CH635860A5 - REACTIVE DYES AND THEIR PRODUCTION. - Google Patents

Description

The invention relates to reactive dyes of the formula

0

cu-0

r- (1st

a - n = n- / bvr = n

(so3h) - ^ _ 3

\

f n -

c c

«

1

11

V Ri n

n

V

* c

1

f

1-2

(i).

where A is a benzene or naphthalene radical which may contain further substituents, the benzene radical B may contain further substituents, R! and R2 independently of one another each have a hydrogen atom or an optionally substituted alkyl radical

65

with 1 to 4 carbon atoms and R3 is a hydrogen atom, an optionally substituted alkyl radical with 1 to 4 carbon atoms, an optionally substituted aralkyl or aryl radical and the radical or radicals of the formula

635 860

r n - ro t J

Ro

(2)

10th

n - c c i i it n n i

f is bound to A and / or to the naphthalene nucleus, which carries one of the two complex-forming oxygen atoms.

The radicals A and B can contain the substituents customary for azo dyes. Further substituents are e.g. the following are contemplated: alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propyloxy, isopropyloxy and butyoxy, acylamino groups having 1 to 6 carbon atoms such as acetylamino, propionylamino and benzoylamino, amino groups such as -NH2, methylamino and ethylamino, the ureido, hydroxyl and carboxy group, halogen such as fluorine, chlorine and bromine, and 20 the sulfonic acid group.

The radical A contains in particular one or more sulfonic acid group (s) as further substituents. The radical B contains a further substituent, in particular in the para position to the complex-forming oxygen atom. If Rj and R2 are alkyl residues 25, these can be substituted, e.g. by chlorine, hydroxy, cyan, carboxy and sulfo. Examples of Rx and R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, ß-hydroxyethyl, ß-chloroethyl, ß-cyanoethyl, ß-cyanomethyl, y -Cyanpropyl, ß-carboxyethyl, sulfomethyl and ß-sulfoethyl. For R3 come e.g. into consideration: hydrogen, the same substituted and unsubstituted alkyl radicals mentioned above for Rj and R2, alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy radical and 1 to 4

30th

35

Carbon atoms in the alkyl radical, such as methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-sulfobenzyl, 4-methylbenzyl, phenethyl and especially phenyl, which is substituted by C ^ alkyl, C ^ alkoxy, acetylamino, Ureido, carboxy, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl may be substituted, or naphthyl which may be substituted by sulfo; furthermore, R2 and R3 can be closed to form a six-membered N-heterocyclic ring which can contain another heteroatom, such as nitrogen, oxygen and sulfur. Examples of the amino radical -NR2R3 in formula (1) are: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, β-methoxyethylamino, y-methoxypropylamino, N, N-dimethylamino, N, N-diethylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, ß-chloroethylamino, ß-hydroxyethylamino, Y-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, piperazino, and especially aromatic amino groups, such as phenylamino, toluene , Xylidino, chloranilino, anisidino, phenetidino, 2-, 3- and 4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, N-sulphomomethylanilino, 3- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2- Carboxy-4-sulfophenylamino, 4-sulfo-naphthyl- (l) -amino, 3,6-dislulfonaphthyl- (l) -amino, 3,6,8-trisulfo-naphthyl- (l) -amino and 4,6, 8-trisulfonaphthyl- (l) amino.

The reactive dyes of the formula (1) can have one or two residues of the formula (2). If a reactive dye of the formula (1) has only one radical of the formula (2), this is bound either to A or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms; however, if it has two radicals of the formula (2), one is bound to A and the other to the naphthalene nucleus mentioned above.

Reactive dyes of the formula are preferred

0

Cu-0

- N = N

(S03H) l-3

1AN -

C C

Ï »

1 11

\ Ri

N N

V1

vc /

N

f

F

(3),

1-2

wherein X is hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or halogen and A, Rj, R3 and R3 have the meanings given under formula (1), in particular reactive dyes of the formula (3), wherein A a benzene residue, which can be substituted by sulfo, methyl, methoxy, carboxy and chlorine, or a naphthalene residue, which can be substituted by sulfo, Rj hydrogen, methyl, or ß-hydroxyethyl, R2 hydrogen, methyl or ethyl, R3 water

45 serstoff, methyl, ethyl, butyl, methoxypropyl, ß-hydroxyethyl, ß-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxy, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl can, or naphthyl, which can be substituted by sulfo, and 50 X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine.

