DEG0010786MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: January 20, 1953 Announced on March 22, 1956

GERMAN PATENT OFFICE

The invention relates to the production of new dyes, the direct cellulose colorations in the ultraviolet light, depending on its composition, have a more or less intense fluorescence. It is to this property that they owe a previously unattainable luminous color in daylight.

It has been found that by coupling, N.

CH = CH- <

let oxidize. In this formula, A means one of carbon atoms adjacent to the nitrogen atoms of the i, 2, 3-triazole ring linked aromatic radicals. All aromatic radicals of these triazole compounds can be further substituted as desired, for example by halogen, alkyl,

tetrazotized 1,4-di- (4'-aminostyryl) -benzene compounds with aromatic amino compounds coupling in the o-position to an amino group with diso-aminoazo dyes can produce which can be prepared by methods known per se to corresponding i, 4-di- [4 '- (arylo-i, 2,3-triazolyl-2) -styryl] -benzene compounds the general formula

Alkoxy, amino, acylamino, carboxyl and sulfonic acid groups. ■, '; ;

These new ι, 4-di- (4 '~ ^ar yl ° triazolyl-styryl) -benzene compounds, provided they contain no further chromophores, such as arylazo groups, yellow dyes, the colorations in

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G 10786 IVbI 22 e

ultraviolet light, depending on its composition and depending on the substrate, more or less intense fluoresce and, as a result, show unprecedented pure, luminous color tones even in daylight. This is especially true for direct cellulose dyeing.

For the production of textile dyestuffs by the process according to the invention, the process according to the invention is especially important ■ the patent 846 849 by condensation of terephthalaldehyde with 5-nitro-2-methylbenzene-i-sulfonic acid aryl esters, Saponification of the aryl sulfonate and reduction of the nitro to amino groups obtainable 1,4-di- (4'-amino-2'-sulfonic acid-styryl) -benzene compound suitable. It can easily be dissolved in an aqueous solution of its alkali metal salts with sodium nitrite and tetrazotize mineral acid by the indirect method and in a neutral to weakly acidic medium with aromatic amino compounds coupling in the o-position to the amino group to form the dis-o-aminoazo dye unite.

Aromatic amino compounds coupling in the o-position to an amino group are used in the invention Process preferably those of the benzene and naphthalene series into consideration, for example the i, 3-diaminobenzene, the 1, 3-diamino-4-methyl- or -4-chlorobenzene, the 1,3-diaminobenzene-4-sulfonic acid, 5-chloro-i-aminonaphthalene, i-aminonaphthalene-4- or -5-sulfonic acid, 2-aminonaphthalene, 2-amino-6-methoxy-naphthalene, a-aminonaphthalene-S ", -6- or -7-monosulfonic acid, the 2-aminonaphthalene-3, 6- or -5, 7-disulfonic acids. But there are also heterocyclic ones, in the o-position aromatic amino compounds coupling to an amino group useful, for example that a-Phenyl-5-amino-i, 2, 3-benzotriazole.

The dis-o-aminoazo dyes are oxidized to give the corresponding arylo-1, 2, 3-triazolyl compounds by known methods, for example in aqueous solution or suspension or in oxidation-resistant organic solvents. Common oxidizing agents are, for example, the cuprite tetrammine salts and the salts of hypochlorous acid. It is often useful to use the oxidation products to be subjected to a subsequent reduction, for example the action of sodium hydrosulfite, in order to convert any 1, 2, 3-triazoloxydin 1, 2, 3-triazole compounds that may be present. Furthermore, any functional groups that may be present in the end products can also be added subsequently be changed, for example amino groups by acylation, if this is desired and advantageous.

As already emphasized, it is advantageous for textile purposes to use 1,4-di- (4'-amino-styryl) -benzene-2 ', 2'-disulfonic acid to use whose tetrazo compound is advantageously combined with those azo components which

CH = CH- <

HSO ₃ - If

SO ₃ H

contain acidic water-solubilizing groups, such as carboxyl or sulfonic acid groups. . Particularly cheap Azo components for the production of cellulose-affine, water-soluble dyes according to the invention are the aminonaphthalenesulfonic acids coupling in the o-position to the amino group, including in particular 2-aminonaphthalene-5, 7-disulfonic acid, because they provide the purest dyes according to the invention.

