CH633820A5 - Process for preparing reactive anthraquinone dyes - Google Patents

Description

633 820

PATENT CLAIMS 1. Process for the preparation of anthraquinone reactive dyes of the formula

(h03s) n

W ^ SOjH VÄ F

wherein

X! -N-R2 'with I

Ri

(I) 5 R1 '= H, CH3,

R2 '= C1-C4-alkyl, optionally substituted by SO3H, OSO3H, OH, COOH; Phenyl carboxyphenyl, m- or p-sulfophenyl, methylphenyl, methoxyphenyl, chlorophenyl, ureido-phenyl, sulfamoylphenyl and 10 R /, R2 '= - CH2-CH2-0-CH2-CH2-, means.

wherein

SOgH

nh nh yx

> ^ so3H V

fi y man compounds of the formula

(h03s) n

SO3H

The present invention relates to a process R H, optionally substituted Cx-C4-alkyl, given for the preparation of reactive dyes of the formula if substituted Q-Q-alkoxy or halogen,

X-N-R2 or optionally substituted hydrazinobe- W Y ** 2 (I)

r, ("° 3s) n

20th

indicates where

Ri = H, optionally substituted C1-C4-alkyl,

R2 = H, optionally substituted C1-C4-alkyl, optionally substituted by SO3H, COOH, halogen, ureido or acylamino, optionally substituted Q-Q-Al- ^

koxy; optionally substituted naphthyl; where Rt and R2 in which together also mean alkylene or alkylene-O-alkylene R H, optionally substituted Q-Q-alkyl,

are n are 0 or 1, characterized in that {all substituted Q-Q-alkoxy or halogen;

X N — R2, or optionally substituted hydrazino,

30 I

(HI) where

R1 = H, optionally substituted Q-Q-alkyl, R2 = H, optionally substituted Q-Q-alkyl, phenyl optionally substituted by SO3H, COOH, halogen, acylamino or ureido, optionally substituted Q-C4-Al-koxy; optionally substituted naphthyl, where Rx and R2 together can also mean alkylene or alkylene-O-alkylene, and n is 0 or 1.

In addition to hydrogen, preferred radicals R are Q-Cralkyl, in particular CH3 and C2H5, Q-Q-alkoxy, in particular OCH3, and also Cl, Br, F.

In addition to H, suitable radicals Rj are, for example, 45 C1-C4-alkyl which is optionally substituted by OH, COOH, S03H or OSO3H.

Suitable radicals R2 are, in addition to H and the radicals mentioned for Rj, in particular phenyl, optionally substituted by sulfo, carboxy, chlorine, methyl, methoxy- or ethoxy, ureido, sulfamoyl.

50 Examples of substituents X are: -NH2, -NHCH3, -N (CH3) 2, -NH-QHs, -N (C2H5) 2,

-nh-c3h7, -nh-c4h9, -nh-ch2-ch2oh, -n-ch2-ch2-oh, -n (ch2-ch2oh) 2,

with cyanuric fluoride to give the compounds of the formula

(ho3 s) n-

SOj H

(IV)

r p and then reacting the reaction product of the formula IV with compounds of the formula h-x.

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

(V)

55 ch3

-nh-ch2-ch2-oso3h, -nh-ch2-ch2-so3h, -nh-ch2-cooh, -n-ch2-ch2-so3h,

ch3

60

/ ch2-ch2s tjrnhw '

F

n-ch2-ch2-oso3h, -n-ch2-cooh, -n 'o,

l l N: h2-ch2

ch3 ch3

5

Phenylamino, m- and p-sulfophenylamino, 3,4-disulfophenylamino, 3,5-disulfophenylamino, carboxyphenylamino, chloro- or methylphenylamino, methoxyphenylamino, urei

3rd

633 820

dophenylamino, sulfamoylphenylamino and N-methyl-N-phe-nylamino.

Preferred dyes are those of the formula

0 NH "

s03h

(ii)

^ so3H V

where X! = —N — R2 'with

I.

