DE1267769B - Process for the preparation of water-soluble dis- and tetrakis-azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German class: 22-5

Number: 1 267 769

File drawing: P 12 67 769.9-43

Filing date: February 23, 1960

Opening day: May 9, 1968

The invention relates to the production of new water-soluble dis- and tetrakis-azo dyes for Dyeing cotton and wool. They can contain reactive groups. On textile fabrics they bring orange to brown tints with excellent bleach fastness as well as higher Washfastness, which is generally characteristic of dyes that are reactive with the fiber. Those new dyes that do not contain reactive groups are suitable for dyeing of cellulose substances modified by cyanuric acid residues and produce orange to brown tints on them, which are also excellent Have the authenticity of the above-mentioned dyes with fiber-reactive groups.

The new disazo compounds prepared according to the invention have the general formula

Xm-Ri-N = N-Ra-N = N-Rj-NHZ Y «(D

in which X and Y the water solubility causing sulfo or carboxyl groups, ζ. B. SO _:! H, COOH or alkali or ammonium salts thereof, Ri the dehydrothio-p-toluidine radical or a benzene or naphthalene radical which is unsubstituted or substituted in the nucleus, for example by chlorine, methyl, ethyl or methoxy groups, Ro a bonded in 1,4-position Benzene or naphthalene radical or a substituted derivative of such a radical, Ri is a p-phenylene radical optionally substituted by the groups indicated above and Z is a methyl or ethyl group. It should be noted that in all of the above cases the benzene or naphthalene radical can be substituted one or two times by chlorine, methyl, ethyl or methoxy radicals, while Ri and Ro, but not R: s, have further sulfo and carboxyl groups can contain up to a total of four in both residues; however, one of the two radicals Ri or Ro can also be free of sulfo and carboxyl groups, provided that the other radical is substituted by at least one of these groups.

The new dyes can be prepared by diazotizing an arylamine of the formula

Process for the preparation of water-soluble
Dis- and tetrakis-azo dyes

Applicant:

E. I. du Pont de Nemours and Company,

Wilmington, Del. (V. St. A.)

Representative:

Dr.-Ing. W. Abitz, patent attorney,
8000 Munich 27, Pienzenauer Str. 28

Named as inventor:
Roy Emerson Starn Jr.,
Wilmington, Del. (V. St. A.)

Claimed priority:

V. St. v. America March 13, 1959 (799 090),

dated December 9, 1959

(858 306)

means), coupling the product with an arylamine the formula

Y «- Rs - NH ₂

(where Ro and Y have the above meanings and // denotes an integer from 0 to 2 inclusive, with the proviso that the sum of m and ;; is not less than 1 and not greater than 4), repeated diazotization and coupling of the Diazotization product with a compound of the formula

Ru - NHZ

wherein R _; s and Z have the above meanings.

If the hydrogen atom of the group - NHZ is replaced by the benzoyl group by adding a Reacts dye of the above general formula with benzoyl chloride, one obtains a acidic dye for wool of the formula

X _n , -R ₁ -N = NR ₂ -N = NR., -

X ", - R, - NH-.

(where Ri and X have the above meanings and /;; any number from 0 to 3 inclusive

Direct dyes for cotton are obtained by phosgenating the new disazo dyes. Here

801 548 310

symmetrical Tetra kis azo dyes of the general formula arise

From Austrian patent specification 200 686, disazo dyes are of the general formula

C ₁ , -, Η

X »-

= NR ₂ -N = NR ₁ -

D-N = N-A-N-C

ii-1 "2 ii-I

C - halogen

CO

X ₁₁₁ -R ₁ -N = NR ₂ -N = NR ₃ -N

An essentially equimolecular one can optionally be used as the starting material for the phosgenation Use a mixture of two different disazo dyes of the formula (I), in which case the product a statistical mixture of symmetrical and asymmetrical tetrakis-azo dyes is formed, whose The main component is the asymmetrical dye.

