CH638826A5 - Process for preparing reactive dyes of the anthraquinone type - Google Patents

Description

The present invention relates to a process for the preparation of new anthraquinone dyes of the formula

0 NH,

CIL, N

S03H

50

(I)

55

(c "* M-CTYz wherein R and Z have the meaning given in claim 1.

3. The method according to claim 1, characterized in that dyes of the formula

60

65

wherein

R represents hydrogen or optionally substituted C) -C4-alkyl,

R, for hydrogen or halogen,

Ri for hydrogen. CrC4-alkyl, CrC4-acoxy or halogen, such as chlorine or bromine,

n for 1, 2, 3 or 4 and

Z represents an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally etherified thiol group or an optionally substituted hydrocarbon radical

638 826

Examples of optionally substituted alkyl groups R are the methyl, ethyl, n-propyl, ß-hydroxyethyl, ß-methoxy-ethyl, carboxymethyl and the ß-sulfoethyl group.

Halogen substituents R are preferably chlorine, bromine or fluorine. Examples of substituents R2 are the methyl, ethyl, methoxy and ethoxy group.

Suitable Z radicals are, for example, amino, mono-C rC4-alkylamino and di-CrC4-alkylamino, where the alkyl group may optionally be substituted, for example by OH, sulfo or OSO3H, phenylamino, optionally substituted by CrC4-alkyl, sulfo, CrC4-alkoxy , Carboxy, halogen, especially chlorine and the corresponding NC, -C4-alkyl-N-phenylamino groups; Phenyl-Q-Q-alkylamino, where the phenyl radical can be substituted as indicated above; and the corresponding N-CrC4-alkyl-N-phenyl-Ci-C4-alkylaminore-ste, naphthylamino optionally substituted by sulfo; Cr C4 alkoxy optionally substituted by hydroxy; Phenoxy, optionally substituted by Q-Q-alkyl, sulfo; CrC4 alkylthio optionally substituted by OH; Phenylthio. Suitable hydrocarbon radicals are, for example, CrC4-alkyl and phenyl.

Examples of substituents Z on the triazine ring are as follows: the amino, methylamino, ethylamino, β-hydroxyethylamino, dimethylamino, morpholino, piperidino, N- (o-, m-, p-sulfophenylamino amino , N- (o-, m-, p-methylphenyl) amino, N- (o-, m-, p-methoxyphenyl) amino, N- (o-, m-, p-chlorophenyl) amino, N- (2,4-or 2,5-disulfophenyl) amino, N- (2-sulfo-4-methoxyphenyl) amino, N- (2-sulfo-4-methylphenyl) amino, N- (2 -Sulfo-4-chlorophenyl) amino, N- (2-carboxy-4- or 5-sulfophenyl) amino, N- (2-carboxyphenyl) amino, N- (2,5-disulfo-4-meth- oxyphenyl) amino, N- (3,5-disulfo-4-aminophenyl) amino, N- (4-sulfomethylphenyl) amino, N-methylaminobenzyl, N-methylaminobenzyl-3-sulfonic acid, N- (5- or 6- or 7- or 8-sulfo-naphthyl-2) -amino, N- (4,8-disulfo-naphthyl-2) -amino group; the methoxy, ethoxy, ß- Hydroxyethoxy, phenoxy, methylphenoxy, phenylthio and the 2-mercapto-benzthiazole group and amino groups with dye character, such as, for example, amino group-containing dye residues of the mono- or polyazo , Phthalocyanine, formazane, anthraquinone, stilbene, oxazine, dioxazine, triphenylmethane, nitro or azomethine series. The radical Z can also contain further reactive groups.

Preferred compounds which can be prepared according to the invention are compounds of the form iH.

wherein R 'represents hydrogen, the methyl or ethyl group and Z' represents an optionally substituted amino group. Compounds of the formula are particularly preferred

S03 H

10th

15

(IV)

wherein

R 'has the meaning given above and D represents the residue of an optionally substituted benzene mono- or disulfonic acid or an optionally substituted naphthalene mono-, di- or trisulfonic acid. The process according to the invention for the preparation of the dyes of the formula I is characterized in that dyes of the formula

25th

30th

R,

(V)

wherein R, R), R2 and n have the meaning given above, with condensation products of the formula

40

(VI)

S03 H

F

where Z has the meaning given above, with elimination of HF. This reaction is generally carried out in aqueous solution or suspension at weakly acidic, neutral or weakly alkaline pH values, the hydrogen fluoride liberated in (II) 43 of the reaction advantageously being continuously neutralized by adding aqueous alkali metal lye, carbonate or hydrogen carbonate.

Examples of compounds of the formula

50

T

55

where R and Z have the meaning given.

