DE1164001B - Process for the preparation of anthraquinone vat dyes. - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C 09 b

Number:
File number:
Registration date:
Display day:

German class: 22 b - ■ 3/03

LIBRARY DES DEURCHEH PATEHTA MTES

1164001
C19087IV c / 22 b May 29, 1959 February 27, 1964

The invention relates to a process for the production of valuable new anthraquinone vat dyes, which contain at least one aroylamino group, the at least one group of the formula

: N-

C-X

(D

Cl

which is connected directly or via a bridge member to an aroyl radical and in which X is a means organic or inorganic substituents. So the new connections correspond preferably of the formula

: Ν ·

- NHCO - aryl - (NH) ir = rC

C-X

Cl Process for the production of anthraquinone vat dyes

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Named as inventor:

Dr. Max Stäuble, Basel,

Dr. Kurt Weber, Bottmingen (Switzerland)

Claimed priority:

Switzerland of May 30, 1958 (No. 60 082) Switzerland of April 14, 1959 (No. 72 049)

(2)

in which A is an anthraquinone radical, m and η are integers with a value of at most 2 and X has the meaning given.

The new dyes are obtained by using one of sulfonic acid and carboxyl groups free aminoanthraquinone with a reactive derivative, in particular a chloride, a Aryl carboxylic acid which has at least one group of the formula (1) directly or via a bridge member contains the aroyl radical bound, reacts and in those of the reaction products obtained, which contain a dichlorotriazine residue, a chlorine atom, optionally with a further substituent, containing at least 2 atoms.

Aminoanthraquinones suitable for the present process are both mono- and Diaminoanthraquinone called, for example 1-aminoanthraquinone and its simple substitution products, such as B. the l-amino-4-methoxyanthraquinone, the l-amino-4-, -5- or -8-acylamino- and especially -benzoylaminoanthraquinones. The latter can, for example, in the benzoyl radicals substituted by halogen atoms, methoxy, alkyl, trifluoromethyl, sulfonamide or alkyl sulfone groups be. There may also be mentioned 1,5- or 1,8-diaminoanthraquinone, 1,5-diamino-4,8-dioxyanthraquinone. There are also such aminoanthraquinones into consideration, the still fused carbocyclic or contain heterocyclic rings, for example 4 - aminoanthraquinone - 2,1 (N) - acridone, the S-Amino-l ^ -isothiazolanthron, the 4- or 5-Aminoanthrapyrimidin, the mono- or diaminoacedianthrones, the 4- or S-amino-lJ'-dianthrimide carbazole, the 4,4'- or S ^ '- diamino-l.r-dianthrimidcarbazole, 4- or S-amino-S'-benzoylamino-dianthrimide carbazole or 4-amino-4'-benzoylaminodianthrimide carbazole, 4 - amino - anthrapyridone, Aminodibenzanthrone, aminoisodibenzanthrone, aminodibenzpyrenquinone, Aminoanthanthrone, aminobenzanthrone, aminoflavanthrone as well as the compound following formula

O NH ₂

NH ₂

409 510/417

The aryl carboxylic acids used are preferably those of the formula

: N-

(HOOC-) jrAryl -

C '

Cl

(3)

in which aryl is preferably a benzene radical, η and ρ are integers with a value of at most 2 and X is an organic or inorganic substituent. Suitable substituents are chlorine atoms, alkyl, phenyl, hydroxy, alkoxy, hydroxyalkoxy, aryloxy, especially phenoxy, primary and secondary amino groups, for example an NH2 group, a mono- or dialkylamino group, for example mono- or Dimethylamino group, mono- or diethylamino group, monobutyrylamino group, ethyleneimino group, mono- or di - ^ - oxyäthylamino group, monochloroethyl or -cyanäthylaminogruppe, mono- or dicarboxymethylamino group, arylamino groups z. B. anthraquinonylamino groups and in particular phenylamino groups, which may optionally be substituted in the phenyl radical, expediently by hydrophilic groups, such as carboxyl, sulfonic acid, sulfonamide, alkyl sulfone or alkoxy groups, also groups that can convert into hydrophilic groups, for example Sulfofluoride, sulfochloride, carboxylic acid chloride, sulfuric acid ester or carboxylic acid ester groups. The radical X can also represent an alkyl or aryl mercapto group, for example a methyl, carboxymethyl, ethyl or phenyl mercapto group.