A dye that is reactive with the fiber (for dyeing textiles that contain OH-, NH-, NHi or ONa residues) is z. B. obtained by reacting a dye of the formula I with Cyanuric acid chloride. With an analogous reaction with an appropriately monosubstituted dichlorotriazine becomes a monosubstituted monochlorotriazine radical of the formula

Ii

C-Cl

obtained, in which Q the NHi flu, an alkylamino group, a hydroxyalkylamino group. may represent an arylamino group, a sulfonated arylamino group, and so on. Furthermore, the group reactive with the fiber can be an aryloxycarbonyl radical. which is introduced by reacting the new dyes of the formula (I) with an NHZ radical with an aryl chloroformate, such as phenyl chloroformate C _(i H ₅ - O - COCl, as described in French patent 1 268 654 the group reactive with the fiber may be a halopyrimidine group which is introduced, for example, by reaction with chloropyrimidine and the like according to British patent specification 822 047.

The dyes according to formula (I) without a reactive radical are suitable for dyeing cellulose fabrics, those modified with cyanuric acid residues or in some other way to introduce a reactive one Binding group in the fiber have been treated. Details on the treatment of 'cellulose for the purpose of introducing reactive linking groups, U.S. Patent 1,886,480 described.

N N

halogen

(III) 15 known, in which D is the remainder of a diazo component containing an azo group and at least one sulfonic acid, A is the remainder of an azo component of the benzene series and η is a positive integer, preferably 1.

In these known disazo dyes, the halogen-substituted 1,3,5-triazine radical is attached to the Azo component A preferably bonded via an NH group. Furthermore, the diazo component D in the known disazo dyes as substituents, inter alia, also hydroxyl or Contain amino groups. However, it has been found that such dyes according to the invention available disazo dyes are inferior in terms of their bleach fastness and that it is for the bleaching fastness of the disazo dye depends on the fact that the chromophoric group is present the molecular member causing the reactivity with the fiber (e.g. the halotriazine residue) an NCHj or NC ^ Hö group is bonded and that also the chromophoric part of the dye molecule has no OH, NH> or NH groups as substituents. The from the invention The disazo dyes produced by the disazo compounds produced meet these requirements by definition.

In the following examples, the parts given relate to amounts by weight.

example 1

980 parts of aniline-2.5-disulfonic acid are dissolved in 6 (X) O parts of water, and the solution is successively with 530 parts of 10N hydrochloric acid. 4000 parts Ice and 860 parts of 5N sodium nitrite solution. After an hour, the excess nitrous acid is with. Sulphamic acid decomposes. Man first gives a solution of 520 parts of 2,5-dimethoxyaniline. 3000 parts of water and 420 parts 10 η-hydrochloric acid and then 40 parts of sodium form iat to. The reaction mixture is stirred for 30 minutes.

heated to 80 C, salted out with table salt to 25 percent by volume and filtered. After drying and When ground, 1182 parts of dry powder are obtained, which contains 86 ° »of the theoretical amount of azo nitrogen.

70 parts of the powder are dissolved in 500 parts of water and 17 parts of 10 η sodium hydroxide solution. One relocates with 49 parts of 5N sodium nitrite solution and adds this solution over the course of an hour to one A solution of 8.2 parts of sulfuric acid in 160 parts of water at 25 ° C. is added. The mixture is stirred for 3 hours, with so much 5N sodium nitrite solution is added that the solution constantly reacts strongly with starch-iodide test paper gives. Then the over-

Excess nitrous acid destroyed with sulfamic acid and 12.2 parts of N-methylm-toluidine are added to the solution. After 3 minutes you sit 40 parts of crystalline sodium acetate are added and the mixture is stirred for a further hour. The mixture is heated to 70 ° C. and salted Table salt to 10 percent by volume and filtered. The product is after drying and grinding a dark brown powder that easily dissolves in water, bluish purple in color in alkaline solution and shows reddish-purple color in acidic solution. This dye has the in the form of its free acid Structural formula