Further preferred compounds are dyes of the formula

(III)

fio

Z '

65

where Z have the meaning given above are, for example:

2,4-difluoro-6-amino-l, 3,5-triazine, 2,4-difluoro-6-phenylamino-1,3,5-triazine, 2,4-difluoro-6- (4'-sulfophenyl) -amino-l, 3,5-triazine, 2,4-difluoro-6- (3'-sulfophenyl) -amino-l, 3,5-triazine, 2,4-difluoro-6- (2'-sulfophenyI) -amino-l, 3,5-triazine, 2,4-difluoro-6- (2 ', 5'-disulfophenyl) -amino-l, 3,5-triazine, 2,4-difluoro-6- (2' , 4'-disulfophenyl) amino-l, 3,5-triazine, 2,4-difluoro-6- (3 ', 5'-disulfo-4-aminophenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2 ', 5'-disulfo-4-methoxyphenyl) amino-l, 3,5-triazine,

2,4-difluoro-6- (2'-carboxy-4-sulfophenyl) amino-l, 3,5-triazine, 2,4-difluoro-6- (2'-carboxy-5-sulfophenyl) amino-l , 3,5-triazine,

638 826

4th

2,4-difluoro-6- (2 '.4'-disulfonaphthyl-1') amino-1,3,5-triazine, 2,4-difluoro-6- (1 ', 5'-disulfo- naphthyl-2 ') - amino-l, 3,5-triazine, 2,4-difluoro-6- (2'-methylphenyl) -amino-l, 3,5-triazine, 2,4-difluoro-6- (2 '-methoxyphenyl) -amino-1,3,5-triazine, 2,4-difluoro-6- (2'-chlorophenyl) -amìno-l, 3,5-triazine, 2,4-difluoro-6- (4th '-methylphenyl) amino-l, 3,5-triazine, 2,4-difluoro-6- (N-methyl-benzyl) -amino-l, 3,5-triazine, 2,4-difluoro-6- ( N-methyl-phenyl) amino-l, 3,5-triazine, 2,4-difluoro-6- (4'-sulfonaphthyl-l ') amino-l, 3,5-triazine, 2,4 Difluoro-6- (6'-sulfonaphthyl-2. ') Amino-l, 3,5-triazine, 2,4-difluoro-6- (4'-sulfomethylphenyl) amino-l, 3,5 -triazine, 2,4-difluoro-6- (2'-carboxy-phenyl) -atnino-l, 3,5-triazine, 2,4-difluoro-6-piperidino-l, 3,5-triazine, 2, 4-difluoro-6-morpholino-l, 3,5-triazine, 2,4-difluoro-6-methylamino-l, 3,5-triazine, 2,4-difluoro-6-ß-hydroxyethylamino-l, 3, 5-triazine, 2,4-difluoro-6-dimethylamino-l, 3,5-triazine, 2,4-difluoro-6-methoxy-l, 3,5-triazine, 2,4-difluoro-6-phenoxy- 1,3,5-triazine,

as well as the intermediate products with dye character, e.g. Reaction products of dyes of the mono- or polyazo, phthalocyanine, formazane, anthraquinone, stilbene, oxazine, dioxazine, triphenylmethane, nitro or azomethine series with 2,4,6-trifluoro-l, 3,5- triazine.

The new dyes are suitable for dyeing and printing materials containing hydroxyl or amide groups, such as textile fibers, threads and fabrics made of wool, silk, synthetic polyamide and polyurethane fibers, and for dyeing and printing true to life on native or regenerated cellulose, the treatment of Cellulose materials are expediently carried out in the presence of acid-binding agents and, if appropriate, by the action of heat by the processes which have become known for reactive dyes.

The formulas given for the dyes are those for the corresponding free acids. The dyes were generally isolated in the form of the alkali salts, in particular the sodium salts, and used for dyeing.

example 1

29.7 g of disodium salt of aniline-2,5-disulfonic acid are dissolved in 0.51 of ice water. 13.5 g of 2,4,6-trifluoro-l, 3,5-triazine are then added dropwise, at the same time adding dilute sodium hydroxide solution in order to maintain a pH of 3-4. After adding the cyanuric fluoride, stirring is continued for a few minutes and then a solution of 45.9 g of the sodium salt of the dye of the formula is added dropwise

SO, well

H-N-H

CI13

in 11 water. At the same time, dilute sodium hydroxide solution is added to the extent that the pH is 7-8. Throwing in ice maintains a temperature of 5-10 ° during the condensation. The result is a blue solution from which the dye is separated by salting out with 25% by volume of table salt. After drying and grinding, a blue powder is obtained, which easily dissolves in water with a blue color. In the form of the free acid, the dye corresponds to the following formula:

■ NH

If one proceeds according to the information in this example, but using an amount of amine equivalent to the aniline-2,5-disulfonic acid, this likewise results in valuable dyes with a similar shade (example 12: bluish green).

example

Amine

2nd

p-sulfanilic acid

3rd

Aniline-2,4-disulfonic acid

4th

Aniline-3,5-disulfonic acid

5

l-amino-2,5-disulfo-4-methoxy-benzene

6

1,4-diamino-2,6-disulfo-benzene

7

4-aminobenzyl sulfonic acid

8th

l-amino-4-sulfonaphthalene

9

l-amino-2,4-disulfonaphthalene

10th

l-amino-4,7-disulfonaphthalene

11

2-amino-l, 5-disulfonaphthalene

12

4'-amino-4- (5,7-disulfonaphtho [1,2-d] triazol-2-yl) -

stilbene-2,2'-disulfonic acid

13

2-aminotoluene-3,5-disulfonic acid

14

l-amino-2-methoxy-5-sulfobenzene

15

l-amino-2-sulfo-4-chloro-benzene

16

l-amino-2-carboxy-4-sulfo-benzene

17th

l-amino-2-carboxy-5-sulfo-benzene

Likewise valuable dyes are obtained if, instead of the anthraquinone dye used in Example 1, the following are used:

Y>

0 NH- ^)

CHjNHjj

SO, H

OCH.

H

Dyeing examples of printing instructions If you print cotton nettle with a printing paste that contains 20 g of the dye shown in Example 1, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate / kg of thickening) and 10 g of soda per kilogram, and that with water 1 kg was filled up, dried, steamed for 1 minute at 103 ° C, rinsed with hot water and boiling with soap, see above

5

10th

15

20th

25th

30th

35

40

45

50

55

60

55

5

638 826

you get a clear, blue print of good wet and light fastness.

Block regulation

30 parts of the dye shown in Example 1 are dissolved in 1000 parts of water. A cotton fabric is padded with this solution and pressed down to a weight loss of 90%. The still moist cotton is treated at 70 ° for 30 minutes in a bath which contains 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate dissolved in 1000 parts of water. The coloring is then usually completed. You get a brilliant blue with excellent wet and light fastness.

Staining instructions 168 ml of water at 20-25 ° are placed in a 300 ml staining cup in a heatable water bath. 0.3 g of that obtained according to Example 1 is used

Dye well with 2 ml of cold water and add 30 ml of hot water (70 °); the dye dissolves. The dye solution is added to the water provided and 10% cotton yarn in this dye liquor is kept constantly in motion. 5 Within 10 minutes, the temperature of the dyeing liquor is increased to 40-50 °, 10 g of anhydrous sodium sulfate are added and the dyeing is continued for 30 minutes. Then you add 4 g of anhydrous sodium carbonate to the dyeing liquor and dye for 60 minutes at 40-50 °. The dyed material is then removed from the dyeing liquor, the adhering liquor is removed by wringing or pressing and the material is rinsed first with cold water and then with hot water until the washing liquor is no longer bled on. The dyed material is then soaped in 200 ml of a liquor which contains 0.2 g of sodium alkyl sulfate for 15-20 minutes at the boiling point, rinsed again and dried at 60-70 ° in a drying cabinet. You get a brilliant blue with excellent wash and light fastness.

M

Claims (2)

638 826 PATENT CLAIMS 1. Process for the preparation of anthraquinone reactive dyes of the formula 2 S03 H 0 NHa (I) R ' CII2Nx ^ v, Z ' (CH2) .nN R wherein R represents hydrogen or optionally substituted CrC4-alkyl, Ri for hydrogen or halogen, R2 for hydrogen, CrC4-alkyl, CrC4-acoxy or halogen, n for 1, 2, 3 or 4 and Z represents an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally etherified thiol group or an optionally substituted hydrocarbon radical, characterized in that dyes of the formula 10th wherein R 'represents hydrogen, the methyl or ethyl group and 15 Z' represents an optionally substituted amino group. 4. The method according to claim 1, characterized in that dyes of the formula 25th (!) jÂî— R ' H CH> U / M S03H (V) * R (CHa) n -N-H wherein R |, Ri, R and n have the meaning given above, with compounds of the formula 35 * VYZ (VI) 40 wherein R 'represents hydrogen, the methyl or ethyl group and D represents the remainder of an optionally substituted benzene mono- or disulfonic acid or an optionally substituted napahthalene mono-, di- or trisulfonic acid, manufactures. 5. The method according spoke 1, characterized in that halogen in the compounds obtained is R2 in the meaning of chlorine or bromine. 45 with the elimination of HF, where Z has the meaning given above. 2. The method according to claim 1, characterized in that dyes of the formula