DE2232447A1 - Mixtures of brominated quinophthalone dyes - prepd by brominating 3'-hydroxy-quinophthalone (derivs) in dilute sulphuric acid - Google Patents

Abstract

Dye mixtures having the formula (I): (where n is >1 to 4), disclosed in Main Patent DT 2 132 681, and dyes and dye mixtures of formula (II), disclosed in DT 2203348 (where R1 is H, Cl, Me, OH, MeO, EtO, Ph or PhO; R2 is H, Cl or Me: R1 and R2 together form part of a fused benzene-ring; X1 is H, F, Cl, OH, MeO, EtO, PhO, 1-4C alkyl, Ph, opt. substd. benzoyl or acylamine, alkylaminocarbonylamino or alkylamino-sulphonylamino; X2 is H, Cl or Me and n >1 to 3, and one of R1, R2, X1 or X2 is other than H).

Description

Process for the preparation of brominated quinophthalone dyes Additive to patent. ... ... (patent application P 21 32 681.8) and the additional patent. ... ... (Patent application P 22 03 348.3).

Subject of the main patent. ... ... (patent application P 21 32 681.8) are quinophthalone dye mixtures of the formula where n> 1 to 4.

Subject of the additional patent. ... ... (patent application P 22 03 348.3) are brominated dyes and mixtures of dyes of the formula I. in which R1 is hydrogen, chlorine, methyl, hydroxy, methoxy, ethoxy, phenyl or phenoxy, R2 is hydrogen, chlorine or methyl, R1 and R2 together are part of a fused benzene ring, xl is hydrogen, fluorine, chlorine, hydroxy, methoxy, ethoxy, Phenoxy, alkyl with 1 to 4 carbon atoms, phenyl, optionally substituted benzoyl, optionally substituted acylamino, Älkylaminooarbonylamino or alkylaminosulfonylamino, hydrogen, chlorine or llethyl and n> 1 to 3, where one of the radicals R1, R2, X1 or x2 of Hydrogen is different.

It has now been found that the dyes of the main and additional patent can be prepared very well if the compounds of the formula or the formula where m is 0, 1 or 2, brominated in dilute sulfuric acid.

With dilute sulfuric acid, about 10 to 80% strength, preferably 20 to 70 goat acids understood.

If appropriate, the bromination can be carried out in dilute sulfuric acid add a catalyst, e.g. iodine, but sulfuric acid generally works itself as a catalyst, so that it acts as a conversion medium and catalyst at the same time serves.

The reaction takes place at temperatures from about 200C to Boiling point that can be increased by pressure. The reactions are preferred made at approximately 40 to 110 cc.

The monobromination is from the German Offenlegungsschrift 1 670 880 of 3'-hydroxyquinophthalone in 80 to 100 point sulfuric acid at 20 to 40 ° C known.

The introduction does not succeed under the specified conditions of several bromine atoms.

Surprisingly, it enables the use of dilute sulfuric acids to achieve a higher degree of bromination.

Since the previously known processes for higher bromination are relatively drastic Conditions require it was unforeseeable that the comparatively mild ones Conditions of the process of the invention allow the introduction of multiple bromine atoms.

Otherwise, the information in the main and additional patent apply accordingly.

Example 1 Bromination in 20% sulfuric acid.

In an enamel kettle with a volume of 50,000 parts there are 1,445 parts 3'-Hydroxyquinophthalone dissolved in 5840 parts of 96 pointers sulfuric acid. The solution is diluted with 22 160 parts of water, the product precipitating in finely divided form.

Then 2500 parts of bromine are added all at once, and the seal is closed Kettle and heated to 105 ° C. with stirring. It is left under autogenous pressure for 8 hours (approx 1 at), then releases the excess pressure and sucks while still warm on a stoneware suction cup away. After washing and drying, 2305 parts of dye with a bromine content are obtained of 41.7 *.

