinophthalone.

With bromine contents of n> 2 it is useful and with n> 3 it is necessary, to add a catalyst, preferably a Lewis acid, during the reaction. at The catalysts with lower bromine contents accelerate the bromination Effect.

Inert solvents are e.g. B. nitrobenzene or nitrochlorobenzene, Inert melts can be made from phthalic anhydride, urea aluminum chloride (or melting according to DBP 878 647) or sodium chloride and / or potassium chloride and Prepare aluminum chloride.

The catalysts are, for. B. sulfuric acid, phosphoric acid, iron trichloride, Titanium tetrachloride, aluminum chloride, boron trifluoride adducts, iodine or sulfur halides to call.

The type of catalyst depends on the choice of solvent or the melt, e.g. B. iron trichloride are particularly suitable in nitrobenzene, Iodine or disulfur dichloride.

The choice of reaction temperature also depends on the solvent or the melt; In general, the reactions can be carried out at temperatures between 50 and 210 0C. Details can be found in the examples.

From the patent literature dyes are already known that more than Contain 2 bromine atoms per quinophthalone molecule and those from defined precursors were synthesized, see e.g.

Belgian patent 693 686, French patent 1 403 435 or US patent 3 399 028.

Compared to these known dyes, the new dye mixtures show a much greater affinity for polyesters. Of particular technical Compounds of the textile material made from polyesters are important for the dyeing process Formula I with n) 1 to 2.

The higher brominated products are especially for coloring Plastics suitable, plastics colored in this way are more difficult to ignite.

In the following examples, parts and percentages relate to unless otherwise noted, by weight.

Example 1 289 parts of 3'-hydroxyquinophthalone are converted into 800 parts by volume Entered nitrobenzene and stirred at 180.degree. To do this, one drips over the course of 20 Hours a solution of 500 parts of bromine in 400 parts by volume of nitrobenzene. Then stir it is allowed to cool for a further 2 hours at 180 to 190,000, and 2000 parts are added Ethanol. The dye is filtered off with suction at room temperature and washed with ethanol and dried at 100 cc.

468 parts of 3'-hydroxyquinophthalone with a bromine content are obtained of 41.6%.

Example 2 The procedure is as in Example 1, but according to the The addition of bromine does not add ethanol, but isolates the dye by steam distillation. After drying, 495 parts of dye with a bromine content of 40.3% are obtained.

Example 3 289 parts of 31-hydroxyquinophthalone and 1000 parts by volume Nitrobenzene are stirred at 185 ° C. To do this, 700 drips over the course of 25 hours Parts of bromine and stirred for a further 1 hour at 200,000. Then you let the melt in Pour in 1600 parts by volume of isobutanol, stir for 1 hour and suction off. After washing with methanol and drying, 438 parts of brominated 3'-hydroxyquinophthalone are obtained with a bromine content of 48.6%.

Example 4 In 8QO parts by volume of nitrobenzene, 15 parts of 96 percent strength are added. Sulfuric acid and 289 parts of 3 '= hydroxy-quinophthalone registered and at 180 00 touched. A solution of 500 parts of bromine in 200 parts by volume of nitrobenzene is added dropwise. so quickly that the bromine is visibly consumed, which is about 10 hours requires. After cooling, it is mixed with 2000 parts by volume of methanol, and the suction The dye is removed and dried at 100,000. 415 parts of brominated 3'-hydroxyquinophthal-one are obtained with a bromine content of 40.3%.

If the sulfuric acid of Example 4 is used in the Catalysts mentioned in the table, the following results are obtained: parts Catalyst duration parts bromine content play hrs. Yield in 5 20 100% sulfuric acid 7 1/2 411 42.3 6 25 orthophosphoric acid 16 415 39.9 7 10 ferric chloride 6 1/2 405 41.0 8 100 ferric chloride 4,357 55.3 9 20 BF3. 2H20 15 398 38.7 10 20 BF3 . 2C2H50C2H5 3 1/2 404 42.9 11 1 iodine 12 411 45.1 12 10 iodine 6 418 44.8 13 10 S2Cl2 3 402 42.0 14 10 Tiql4 5 1/2 419 40.4 Example 15 In a prepared according to DBP 878 647 Melt of 1000 parts of anhydrous aluminum chloride and 150 parts of urea are entered at 75 0 144.5 parts of 3Ç-Hydroxyquinophthalone. To do this, one drips 360 parts of bromine in 4 hours with stirring and stirring is continued at 75 ° for 1 hour. The melt is poured onto ice / hydrochloric acid, the dye is suctioned off and with Boiled 2 percent hydrochloric acid. After drying, 284 parts of brominated material are obtained 3'-hydroxy-quinophthalone with a bromine content of 51.0%.

