DE1270713B - Process for the preparation of anthraquinone dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

C09b

German KL: 22 b-3/03

1270713
P 12 70 713.0-43 November 30, 1961 June 20, 1968

The invention relates to the production of valuable anthraquinone dyes free of acidic water-solubilizing groups, in particular sulfonic acid groups, which have an anthraquinone radical consisting of at most four fused rings and a 1,3,5-triazine radical of the formula Process for, which is linked to the anthraquinone radical via an - NH group Manufacturing
of anthraquinone dyes

C-Y

Il

N
^S R>

contain, in which Rj and R2 denote hydrogen atoms, an alkyl, cycloalkyl or hydroxyalkyl group, where the radicals Ri and R2 can optionally form a heterocyclic ring together with the nitrogen atom, where the alkyl radicals can optionally be substituted, and Y denotes a phenyl radical.
i

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. Dr. jur. F. Redies,

Dr. rer. nat. B. Redies, Dr. rer. nat. D. Turk and Dipl.-Ing. Ch. GUIe, patent attorneys, 4000 Düsseldorf-Benrath3,

Erich-Ollenhauer-Str. 7th

Named as inventor:

Dr. Kurt Weber, Basel (Switzerland)

Claimed priority:

Switzerland of! December 1960 (13514)

The dyes
formula

25 fused rings consisting of an anthraquinone radical preferably correspond to the one containing 1 mol of an amine of the formula

X O NH-C

C-Y

i!

'R, HN

II

XOX

where Ri and R2 are hydrogen atoms, an alkyl, Cycloalkyl or hydroxyalkyl groups, where the radicals Ri and R2 may optionally be taken together can form a heterocyclic ring with the nitrogen atom, Y a phenyl radical, X hydrogen or halogen atoms, alkoxy, aryl mercapto or acylamino groups, e.g. B. an acetylamino or Means benzoylamino group.

Examples of suitable alkyl radicals are the methyl, ethyl, propyl, isopropyl, butyl, / i-hydroxyethyl, called y-hydroxypropyl or cyclohexyl groups.

The new dyes are obtained if 1 mole of a 4-halo-6-phenyl-2-anthraquinonyI-amino-1,3,5-triazine, which consists of a maximum of four X ₁

wherein Rj and R _{2 have} the meaning given, condensed. Examples of amines are: methylamine, ethylamine, oxyethylamine, n-propylamine, isopropylamine, η-butylamine or isobutylamine, dimethylamine, diethylamine, di (oxyethyl) amine, cyclohexylamine, pyrrolidine, piperidine or morpho-Hn.

Compounds of the formula are preferably used as starting materials

NH-C

/ ^N \

XOX

Cl

in which X and Y have the meaning given above. Such connections are

«M 560 441

hold by condensation of 1 mole of an aminoanthraquinone, especially one of the formula

X Ο-- NH ₂

IV

O X

10

wherein X has the meaning given, with 1 mole of phenyldichlorotriazine.
Suitable aminoanthraquinones are:

1-aminoanthraquinone,

I-amino-4-chloroanthraquinone, l-amino-4-methoxyanthraquinone, l-amino-4-benzoylaminoanthraquinone, l-amino-4-phenylmercaptoanthraquinone, I-amino-5-phenylmercaptoanthraquinone,

l-amino-5-benzoylaminoanthraquinone, l-amino-S-acetylammoanthraquinone, S-amino-l ^ -isothiazole anthraquinone.

The new dyes can also be obtained by using a monoaminoanthraquinone, its anthraquinone residue Contains a maximum of four condensed rings, with a halotriazine of the formula

Cl-C

/ ^N \

C-Y

Il

3 °

35

wherein Ru R2 and Y are those given above Meaning condensed. It is expedient to start from aminoanthraquinone of the formula IV. The halotriazines of the formula V are obtained by condensation of 1 mol of phenyldichlorotriazine with 1 mole of the amine of the formula given.

The reactions are expediently carried out in an inert solvent, e.g. B. nitrobenzene. Chlorobenzene or -o-dichlorobenzene, at elevated temperature.