The following are examples of suitable arylcarboxylic acids of the formula (3):

2-carboxyphenylamino-4,6-dichlorotriazine, I-carboxyphenylamino- ^ amino-o-chlorotriazine, 2-carboxyphenylamino-4-dimethylamino-

6-chlorotriazine,
2-carboxyphenylamino-4-ethyleneimino-6-chlorotriazine.

2,4-Di- (carboxyphenylamino) -6-chlorotriazine, 2-carboxyphenyl-4,6-dichlorotriazine, 2,4-Di- (carboxyphenyl) -6-chlorotriazine, 2- (3 ', 5'-dicarboxyphenylamino) -4-amino-6-chlorotriazine.

The implementation of the aminoanthraquinones with the reactive derivatives, especially chlorides, the aryl carboxylic acids are expediently carried out in an inert organic solvent, for example Nitrobenzene, chlorobenzene or o-dichlorobenzene. at elevated temperature. Aryl monocarboxylic acids of formula (3) is expediently used in a molar ratio of 1: 1 with monoaminoanthraquinones or in a molar ratio of 2: 1 with diaminoanthraquinones. Aryldicarboxylic acids of the formula (3) it is expedient to react with monoaminoanthraquinones in a molar ratio of 1: 2.

If one starts from such arylcarboxylic acids of the formula (3) in which X is a chlorine atom, So of compounds that contain a dichlorotriazine, so you can get in the Arylid replace a chlorine atom with a substituent containing at least 2 atoms, so for example a hydroxy, alkoxy, hydroxyalkoxy, aryloxy or one of the above-mentioned primary or secondary amino or mercapto groups.

A modification of the present process is that one has an anthraquinone compound the formula

A - NH - COAryl - NH ₂ (4)

with a compound of the formula

Cl-C C-X

I Il (5)

N N

\ f- /

Cl

condensed, in which X has the meaning given, and in those of the reaction products obtained which still have 2 chlorine atoms on the triazine radical contain, replaced a chlorine atom by a substituent containing at least 2 atoms, ie for example 1 mole of a compound of the formula (4) is reacted with 1 mole of cyanuric chloride and the obtained Dichlorotriazine optionally reacts with a primary or secondary amine, or 2 moles of the Reacts compound of formula (4) with 1 mol of cyanuric chloride.

The dyes obtained can be isolated from the production medium and in spite of the presence of exchangeable halogen atoms can be processed into usable dry coloring preparations. the Isolation is preferably carried out by filtration. The filtered dyes can optionally are dried after adding neutral or slightly alkaline reacting agents; drying is preferably carried out at temperatures that are not too high, if appropriate at reduced temperatures Pressure made.

The new dyes are suitable for dyeing a wide variety of materials, but in particular for dyeing or printing textile materials made of natural or regenerated cellulose the usual vat dyeing and printing processes.

Since the reactivity of the halogen atoms in the triazine ring may differ slightly from case to case can, it is advantageous to the staining method, so in particular the concentration of the alkali and the Adapt the reducing agent, as well as the duration and temperature when dyeing or steaming the dye. The most favorable conditions can easily be determined through preliminary tests.

Since the dyes, in contrast to the conventional vat dyes, are made from hot dimethylformamide can usually no longer be detached from the fiber significantly, one must assume that they are chemically bonded to the fiber.

The dyeings obtained with the dyes according to the invention are therefore also fast to dry cleaning and migration-real. The dyed fabrics can therefore with synthetic resins, for example

Polyvinyl chloride, without the dye migrating into the plastic, which is especially important in the production of artificial leather.

Compared to the reactive, sulfonic acid group-containing dye of Example 6 from the Belgian Patent specification 560 734 has the next comparable vat dye according to the present invention The advantage is that it produces dyeings on cotton which are significantly better resistant to soda cooking; compared to the disperse dye mentioned under no. 29 on page 13 of Belgian patent 558 433, the one obtained according to the invention stands out The closest comparable vat dye is characterized by the fact that it has cotton dyeings with better hypochlorite bleaching fastness results.

In the following examples, unless otherwise specified, the parts are parts by weight, the percentages are percentages by weight, and the ίο Temperatures are given in degrees Celsius.

3.9 parts of the triazine derivative of the formula

example

HOOC

NH-C

• N

C-NH

COOH

N N

Cl

are suspended in 100 parts of dry nitrobenzene and with stirring with 4 parts of thionyl chloride at 100 to 105 ° into the corresponding dicarboxylic acid chloride convicted. The excess thionyl chloride is thereupon from the clear solution in Removed vacuum and then 6.9 parts of 1-amino-5-benzoylamino-anthraquinone registered. The temperature is increased to 160 to 170 ° and stirring is continued at this temperature for a further 3 hours. To as it cools down, the orange suspension of the new dye becomes of the formula

O NH-CO

NH-C

CO-NHO

C-NH

CO-NHO

N N

Cl

O NH-OC

filtered off, washed with nitrobenzene, then with alcohol and dried in vacuo at 60 to 70 °.