Example 2 Bromination in 40 point sulfuric acid.

1445 parts of 3'-hydroxy-quinophthalone are in an enamel kettle of 50,000 parts by volume dissolved in 11,680 parts of 96 pointers sulfuric acid. To do this, lets 16,320 parts of water are run in so that the temperature does not exceed 75.degree. Then 2500 parts of bromine are added all at once and the mixture is then stirred with the lid closed Boiler at 7500 for 16 hours. A pressure of approximately 0.4 atmospheres is established. It is then diluted with 14,000 parts of water, filtered off with suction while warm and washed with warm Water neutral. After drying, 2398 parts of dye with a bromine content are obtained of 40.8%.

Example 3 Bromination in 60% sulfuric acid.

289 parts of 3'-hydroxy-quinophthalone are dissolved in 3500 parts of 96% strength sulfuric acid registered and until the complete dissolution touched. Then drips 2100 parts of water are added, a finely divided dye suspension being formed. Afterward the mixture is heated to 100.degree. C. and 500 parts of bromine are left in over the course of 6 hours while stirring run under the surface of the liquid. Then another 4000 parts of water are added closes, sucks off warm and washes neutral with warm water. One receives after drying 480 parts of dye with a bromine content of 40.0 at 100 ° C.

Example 4 Bromination in 60% sulfuric acid.

In an enamel kettle with a capacity of 50,000 parts, 17,500 parts are made 96 goat sulfuric acid presented. 1445 parts of 3'-hydroxyquinophthalone are carried and stir until a clear solution is obtained. To do this, 10,425 parts are left Run in water, whereby the temperature may rise to 50 ° C.

2500 parts of bromine are then added and the kettle is closed and stirred for 20 hours at 50 oC. After opening the kettle, add another 20 000 parts of water and squeezes the contents on a stoneware suction filter. One washes neutral with hot water and dry the dye at 100 ° C. Yield 2395 parts with a bromine content of 40.4%.

Example 5 Bromination in 80% sulfuric acid.

289 parts of 3'-hydroxyquinophthalone are in 4664 at room temperature Parts of 96% sulfuric acid entered. After the product has dissolved, drips 936 parts of water are added and the temperature is raised to 90 °. The mixture is then left with stirring 500 parts of bromine run under the surface of the solution in the course of 10 hours - the brominated dye begins to precipitate after the first 2 hours. To the end of the feed is stirred for a further 1 hour at 90 oC and with further 4000 parts of water diluted. It is suctioned off warm, washed acid-free with warm water and dried at 10000. Yield 436 parts of dye with a bromine content of 43.8 %.

In accordance with the procedure given, the following others were used Dyes produced by bromination in dilute sulfuric acid: Example parts Subst. 3'-hydroxy parts parts% Br quinophthalone bromine dye 6 1294 3-chloro 2000 1964 34.0 7 1535 4-fluoro 2500 2408 36.6 8 1472 4-bromo 2000 2044 45.1 9 1515 4-methyl 2500 2438 38.0 10 1460 4-Phenyl 2000 2156 32.1 11 1656 4-Hexahydro-2000 2368 29.8 benzoylamino 12 1269 4-phenylaminocar, 1500 1805 31.0 bonylamino 13 1472 6'-bromo 2000 2017 43.3 14 1585 6 ', 8'-dimethyl 2500 2454 35.2 15 1350 3-chloro-6'-methyl 2000 2004 32.2 16 1356 5 ', 6'-Benzo 2000 2184 38.1 17 1198.5 4-Phenyl-8'-chloro 1500 1707 29.6

Claims (1)

Claim Process for the preparation of brominated quinophthalone dyes according to the patent. ... ... (patent application P 21 39 681.8) and additional patent. ... ... (patent application P 22 03 348.3) by bromination of compounds of the formula or the formula where m is 0, 1 or 2, characterized in that the bromination is carried out in dilute sulfuric acid.