R /

r1 '= h, ch3)

R2 '= C1-C4-alkyl, optionally substituted by S03H, 0S03H, OH, COOH;

such dyes (II) with ri '= h, ch3,

R2 '= phenyl, carboxyphenyl, m- or p-sulfophenyl, methylphenyl, ureidophenyl, suifamoylphenyl and

^; j = -ch2-ch2-o-ch2-ch2-.

The dyes (I) can be prepared in a manner known per se (cf. German Offenlegungsschrift 26 11 550).

The process according to the invention is characterized in that compounds of the formula

(h03s) n so3h

(III)

NHy ^ NH2

7 ^ S03H R 3

with cyanuric fluoride to give the compounds of the formula

(ho3 s) n-

so3h

(IV)

NKy ^ -NHN ^ N ^ P

r and then with compounds of the formula H-X

(v)

be carried out in the presence of the above-mentioned alkaline condensing agents.

It is particularly advantageous to immediately react the compounds (IV) with the compounds (V) s without intermediate insulation.

Suitable compounds (V) are, for example, ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, isobutylamine, 2-aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) amine, 10 sulfuric acid mono- (2 -aminoethyl) -ester, 2-aminoethanesulfonic acid, 2-methylaminoethanesulfonic acid, aminoacetic acid, methylaminoacetic acid, morpholine,

further aniline, 3- or 4-aminobenzenesulfonic acid, 4-aminobenzene-l, 2-disulfonic acid, 4-amino-5-methylbenzene-151,2-disulfonic acid, 5-aminobenzene-1, 3-disulfonic acid, 2-, 3-or 4-aminobenzoic acid, 2-, 3- or 4-aminotoluene, 2-, 3- or 4-chloroaniline, 2-, 3- or 4-methoxyaniline, N-methylaniline, 2-, 3- or 4-aminobenzenesulfonamide, 3- or 4-aminophenylurea, N-methylaniline, 7-aminonaphthalene-l, 3-di-20 sulfonic acid or 3-aminonaphthalene-l, 5-disulfonic acid.

The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds, they find preferred interest for dyeing hydroxyl-containing and nitrogen-containing textile materials, in particular textile materials made from native and regenerated cellulose, and also from wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive fluorine substituent (s) in the triazine ring, the products are particularly suitable as reactive dyes for dyeing cellulosic materials according to the techniques known for this purpose.

The formulas given in the description and examples are those of the free acids. In general, the alkali salts, especially the sodium salts, are obtained.

The temperature information is ° C.

35

example 1

A. 12.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 240 ml of water. The solution is made up with in disodium hydrogen phosphate solution

40 pH 4.5, drops 3.8 g of 2,4,6-trifluorotriazine-1,3,5 dropwise at 0-5 ° within 5-10 minutes and keeps the pH value at 4 with the secondary phosphate solution, 5. The reaction is complete ten minutes after the reactive component is added dropwise.

B. Now set a neutralized one, cooled to 0-5 °

45 solution of 4.8 g of 3-aminobenzenesulfonic acid in 150 ml of water to the dye solution and then keeps the pH in the mixture at 5.5-6.0. After 3 hours, the condensation of the 3-aminobenzenesulfonic acid with the difluorotriazinyl dye is complete.

50 The dye solution is allowed to warm to room temperature and the dye is salted out with so much sodium chloride that the sodium chloride concentration in the solution is approximately 18%. The precipitated dye is filtered off and washed with 500 ml of 20% sodium chloride solution. After drying at 40 ° in vacuo, a dye of the formula is obtained

The reaction of the compounds (III) with cyanuric fluoride is preferably carried out in an aqueous or organic-aqueous medium at temperatures from -10 ° to + 20 °, in particular 0 ° to + 10 °, in the presence of alkaline condensing agents, such as aqueous alkali metal hydroxide, alkali metal carbonate, Alkali hydrogen carbonate, alkali phosphate or alkali hydrogen phosphate solutions, at pH values of 2.0-7.0, preferably 3.0-6.0.

The further reaction of the compounds (IV) with the compounds (V) can be carried out at from -10 ° to + 50 °, preferably from 0 ° to 20 °, at pH values from 3 to 10, preferably 5-9, in aqueous or organic-aqueous medium

60

65

so3h trr, xvsHtr ° 'H

f

^ i303H

the cotton pull-out process from a long liquor at 40 °, in the block-cold dwell, block-steaming or block-heat-setting process dyes in wet and lightfast blue tones.