A dyestuff powder which is yellow-brown in the dry state and which is regenerated by cotton Cellulose dyes orange-yellow shades of very good fastness properties. The fixation of the dye on the fiber is so good that the color strength even when treated with hot organic Solvents, such as dimethylformamide or pyridine, no longer decreases significantly.

The 2,4-di- (carboxyphenylamino) -6-chlorotri ~ used as acylating component in this example Azine can, for example, by condensation of equimolecular amounts of the sodium salt of 4-aminobenzoic acid and cyanuric chloride in a molar ratio of 2: 1 in an aqueous medium at temperatures of 0 to 40 ° can be achieved by condensing at a slowly increasing temperature for so long until no more aminobenzoic acid can be detected. For the isolation of the dicarboxylic acid derivative the pH of the aqueous suspension is expediently adjusted to 2 with dilute hydrochloric acid and the the precipitate which has separated out is filtered off, washed free of acid with water and dried at 70 ° in vacuo.

Dyeing prescription

14 parts of dye are finely ground in a ball mill with 126 parts of a neutral solution of 125 parts of dinaphthylmethanedisulfonic acid in 1000 parts of water.
7.5 parts of the paste thus obtained are suspended in 250 parts of warm water. The dye suspension thus obtained is poured into a 50 ° warm solution of 10 parts by volume of 30% sodium hydroxide solution and 6 parts of sodium hydrosulfite in 1750 parts of water and vat for one minute.

In the dyebath thus obtained, 50 parts of cotton are dyed for 45 minutes at 50 to 60 ° with the addition of 60 parts of sodium chloride. After dyeing, the material to be dyed is washed out, oxidized, acidified, rinsed well again and soaped at the boil. You get an orange-yellow Dyeing of very good fastness properties.

Example 2

15.4 parts of 2,4-bis (4'-carboxyphenylamino) -6-chloro-1,3,5-triazine are in 300 parts of nitrobenzene with 24 parts of thionyl chloride and 3 parts of dimethylformamide heated to 120 ° for one hour with stirring. After distilling off the excess

Schüssigen thionyl chloride under vacuum and heated to 120 ° for 3 hours. The on at 100 ° 20 parts of 1-aminoanthraquinone entered customary manner isolated dye of the formula

O NH-CO

NH-C

: Ν ·

c-

Cl

C-NH

CO-NHO

gives yellow dyeings of good fastness properties on cotton and regenerated cellulose.

The corresponding dye from l-amino-4-benzoylaminoanthraquinone results in red dyeings of similarly good fastness properties.

In the above example, instead of 1-aminoanthraquinone, an equimolecular amount is used of the l-amino-oJ-dichloroanthraquinone, so obtained an orange-yellow dye with also very good fastness properties.

Dyeing prescription

14 parts of dye are mixed with 126 parts of a neutral solution of 125 parts of dinaphthylmethanedisulfonic acid finely ground in 1000 parts of water in a ball mill. 10 parts of the paste thus obtained are suspended in 100 parts of water. A cotton fabric is impregnated with this suspension, so that it gains 75% of its weight, and then dried. Then you impregnate it Tissue with a solution containing 16 g of sodium hydroxide, 10 to 300 g of sodium chloride and 30 g per liter Rongalit contains, squeezes to 75% weight gain, dampens the color during 1 to 9 minutes at 100 to 101 °, rinsing thoroughly in cold water, treated in a 0.5% sodium bicarbonate solution, rinses, soaps for 20 minutes at boiling temperature in a 0.3% solution of a ion-free detergent, rinses and dries. A clear yellow dyeing with good fastness properties is obtained.

3.9 parts of the triazine derivative of the formula

Example 3

HOOC

NH-C C-NH

Il I

N N

COOH

Cl

are suspended in 70 parts of dry nitrobenzene 45 6.9 parts of l-amino-5-benzoylaminoanthraquinone

dated and carried with stirring with 4 parts of thionyl chloride. The temperature is increased to 160 °

at 110 ° into the corresponding dicarboxylic acid chloride and, after adding 0.1 part of pyridine, still stirs

convicted. The excess thionyl chloride is continued for 1 hour at this temperature. After this

removed from the solution in vacuo and then cooling becomes the new dye of the formula

O NH-CO

NH-C

CO-NHO

C-NH

CO-NHO

O NH-OC

Cl

isolated by filtration, washed with nitrobenzene, then with alcohol and in vacuo at 80 ° dried.