SO ₃ H

OCH ₃

SO ₃ H

N = N

OCH ₃

NHCH ₃

If in this example the 12.2 parts of N-methyl-m-toluidine are replaced by 13.6 parts of N-ethylm-toluidine, this is how the homologous end product is obtained. You can also use aniline-2,5-disulfonic acid instead of use an equivalent amount (785 parts) of 2-methoxyaniline-5-sulfonic acid in the first process stage and perform the rest of the procedure in the same manner. In this case you get that Product analogous to the above formula, which has very similar physical and chemical properties owns.

Example 2

35 parts of 10 η-hydrochloric acid become a solution of 34.7 parts of 2-amino-6,8-naphthalenedisulfonic acid. 4 (X) parts of water, 26 parts of 5N sodium nitrite solution and added enough ice to bring the temperature down to 8C. To Stirring for 15 minutes at 8 to K) C is the excess nitrous acid with sulfamic acid destroyed and the pH adjusted to 4 by adding 16 parts of K) η sodium hydroxide solution. Relies on this a solution of 20.1 parts of l-amino-6-naphthalenesilphonic acid in 100 parts of water and enough sodium hydroxide to bring the pH to 8 bring to. Then over the course of 15 minutes 11 parts of 10 η sodium hydroxide solution are added, whereupon the mixture is stirred for a further 10 minutes. The excess diazo compound is destroyed by adding 33 parts of K) η sodium hydroxide solution and the mixture for 10 minutes touched. The solution is then cooled to 5 ° C. and successively with 22 parts of 5N sodium nitrite solution and 64 parts of K) η-hydrochloric acid are added. The mixture is stirred for 30 minutes at 8 to 10 ° C. and the excess nitrous acid with sulfamic acid and initially sets 11.9 parts of N-methyl-m-toluidine and then 65 parts of crystalline sodium acetate. After a few hours you add so much Sodium chloride so that a 10 percent by volume sodium chloride solution is formed, and the product is filtered off. To After drying and grinding the product is a brown powder which easily dissolves in water blue-violet color dissolves. In the form of its free acid, the dye has the structural formula

SO ₃ H

N = N

HO ₃ S

SO ₃ H

Example 3

A solution of 75.8 parts of 2-amino-p-benzenedisulfonic acid. 1200 parts of water and 52 parts of 10 η-hydrochloric acid are cooled to 5 C and 77 parts 5 N sodium nitrite solution added. After 30 minutes, the excess nitrous acid is with Sulphamic acid decomposes. A slurry of 60.4 parts of 1-amino-6-naphthalenesulfonic acid is added in 300 parts of water and adjusts the pH by adding 78 parts of 10N sodium hydroxide solution on 4 a. Then 30 parts of crystalline sodium acetate are added and the mixture is stirred for 40 minutes. The mixture is heated to 60 ° C., 140 parts of sodium chloride are added and the precipitate is filtered off.

The aminoazo compound is dissolved in 1700 parts of water and the pH is adjusted to 7.5. It is then cooled to 15 ° C. by adding ice. successively sets 70 parts of 5N sodium nitrite solution and 98 parts of 10η-hydrochloric acid. stirs for 1 hour at 15 to 20 C and destroys the excess nitrous Acid with sulfamic acid. Then 32.6 parts of N-methyl-m-toluidine and KX) TeUe of crystalline sodium acetate and stirred overnight at room temperature. The solution will be heated to 55 to 60 ° C., the pH value was adjusted to 9.5 with sodium hydroxide solution and the product was added salted out of table salt until a 20 percent by volume solution is reached and filtered off. After drying and grinding, one obtains a

7 '8

brown powder, which easily dissolves in water with a red-violet color. The dye has in Its free acid form the structural formula

SO ₃ H

SO ₃ H

NHCH,

SO ₃ H

Example 4

In Example 3, the slurry of 60.4 parts of 1-amino-6-naphlhalinsulfonic acid is replaced in 300 parts Water by a solution of 41 parts of 5-methyl-2-methoxyaniline (cresidin) in 300 parts of water and 35 parts of 10n hydrochloric acid, a dye of the structural formula is obtained

SO ₃ H

N = N

NHCH ₃

SO ₃ H

OCH ₃

in the form of a dark powder, which easily dissolves in water with a purple color.