633 820

4th

The procedure is completely analogous if you want to condense the dye intermediate A with 4-aminobenzenesulfonic acid. A dye with very similar properties is then obtained.

For better storage stability, the dyes can be pasted in water with a solution of 0.6 g sodium dihydrogen phosphate (NaH2P04 • 2HzO) and 0.3 g disodium hydrogen phosphate (Na2HP04, calcined) before drying.

Example 2

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 250 ml of water with soda at pH 4.5. 2.8 g of 2,4,6-trifluorotriazine-l, 3.5 are added dropwise at 0.5 ° in the course of 5-10 minutes and the pH is kept at 4.2-4.7.10 with sodium carbonate solution The reaction is complete minutes after dropping.

B. 2.4 g of 2-aminotoluene are added to the solution of the above intermediate and the pH is then kept at 5.0-5.5 with sodium carbonate solution. The condensation has ended at 0-5 ° after one hour. The dye obtained is salted out at 20 ° with 35 g of sodium chloride, filtered off and washed with 400 ml of 10% sodium chloride solution. The dye is dried at 40 ° in a vacuum. It corresponds to the formula

Example 4

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 250 ml of water with 2.8 g of 2,4,6-trifluorotriazine-l , 3.5 at 0-5 ° and pH 4.2—4.7 analogous to

5 game 2 A implemented.

B. After the condensation of the cyanuric fluoride has ended, a solution of 3.0 g of 2-aminobenzoic acid in 200 ml of water, which is set to pH 6.0 and 0-5 °, is added to the dye solution. The condensation of the ic dye intermediate with the 2-aminobenzoic acid is completed in about 3 hours, the pH being kept between 5.5 and 6.0 by the dropwise addition of sodium carbonate solution. Adding 15% potassium chloride to the dye solution at 20 °, suction, washing with 400 ml of 20% potassium chloride solution and drying in vacuo at 40 ° gives one of the formula

0 NH2

20th

cooh

0 nh '

9 Wz so, h ch

XOTt) '

so £ "y1

p and dyes cotton in a pull-out process from a long liquor or according to the padding process common in dyeing technology in blue tones of good light and wet fastness.

Example 3

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 250 ml of water with 2.8 g of 2,4,6-trifluorotriazine-l , 3.5 at 0-5 ° and pH 4.2-4.7 implemented as in Example 2A.

B. After the condensation of the cyanuric fluoride has ended, a solution or suspension of 3.3 g of 3-aminophenylurea in 200 ml of water, cooled to 0-5 °, is added to the dye solution A. The condensation of the dye intermediate from A with the urea component becomes 0-5 ° and maintaining a pH value of 5.5-5.8 by dropping in soda solution in 2 to 3 hours to the end. By adding the solution with 50 g of sodium chloride at room temperature, suction, washing the filter cake with 300 ml of 10% sodium chloride solution and drying, a dye is obtained which has the formula

25th

Corresponding dye, which gives light and wet-fast blue tones on cotton according to the dyeing techniques known for reactive dyes.

30 Example 5

A. 12.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 240 ml of water with 3.8 g of 2,4,6-trifluorotriazine-l , 3.5 condensed at pH 4.2-4.7 and 0-5 °, the pH being maintained with in soda.

35 B. To the condensed solution is added a solution containing 3.2 g of 2-aminoethanesulfonic acid in 150 ml of water, adjusted to pH 6.5 and cooled to 0-5 °. The pH in the reaction mixture is kept at 6.5-6.8 with sodium carbonate solution. After 3 hours, the reaction mixture is left on

40 20 ° come out, salted out with 140 g of sodium chloride, suction filtered, washed the dye with 300 ml of 20% sodium chloride solution and dried at 40 ° in a vacuum. It corresponds to the formula

0 NHg s03h

45

so3h

30jH '

t f

DEAD

nh-c0-nh2

and dyes cotton from a long liquor in a pull-out process in light and wet fast blue tones.