Cotton and regenerated cellulose are dyed in yellow shades with very good fastness properties.

The acylating component used in this example can, for example, by condensation equimolecular amounts of the sodium salt of 3-aminobenzoic acid and cyanuric chloride in a molar ratio 2: 1 in an aqueous medium at temperatures from 0 to 45 ° can be prepared by at slowly increasing temperature is condensed until there is no more aminobenzoic acid can be proven. To isolate the dicarboxylic acid

ίο

derivatives, the ρκ value of the solution is expediently filtered and the precipitate is filtered off and washed free of acid adjusted to 2 with dilute hydrochloric acid and dried off and at 60 to 70 ° in vacuo.

3.9 parts of the triazine derivative of the formula

Example 4

HOOC

NH-C C-NH-

COOH

N N

\ _c /

Cl

are suspended in 100 parts of trichlorobenzene dimethylformamide, the temperature is increased and while stirring with 4 parts of thionyl chloride at 20 to 160 to 170 ° and stirred for 3 hours at this 100 to 105 ° in the corresponding dicarboxylic acid temperature,
chloride transferred. After adding 6.9 parts
l-amino-5-benzoylamino-anthraquinone and 0.1 part

O NH-CO - <(^> After cooling, the dye becomes of the formula

NH-C C-NH

Il I

N N

CO-NHO

CO-NHO

Cl

isolated by filtration with trichlorobenzene, then washed with alcohol and in vacuo at 70 to 80 ° dried.

Cotton and regenerated cellulose are dyed in yellow shades with very good fastness properties.

The acylating component used in this example can be prepared, for example, as follows will:

Equimolecular amounts of the sodium salt of 3-aminobenzoic acid and cyanuric chloride are condensed in a molar ratio of 1: 1 in an aqueous medium at 0 to 5 °. After the monocondensation has ended 1 mole of 4-aminobenzoic acid is added as an aqueous neutral solution of the sodium salt and the mixture is condensed with increasing temperature up to 40 °, until no more aminobenzoic acid can be found.

O NH-OC O NH-OC

lets show. For the isolation of the asymmetrical dicarboxylic acid derivative is acidified, filtered, washed with water and dried in vacuo at 70 °.

Example 5

3.4 parts of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are suspended in 50 parts of dry nitrobenzene and 1.0 part of dimethylformamide and 3.0 parts of thionyl chloride are added with stirring. The mixture is heated to 90 to 100 ° until it is clear Solution of the acid chloride has arisen. 3.4 parts of 1-amino-5-benzoylamino-anthraquinone are then added registered. The temperature is increased to 125 ° to 130 ° and the mixture is stirred for a further 6 hours Temperature further, then cools to room temperature and isolates the dye of the formula

-N

NH-

CO - NHO NH ₂

C-Cl

by filtration, washing with methanol and drying. The 2- (4'-carb-

at 70 °. 65 oxyphenylamino) -4-amino-6-chloro-1,3,5-triazine can

A fine suspension is obtained on cotton and regenerated by aqueous condensation

of 2-amino-4,6-dichloro-1,3,5-triazine and the sodium salt of 4-aminobenzoic acid in the molar ratio

Cellulose with this dye very real orange-yellow prints.

409 510/417

1: 1 at 30 to 40 °, or cyanuric chloride and the sodium salt are first condensed of 4-aminobenzoic acid in an aqueous medium at 0 to 4 ° to 2- (4'-carboxyphenylamino) -4,6-dichloro-1,3,5-triazine and then sets another chlorine atom at 30 to 40 ° with a little excess ammonia around.

Good results are also obtained if the acylating component is 2- (4'-carboxyphenylamino) -4-dimethylamino-6-chloro-1,3,5-triazine the formula

HOOC

Cl

HOOC

NH-C

C-Cl

N (CHs) ₂

or 2- (4'-carboxyphenylamino) -4-diethylamino-6-chloro-1,3,5-triazine the formula

N (C ₂ Hs) ₂
is used. These acylation components

ίο can be done in a similar manner as this for the 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine is described in this example, by aqueous condensation of the sodium salt of 4-aminobenzoic acid with 2-dimethylamino-4,6-dichlorotriazine or with 2-diethylamino-4,6-dichlorotriazine will.