Example 5

It is set at a pH of 7.5 aUs 300 parts Water and 28.2 parts of the coupling product of diazotized 2-amino-6,8-naphthalenedisulfonic acid and m-toluidine, mixed with 13.5 parts of 5N sodium nitrite solution, cooled to K) C and adds 23 parts of 10 η-hydrochloric acid. The mixture is stirred for 45 minutes at 10 to 15 C and the excess is destroyed nitrous acid with silfamic acid. After adding 5.9 parts of N-methylaniline, the mixture is stirred over Night at room temperature. Then 15 parts of crystalline sodium acetate are added and the mixture is stirred 24 hours at room temperature. The aminodisazo compound is isolated by adjusting the pH adjusts to 7 with 10 η sodium hydroxide solution, heated to 50 C, salted out with table salt to 20 percent by volume, acidified with 28 parts of 10 η hydrochloric acid and the product filtered off. Possesses in the form of its free acid the dye has the structural formula

SO ₃ H

CH,

HO ₃ S

N = N

N = N

NHCH,

The 5.9 parts of N-methylaniline can be replaced by 6.7 parts of N-ethylaniline or by 9.5 parts of N-methyl-2-chloro-5-methoxyaniline be replaced. Similar dyes are obtained in both cases.

B e i s ρ i e 1

In Example 3, the 75.8 parts of 2-amino-p-benzoidisulfonic acid are replaced by 117 parts of dehydrothiophetoluidine disulfonic acid. The dye, which in the form of its free acid has the structural formula

N = N

NHCH ₃

SO ₃ H

possesses, you get as a dark brown powder, which is easily soluble in water.

Example 7

A solution of 33 parts of the MethylaminodisazofarbsiofTes prepared according to Example 1 in 400 parts Water is adjusted to a pH of 6.5 and cooled to 0 to 5 ° C. One relocates with a solution of 9.3 parts of cyanuric acid chloride in 40 parts of acetone. Then one stops in the course one hour at a temperature of 0 to 5 C the pH by adding about 31 parts

10

2 N sodium carbonate solution between 4.0 and 5.0. The mixture is warmed to 25 ° C. and the pH value is maintained for 30 minutes by adding about 48 parts of 2N sodium carbonate solution to 6.0 to 6.5. Then it is filtered, the filtrate with common salt Salted out 20 percent by volume and the product filtered off and dried in a vacuum desiccator. In In the form of its free acid, the product has the structural formula

SO ₃ H OCH, CH,

J = N - <^ Y - N = N SO ₃ H OCH ₃

Cl

N Y

N-C C-Cl

I \,

CH ₃

'N'

If the above product is padded on cotton at room temperature and then the fabric is dried and treated further according to Example 18, one obtains scarlet tints of excellent Fastness to light and chlorine bleach.

30 Example 8

The dye obtained according to Example 7 is dissolved in 200 parts of water and the solution in 2.7 parts concentrated ammonium hydroxide. The mixture is stirred for 3 hours at room temperature and then

1 hour at 40 to 45 C. Then 2.7 parts of concentrated ammonium hydroxide are added and the pH value for another hour by adding

2 N sodium carbonate solution between 8.5 and 9.0. It is then cooled to room temperature and stirred over At night, the product is filtered off and dried at 80 C. The dye possesses in the form of its free acid the structural formula

Cl

N N

SO ₃ H OCH ₃ CH ₃

N = N - <V- N = N - / Y- NC C - NH ₂

ι ρο N

S0, H OCH, * - " ³

The dye product is a brown powder that is readily soluble in water. When dyeing cotton according to Example 18, it provides scarlet tints of excellent fastness to light and chlorine bleach.