0 nhy ^ y ^ NH ^ »^ NH-CH2-CH2-SO3H

and dyes cotton in a pull-out process from a long fleet 55 and according to the well-known block process in light and wet fast shades of blue.

A similar dye is obtained if, instead of 3.2 g of 2-aminoethanesulfonic acid, 4.0 g of mono-sulfuric acid (2-aminoethyl ester) is used.

50

Example 6

12.0 g of l-amino-4- (3'-aminophenylamino) anthraquinone-2,4'-disulfonic acid are condensed with cyanuric fluoride in the manner described in Example 2A. An aqueous solution, adjusted to pH 7, of 3.9 g of 2-methylaminoethanesulfonic acid in 40 ml of water is added to solution 65 of the reactive intermediate at 0-5 ° and the pH is kept at 6.5-6.8 with 2N sodium carbonate solution .

5

633 820

The condensation has ended after about 2 hours. The dye is now salted out at 20 ° and pH 6.5 with 18 g of potassium chloride, suction filtered and the filter cake is washed with 5% potassium chloride solution. After drying in vacuo at 40 °, a product is obtained which has the formula ch »

i 3

^ y: rsir ^ nh ^ nv-n-chg -cel, -s03 h and dyes cotton in the pull-out process and block process in blue tones of good light and wet fastness.

Example 7

To a solution of the condensation product prepared as in Example 2A of 12.0 g of l-amino-4- (3'-aminophenylamino) anthraquinone-2,4'-disulfonic acid and 3.8 g of cyanuric fluoride in 280 ml of water are given at 0-5 ° a solution of 1.7 g of 2-aminoethanol in 50 ml of water, which was previously adjusted to pH 7.0 with hydrochloric acid. The acid liberated during the onset of reaction is blunted by the dropwise addition of 2N sodium carbonate solution in such a way that a pH of 6.5-6.8 is maintained in the reaction mixture. The reaction is complete after about half an hour. The mixture is warmed to 20 ° and the dye of the formula so3h mXXm ^ ï is salted

F

nh-ch2-ch2-oh corresponds, is salted out by adding 150 g of sodium chloride and stirring for two hours, filtered off, washed with 15% sodium chloride solution and dried at 40 ° in vacuo. It dyes cellulose materials after the pull-out process, in block or print processes in light and wet-fast blue tones.

A similar dye is obtained if 3.5 g of 3-aminobenzoic acid are used instead of the 4-aminobenzoic acid.

10 Example 9

A. 9.0 g of l-amino-4- (3'-amino-6'-methoxy-phenylamino) -anthraquinone-2,4'-disulfonic acid are dissolved in 200 ml of water and the solution is adjusted to pH 4.5. After cooling to 0-5 °, 2.6 g of 2,4,6-trifluorotriazine are left in over 5 minutes.

Add 151.3.5 and keep the pH at 4.2-4.5 with soda solution. The mixture is stirred for a further 10 minutes, after which the condensation has ended.

B. 1.9 g of o-toluidine are then run into solution A and the pH is adjusted to 5.5-5.7. The free in the reaction

Acid becoming 20 is still blunted with in soda solution so that a pH value between 5.5 and 6.0 is maintained. After the condensation is complete in about Vh hours, the reaction mixture is allowed to come to 20 ° and the dye of the formula so3h is salted

30th

h3c0

NHN ^ Y "NHyN ^ NH

-V-

vS03H y f

35 with 82 g of sodium chloride, sucks off and washes the product with 15% sodium chloride solution.

After drying at 40 ° in a vacuum, a salt-containing dye is obtained which dyes cotton in light and wet fast, somewhat greenish blue tones.

with 100 g of sodium chloride, sucks it off and washes with 20% sodium chloride solution. After drying at 40 ° in a vacuum, he dyes cellulosic materials in light and wet-fast shades of blue using the exhaust process or block-steaming or block-heat-setting process.