Reactive dyes of the formula y4 / ~ n "N ~ v = y N are particularly preferred

(SO3H) 1_2 X

N - C

I t

R,

C.

ti

N N

N-R, R «,

(4),

where R! Hydrogen or methyl, R2 can be hydrogen, methyl or 65 fo substituted, and X is hydrogen, methyl, ethyl, ethyl, R3 is hydrogen, phenyl which is sulfo, methyl, ethyl, methoxy, ethoxy or chlorine.

Methoxy, ethoxy, acetylamino, carboxy, chlorine, sulfamoyl and a valuable reactive dye which can be substituted by formula (4) defi-carbamoyl, or naphthyl which is by the sulfonated class is the reactive dye of the formula

635 860

s ° 3H

- n so3h

The inventive production of the reactive dyes of the formula (1) is characterized in that a dye of the formula n - c c - nh,

I!

cho n n

3 * C '

I.

F

(5).

0 - Cu

A - N - N

(S03H) ^ _ 3

nu i

r,

1-2

(6),

wherein the amino group (s) of the formula

-NH I

Ri

(7) 25

is attached to A and / or to the naphthalene nucleus, which carries one of the two complex-forming oxygen atoms, 1 30 and 1 or 2 moles of an amino compound of the formula or 2 moles of 2,4,6-trifluoro-s-triazine of the formula f - cc - f

1 n n n

1

f

HN-R,

(9)

(8th)

R?

35

condensed with each other in any order.

A preferred embodiment is characterized in that dyes of the formula

0

/

a - n = nh ^ j ^ -n = n where X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or halogen and A and Rj have the meanings given under formula (1) as starting materials used.

In particular, the starting materials used are dyes of the formula (10), in which A is a benzene radical which can be substituted by sulfo, methyl, methoxy, carboxy and chlorine, or a naphthalene radical which can be substituted by sulfo, Rj is hydrogen, methyl or ß- Hydroxyethyl and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and amino

0 -

-n-n-n (s03h) 1_2 X h03s

(so3h) 1_3

(10),

1-2

Compounds of formula (9), wherein R2 is hydrogen, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl, methoxypro-50 pyl, ß-hydroxyethyl, ß-sulfoethyl, phenyl, which by sulfo, methyl, methoxy, ethoxy, acetylamino , Ureido, carboxy, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl, and carbamoyl, or naphthyl, which can be substituted by sulfo.

55

The preferred reactive dyes of formula (4) are obtained by using a dye of formula

(11).

2,4,6-trifluoro-s-triazine of the formula (8) and an amino compound of the formula (9) are condensed with one another in any order, where R1; R2, R3. And X in formulas (11) and (9) have the meanings given under formula (4).

7

635 860

Since the individual process steps specified above, namely multiple condensation in different orders, possibly also partially simultaneously, can be carried out, different process variants are possible. The starting materials to be used for each partial reaction result from formula (1). In general, the reaction is carried out step by step, the sequence of the simple reactions between the individual reaction components of the formulas (6), (8) and (9) being freely selectable.

The two most important process variants are characterized in that one

1. a dye of the formula (6) is condensed with 1 or 2 moles of 2,4,6-trifluoro-s-triazine of the formula (8) and the mono- or diprimeric condensation product obtained with 1 or 2 moles of an amino compound of the formula (9 ) condenses; 2.2,4,6-5 trifluoro-s-triazine of the formula (8) condensed with an amino compound of the formula (9) and 1 or 2 mol of the primary condensation product obtained is condensed with a dye of the formula (6).

The preferred method of preparing the reactive dye of the formula (5) is characterized in that the dye of the formula is condensed with 2,4,6-trifluoro-s-triazine and the primary condensation product obtained is condensed with ammonia.

The dyes of the formula (6) to be used as starting materials are obtained by a diazotized aminobenzene or aminonaphthalene, which may be further substituted as indicated above, on an ortho-alkoxy or hydroxyaminobenzene, which is also further substituted as indicated above can be, such as o-anisidine, cresidine, 2,5-dimethoxyaniline or 2-acetylaminophenol, the monoazo compound obtained, optionally after saponification of the amino group to be diazotized, diazotized and coupled with a naphtholsulfonic acid or aminonaphtholsulfonic acid and copper the resulting diazo dye by reaction with copper-donating agents, in particular dealkylating copper.