The new dyes can also be used directly for dyeing those modified with cyanuric acid residues (or treated in an analogous manner) cellulose fibers can be used, which in turn according to Example 1 the USA.-Palentschrift 1 886 480 can be produced. The fiber treated in this way can with the New disazo compounds prepared according to the invention according to Example 5 of the USA.-Palentschrift 1 886 480 or according to the following example 19 (, 5 be treated.

In all cases, pale-fast and light-fast dye colors are obtained from the following shades:

When using the dye
according to the example

Color tint

scarlet

Brown

Yellow-brown

Leather brown

orange

The following examples illustrate the preparation of new dyes that are reactive with the fiber.

801 Md 310

Example 9

The moist cake obtained according to Example 2 is dissolved in 8 (K) parts of water at 20 to 25 ° C and the solution is adjusted to pH 6. 520 parts of a solution are added, the 37.7 parts contains primary condensation product of sodium metanilate and cyanuric acid chloride. The pH

the solution is kept at 5.5 ± 0.3 by gradually adding K) η sodium hydroxide solution over the course of an hour at 20 to 25 C and in the course of 30 minutes at 40 to 50 C is added. The solution is made with table salt salted out to 15 percent by volume, and the precipitated dye is filtered off and heated to 80.degree dried.

The dye has the structural formula

SO ₁ Na

NaO ₃ S

N = N

N = N

SO ₃ Na

Cl

N N

I i!

N-C

I \

CH ₃

SO ₃ Na

Il / - \

is a brown powder and dissolves in water to form a brown solution. He dyes cotton after that in the method described in Example 18 in brown shades of excellent lightfastness and washfastness and be of particularly great authenticity the bleach with 0.3 "" chlorine.

The 520 parts of the above primary condensation product can be prepared as follows will:

A solution of 20.7 parts of cyanuric acid chloride in 100 parts of acetone is added to 167 parts of ice and 50 parts of water. This slurry is mixed with a solution of 21.4 parts of sodium metanilate over the course of 15 minutes. 33 parts of water and sufficient hydrochloric acid to adjust the pH to 6 and 17.3 parts of crystalline sodium acetal were replaced. After a short time, the test for diazolizable amine is negative, and 11.7 parts of 25 are added

10 n sodium hydroxide solution. to neutralize the acetic acid.

Example 10

The moist cake obtained according to Example 3 is dissolved in 2700 parts of water and the pH is adjusted to 6 set. The solution is mixed with 1750 parts of a solution, the 127 parts of the primary condensation product of cyanuric acid chloride and sodium metanilate (prepared according to Example 9). By adding small amounts of 10 N sodium hydroxide solution, the pH value is increased for 1 hour at 20 to 25 C and held at 5.5 ± 0.3 for another hour at 40 to 50 C. The solution is made with table salt to 20 percent by volume salted out and the product filtered off and dried at 80.degree. The product has the formula

SO ₃ Na

SO ₃ Na

N = N

SO ₃ Na

SO ₃ Na

and is a brown powder that dissolves in water with a brown color. It dyes cotton according to Example 18 in brown shades of excellent fastness to washing, chlorine bleach and light.

Replaces the N-methyl-m-toluidine of the example 3 by 29 parts of m-tohiidine and otherwise works according to Example 3 and the above procedure of this example, a dye is obtained in the form of a brown powder, which is in water dissolves with brown paint. Following the procedure of Example 18, the dye dyes cotton brown Tints. However, these dyeings have a much poorer chlorine fastness than those dyeings which are carried out with the dye prepared from N-methyl-m-toluidine, which the - N group

CH: i

between the chromophoric dye group and the triazine ring.