The compounds which can be prepared according to the invention are valuable dyes and dye intermediates The dyes containing aroylamino groups are suitable, for example, as vat dyes. However, the dyes which can be prepared according to the invention are of particular interest as disperse dyes. They are excellent, in particular after a suitable contamination, for dyeing and printing synthetic fibers, for example from Cellulose esters, polyamides, polyacrylonitrile. Polyvinyl chloride and especially aromatic polyesters, such as polyethylene terephthalates. It is then obtained by the customary dyeing process, for example from a dye liquor, which is a dispersion of the dye and expediently a dispersant contains, at temperatures close to 100 "C, optionally with the addition of a swelling agent, such as. B. o-Hydroxydiphenyl or at temperatures above 100 ° C using overpressure, vigorous Dyeings that are characterized by good fastness properties, particularly good lightfastness and sublimation fastness distinguish.

The present invention can be prepared dyes are also suitable for dyeing by the so-called thermofixing process, after which the fabric to be dyed with an aqueous dispersion of the dye, which advantageously from 1 to 50% urea and a thickener, in particular sodium alginate, preferably at temperatures of not more than 6O ⁰ C impregnated and squeezed off as usual. It is expedient to squeeze in such a way that the impregnated product retains 50 to 100% of its initial weight of dyeing liquid.

To fix the dye, the fabric impregnated in this way is expediently dried after prior drying, e.g. B. in a warm air stream, to temperatures of over 100 ⁰ C, for example between 180 to 240 ^; C, heated.

The heat setting process just mentioned is of particular interest for dyeing blended fabrics made of polyester fibers and cellulose fibers, especially cotton. In this case contains the padding liquid, in addition to the dyes which can be prepared according to the invention, also for dyeing cotton suitable dyes, for example vat dyes, or in particular so-called reactive dyes, d. H. Dyes that can be fixed on the cellulose fiber by forming a chemical bond are, for example dyes, containing a chlorotriazine or chlordiazine radical. In the latter case It proves to be expedient to add an acid-binding agent, for example an alkali metal carbonate, to the padding solution or alkali phosphate, alkali borate or perborate or mixtures thereof. at The use of vat dyes is a treatment of the padded fabric after the heat treatment with an aqueous alkaline solution of a reactant customary in vat dyeing necessary.

Compared to the dye described in Example 3 of German Patent 1,099,543, the shows next comparable dye that can be produced according to the invention has the advantage of cellulose fibers from the vat to be colored in stronger and purer tones.

In the following examples, the parts mean. unless otherwise stated. Parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

C-NH-CH ₃

VI

O NH

13.6 parts of 2-phenyl-4,6-dichlorotriazine are dissolved in parts of N-methylpyrrolidone at 55 to 60 ^: .

Then 10.3 parts of 1-amino-4-benzoylaminoanthraquinone are added entered and heated in the course of 2 hours to 100 ° and for 5 hours at stirred at this temperature. After cooling, it is filtered off and washed with methanol.

6 parts of the condensation product of the formula thus obtained

O NH-C

VII

O NH-C

Il

CH ₃

VIII

200 parts of the dye paste described above, 300 parts of sodium alginate 1: 100
500 parts of water

1000 parts

A polyester fabric is padded on the padder with the treatment bath described (two passages) so that it ^{increases in weight by 50 to 60 0} O, and then dried at 60 ". The fabric is then subjected to a heat treatment at a temperature of 200 to 220 ° during Subjected for 15 to 120 seconds and then treated in a bath containing 4 g per liter of sodium hydrosulfite, 6 g per liter of sodium hydroxide solution of 36 ° Be and 30 g per liter of table salt, for 10 minutes at 60 ° and then for 20 minutes at 50 °. It is then oxidized, rinsed, soaped at the boil and finished as usual, giving a yellow dyeing with excellent fastness properties.

O NH-CO

are stirred in 200 parts of nitrobenzene and heated to 65-75. During 6 hours Monomethylamine passed through.

After cooling, it is filtered, washed with nitrobenzene, alcohol and water and dried. According to dyeing instruction B, the dye gives excellent red dyeings on polyester fibers Fastnesses.

If dimethylamine is used instead of monomethylamine, the dye of the formula is obtained

NH ₂

35

40

45 6.3 parts of 4-chloro-6-phenyl-2- [anthraquinonyl- (1) -amino] -1,3,5-triazine (obtained by condensation of 1 mole of 1-amino-anthraquinone with 1 mole of 2-phenyl-4,6 -dichlorotriazine- (1,3,5) in N-methylpyrrolidone according to the information in Belgian patent 561 166) are stirred with 500 parts of nitrobenzene in a steel autoclave. The pressure is adjusted to 8 atm by forcing in ammonia at room temperature. The reaction mixture is heated to 140 to 150 hours for 15 hours, the pressure increasing to about 38 atm. After cooling, it is filtered, washed with nitrobenzene, ethanol and water and dried.