The diazotization of the diazo components is usually carried out by the action of nitrous acid in aqueous mineral acid solution at low temperature, the coupling to the coupling components at weakly acidic, neutral to weakly alkaline pH values.

As a copper donor, one can use salts containing the copper as a cation, e.g. Copper sulfate, copper chloride or copper acetate. In some cases the use of complex copper compounds is advantageous, e.g. in the form of copper-amine complexes, such as copper tetramine sulfate from copper sulfate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain the copper in a complex bond, e.g. complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, such as glycollate, lactic acid and especially tartaric acid, such as sodium copper tartrate.

The treatment with the copper donating agent is carried out in aqueous or organic-aqueous medium, e.g. at room temperature, if readily metallizable starting compounds are present or, if a de-alkylation must take place at the same time as the metallization, by heating to temperatures between 50 and 120 ° C in an open vessel, e.g. with reflux cooling or, if appropriate, in a closed vessel under pressure, the pH ratios being given by the type of metallization process chosen; e.g.

acidic coppering with copper sulfate, alkaline coppering with copper tetramine sulfate.

If desired, solvents such as e.g. Alcohol, dimethylformamide, etc. can be added.

The following can be mentioned as starting compounds for the preparation of the dyes of the formula (6):

a) Aminobenzenes and aminonaphthalenes (residue A):

(12)

Aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, a- and ß-naphthylamine, 2.5 -Dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodi-25 phenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 4-aminobenzenesulfonamide or -sulfomono -methyl- or ethylamides or -sulfondimethyl- or -sulfondi-ethylamides, aniline-2-, -3- and -4-sulfonic acid, aniline-2,5-disulphonic acid, 2,4-dimethylaniline-6-sulfonic acid, 4 -Chloro-5-methyl-30 aniline -2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 2-amino-4- or -5-sulfobenzoic acid, 2-methyl-aniline 3,5-disulfonic acid, 2-methylaniline-5-sulfonic acid, 2-methoxy aniline-3,5-disulfonic acid, 2-chloroaniline-4-sulfonic acid,

2,3-dimethylaniline-4,6-disulfonic acid, 2,5-dimethylaniline-4,6-35 disulfonic acid, 5-chloro-4-methylaniline-2-sulfonic acid, 3-acetyl-

aminoaniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 3,4-dichloroaniline-6-sulfonic acid,

4-methylaniline-2-sulfonic acid, 3-methylaniline-6-sulfonic acid,

2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfone-40 acid, 5-methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sul-

fonic acid, 2,4-dimethylaniline-5-sulfonic acid, 2-methoxyaniline

5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxy aniline, -3-sulfone

45 acid, 3,4-dichloroaniline, o-, m- and p-nitroaniline, m- and p-aminoacetanilide, 4-amino-2-acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid, l- Aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-l-, -5-or -6-sulfonic acid, l-aminonaphthalene-3,6- or -5,7-disul-50-fonic acid, 2-aminonaphthalene-l, 5-, -1,7-, -3,6-, -5,7-, -4,8-or -6,8-disulfonic acid , l-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-l, 5,7-, -3,6,8- or -4,6,8-trisulfonic acid, l-amino-2 -hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-l-hydroxynaphthalene-4,8-disulfonic acid, l-amino-3-55 acetylaminobenzene (saponified), l-amino-3-acetylaminobenzene-5-or -6 -sulfonic acid (saponified), l-amino-4-acetylaminobenzene-2-suifonic acid (saponified), l-amino-3- (N-acetyl-N-methylamino-no) -benzene (saponified), 3- or 4-nitroaniline (reduced), 2-methoxy-4- or -5-nitroaniline (reduced), 2-methoxy-3-nitro-5-60 methylaniline (reduced) and 2-methoxy-3-nitro-5-chloroaniline.

b) o-alkoxy- or o-hydroxyaminobenzenes (radical B):

1-amino-2-methoxy-5-methylbenzene, l-amino-2,5-dime-thoxybenzene, l-amino-2-methoxybenzene-l-amino-2-methoxy-5-chlorobenzene, l-amino-2- methoxy-5-ethylbenzene, 1-amino