The new 1,4-di- [4 '- (arylo-i, 2, 3-triazolyl-2) -styryl] -benzene Verbin fertilize represent yellow powder and, if they are acidic, water-solubilizing groups contain, in the form of their alkali salts, soluble in water with a yellow color. They have one depending on their composition more or less pronounced affinity for cellulose.

The following examples illustrate the invention, without restricting them. Unless otherwise stated, the parts are understood to be parts by weight. Parts by weight have the same relationship to parts by volume as kilograms are to liters.

example 1

47.2 parts of i, 4-di- (4'-aminostyryl) -benzene-2 ', 2'-disulfonic acid are dissolved neutrally with sodium hydroxide in 1400 parts of hot water, an aqueous solution of 13.8 parts of sodium nitrite is added and with 50 parts of concentrated hydrochloric acid indirectly tetrazotized ^{at 10 to 12 0.} Stirring is continued for 1 hour and then the suspension is of the tetrazo compound at 10 to 12 ⁰ to a solution of 44.6 parts of 2-Aminonaphthaliri-6-sulfonic acid, the 'man-crystallized with 8.2 parts of sodium hydroxide and 50 parts of sodium acetate in 500 parts of Water has dissolved. After the coupling has ended, the dye is completely precipitated by adding sodium chloride and filtered off. The wet pigment is then ° a clear solution in water with the addition of 40 parts of 25 ° / ₀ by weight ammonia at 92-97 and the solution of 120 parts of crystalline copper sulfate in 480 parts of water ,, mixed with 240 parts of 25 ° / ₀ by weight ammonia, admitted. Is kept for several hours at a temperature of 92-97 ^0, has disappeared completely to the azo dye, then allowed to cool and the precipitates Ditriazolylverbindung completely by addition of sodium chloride. The crude product is dissolved in hot water in the presence of excess sodium sulfide, the copper sulfide formed is filtered off, the excess alkali metal sulfide compound is decomposed by hydrochloric acid and the product is further purified by dissolving it from water with the addition of a little sodium hydrosulfite and animal charcoal. The sodium salt of the i, 4-di- [4 '- (naphtho-i ", 2": 4,5-1, 2, 3-triazolyl-2) -styryl] -benzene-2', 2 ', 6 " , 6 "-tetrasulfonic acid of the formula

-CH = CH

—N — N

is obtained as a brownish yellow substance.

Dyed onto cellulose fibers, this results in

SO ₃ H

bond a glow that is previously unattainable in daylight, yellow hue. In ultraviolet light

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G 10786 IVb / 22e

the fibers dyed with it glow bright yellow. The fastness properties of the cellulose dye are good. Also wool and silk are dyed in a weakly acidic bath; the dyeings obtained show pure nuances and fluoresce very strongly in ultraviolet light.

If you replace the 2-amino-

naphthalene-6-sulfonic acid with 44.6 parts of 2-aminonaphthalene-5-sulfonic acid, the sodium salt of 1,4-di [4 '- (naphtho-i ", 2": 4,5-1, 2, 3-triazolyl-2) -styryl] -benzene-2', is thus obtained 2 ', 5 ", 5" -tetrasulfonic acid as a yellow-brown powder. The cellulose color of this compound shows an even greener shade of yellow and has similar interesting properties as the product described above.

Example 2

The tetrazo suspension prepared according to Example 1 from 47.2 parts of 1, 4-di- (4'-aminostyryl) -benzene-2 ', 2'-di-

SCLH

HSO,

CH = CH-

sulfonic acid is combined with a solution of 60.6 parts of 2-amino-naphthalene-5, 7-disulfonic acid, 16.4 parts of sodium hydroxide and 50 parts of crystallized sodium acetate in 400 parts of water at a temperature of 10 to 12 ⁰ . After the coupling has ended, the dye is precipitated by adding sodium chloride and filtered off. The wet pigment is then / _o ammonia in hot water a clear solution with addition of 40 parts of 25 ° and with a mixture of 120 parts of crystalline copper sulfate in 480 parts of water and 240 parts of 25 ° / ₀ ammonia at a temperature of 92-97 ° oxidized to the ditriazolyl compound. The product is, as described in Example 1, decoppered with sodium sulfide and purified, using the sodium salt of the i, 4-di- [4 '- (naphtho-i ", 2": 4,5-1, 2, 3- triazolyl-2) -styryl] -benzene-2 ', 2', 5 ", 5", 7 ", 7" -hexasulfonic acid of the formula