Example 11

Example 10 is followed, but the moist cake obtained according to Example 4 is used the end. The product is a brown powder that dissolves in water to form a leather-brown solution. Of the Fabric dyes cotton using the method of

Example 18 in leather brown tints of excellent Authenticity against washing. Chlorine bleach and light.

Example 12

The moist filter cake obtained according to the first paragraph of Example 5 is divided into 500 parts Dissolved water at 55 to 60 C and the solution with 13 parts of 10 n sodium hydroxide to a pH value of 6 set. This solution is mixed with 450 parts of a solution containing 32 parts of the primary condensation product of cyanuric acid chloride and 2-aminop-benzenedisulfonic acid contains. The pH is 30 minutes by carefully adding 9 parts of 10 »sodium hydroxide solution at a temperature of 55 to 60 C kept in the range from 4.0 to 5.5.

The solution is alis salted to 20 percent by volume with common salt and replaced with 405 parts of 10 η-hydrochloric acid and the precipitate is filtered off. The light cake is made in 100 parts of water and 560 parts Slurried dimethylformamide. The salt is filtered off and the filtrate with 5500 parts of acetone offset. The product which separates out as a precipitate is filtered off and dried.

The dye, a yellow powder, dissolves in water with an orange-yellow color. It dyes cotton following the procedure of Example 18 in a yellow-orange-colored tint. The colorations are excellent Fastness to washing, chlorine bleach and light.

The solution of the primary condensation product of 2-amino-p-beiizoldisulfonic acid and cyanuric acid chloride can be made as follows:

A solution of 21.2 parts of 2-amino-p-benzene disulfonic acid, 50 parts of water and 12 parts of 10 η sodium hydroxide solution become a slurry added by dissolving 14.7 parts of cyanuric acid chloride is made in 55 parts of acetone and the addition of 160 parts of ice. By adding a Solution of 16.2 parts of trisodium phosphate dodeahydrate in 100 parts of water over the course of 2 hours the pH is kept at a temperature of 0 to 5 C in the range of 3.5 to 5.5.

If the primary condensation product of cyanuric acid chloride and sodium metanilate (Example ¹ ) is condensed with the melhylaminodisazo compound according to Example 1 by the general process described above, a dye of the structural formula which is reactive with the fiber is obtained

Cl

SO., Well OCH., CH,

_/ - N = N-- -N = N-

SO ₁ Well OCH.,

N N

- N - C C C - NH

^; N ''
CU,

SOjNa

This dye is a water-soluble, brown puKer. what cotton according to the procedure of example 18 colors scarlet red.

The following examples serve to further illustrate the preparation of more direct, developed ones or dyes reactive with the fiber.

dye
Example _dtfs example

I nmeset / t nut

Usable as

Preserved color

ClC OCiH.-,

Trichloropyrimidine

ClOC

NO-

and subsequent reduction with Na ^ S

ClOC - CHoCl
COCl ..

reactive dye for yellow brown
cotton

reactive dye for yellow brown
Cotton !

developed dye for
cotton

reactive dye for
Wool

Direct dye for cotton

Brown, if with, / - naphthol
developed

Red-brown
Brown

In the following some implementation will be made that the weight gain of the fabric is 60 " ₍₎ .

Coloring requests described. After drying, the fabric is again in

. . · Padded the same way with a solution that

Typical dyeing process _{& 5 2} 5 »., Sodium chloride and 1.2% sodium hydroxide

A 4.15 "aqueous solution of any containing. The wet fabric is steamed for 2 minutes

Dyes prepared according to Examples 8 to 12 and then with a solution at the boiling point for 2 minutes

is padded on cotton cloth at 70 C. washed, the 0.3 "0 sodium carbonate and 0.2%

Contains condensation product of 20 moles of ethylene oxide and 1 mole of CV alcohol.