According to dyeing instruction B, the dye gives excellent yellow dyeings on polyester fibers Fastnesses.

O NH-CO

which, dyed by the same method, gives red dyeings of excellent fastness properties.

Dyeing instruction B

14 parts of the dye of the formula VI are in a ball mill with 126 parts of a solution of 125 parts of the sodium salt of dinaphthylmethanedisulfonic acid finely ground with 1000 parts of water.

Prepare a pad bath with the following composition:

C-NH ₂

7.5 parts of 4-chloro-6-phenyl-2 - [(4) -benzoylaminoanthraquinonyl- (1) -amino] -1, 3,5-triazine are stirred with 400 parts of nitrobenzene in a steel autoclave. Then at room temperature it will last so long Ammonia pressed in until the pressure is about 8 atm. Now it is heated to 140 to 150 "and Stirred for 15 hours at this temperature. After cooling, it is filtered, washed with benzene,

Ethanol and water and dried. According to the dyeing instructions, the dye yields C on polyester fibers red dyeings of excellent fastness properties.

Dyeing instruction C

14 parts of the dye of the formula X are mixed with 14 parts of the sodium salt of dinaphthylmethanedisulfonic acid finely ground with 112 parts of water in a ball mill.

Prepare a pad bath with the following composition:

200 parts of the dye paste described above, 300 parts of sodium alginate 1: 100 500 parts

1000 pieces of ^D

A polyester-cotton blend fabric is made on the padder with the treatment bath described padded (two passages) so that it increases by 50 to 60% of its weight, and then dried at 60 °. The fabric is then heat treated at a temperature of 200 to 220 " subjected for 15 to 120 seconds and then in a bath containing 4 g per liter Sodium hydrosulfite, 6 g per liter of sodium hydroxide solution of 36 ° Be and 30 g per liter of table salt, for 10 minutes treated at 60 ° and then for 20 minutes at 50 °. Then it is oxidized, rinsed and boiled soaped and finished as usual. A yellow dyeing with excellent fastness properties is obtained.

35

40

45

O NH-C C -NH- < H

O NH-CO

6 parts of 4-chloro-6-phenyl-2 - [(4) -benzoylaminoanthraquinonyl - (1) - amino] -1,3,5 - triazine are in 100 parts of cyclohexylamine are stirred and heated to 95 to 100 ° for 2 hours, the reaction product goes into solution. After cooling, the dye can be precipitated by adding dropwise 150 parts of ethanol will. It is then filtered, washed with ethanol and water and dried. The dye produces red dyeings of excellent fastness properties on polyester fibers according to dyeing instructions B.

Claims (5)

Patent claims: 1. Process for the production of anthraquinone dyes, which are free of acidic water-solubilizing groups, thereby characterized in that 1 mol of a 4 - halogen - 6 - phenyl - 2 - anthraquinonylamino-1,3,5-triazine, the one out of a maximum of four 55 60 65 Contains dense rings existing anthraquinone radical, with 1 mole of an amine of the formula HN where Ri and Ro are hydrogen atoms, an alkyl, Cycloalkyl or hydroxyalkyl groups, where the radicals Ri and R2 may optionally be taken together can form a heterocyclic ring with the nitrogen atom, the alkyl radicals may optionally be substituted, condensed. 2. The method according to claim 1, characterized in that one of compounds of formula X O NH-C C-Y N N Cl XOX starts out, in which the X hydrogen or halogen atoms, alkoxy, aryl mercapto or acylamino groups and Y is phenyl. 3. Modification of the method according to claim 1, characterized in that a monoaminoanthraquinone, the anthraquinone radical of which contains at most four condensed rings, with a halotriazine of the formula
λΝ \ Cl-C C-Y condensed, wherein Rj, R2 and Y are those in the Claims 1 and 2 have the meaning given. 4. The method according to claim 3, characterized in that one of an aminoanthraquinone the formula NH, O X starts out, in which the X have the meaning given. 5. Process according to Claims 1 to 4, characterized in that the reaction is carried out carried out in an inert, organic solvent at elevated temperature. Considered publications:
German patent specification No. 1 099 543. When the application was announced, a coloring table provided with explanations was displayed.