65 2,5-diethoxybenzene, l-amino-2-ethoxybenzene and 2-acetylaminophenol (saponified).

c) Naphtholsulfonic acids or aminonaphtholsulfonic acids:

2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-6-

635 860

8th

hydroxynaphthalene-8-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-aminobenzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (4'-aminophenylamino) -5-hydroxynaphthalene-3 ', 7-disulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, l-aminobenzoylamino-8-hydroxynaphthalene-3,6-di sulfonic acid, 2-amino-5-hydroxynaphthalene-4,8-disulfonic acid,

1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,

2-N-phenylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-N-acetyl-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-N- (2'-Hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-N-methylamino-8-hydroxynaphthalene-6-sulfonic acid, 3-amino-2-hydroxynaphthalene-7-sulfonic acid, l-hydroxynaphthalene-3,6-disulfonic acid , l-hydroxynaphthalene-4,8-disulfonic acid,

1-hydroxynaphthalene-3,8-disulfonic acid, 1-hydroxynaphthalene-3,6,8-trisulfonic acid and l-hydroxynaphthalene-4-, -5- or -8-sulfonic acid.

The preparation of the dyes of the formula (6) is not described in all cases in the following exemplary embodiments, but is readily derived from what has been said above.

Other starting materials which can be used to prepare the reactive dyes of the formula (1) include 2,4,6-trifluoro-s-triazine of the formula (8) (cyanuric fluoride) and, for example, the following amino compounds of the formula ( 9):

Ammonia, methylamine, dimethylamine, ethylamine, di-ethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec-butylamine, tert-butylamine, hexylamine, methoxyethylamine, ethyloxyamine, methoxypropylamine, chloroethylamine, hydroxy Dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, β-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o- m- and p-to-luidine, 2,3-, 2,4-, 2,5-, 2,6-, 3rd , 4- and 3,5-dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4 -Methylaniline, o-, m- and p-phenylenediamine, 3-amino-4-methylaniline, 4-amino-3-methylaniline,

2-amino-4-methylaniline, o-, m- and p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline, 2-ethoxy-5-methoxyanine, 4-bromoaniline, 3-aminobenzamine, 4-aminophenylsulfamide, 3-trifluoromethylaniline, 3- and 4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-l-hydroxy-naphthalene, l-amino-4-hydroxy-naphthalene , l-amino-8-hydroxy-naphthalene, l-amino-2-hydroxy-naphthalene, l-amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline-2 , 5-disulfonic acid, aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid,

4-aminophenylmethanesulfonic acid, aniline-N-methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, p-aminosalicylic acid, l-amino-4-carboxy-benzene-3-sulfonic acid, l-amino-2-carboxy-benzene-5-sulfonic acid, 1-amino

5-carboxy-benzene-2-sulfonic acid, l-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, 2-naphthylamine-l-, - 3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, l-naphthylamine-2,4-, -2,5-, -2,7-, -2,8- , -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 2-naphthylamine-l, 5-, -1.6-, -1.7-, -3.6-, -3.7-, -4.7-, -4.8-, -5.7- and -6,8-disulfonic acid, 1-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-l, 3.7-, -1.5.7-, -3.5.7-, -3.6.7-, -3, 6,8- and -4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine, 2-amino-benzothiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine, morpholine, piperidine and piperazine.

The condensation of the 2,4,6-trifluoro-s-triazine of the formula (8) with the dyes of the formula (6) and the amino compounds of the formula (9) are preferably carried out in aqueous solution or suspension, at low temperature and in the case of slightly acidic , neutral to weakly alkaline pH, and so that in the finished reactive dye of formula (1) 5 at least one fluorine atom remains as a removable residue. The hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

The copper complex dyes of the formula (1) are fiber-lo active, since they each contain a releasable fluorine atom in the s-triazine radical or in the two s-triazine radicals.

Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides 15 to form covalent chemical bonds.

The reactive dyes of the formula (1) can be isolated and processed into usable, dry dyeing preparations. The isolation is preferably carried out at the lowest possible temperatures by salting out and filtering. The filtered dyes can optionally be added after adding coupling agents and / or buffering agents, e.g. after adding a mixture of equal parts of mono- and disodium phosphate, dried 25; drying is preferably carried out at temperatures which are not too high and under reduced pressure. In certain cases, the dry preparations according to the invention can be spray dried directly by atomization of the entire preparation mixture, i.e. Manufacture without intermediate insulation of the 30 dyes.