Example 8

To a solution of the condensation product prepared as in Example 2A of 12.0 g of l-amino-4- (3'-aminophenylamino) anthraquinone, 2,4'-disulfonic acid and 3.8 g of cyanuric fluoride in 280 ml of water a solution of 3.5 g of 4-aminobenzoic acid at 0-5 °, which was prepared by neutralizing the acid in 200 ml of water with 2N sodium hydroxide solution up to pH 6.0. A pH of 5.5-6.0 is maintained in the reaction mixture by dropwise addition of sodium carbonate solution at 0-5 °, after 2V2 hours the cooling is removed and the temperature is allowed to rise to 20. After stirring overnight, the mixture is adjusted to pH 5.7. The dye that corresponds to the formula so3h

"SO5H y p

Example 10

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 250 ml of water with 2.8 g of 2,4,6-trifluorotriazine -1.3.5 condensed analogously to Example 2A. 45 B. When the reaction has ended, a solution of 0.7 g of methylamine in 20 ml of water, cooled to 0-5 °, is run in, the pH of which is adjusted to 6.5 with 10% hydrochloric acid. The pH is kept at 6.5-7.0 with in soda solution. After the condensation with 50 methylamine has ended after 3 hours, the mixture is warmed to 20 ° and the resulting dye is gradually salted out with 50 g of sodium chloride. Sucking off the precipitate, washing the filter cake with 10% sodium chloride solution and drying at 40 ° in vacuo gives a salty dye of the formula

55

60

s03h nh-ch,

^ "" iSOjH Y

p

Dyes 65 of the cellulose materials in blue tones.

A similar dye is obtained if the intermediate of stage A is condensed with 1.0 g of dimethylamine instead of 0.7 g of methylamine.

633 820

6

Example 11

A. 9.0 g of l-amino-4- (3'-amino-6'-methoxy-phenylamino) -anthraquinone-2,4'-disulfonic acid are dissolved in 180 ml of water. The solution is adjusted to pH 4.5 using 2N sodium carbonate solution and cooled to 0-5 °. Condensation is carried out by dropwise addition of 2.6 g of 2,4,6-tri-fluoro-triazine-1,3,5 within 5 minutes and maintaining a pH of 4.0-4.5 using 2N sodium carbonate solution to the difluorotriazinylamino dye, which is completed 10 minutes after the cyanuric fluoride is dropped.

B. A neutralized solution of 3.3 g of 3-aminobenzene-sulfonic acid in 70 ml of water is added to the solution of the intermediate product in this way at 0-5 °, the pH is then kept at 5.5-5.8 and after 4 hours the temperature rises to 20 °. The resulting dye, which of the formula

-so, h f

corresponds to, salted out with 50 g of potassium chloride, suction filtered and washed with 15% potassium chloride solution. After drying at 40 ° in vacuo, a salt-containing product is obtained which dyes cellulose fibers in greenish blue tones.

Example 12

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are dissolved in 200 ml of water analogously to Example 2A with 2.8 g of 2,4,6 -Trifluorotriazine-l, 3.5 condensed.

B. Now add a solution of 1.6 g aminoacetic acid in 40 ml water at 0-5 °, adjusted to pH 6.5-6.8, and keep the pH in the reaction mixture at 6.8- with 2N sodium carbonate solution. 7.0.

After the condensation has ended, the pH is adjusted to 5.5-5.7 using hydrochloric acid, so much potassium chloride is added to the solution that the KCl content is 19-20 percent by weight and stirring is continued at 20 ° overnight. The salted-out dye is filtered off, washed with 25% potassium chloride solution and dried at 40 ° in vacuo. It corresponds to the formula s03h

- nhv_ «ny'nh-chg -cooh

^^ SOjH Y f product and then maintains the pH at 0-5 ° with 2N soda solution to 5.6-5.8. When this second condensation reaction is complete after about 3 hours, the mixture is allowed to come to 20 ° and the dye is salted out with 50 g of potassium chloride. The product which has the formula s03h h3co

^ "" ^ COOH

03hV

15 corresponds to, is suctioned off, washed with 10% potassium chloride solution and dried at 40 ° in vacuo.

It dyes cellulose fibers in slightly greenish blue tones with excellent light and wet fastness.