Similar, cotton and regenerated cellulose in those in column III of the table below Dyes coloring specified shades are obtained if in the above example instead of the l-Amino-5-benzoylamino-anthraquinones the equimolecular Amount of the starting materials listed in column II of the table below used will:

III

O NH ₂

Cl
Cl

Orange yellow

N N

yellow

H ₂ NO

O NH-OC

NH ₂

yellow

O NH ₂

NH ₂

Red

Printing specification

28 parts of dye are mixed with 112 parts of a neutral solution of 125 parts of Dinapthylmethandisulfonsäure in 1000 parts of water in a ball mill ground.

A printing paste is prepared with the following composition:

100 parts of the dye paste described above, 300 parts of water,
600 parts of thickening KD,
1000 parts

Thickening KD

ί 20 parts of locust bean gum are used in
\ 450 parts of water sprinkled.

15 parts of wheat starch are added
20 parts of water slurried and with
Diluted 495 parts of boiling water.

a and b are put together, boiled for 20 minutes and stirred until cold. As a preservative 1 part by volume of a 30% strength aqueous formaldehyde solution is added.

The printing paste is applied to a cotton or rayon fabric with the aid of a blind printing machine

imprinted. The fabric is dried, impregnated with a solution containing 24 g of sodium hydroxide per liter, Contains 70 g of sodium hydrosulphite, 50 g of sodium sulphate and 20 g of borax, for a 70% weight gain squeezed off and fixed in the Monforts reactor at 120 ° for 24 seconds. Then it will be rinsed thoroughly with cold water, reoxidized at 40 °, with a solution containing 5 parts by volume per liter Contains hydrogen peroxide (30%) and 3 parts by volume of acetic acid (40%), rinsed, 15 minutes Soaped at the boil, rinsed and dried.

A clear, orange-yellow print with excellent fastness properties is obtained.

Example 6

3.2 parts of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are in 100 parts of nitrobenzene with 2.5 parts of thionyl chloride at 95 to 100 ° in the corresponding carboxylic acid chloride converted. After adding 0.2 parts of pyridine, 1.4 parts are obtained L, 5-diamino-4,8 ~ dioxyanthraquinone registered in the solution and the temperature with stirring at 120 to 125 ° held for 2 hours. Finally, 1 hour at 150 to 155 ° heated, then cooled to room temperature and the dye of the formula

• N

HO O NH - OC

NH-

H ₂ N - C

C-NH

C-NH ₂

CO -NHO OH

Cl

N N

V /

Cl

isolated by filtration and dried.

The dye dyes cotton and regenerated cellulose in blue-violet shades of very good Solvent fastness.

Example 7

6.4 parts of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are in 100 parts of nitrobenzene with 5 parts of thionyl chloride with the addition of 0.5 part of pyridine at 90 to 100 ° in the corresponding Carboxylic acid chloride transferred. The excess thionyl chloride is removed from the solution in vacuo removed and then entered 2.4 parts of 1,5-diaminoanthrene ^ quinone. Then you raise * the temperature in the course of an hour to 150 to 155 ° and stirring is continued for 3 hours at this temperature. The yellow-brown suspension of the dye of the formula

O NH - OC

NH-C C-Cl

«Να — c

NH ₂

C-NH

Il

CO - NH O _c
NH ₂

is isolated by filtration, washed with nitrobenzene, then alcohol and in vacuo at 70 ° dried.

Cotton and regenerated cellulose are made with this dye in shades of very orange good fastness properties. The color is also resistant to hot organic solvents.

Is used in this example instead of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine an equimolecular amount of the 2- (4'-carboxy-

phenylamino) -4-dimethylamino-6-chloro-1,3,5-triazine or 2- (4'-carboxyphenylamino) -4-diethylamino-6-chloro-1,3,5-triazine or of 2- (3'-carboxyphenylamino-4-amino-6-chloro-1,3,5-triazine, this gives dyes with similar properties.

Example 8

5.1 parts of the condensation product from 4-aminobenzoic acid, Cyanuric chloride and sulfanilic acid of the formula

HOOC

NH SO ₃ H

are used as acylation components with 5.0 parts of thionyl chloride and 1.0 part of dimethylformamide by heating for 2 hours at 90 to 100 ° in 100 parts of nitrobenzene into the corresponding Carbonsäuresulfonsäuredichlorid converted. 3.0 parts of 1-amino-5-benzoylaminoanthraquinone are then added added and heated to 130 to 135 ° for 3 hours. After cooling to room temperature the orange dye suspension isolated by filtration and washed with alcohol and in vacuo dried at 70 to 80 °.

