DE2847307A1 - SUBSTANTIVE DISAZO DYES, THEIR PRODUCTION AND USE - Google Patents

Description

DR. BERG D: PL.-lNG. STAPF DIPL.-ING. SCHWABE DR. DR. SAtfDMAIR

PATENTANWÄLTE PO Box 860245 8000 Munich 86

2 8 A 7 3 O 7

Attorney's file: 29

October 31, 1978

CIBA-rGEIGY AG Basel / Switzerland

Nouns disazo dyes, their preparation and use.

Case: 1-11415 / -

■ »(089) 988272 988273 988274 lü

Telegrams: 9098 BERGSTAPFPATENT Munich TELEX: 0524560 BERG d Bank accounts: Hypo-Bank Munich 4410122850 (BLZ 70020011) Swia Code: HYPO DE MM Bayec Vereinsbank Munich 453100 (bank code 70020270) Post check Munich 65343-808 (bank code 70010080)

CLBA-GEFGY AG, CH-4002 Basel VVBe- * ■ # * V-i »L *» ä% ™ l yy

1-11415 / - Germany

Nouns disazo dyes, their preparation and use

The present invention relates to substantive disazo dyes of the formula

(D,

in which D- and D _2, independently of one another, are each a radical of a diazo component, R- and R "independently of one another are hydrogen or methyl, R, hydrogen or hydroxyethyl and R ^ is hydroxyethyl.

A radical of a diazo component, D, and Ό2, is a radical of the benzene or naphthalene series or of the heterocyclic series.

In particular, D and D are residues of nouns Disazo components.

Substantive azo dyes of the formula (1) in which D, and D _? are the same residues.

Preference is also given to substantive azo dyes of the formula (1) in which D and D ″ each independently of one another Remainder of a diazo component of the benzene or naphthalene series

9Q98T9 / 0747

is and R ,, R _? , R ₃ and R, have the meanings given under formula (1).

Substantive disazo dyes of the formula (1) in which D ^ and D ^ independently of one another are phenyl, which can be substituted by SuIfο, methyl, methoxy, ethoxy and chlorine, or naphthyl, which can be substituted by SuIfο, R ^ and R, are particularly preferred _{2 is} independently hydrogen or methyl and R ₃ and R ^ are hydroxyethyl.

Valuable preferred embodiment dyes are the nouns azo dyes of the formulas

SO ₃ H SO ₃ H

(2)

CH ₃ O- ^ J) -N = N

N (CH ₂ CH ₂ OH)

1 HO-, S

SO ₃ H

The noun disazo dyes of formula (1) are prepared by adding diazotized amino compounds of the formulas

D ₁ - NH ₂ (4) and

Coupling components of the formula OH

- NH

HO ₃ S

NH 1

(6) and

HO,

NH R ₂

909819/0747

■ 's

2,4,6-trihalo-s-triazine of the formula

X-CC-X (8),

I Il

N N

'■ X

wherein X is fluorine, chlorine or bromine, and an amino compound the formula

W ^ ⁴ (9)

by coupling and condensation in any order to give a noun disazo dye of the formula (1).

The starting materials used are preferably amino compounds of the formulas (4) and (5) in which D and D _{2 are} identical radicals.

In particular, starting materials of the formulas (4), (5), (6), (7) and (9) are used, in which D, and D _2, independently of one another, are each a radical of a diazo component of the benzene or naphthalene series and R ,, R ", Ro and R, have the meanings given under formula (1).

A preferred embodiment is characterized in that starting materials of the formulas (4), (5), (6), (7) and (9) are used, in which D, and D _{2 are} independently phenyl, which is replaced by sulfo, methyl, methoxy , Ethoxy and chlorine can be substituted, or naphthyl, which can be substituted by SuIfο, R, and R _{2 are} independently hydrogen or methyl and R ~ and R, hydroxyethyl.

909819/0747

Because the individual process steps specified above which can be carried out in a different order, possibly also partially simultaneously, are different Process variants possible.

In general, the reaction is carried out step-by-step, one after the other, with the order of the simple reactions can be freely chosen between the individual reaction components of the formulas (4) to (9).