The reactive dyes of formula (1) are new. They are characterized by high reactivity and they result in dyeings with good wet and light fastness. It is particularly noteworthy that the dyes have good solubility and electrolyte solubility with good extraction properties and high dye fixation, and that the non-fixed portions can be removed easily.

The reactive dyes of formula (1) are suitable for dyeing and printing a wide variety of materials, such as silk, 40 leather, wool, superpolyamide fibers and superpolyamide urethanes, but in particular cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, where the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

50 They are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. of blended fabrics containing wool, silk or wool.

It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent which promotes the diffusion of the unfixed portions.

Similar dyes are known from Swiss Patent 60 No. 495 462. These differ from the reactive dyes according to the invention in that they have different non-chromophoric substituents on the monofluorotriazine residue.

In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

example 1

10 parts of the dye of the formula

9

635 860

are dissolved in 70 parts of water at pH 7 and the solution is cooled to 0 ° by adding 40 parts of ice. 2 parts of 2,4,6-trifluorotriazine are added dropwise with thorough stirring, a pH of 6.5 being maintained by simultaneous addition of sodium carbonate solution.

Then 3 parts by volume of concentrated aqueous ammonia solution are added and the mixture is stirred at 5 to 10 ° for 2 hours. The resulting reactive dye is separated by sprinkling sodium chloride, filtered off, the dye paste mixed with an aqueous disodium phosphate solution and dried.

The dye obtained dyes cotton from a long liquor in intense navy blue tones.

If the amines listed in the table below are used instead of ammonia, navy blue dyes with similar properties are obtained.

example

Amines

2nd

N-methylamine

3rd

N-methylaniline

4th

2-methylaniline

5

4-methoxyaniline

6

3-aminobenzenesulfonic acid

7

4-aminobenzoic acid

8th

4-methylaniline

9

3-methylaniline

10th

4-aminobenzenesulfonic acid

11

2-amino-4-methylmethoxybenzene

12

3 -Trif luormethylaniline

13

4-aminobenzyl sulfonic acid

14

Butylamine

15

2-aminoethanesulfonic acid

16

2-aminoethanol

17th

aniline

18th

3 - aminoacetanilide

19th

4-aminophenylurea

20th

2-aminonaphthalene-6-sulfonic acid

21st

2-aminonaphthalene-4,8-disulfonic acid

Example 22

25.3 parts of aniline-2,4-disulfonic acid are diazotized in a conventional manner and coupled with 13.7 parts of 15 3-amino-4-methoxytoluene in a weakly acidic solution. The resulting amino noazo dye is precipitated by adding sodium chloride, filtered off and redissolved in water. It is diazotized by adding hydrochloric acid and sodium nitrite and coupled at a pH of 8 to 8.5 with 29.5 parts of N-acetyl-N-me-20-ethyl-2-amino-5-hydroxynaphthalene-7-sulfonic acid. 100 parts by volume of concentrated aqueous ammonia solution and 140 parts by volume IN copper sulfate solution are now added to the resulting deep violet solution and the mixture is stirred under reflux at 95 ° for 12 hours. The copper complex is precipitated from the deep blue solution by adding sodium chloride and suctioned off. To saponify the acetyl group, the dye is heated to 85 ° for 2 hours in 1N sodium hydroxide solution, then, after cooling to 25 °, acidified to pH 3 with hydrochloric acid and suction filtered.

35.5 parts of the copper complex dye are dissolved neutral in 250 parts of water and cooled to 0 °. 150 parts of ice are added and 7.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise to the solution at a pH of 6 to 7. After the condensation has ended, a solution of 5.4 parts of 4-aminotoluene in acetone is added and the mixture is condensed at 5 to 10 ° and pH 7.5. The dye is isolated as a blue-black powder by evaporating the reaction mixture to dryness. It dyes cotton in real navy blue tones.

45

by double coupling and demethylating coppering, copper complexes of aminodisazo dyes are obtained which, by condensation with cyanuric fluoride and a second tri-azine substituent T, give further real dyes.

Analogously, components A = initial component B = middle component N = final component

30th

No. A = initial component

23 aniline-2,4-disulfonic acid

24 th.

B = middle component

3-amino-4-methoxytoluene do.