The likely formula dye

O NH

CO-NHO

NH

SO ₂ Cl

dyes cotton and regenerated cellulose in yellow shades of very good washfastness.

The acylating component used in this example can be carried out in an aqueous medium Condensation of the sodium salt of 4-aminobenzoic acid with cyanuric chloride at 0 to 5 ° in a molar ratio 1: 1 and further by adding a molecular weight of the sodium salt of sulfanilic acid can be made by running this second condensation at 30 to 40 ° and for so long at one pH 6.0 to 7.5 sodium hydroxide solution is added dropwise until a solution is formed and no more sulfanilic acid can be detected. By adding sodium chloride, the condensation product can from seine'Lösung, deposited as disodium salt in crystalline form and isolated by filtration will.

Example 9

45 10.1 parts of 2,4-bis (4'-carboxyphenyl) -6-oxy-1,3,5-tri-

Azine are dissolved in 100 parts of nitrobenzene with the addition of 24 parts of thionyl chloride and 2 parts of dimethylformamide slowly heated to 110 ° with stirring.

The resulting clear solution is kept at 110 ° for 45 minutes and then cooled, with the product crystallized in long fine needles. It is filtered off and washed with dry petroleum ether and dried under vacuum at room temperature.

The product of the formula

Cl-CO

CO - Cl

crystallizes from acetone in long fine needles and has a melting point of 212 ° (uncorrected).

4 parts of this acid chloride are dissolved in 150 parts of nitrobenzene at 60 ° to give a clear solution. Then 6.9 parts

1-Ammo-5-benzoylamino-anthraquinone entered this temperature kept. The usual way and slowly heated to 120 ° and 5 hours with isolated dye of the formula

O NH-CO

CO-NHO

/ ^N \

C C

CO-NHO

Cl

O NH-CO

gives clear yellow dyeings of good fastness properties on cotton and regenerated cellulose. Of the Corresponding dye from 1-aminoanthraquinone gives off a greenish yellow color, that one I-Amino-4-benzoylamino-anthraquinone red shades.

The analogous dye of the formula

dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat in greenish blue Tones of good fastness properties.

2,4-bis- (4'-carboxyphenyl) -6-oxy-1,3,5-triazine can from 2,4-bis- (4'-tolyl) -6-oxy-1,3,5-triazine through Oxidation can be obtained with potassium permanganate in alkaline aqueous solution.

Example IO
9.4 parts of 2- (4'-carboxyphenylamino) -4,6-dichloro-1,3,5-triazine are heated to 110 ° in 350 parts of nitrobenzene with 12 parts of thionyl chloride and 1.5 parts of dimethylformamide for 2 hours. After the excess thionyl chloride has been distilled off in vacuo, 10.2 parts of 4-aminoanthraquinone-2,1 (N) -acridone are introduced at 50 ° and heated to 80 ° for 16 hours and to 100 ° for 6 hours. The dye of the formula isolated in the usual way

O NH-CO

Cl

NH-C C-Cl

N _n /

dyes cotton and regenerated cellulose in green-blue shades with good fastness properties.

Example 11

8.8 parts of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are dissolved in 350 parts of nitrobenzene with the addition of 12 parts of thionyl chloride and.

1.5 parts of dimethylformamide slowly heated to 120 ° with stirring, the compound with evolution of hydrochloric acid goes into solution. After 15 minutes the excess thionyl chloride is removed under vacuum distilled off, and at 70 ° 10.2 parts of 4-aminoanthraquinone-2, l (N) -acridone entered and heated to 100 ° and 1 hour to 120 ° for 2 hours. After this

409 510/417

The blue dye in the formula will cool down

O NH - CO

NH-C C-Cl

I Il

N N

isolated by filtration and, after washing with alcohol, dried in vacuo at 90 to 100 °. Cotton and regenerated cellulose are good with this dye in green-blue tones Dyed fastness properties.

NH ₂

Example 12

4.2 parts of aminoacedianthrone are mixed with 3.2 parts of the carboxylic acid chloride of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine acylated in 100 parts of nitrobenzene and 0.2 part of pyridine by heating for 6 hours with stirring at 140 to 150 °.

After cooling to room temperature, the dye has the formula

Cl

N N

NH-OC

NH

NH ₂

isolated by filtration, with nitrobenzene, then 40 Similar good results are obtained when in this

Washed alcohol and dried in vacuo at 70 °.

Cotton and regenerated cellulose are dyed in real brown tones.