20 Example 14

A. 9.0 g of l-amino-4- (3'-amino-6'-methoxy-phenylamino) anthraquinone-2,4'-disulfonic acid are dissolved in 180 ml of water with 2.6 g of 2,4,6- Trifluorotriazin-l, 3.5 as in Example IIA implemented.

25 B. To dissolve the intermediate formed, a solution of 1.2 g of 2-aminoethanol in 50 ml of water was added, which had previously been adjusted to pH 7.0 with hydrochloric acid and cooled to 0-5 °. A pH of 6.5-7.0 is now maintained in the mixture by means of soda solution and the condensate

30 tion ended by stirring for one hour. The batch is then heated to 20 ° under further pH control within one hour and then 80 g of sodium chloride are gradually added. The precipitated dye of the formula

35

40

so3h nbsv ^ nhvnynh-ch, -ch, -oh h3 co ^ asqjh and dyes cellulosic materials in light and wet-fast shades of blue.

A very similar dye is obtained by using 1.9 g of N-methylaminoacetic acid instead of 1.6 g of aminoacetic acid.

Example 13

A. 9.0 g l-amino-4- (3'-amino-6'-methoxy-phenylamino) -anthraquinone-2,4'-disulfonic acid are dissolved in 180 ml water and mixed with 2.6 g 2,4, 6-Trifluorotriazin-l, 3,5 condensed in the manner given in Example IIA.

B. 2.4 g of 4-aminobenzoic acid are dissolved in 120 ml of water at pH 6.0 with sodium hydroxide solution. After cooling to 0-5 °, the solution is left to the condensation prepared under A

is filtered off, the filter cake washed with 20% sodium chloride solution and dried at 40 ° in vacuo. 45 A salt-containing product is obtained which dyes cellulose fibers in somewhat greenish blue, wet and light-fast tones.

Example 15

A. 9.5 g of l-amino-4- (3'-amino-6'-methyl-phenylamino) -50 anthraquinone-2,4'-disulfonic acid are dissolved in 200 ml of water by neutralization. 2.7 g of 2,4,6-trifluorotriazine-l, 3.5 are added dropwise at 0-5 ° in the course of 5 minutes and the pH is kept at 4.2-4.7 using 2N sodium carbonate solution. The implementation is completed 10 minutes later.

55 B. A solution of 3.5 g of 3-aminobenzenesulfonic acid in 100 ml of water, which is adjusted to pH 6 and cooled to 0-5 °, is added to solution A. The pH is kept at 5.5-5.8 by dropwise addition with 2N sodium carbonate solution and the temperature is allowed to rise to 20 ° after 3 hours. The resulting dye of the formula

60

65

so3h vn v-nh-v ^ n ^ so, h xx0. "v xj h, c

"SOjH t f

7

633 820

is salted out with 100 g of sodium chloride, suction filtered and washed with 20% sodium chloride solution. After drying at 40 ° in a vacuum, a product is obtained which dyes cotton in wet-fast and lightfast shades of blue.

Example 16

A. 9.5 g of l-amino-4- (3'-amino-6'-methylphenylIamino) anthraquinone-2,4'-disulfonic acid are, as in Example 15A, in 200 ml of water with 2.7 g of 2nd , 4,6-Trifluorotriazin-l, 3.5 condensed at 0-5 ° and pH 4.2-4.7.

B. 2.1 g of 2-aminotoluene are added to the condensed-out solution and the pH is kept at 0-5 ° with in soda solution to 5.5-6.0.2 hours later, the dye of the formula formed is salted into the solution brought to 20 ° and mixed with 80 g of sodium chloride. The unusual dye of the formula is sucked in

0 nh,

hoj s sojh cil

SOYH

XCHïNrra ^ 3

■ sojh y f

soj h

NU -rr- "NH

h3 cäj ^ -sojh f

cooh corresponding product, which dyes cotton in light and wet fast shades of blue.

10th

0

, u uj h3co

"^ Asc ^ H" Y "

f, washes the filter cake with 20% sodium chloride solution and dries it at 40 ° in a vacuum. The dye dyes Cellu-15 loose materials in light and wet fast greenish blue tones.

at 20 ° with 40 g of sodium chloride, suction and wash the filter cake with 10% sodium chloride solution. Drying at 40 ° in a vacuum gives a salty dye which dyes cellulose materials in blue tones with good light and wet fastness.