N = final component

T = triazine substituent hue on cotton

2, N-methylamino-5-hydroxy-ammonia naphthalene-7-sulfonic acid

2, N- (2'-hydroxyethylamino) - aniline 5-hydroxynaphthalene-7-sulfonic acid navy blue do.

25 aniline-2,5-disulfonic acid do.

2-amino-5-hydroxynaphtha- 3-aminotoluene in-1,7-disulfonic acid do.

26 do.

2-amino-1,4-dimethoxybenzene do.

4-aminobenzoic acid do.

635 860

10th

(Continuation)

No. A = initial component

B = middle component

N - final component

T = triazine substituent hue on cotton

27 aniline-2,5-disulfonic acid 2-aminoanisole

2-amino-5-hydroxynaphthane-n-butylamine lin-7-sulfonic acid navy blue

28 do.

29 do.

30 aniline-3-sulfonic acid

31 aniline-4-sulfonic acid

3-amino-4-methoxytoluene do.

do.

do.

2-amino-8-hydroxynaphtha- 2-aminoethanol lin-6-sulfonic acid do.

2-methylamino-8-hydroxy-2-amino-l, 4-dimethyl-do.

naphthalene-6-sulfonic acid benzene

2-N-methylamino-5-hydroxy-aniline-3-sulfonic acid do. naphthalene-7-sulfonic acid do.

Aniline-3,5-disulfonic acid do.

32 aniline-3,5-disulfonic acid do.

do.

4-aminoanisole do.

33 2-Amino-5-sulfobenzoic acid do.

do.

4-chloroaniline do.

34 2-Amino-4-sulfobenzoic acid do.

do.

4-aminoacetanilide do.

35 5-Amino-4-methylbendo. zol-1,3-disulfonic acid

36 2-aminonaphthalino. 1,5-disulfonic acid

37 1-aminonaphthalino. 2,5,7-trisulfonic acid

38 2-aminotoluene-4-sulfonic acid

39 2-Amino-5-methylbenzenesulfonic acid

40 5-amino-4-methoxybenzene-1,3-disulfonic acid

41 4-Amino-3-chlorobenzenesulfonic acid

42 4-amino-3-methylbenzenesulfonic acid

43 2-aminobenzenesulfonic acid

44 4-aminobenzenesulfonic acid

3 - amino-4-methoxychlorobenzene

3-amino-4-methoxytoluene

3-amino-4-methoxy-ethylbenzene

2-acetylaminophenol (saponified)

3-amino-4-methoxytoluene

3-amino-4-methoxytoluene do.

2-amino-8-hydroxynaphtha-lin-3,6-disulfonic acid

2-amino-8-hydroxynaphtha-lin-6-sulfonic acid

2-amino-5-hydroxynaphtha-lin-7-sulfonic acid

2-amino-5-hydroxynaphtha-lin-1,7-disulfonic acid

2-amino-5-hydroxynaphtha-lin-4,8-disulfonic acid

3-amino-2-hydroxynaphtha-lin-7-sulfonic acid

8-amino-l-hydroxynaphtha-lin-3,6-disulfonic acid

8-amino-1-hydroxynaphtha-lin-3,5-disulfonic acid

2-N-methylamino-5-hydroxy-naphthalene-7-sulfonic acid do.

3-aminophenyl urea

3 - aminobenzamide

4-aminophenyl sulfamide

3-methoxypropyl amine

Ethylamine

N-methylaniline

4-bromoaniline

Diethylamine do.

blue-black do.

navy blue dark blue blue blue blue

4-aminophenylmethane navy blue sulfonic acid l-amino-3,4-dimethyl-do.

benzene

45 do. do.

46 2-aminobenzene-1,4-do. disulfonic acid do.

do.

l-amino-4-methoxy-do. ethoxybenzene

4-aminoethoxybenzene do.

47 do.

2-aminoanisole do.

4-methylaniline do.

11

635 860

(Continuation)

No. A - Anl'angs component

B = middle component

N = final component

T = triazine substituent hue on cotton

48 2-aminobenzene-1,4-disulfonic acid

49 do.

2-amino-1,4-dimethoxybenzene

2-amino-1,4-diethoxybenzene

2-N-methylamino-5-hydroxy-ammonia naphthalene-7-sulfonic acid do.