Example instead of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine the equimolecular amount of 2- (4'-carboxyphenylamino) -4-phenyl-6-chloro-1,3,5-triazine the formula

HOOC

N N

II NH-C C

or of 2- (4'-carboxyphenylamino) -4-phenoxy-6-chloro-1,3,5-triazine of the formula

Cl \

HOOC

il NH-C N
CO

be used. These acylation components can by aqueous condensation of equimolecular Quantities of the sodium salt of 4-aminobenzoic acid and finely suspended

2-phenyl-4,6-dichlorotriazine or 2-phenoxy-4,6-dichlorotriazine produced at 40 ° in crystalline form will.

Example 13

j, 2 parts of 2- (3'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are suspended in 100 parts of dry nitrobenzene and stirred with

2.0 parts of thionyl chloride were added. The mixture is heated to 90 to 100 °, with one over the course of 2 hours clear solution of the corresponding carboxylic acid chloride has formed. 3.45 parts are worn on it 1 - amino - 5 - benzoylaminoanthraquinone and increases the temperature to 135 to 140 °. At this Temperature is stirred for a further 6 hours, then cooled to room temperature. The dye the formula

O NH-OC

CO - NH O

is isolated by filtration, washed with alcohol and dried in vacuo at 70 °.

Cotton and regenerated cellulose are dyed in very real, orange-yellow tones.

The 2- (3'-carboxyphenylamino) -4-amino-6-chloro used in this example 1,3,5-triazine can be obtained by aqueous condensation of a fine suspension of 2-amino-4,6-dichloro-1,3,5-triazine and the sodium salt of 3-aminobenzoic acid in a molar ratio 1: 1 at 30 to 40 °.

• N

NH-C

y /

C-NH ₂

Cl

Example 14

6.1 parts of the carboxylic acid chloride of 2- (4'-carboxyphenylamino) - 4,6 - dichloro -1,3,5 - triazine dissolved in 200 parts of nitrobenzene at 100 °. Then 9.6 parts of 1-aminoanthraquinone are entered, heated in the course of 45 minutes to 160 ° and stirred for 5 hours at this temperature held.

The dye of the formula

Cl

N N

O NH-CO

NH-C

C - NHO

O O

gives yellow dyeings of very good fastness properties on cotton and regenerated cellulose. The analogue represented dye of the formula

Cl

O NH-

NH-C C - NHO

results from
Colorations.

CO -NHO

alkaline hydrosulphite vat golden yellow

Example 15

7 parts of 2- (4'-carboxyphenyl) -4,6-dioxy-1,3,5-triazine are in 250 parts of nitrobenzene with stirring

O NH-CO

heated with 24 parts of thionyl chloride and 3 parts of dimethylformamide to 105 ° and 2 hours at this Temperature held. Then the excess thionyl chloride is distilled off under vacuum. At 80 13.7 parts of 1-aminoanthraquinone are entered and heated to 100 ° over the course of 30 minutes. Then 4 hours to 100, 2 hours to! 20

23 24

and heated to 140 ° for 3 hours. The dye of the formula isolated in the usual way

O NH - CO

/ ^N \

C C -NHO

N N

\ _c /

Cl

gives clear yellow dyeings with good fastness properties on cotton and regenerated cellulose. The analogue represented dye of the formula

O NH - CO

CO - NH O

results from alkaline hydrosulfite vat dyed on cotton and regenerated cellulose golden orange Dyeings of good fastness properties.

Red dyeings of similarly good fastness properties are obtained with the analogous dye from 1-amino-4-benzoylaminoanthraquinone obtained while the dye from 4-aminoanthraquinone-2, l (N) -acridone gives green-blue nuances.

2- (4'-Carboxyphenyl) -4,6-dioxy-1,3,5-triazine can be obtained from 2- (4'-tolyl) -4,6-dioxy-1,3,5-triazine by oxidation be obtained with potassium permanganate in alkaline aqueous solution.

c - NHO
I Il V CO / ^N < V I.
NH- 16 c ^y X i play CI Il
0 Be

6.5 parts of 2- (4'-carboxyphenylamino) -4-phenyl-6-chloro-1,3,5-triazine are in 120 parts of nitrobenzene with the addition of 4.8 parts of thionyl chloride for 1 hour heated to 110 °. From the resulting clear solution the excess thionyl chloride is removed by distilling off under vacuum. Be at 80 ° Entered 4.6 parts of 1-aminoanthraquinone and held at 80 ° for 24 hours. The usual way isolated dye of the formula

O NH

dyes cotton and regenerated cellulose in clear yellow tones of good entities. The dye of the formula

O NH-CO

NH-C

/ ^N \

C-O

Il

Cl

which is obtained if, in the above example, 7.6 parts of 2- (4'-carboxyphenylamino) -4-phenoxy-6-chloro-1,3,5-triazine begins, results in similar, slightly greener nuances.