Example 16 In a melt consisting of 1000 parts of anhydrous Aluminum chloride, 125 parts of sodium chloride and 25 parts of potassium chloride are used in 120 ° C 144.5 parts of 3'-hydroxyquinophthalone entered. To do this, one drips in the course 360 parts of bromine for 2 hours and stirring is continued at 120 oC for 1 hour. Afterward the melt is poured onto ice / hydrochloric acid, the reaction product is suctioned off and boiled with 2 percent hydrochloric acid. After drying, 305.5 parts are obtained Dye with a bromine content of 52.7%.

Example 17 Phthalic anhydride melted in 500 parts 144.5 parts of 3'-hydroxyquinophthalone entered. Then one drips at 180 ° C within 300 parts of bromine are added over a period of 12 hours and the mixture is subsequently stirred at 190.degree. to 200.degree. C. for 1 hour. The melt is then poured into 5000 parts of 7 percent sodium carbonate solution. The dye suspension is heated to the boil and suctioned off while hot. You wash with hot water neutral and dries at 10000. Yield: 247 parts of brominated 3'-hydroxy-quinophthalone with a bromine content of 40.7%.

Example 18 In a melt of 500 parts of phthalic anhydride, 10 parts of anhydrous ferric chloride and 144.5 parts of 3'-hydroxy-quinophthalone 300 parts of bromine were added dropwise at 180 ° C. (8 hours). The mixture is stirred for a further 1 hour 190 0 and poured into 5000 parts of 7 percent sodium carbonate solution. Then heated one to the boil, sucks hot and washed with hot water. For removing other things that have fallen Iron hydroxide, the dye is boiled with 5 percent hydrochloric acid and again sucked off. After washing neutral and drying, 263 parts of brominated are obtained 3'-Hydroxyquinophthalone with a bromine content of 43.9%.

When using the catalysts specified in the table, one obtains following results: At- parts catalyst duration parts yield Bromine content play hours in 19 20 AlOl3 4 275 47.0 20 1 J2 8 251 41.2 21 10 J2 6 263 43.9 22 15 S2Cl2 5 266 44.8 23 10 TiCl4 5 270 44.9 24 50 FeCl3 4 269 45.3 Example 25 600 Parts of phthalic anhydride are melted and stirred at 210.degree. In addition one gives 101.5 parts of 3-hydroxy-quinaldine-4-carboxylic acid in the course of 2 hours. The mixture is stirred for a further 1 hour at 210.degree. C., allowed to cool to 180.degree. C. and 250 is added dropwise Part bromine onto the surface of the melt over the course of 10 hours. Then you stir another 1 hour at 190 cc and works as described in Example 17 aul.

231 parts of brominated 3'-hydroxyquinophthalone are obtained with a Bromine content of 40.9%.

Example 25 is obtained using the in the table mentioned amounts of bromine and, with the addition of the catalysts before the addition of bromine, the following Results: ~ parts catalyst parts bromine duration parts bromine content play hours Yield in o 26 1 j2 200 8 237 38.7 27 1 J2 350 13 302 49.4 28 10 FeCl3 300 7 279 46.2 29 10 FeCl3 250 5 258 43.2 30 20 S2C12 250 6 251 43.9 31 15 triol 250 6 250 44.8

Claims (4)

Claims 1. Quinophthalone dye mixtures of the formula in which n> 1 to 4. 2. Dyestuff mixtures according to claim 1, wherein n> 1 to 2 is. 3. The use of the dye mixtures according to claim 1 or 2 for Dyeing of textiles or plastics in bulk. 4. A process for the preparation of dye mixtures according to claim 1 or 2, characterized in that compounds of the formula in which m = O to 2, in solvents or melts which are inert under the reaction conditions, the amount of bromine required to achieve the total bromine content of m> 2 is reacted, optionally in the presence of a catalyst.