SO ₃ H

-CH = CH

SOoH

SO, H

SOoH

obtained as a yellow-brown powder. The compound is easily soluble in water; their solutions are colored pure yellow. Dyed on cellulose fibers, the result is a greenish yellow shade of extraordinary Purity and luminosity in daylight. The cellulose dyeings have good fastness properties. In the ultraviolet Light they shine bright greenish yellow. The compound can also be based on acid bath Wool and silk are dyed, resulting in very pure, greenish-yellow colorations.

If you replace the 2-amino-naphthalene-5 in the above example, 7-disulfonic acid with 60.6 parts of 2-aminonaphthalene-6,8-disulfonic acid, the sodium salt of the i, 4-di- [4 '- (naphtho-i ", 2": 4,5-i, 2,3-triazolyl-2) -styryl] -benzene-2 ', 2', 6 ", 6", 8 ", 8" -hexasulfonic acid as a yellow-brown powder. On cellulose colored, this compound shows a more reddish-tinged yellow tone and has similar interesting properties on like the product described above.

H ₉ N

CH = CH-

SOoH

as a brownish yellow powder. The aqueous solutions of the alkali salts are colored yellow. On cellulose fibers colored, an intense yellow color is obtained, which fluoresces strongly yellow in ultraviolet light. Acetylation of the

Example 3

47.2 parts of 1,4-di- (4'-aminostyryl) -benzene-2 ', 2'-disulfonic acid are, as described in Example 1, indirectly diazotized and the tetrazo compound with a solution of 21.7 parts 1,3 -Diaminobenzene and 20 parts of concentrated hydrochloric acid combined in 400 parts of water. At a temperature of 10 to 12 ⁰ , a solution of 77 parts of crystallized sodium acetate is slowly added dropwise. After the tetrazo compound has completely disappeared, the dye is salted out and filtered off. Dissolve the filter cake with the addition of 40 parts of 25 ° / ₀ ammonia in hot water and oxidized at 92-97 ⁰ with a mixture of 120 parts of crystalline copper sulfate in 480 parts of water and 240 parts of ² 5 ° / oig ^em ammonia. The ditriazolyl compound is, as described in Example 1, decoppered and purified. The sodium salt of 1,4-D1- [4 '- (5 "-amino-benzo-1", 2 ": 4,5-1, 2, 3-triazolyl-2) -styryl] -benzene-2 is obtained ', 2'-disulfonic acid of the formula

-CH = CH

, -NH,

SO "H

Written compound is obtained the 1, 4-D1- [4 '- (5 "-acetamino-benzo-i", 2 ": 4, 5-1, 2, 3-triazolyl-2) -styryl] -benzene-2 ', 2'-disulfonic acid. This compound shows otherwise similar properties to cellulose fibers a greener shade.

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G 10786 IVb / 22 e

Replacing the m-phenylenediamine in the above example by 27.4 parts of i-amino ^ -methyl-s-methoxybenzene, the sodium salt of 1,4-di- [4'-

-CH = CH-

SO.H

as a brownish yellow powder. Dyed onto cellulose fibers, an intense yellow color is also obtained Coloring with similar properties to the product described above.

Example 4

To a neutral solution of 37.6 parts of 1,3-D1-aminobenzene-4-sulfonic acid, 8.2 parts of sodium hydroxide and 50 parts of crystallized sodium acetate in 500 parts of water are added at 10 to 12 ^% one of 47.2 parts 1, 4-di- (4'-amino-styryl) -benzene-2 ', 2'-disulfonic acid prepared according to Example 1 suspension of the

CH = CH-

SO ₃ H

- as a brownish yellow powder. The aqueous solutions of the alkali salts of this compound are pure yellow. on Cellulose fibers give a yellow color of pure shade. The solutions and dyes of this Products show a strong, yellow glow in ultraviolet light.