Example 17

3.2 parts of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5-triazine are in 100 parts of nitrobenzene with 4 parts of thionyl chloride with the addition of 0.5 part of dimethylformamide at 100 to 110 ° in the corresponding carboxylic acid chloride converted. The excess thionyl chloride is from the Removed solution in vacuo and then registered 4.7 parts of aminodibenzanthrone. After adding 0.5 part of pyridine is heated with stirring for 6 hours at 140 ° to 150 °, then for a further 3 hours

to 160 to 170 °. After cooling, the dye becomes of the formula

NH-OC

isolated by filtration, washed with nitrobenzene, then alcohol and dried in vacuo at 70 °.

Cotton and regenerated cellulose are dyed in very real black-green tones.

If, in this example, the aminoisodibenzanthrone is used instead of the aminodibenzanthrone, in this way a dye is obtained which dyes cotton in violet shades of similar properties.

Cl

N N

NH-C

C-NH ₂

Example 18

2.3 parts of 4,5 ^/ -Diamino-l, r-dianthrimide carbazole are mixed according to Example 7 with 3.2 parts of the carboxylic acid chloride of 2- (4'-carboxyphenylamino) -4-amino-6-chloro-1,3,5 -triazines acylated and isolated.

The dye of the formula

H ₂ NC

Cl

C-NH

CO -NHO

O NH - OC

NH

Cl -C

N N

C C-NH ₂

colors cotton and regenerated cellulose in brown amino) -4-amino-6-chloro-1,3,5-triazine equimolecular Shades of very good fastness properties. Amounts of 2- (4'-carboxyphenylamino) -4-phenyl-

Is used in place of 2- (4'-carboxyphenylamino-6-chloro-1,3,5-triazine of the formula

HOOC

C-NH

or of 2- (4'-carboxyphenylamino) -4-cyclohexylamino-6-chloro-1,3,5-triazine of the formula

HOOC- / V-NH-C C-NH

N N

Cl

this gives dyes with similar properties. rigem medium by condensation of the sodium these Acylating components can be mixed in the aqueous salt of 4-aminobenzoic acid with cyanuric chloride

409 510/417

in a molar ratio of 1: 1 at 0 to 5 ° and further by adding a molar weight of aniline hydrochloride or cyclohexylamine hydrochloride are produced by this second condensation at 30 carried out up to 40 ° and allowed to drop in sodium hydroxide solution at a pH value of 6.5 to 7.5, until no more primary amino group can be detected. By adding dilute hydrochloric acid the free carboxylic acid is then completely precipitated and isolated by filtration.

Claims (3)

Patent claims: 1. Process for the production of anthraquinone vat dyes, characterized in that one of sulfonic acid and carboxyl group-free aminoanthraquinone with a reactive derivative of an aryl carboxylic acid, the at least one group of the formula ; N- - C C-X Cl
wherein X is an organic or inorganic 10 Substituents means, contains directly or via a bridge member attached to the aroyl radical, converts and in those of the reaction products obtained which contain a dichlorotriazine residue contain, one chlorine atom optionally by one containing at least 2 atoms Substituents replaced. 2. The method according to claim 1, characterized in that there is an aminoanthraquinone with a compound of the formula (ClCO ^ aryl - (NH) j ^ : N- C.
Cl c - x Il where aryl is a benzene residue, X is a chlorine atom or an amino group, η and ρ are integers with a value of at most 2. 3. The method according to claim 2, characterized in that that a monoaminoanthraquinone with a dicarboxylic acid chloride of the formula ClCO - aryl - c- Cl in a molar ratio of 2: 1, in which aryl is a benzene radical and η is an integer with a value of at most 2. 4. Modification of the method according to claim 2 and 3, characterized in that one an anthraquinone compound of the formula A - NH - CO - aryl - NH ₂
with a compound of the formula CI-C C-X 50 C - (NH) iprAryl - COCl converts, in which X has the meaning given in claim 1. 5. The method according to claim 4, characterized in that cyanuric chloride with a Compound of formula A - NH - CO - aryl - NH ₂
in a molar ratio of 1: 2. 55 Considered publications:
Belgian patents nos. 558 433, 560 734. When the application was announced, two coloring tables with explanations were laid out. * C ' Cl