A similar dye is obtained if 1.9 g of aniline is used in place of the 2-aminotoluene.

Example 17

A. 9.5 g of l-amino-4- (3'-amino-6'-methylphenylamino) anthraquinone-2,4'-disulfonic acid are dissolved in 200 ml of water with 2.7 g of 2,4,6- Trifluorotriazin-l, 3.5 condensed at 0-5 ° and pH 4.2-4.7 analogously to Example 15.

B. A solution of 2.7 g of 4-aminobenzoic acid in 130 ml of water, adjusted to pH 6, is added to the solution obtained at 0-5 °, and the pH in the mixture with 2N sodium carbonate solution is kept at 5.7-6.0 . After 3 hours, the mixture is warmed to 20 °, the dye is salted out with 75 g of potassium chloride and suction filtered. After washing with 15% potassium chloride solution and drying at 40 ° in vacuo, one of the formula is obtained

Example 19

A. 11.5 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-20 non-2,4 ', 5-trisulfonic acid are dissolved in 200 ml of water at pH 4.5 and at 0-5 ° condensed with 2.9 g of trifluorotriazine-1.3.5 while maintaining a pH of 4.2-4.5.

B. 3.1 g of 3-aminophenylurea are dissolved in 180 ml of water at 40 °. The solution is allowed to cool and added dropwise

25 0-5 ° to the solution prepared under A of the reactive intermediate. During the dropping, the pH in the mixture is kept at 5.5-5.8 and stirring is continued at this pH for 3 hours. Then the dye is salted out at 20 ° with 130 g of sodium chloride, suction filtered and washed with 20% 30 sodium chloride solution. After drying in vacuo, a dye is obtained which has the formula

0 nh-

s03h f

nh-co-nh-

40

corresponds to and cellulose materials in somewhat greenish,

light and wet-fast blue tones.

Example 20

A. 10.0 g of l-amino-4- (3'-amino-phenylamino) -anthrachi-non-2,4'-disulfonic acid are mixed at pH 4.5 in 150 ml of water with 2.8 g of 2.4. 6-Trifluorotriazin-l, 3.5 at 0-5 ° and pH 4.2-4.7 condensed analogously to Example 2A *.

5Q B. A solution of 2.2 g of bis (2-hydroxyethyl) amine in 20 ml of water, adjusted to pH 7 with hydrochloric acid and cooled to 0-5 °, is added to the condensed-out solution and the pH is kept at 2N Soda solution to 6.5-6.8. After the condensation has ended in about 1 hour, the temperature is increased to 20 ° and the solution is saturated with potassium chloride. The excreted dye of the formula

Example 18

A. 12.0 g of l-amino-4- (3'-amino-6'-methoxy-phenylamino-no) -anthraquinone-2,4 ', 6-trisulfonic acid are dissolved in 200 ml at pH 4.5. The solution is added at 0-5 ° within 5 minutes with 2.8 g of 2,4,6-trifluorotriazine-l, 3.5 and the pH is kept at 4.2 ^ 1.5 with 2N sodium carbonate solution. The condensation is completed in a further 10 minutes.

B. 2.3 g of 2-aminotoluene are added to the solution thus obtained. This second condensation stage is brought to an end by adjusting the pH to 5.5-5.8 and maintaining it at 0-5 ° with 2N soda solution. After 2 hours

60

65

so3h ch2 -ch2 oh

03 f ch2 -ch2 oh is isolated from the solution and dried at 40 ° in a vacuum. It dyes cellulose materials in wet and lightfast shades of blue.

633 820

8th

Analogously, further dyes are obtained if the anthrachi-non-compounds of the general formula in which R and n have the meaning explained in the general part contained in the left column I of the table with 2,4,6-trifluorotriazine-1,3 , 5 and the intermediate products thus obtained are condensed with the amino compound indicated in the right-hand column II of the table.

table

No.

I.

II

hue

21st

l-amino-4- (3'-aminophenylamino) -

ammonia

blue

anthraquinone-2,4'-disulfonic acid

22

do.