3-aminotoluene navy blue do.

Example 50

14 parts of the copper complex disazo dye of the formula n

(as trisodium salt)

are dissolved in 100 parts of water and the solution is cooled to 0 ° by adding ice. 1.4 parts of disodium hydrogenphosphate are added and 2.75 parts of 2,4,6-trifluoro-l, 3,5-triazine are now added dropwise with thorough stirring, the pH of the reaction mixture being added by simultaneous addition of sodium hydroxide solution holds at 6.5. After completion of the reaction, which is monitored by thin layer chromatography, 2.2 parts of 3-aminotoluene are added and the mixture is allowed to warm to 20 °, the hydrogen fluoride released during the condensation again being neutralized continuously. By concentrating the dye solution obtained in vacuo, a dark color powder is obtained. The dye dyes cellulosic fiber materials. ,

m real shades of blue.

Example 51

10 parts of the copper complex disazo dye of the formula

P

n— ^ ~ v-n = n

ŒLT H03S

Salt is separated into the solution, filtered off and dried. It is identical to the product obtained according to Example 4.

45

are dissolved in 100 parts of water at pH 7. A solution of 3.3 parts of 2- (2'-methylphenylamino) -4,6-difluoro-1,3,5-triazine in 15 parts of acetone is added and the mixture is stirred at 15 ° for 8 hours, with dropping of IN sodium hydroxide the pH is kept at 6.5 to 7. After the reaction time given in Example 52, no starting material is detectable chromatographically. To a solution of 34.6 parts of the disodium salt of the rial. The dye is obtained by sprinkling dye of the formula

H2

n-h ch,

in 600 parts of water, 14 parts of 2,4,6-trifluoro-l, 3,5-triazine are added dropwise at 0 ° with thorough stirring, the pH being kept at 6 by adding sodium bicarbonate solution. After the reaction is complete, 19 parts of 3-aminobenzenesulfonic acid are added and the mixture is stirred for 3 hours at pH 7.5 and a temperature of 25 °. The dye of the formula obtained

635 860

12

dyes cotton in real dark blue tones.

Dyeing Instructions I

2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the solution obtained so that it increases by 75% of its weight, and then dried.

Then the fabric is impregnated with a 20 ° warm solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75% weight gain, the dye is dampened for 30 seconds at 100 to 101 °, rinsed, soaped in for a quarter of an hour a 0.3% boiling solution of an ion-free detergent, rinses and dries.

Staining instructions II

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dye bath.

20th

The temperature is increased to 40 °, 4 parts by volume of 30% sodium hydroxide solution, 10 parts of calcined soda and another 60 parts of sodium chloride being added after 30 minutes. The temperature is kept at 40 ° for 30 minutes, rinsed and then soaped for 25 minutes in a 0.3% boiling solution of an ion-free detergent for 15 minutes, rinsed and dried.

C.

Claims (12)