If the compound described in the above example is acetylated, the 1,4-di- [4 '- (5 "-acet ~ amino-benzo-i ", 2": 4,5-1, 2, 3-triazolyl-2) -styryl] -benzene-2 ', 2'-4 ", 4" -tetrasulfonic acid. This connection

■■■■ - 'dung gives on cellulose fibers with otherwise similar Properties of greener, yellow colorations than that of the non-acetylated product.

Example 5

47.2 parts 1,4-di- (4'-aminostyryl) -benzene-2 ', 2'-disulf Onic acid are, as described in Example 1, indirectly diazotized. To the suspension of the Tetrazo connect

N-N

CH = CH- (4 "-methyl-5" -methoxy-benzo-i ", 2": 4,5-1, 2, 3-triazolyl-2) -styryl] -benzene-2 ', 2'-disulfonic acid of the formula

-CH = CH

, —N

SO.H

OCH ₃

CH '

Tetrazo compound. After coupling has ended, the dye is salted out and filtered off. The moist dye is dissolved in hot water with the addition of 40 parts of 24% ammonia and ^{oxidized at a temperature of 92 to 97 0} with a mixture of 120 parts of crystallized copper sulfate in 480 parts of water and 240 parts of 25% ammonia to give the ditriazolyl compound. The copper is removed with sodium sulfide and the product is purified as described in Example 1, and the sodium salt of the 1,4-di [4 '- (5 "-amino-benzo-i", 2 ": 4, 5-1) is obtained , 2, 3-triazolyl-2) -styryl] -benzene-2 ', 2', 4 ", 4" -tetrasulfonic acid of the formula

-CH = CH

NH ₂ ! -SO ₃ H

A solution of 37.5 parts of 2,3-aminonaphthoic acid, 8.2 parts of sodium hydroxide and 50 parts of crystallized sodium acetate in 500 parts of water at a temperature of 10 to 12 ^{0 is} added. After the coupling has ended, the dye is precipitated by adding sodium chloride and filtered off. The moist dye is dissolved in hot water with the addition of 40 parts of 25% strength ammonia and at. a temperature 92-97 ⁰ crystallized with a mixture of 120 parts of copper sulfate in 480 parts of water and 240 parts of 25 ° / ₀ oxidizes ammonia to Ditriazolylverbindung. One decoppered by repeated boiling with 3% hydrochloric acid, slurried the dye in excess of 2 ° / _o sodium carbonate solution, and so the sodium salt receives the i, 4-di [4 '- (naphtho-i ", 2": 4, 5-1, 2, 3-triazolyl-2) -styryl] ⁱ -benzene-3 ", 3" -dicarboxy-2 ', 2'-disulfonic acid of the formula

-CH = CH

SO ₈ H

-COOH

SO ₃ H
HOOC

as a yellow-brown powder.

Dyed onto cellulose fiber results in this compound a yellow hue that shines in daylight. Those colored with it glow in ultraviolet light Fibers bright yellow. The compound can also be dyed from acid bath on wool and silk and results in very pure, greenish yellow colorations. ■ ·

Claims (5)

PATENT CLAIMS: '... '. . " i. Process for the production of fluorescent Dyes, characterized in that 098/458 G 10786 IVb / 22 e one optionally further substituted ι, 4 - di- (4'-aminostyryl) - Benzene compounds tetrazotized and with coupling in the o-position to the amino group aromatic amino compounds to dis-o-amino a: -CH = CH- 'N' wherein A is one on adjacent carbon atoms with the nitrogen atoms of the i, 2, 3-triazole ring Connected aromatic radical means, with the aromatic rings still arbitrary can be further substituted. 2. The method according to claim 1, characterized in that that tetrazotized 1,4-di- (4'-aminostyryl) -benzene-2 ', 2'-disulfonic acid is used. 3. Process according to Claims 1 and 2, characterized in that there is used as the coupling compound azo dyes combined, which one by methods known per se to bis-triazole compounds of general formula (I) oxidized, -CH = CH (I) Nenten in the o-position to an amino group coupling amino compounds of the benzene and naphthalene series used. 4. Process according to Claims 1 to 3, characterized in that the coupling components are used Aminonaphthalenesulfonic acids coupling in the o-position to the amino group are used. 5. Process according to Claims 1 to 4, characterized in that that 2-aminonaphthalene-5, 7-disulfonic acid is used as the coupling component. © 509 698/458 3.56