Aniline do.

23

do.

N-methylaniline do.

24th

do.

2-methoxyaniline do.

25th

do.

4-methoxyaniline do.

26

do.

4-aminotoluene do.

27th

do.

3-aminotoluene do.

28

do.

3-amino-4-methy! Benzenesulfonic acid do.

29

do.

5-aminobenzene-1,3-disulfonic acid do.

30th

do.

2-chloroaniline do.

31

do.

4-chloroaniline do.

32

1 - amino-4- (3'-amino-6'-methoxy-

4-aminobenzenesulfonic acid

phenylamino) -anthraquinone-2,4'-di-

blue

sulfonic acid

33

do.

3-aminobenzoic acid do.

34

do.

3-aminobenzenesulfonamide do.

35

do.

3-aminotoluene do.

36

do.

2-methoxyaniline do.

37

1 -Amino-4- (3 '-amino-6' -

2-aminoethane sulfonic acid do.

methoxy-phenylamino) -anthra-

quinone-2,4'-disulfonic acid

38

do.

2-aminoethanol do.

39

do.

Amino acetic acid do.

40

do.

n-propylamine do.

41

do.

3-chloroaniline do.

42

do.

Diethylamine do.

43

do.

6-aminonaphthalene-1,3-disulfonic acid do.

44

do.

Ammonia do.

45

do.

3-aminophenylurea do.

46

do.

Bis- (2-hydroxyethyI) amine do.

47

do.

2-methylaminoethanesulfonic acid do.

48

1 - amino-4- (3 '-amino-6' -methyl-phe-

4-aminobenzenesulfonic acid

blue

nylamino) anthraquinone-2,4'-disulfone

acid

49

do.

3-aminobenzoic acid do.

50

do.

2-aminobenzoic acid do.

51

do.

3-aminophenylurea do.

62

do.

4-aminobenzenesulfonamide do.

53

do.

N-methylaminoacetic acid do.

54

do.

2-methylaminoethanol do.

55

do.

2-aminoethanol do.

56

do.

2-aminoethanesulfonic acid do.

57

do.

2-methylaminoethanesulfonic acid do.

58

do.

4-amino-5-methylbenzene

do.

1,2-disulfonic acid

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

9

I.

l-Amino-4- (3'-aminophenylamino) anthraquinone-2,4'-disulfonic acid do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

1 -Amino-4- (3 '-amino-2'-methyl-

phenylamino) anthraquinone

2,4'-disulfonic acid do.

1 - amino-4- (3 '-amino-phenyl-

amino) -anthraquinone-2,4 ', 6-

trisulfonic acid do.

do.

l-amino-4- (3'-aminophenyl-

amino) -anthraquinone-2,4 ', 7-

trisulfonic acid do.

1 - amino-4- (3'-amino-6'-methoxy-

phenylamino) anthraquinone-2,4 ',

6-trisulfonic acid do.

1 - amino-4- (3 '-amino-phenyl-

amino) -anthraquinone-2,4 ', 5-

trisulfonic acid do.

do.

1 - Amino-4- (3 '-amino-6' -chlor-

phenylamino) anthraquinone

2,4'-disulfonic acid do.

do.

II

3-aminobenzenesulfonamide morpholine

4-amino-5-methylbenzene-1,2-disulfonic acid

Cyclohexylamine n-butylamine

2-methylaminoethanol 4-aminobenzenesulfonamide piperidine

3-NitroaniIin isopropylamine

2-aminobenzoic acid ethyl ester

4-aminobenzamide

7-aminonaphthalene-1,3-disulfonic acid

3-aminonaphthalene-1,5-disulfonic acid 3-aminoglycolic anilide 2-amino-5-sulfobenzoic acid 2-aminotoluene

3-aminobenzenesulfonic acid aniline

2-aminoethanol

3-aminobenzenesulfonamide 2-aminotoluene

3-aminophenylurea 2-aminotoluene

4-chloroaniline 4-aminobenzoic acid

Bis (2-hydroxyethyl) amine

2-methoxyaniline

3-aminobenzenesulfonic acid

2-aminotoluene 4-aminobenzoic acid