635 860 PATENT CLAIMS 1. Reactive dyes of the formula A - N = N- <S ° 3H> l-3 wherein A is a benzene or naphthalene radical which may contain further substituents, the benzene radical B may contain further substituents, Rj and R2 independently of one another each is a hydrogen atom or an optionally substituted alkyl radical having 1 to 4 carbon atoms and R3 is a hydrogen atom, an optionally substituted alkyl radical having 1 to 4 carbon atoms, an optionally substituted aralkyl or aryl radical and the radical or radicals of the formula 15 n - r ~, Ro 1-2 where X is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or halogen and A and Ri have the meanings given in claim 6, used as starting materials. 1-2 wherein the amino group (s) of the formula -nh I. Ri 1-2 where A is a benzene or naphthalene radical, which may contain further substituents having 1 to 4 carbon atoms and R3 a hydrogen atom, the benzene radical B may contain further substituents 10 optionally substituted alkyl radicals having 1 to 4 carbon atoms, Rj and R2 independently of one another is a hydrogen atom, an optionally substituted aralkyl or aryl radical or an optionally substituted alkyl radical and the radical or the radicals of the formula - N - C i i r-, C. II n N! F N - R3 Ro 1-2 wherein X is hydrogen, alkyl having 1 to 4 carbon atoms, alk-oxy having 1 to 4 carbon atoms or halogen and A, Rj, R2 and R3 have the meanings given in claim 1. 1-2 (1), 2,4,6-trifluoro-s-triazine of the formula (8) and an amino compound 25 10. The process according to claim 9 for the preparation of the re-end of the formula (9), in which R2 and R3 are the active dye of the formula given above Have meanings condensed with one another in any order. s03h = N— so3h characterized in that the dye of the formula 0 40 (2) to A and / or to the naphthalene residue, which carries one of the two complex-forming oxygen atoms, characterized in that a dye of the formula a - n (so3h) 1-3 (2) (is bound to A and / or to the naphthalene nucleus which carries one of the two complex-forming oxygen atoms. 2. Reactive dyes according to claim 1, of the formula 0 Cu 0 A - N = N (S03H) 1_3 3rd 635 860 AT *! (S03H) 1_3 3. A reactive dye according to claim 2, wherein A is a benzene radical which can be substituted by sulfo, methyl, methoxy, carboxy and chlorine, or a naphthalene radical which can be substituted by sulfo, Rj is hydrogen, methyl or β-hydro- xyethyl, R2 hydrogen, methyl or ethyl, R3 hydrogen, methyl, ethyl, butyl, methoxypropyl, ß-hydroxyethyl, ß-sul-foäthyl, phenyl, which is replaced by sulfo, methyl, methoxy, ethoxy, acetylamino, ureido, carboxy, chlorine, Bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl may be substituted, or naphthyl, which may be substituted by sulfo, and X 4o is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine. (3), (4), 4th - n - c i i R1 * Nx c m n n \\ C ' i f n i r, R. 4- N - c c - N / » i n i V1 N N i F r2 (l), (4), wherein R1 can be hydrogen or methyl, R2 can be hydrogen, methyl or fo, and X can be hydrogen, methyl, ethyl, ethyl, R3 hydrogen, phenyl which is sulfo, methyl, ethyl, methoxy, ethoxy or chlorine. Methoxy, ethoxy, acetylamino, carboxy, chlorine, sulfamoyl and 55 5. The reactive dye according to claim 4, which may be substituted by the formula carbamoyl, or naphthyl, which is substituted by sul- s03h ^ a_n = n 4. reactive dyes according to claim 2, the formula - n - C ! t r-, n i F C - N - Ro n r J N Rq 2. (5), (5). (6), 6. Process for the preparation of reactive dyes of the formula / a • n - c c - nh0 I I II £ • chq n n 3 I. F ^ 7 ^ - n = n (s03h) 1_2 x 7. The method according to claim 6, characterized in that dyes of the formula 0— Cu / A - N = N - N = N (S03H) i_3 (7) " 1 or 2 moles of 2,4,6-trifluoro-s-triazine of the formula is (are) bound to A and / or to the naphthalene nucleus which carries one of the two 40 and 1 or 2 moles of an amino compound of the formula complex-forming oxygen atoms F - C C - F «» N N t F hn-r3 I R2 8. The method according to claim 7, characterized in that dyes of the formula (10), in which A is a benzene radical which can be substituted by sulfo, methyl, methoxy, carboxy and chlorine, or a naphthalene radical which can be substituted by sulfo, Ri is hydrogen, methyl or β-hydroxyethyl and X is hydrogen, methyl, ethyl, methoxy, ethoxy or chlorine, and amino compounds of the formula (9), in which R2 is hydrogen-60, methyl or ethyl and R3 is hydrogen, methyl, ethyl, butyl , Methoxypropyl, ß-hydroxyethyl, ß-sulfoethyl, phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy, acetylamino, urodo, carboxy, chlorine, bromine, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, or naphthyl, which 65 can be substituted by sulfo, is used as starting materials. (8th) condensed with each other in any order. 9. The method according to claim 7 for the production of reactive dyes of the formula 635 86fr (9) 45 10th in which Ri can be hydrogen or methyl, R2 can be hydrogen, methyl or fo, and X can be hydrogen, methyl, ethyl, Ethyl, R3 is hydrogen, phenyl, which is sulfo, methyl, ethyl, methoxy, ethoxy or chlorine, characterized in that methoxy, ethoxy, acetylamino, carboxy, chlorine, sulfamoyl and a dye of the formula carbamoyl can be substituted, or naphthyl by Sul- (10), (11), (12) condensed with 2,4,6-trifluoro-s-triazine and the primary condensation product obtained is condensed with ammonia.