Coloring of cellulose modified by cyanuric acid residues

A solution of 2.5 parts of any of the dyes obtained according to Examples 1 to 6 is prepared, 100 parts of water and 1.5 parts of sodium bicarbonate. In the solution there will be 10 parts cotton yarn modified by cyanuric acid residues, which according to Example 1 of the LLSA.-Pafentschrift 1 886 480 is made. The mixture is then heated to 100 ° C. over the course of 30 minutes continues the dyeing process at this temperature for 60 minutes. The yarn comes out of the solution taken out and washed at boiling point for 2 minutes with a solution containing 0.3 ° ό sodium carbonate and 0.2 "/ (i contains the condensation product of 20 moles of ethylene oxide and 1 mole of cis-alcohol Rinsing is used to dry the yarn.

The details described in the above examples can be further understood by those skilled in the art current limits can be changed. So the radicals Ri, R; and R: s except those in the above Examples given special meanings also have the following meanings:

Ri can be aniline, metanilic acid, p-aminobenzoic acid, p-chloroaniline. l-aminonaphthalm-3,6,8-trisulfonic acid, Cresidin. Mean 4-chloro-2-aminotoluene or 5-chloro-2-aminotoluene.

Ri can be o-phenetidine. 3-ethylaniline, 2-ethyl-oxy-1-naphthylamine. l-aminonaphthalene-7-sulfonic acid. 1 - aminonaphthalene - 6.8 - disulfonic acid. m - chloraniline or 2-amino-4-methoxybenzoic acid.

R: s can be N-ethyl- or N-methyl-m-chloroaniline, N - methyl - m - ethylaniline. N - methyl - m - anisidine, N - ethyl - m - anisidine, N - methyl - ο - toluidine, N - methyl - 2,5 - dimethylaniline. 5 - chloro - 2 - methyl-N - methylaniline. N - methyl - ο-anisidine, 2,5 - dimethoxy-N-methylaniline or 5-methyl-2-methoxy-N-methylaniline.

In the examples, the substituent Q of the triazine ring is a residue of metanilic acid or 2-aminop-benzenedisulfonic acid. Instead of these triazines, one can also use condensation products of cyanuric acid chloride (condensed on the first chlorine atom) use with the following materials: ammonia: primary aliphatic amines, such as methylamine, Ethylamine, butylamine. Monoethanolamine and 3-methoxypropylamine; the usual primary aromatic amines such as o-, m- or p-toluidine, ο-, m- or p-chloroaniline and anthranilic acid; sulfonated aromatic amines such as 7-aminonaphthalene-1,3-disulfonic acid and 8-aminonaphthalene-1,3.6-trisulfonic acid; secondary aliphatic amines such as dimethylamine, dibulylamine. Methylisopropylamine, Diethanolamine and N-methyl-3-methoxypropylamine; secondary aromatic Amines such as N-methylaniline or N-ethyl-m-toluidine; lower alcohols such as methyl, ethyl or butyl alcohol; Thio alcohols such as methyl mercaplan or isopropyl mercaptan; etc.

In general, triazine compounds can be used in which the radical Q of the triazine ring the can have the following meanings: O-alkyl groups, S-alkyl groups, primary amino groups, monoalkylamino, Dialkylamino-. Monoalkanolamino-. Dialkanolamino, arvlamino and N-alkvl-arvlamino groups. the arylamino- and N-alkyl-arylaminoresles, the groups optionally brought about by the water-soluble wedge, such as the sulfo or Carboxyl group, the alkyl and alkanol groups having 1 to 4 carbon atoms and the arylresle of the benzene or naphlalin series.

It should be noted that the radicals Ri and R-> are to be selected according to the invention in such a way that they are in the structural unit

Ri-N = -N-R-.

one to four ionogenic. causing the water solubility Groups are located. The substituent Q of the triazine ring can also be the water-soluble wedge own inducing groups. As a result, the dyes obtained as end products can under May contain seven sulfo groups. It should also be noted that to ensure a good Water solubility the whole molecule should preferably contain not less than two sulfo groups. Therefore, if the group

R, - N - N - Ri

Contains only one sulfo group, the choice of an aryl radical is recommended for the radical Q, which is at least contains a sulfo group.

In the examples, the dyes are isolated in the form of their sodium salts. By salting out with Potassium chloride leads to the corresponding potassium salts. The isolated dyes can also by treatment with aqueous acids (e.g. sulfuric acid or hydrochloric acid) in the free SO: iH- or COOH form, and the acidic solutions can be with any Alkali hydroxide (especially NaOH, KOH or LiOH) or neutralized with ammonium hydroxide so that the corresponding alkali metal salts or ammonium salts are obtained.

Many other possible modifications are familiar to the person skilled in the art.

The fiber-reactive dyes are suitable for ■ dyeing materials that contain exchangeable hydrogen atoms own, e.g. B. of textile fibers. especially cellulose fiber !!, wool. Silk, super polyamides and similar materials including paper. Leather. Plastic films etc .. the remnants, such as OH, ONa, or NH NHi, included. These reactive dyes deliver orange to brown tints and are particularly characterized by their authenticity Bleach solutions. that contain significant amounts of chlorine (0.3 "(1)). Another beneficial property except for the excellent wash fastness that can be expected from reactive dyes the excellent lightfastness. So has z. B. the orange dye according to Example 12 in the Measurement in a lightfastness meter shows a durability of 80 to 160 hours. Generally own the new dyes have excellent acid and alkaline perspiration fastness as well as etchability.

Claims (2)

Patent claims: 1. Process for the production of water-soluble Dis- and Teliakis-a / olarbsioffen. there - characterized by that one Arylamine of the formula X, "- Ri-NH ₂ where X is sulfo or carboxyl groups causing the solubility in water, m is an integer from 0 to 3 and Ri is a benzene, naphthalene, dehydrothio-p-toluidine radical or a radical formed by Cl, CH _:! , C ₂ H-, or OCH _:! Substituted benzene or naphthalene radical means, diazotized, the product with an arylamine of the formula 15th in which Y sulfo or carboxyl groups causing the solubility in water, // an integer from 0 to 2, R _{2 is} an unsubstituted benzene or benzene group bonded in the 1,4-position or substituted by Cl, CH:!, C _{2 H-, or OCHs} Naphthalene radical means, couples, the coupling product is diazotized again and the product of the second diazotization with a compound of the formula Rn - NHZ, in which R _{: i is} an unsubstituted or bonded in 1,4-position by Cl, CH _{: i} . C ₂ H.- ,. or 0CH _:! substituted benzene radical and Z is an alkyl radical having 1 or 2 carbon atoms, with formation of a disazo dye of the general formula 30 X _1n -R ₁ -N = NR ₂ -N = NR ₃ -NHZ Y " where m + η is not less than 1 and not greater than 4, coupling, whereupon either the hydrogen atom of the NHZ radical is replaced by a benzoyl group or a group reactive with the fiber or a phosgenation of the disazo dye to form a tetrakis azo dye general formula Y " X ₁₁₁ -RJ -N = NR ₂ -N = NR, -N X ₁₁₁ -R ₁ -N = NR ₂ -N = NR ₃ -N ⁷
Y ₁ , feels through. 2. The method according to claim 1, characterized in that one introduces the reactive group as reaction partner a substituted or unsubstituted halotriazine, a Halogenpyrimidin or an aryl chloroformate with 6 to 12 carbon atoms in the Aryl core used. Considered publications:
Austrian patent specification No. 200 686:
French Patent No. 1,268,654;
British Patent No. 822 047. When the registration is announced, there are two color tables with explanations and an insurance report has been laid out.