Important process variants for the preparation of the dyes of the formula (1) are characterized in that man

1) 2-Amino-5-hydroxynaphthalene-7-sulfonic acid, formula (6) or (7), in a molar ratio of 2: 1 with a 2,4,6-trihalo-s-triazine of the formula (8) condensed, on the secondary condensation product obtained 2 equivalents of one diazotized amino compound of the formula (4) or (5), couples, and finally the disazo compound obtained with a Condensed amino compound of formula (9);

2) a diazotized amino compound of the formula (4) is coupled to 2-amino-5-hydroxynaphthalene-7-sulfonic acid, the monoazo compound condensed with a 2,4,6-trihalogeno-s-triazine of the formula (8), furthermore a diazotized amino compound of formula (5) to 2-amino-5-hydroxynaphthalene-7-sulfonic acid couples, the two intermediate products are condensed with one another and the disazo dye obtained with an amino compound of the formula (9) condensed.

The particularly valuable disazo dyes of formulas (2) and (3) are prepared by

a) 2-Amino-5-hydroxynaphthalene'-7-sulfonic acid in a molar ratio 2: 1 condensed with cyanuric chloride, diazotized 2 equivalents on the secondary condensation product obtained 4-Methoxy-aniline-2-sulfonic acid couples and the obtained Disazo compound condensed with diethanolamine [formula (2),

909819/0747

Method variant 1)] ;

b) 4-methoxyaniline-2-sulfonic acid and diazotized to 2-amino-5-hydroxynaphthalene-7-sulfonic acid couples and the monoazo compound formed is condensed with cyanuric chloride, furthermore 2-aminonaphthalene-1-sulfonic acid diazotized and based on 2-amino-5-hydroxynaphthalene-7-sulfonic acid coupled, the monoazo compound obtained is condensed with the abovementioned intermediate and the disazo compound formed is condensed with diethanolamine condensed [formula (3), process variant 2)].

As starting materials that are used to produce the nouns Disazo dyes of the formula (1) that can be used are:

Amino compounds of the formulas (4) and (5), diazo components

Aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, α- and ß-naphthylamine, 2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2,3- and -4-carboxylic acids, 2-aminodiphenyl ethers, 2-, 3- or 4-aminobenzenesulfonamide or -sulfomonomethyl- or -äthylamide or -sulfondimethyl- or -sulfondiäthylamide, dehydrothio-p-toluidine monosulfonic acid or dehydrothio-p-toluidinedisulfonic acid, aniline-2-, -3- and -4-sulfonic acids, aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulf onic acid,. . ■ --_-

4-chloro-5-methylaniline-2-sulfonic acid, 5-chloro-4-methy! Aniline-2-sulfonic acid, 3-acetylaminoaniline-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-methox3 ⁷ aniline-2-sulfonic acid and 5-methoxyaniline -2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, - ''. "- -v.

2,4-dimethylaniline-5-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 4-nitro-

909819/0747

28A7307

aniline-2-sulfonic acid, 4-amino-4'-nitro-stilbene-2,2'-disulfonic acid, 4-aminostilbene-3,4'-disulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid , 4-acetylaminoaniline, dehydrothio-p-toluidine, 4-ethoxyaniline-3-sulfonic acid, 3j4-dichloroaniline ₅ 4-amino-3-methoxy-3'-sulfoazobenzene, 4-amino-4'-sulfoazobenzene, 4-amino-3 , 4'-disulfo-azobenzene, 1-amino-3-methy1-4- (4 ¹ , 8'-disulfonaphthyl-2-azo) -benzene, o-, m- and p-nitroaniline, m- and p-aminoacetanilide , 4-Aπιino-2-acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic acid,

l-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, l-aminonaphthalene- Sjo- or -5,7-disulfonic acid, 2-aminonaphthalene-I ₃ 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-1-hydroxynaphthalene-4,8-disulfonic acid.

Coupling components of formulas (6) and (7 )

Z-Amino-S-hydroxynaphthalene ^ sulfonic acid, 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid.

2,4,6-trihalo-s-triazines of the formula (8)

2,4,6-trichloro-s-triazine (cyanuric chloride), 2,4,6-tribromo-s-triazine (cyanuric bromide), 2,4,6-trifluoro-s-triazine (cyanuric fluoride).

Amino compounds of formula (9)

Hydroxyethylamine, dihydroxyethylamine. ;

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The amino compounds of the formulas (4) and (5) are generally diazotized by the action of nitrous oxide Acid in aqueous mineral acid solution at low temperature, the coupling to the coupling components of the formulas (6) and (7) for weakly acidic, neutral to weakly alkaline pH values.

The condensation of the 2,4,6-trihalogeno-1,3,5-triazine of the formula (8) with the coupling components of the formulas (6) and (7) and the amino compounds of the formula (9) are preferably carried out in aqueous solution "or suspension, at low temperature and at weakly acidic, neutral to weakly alkaline pH. The at the hydrogen halide released by the condensation continuously by adding aqueous alkali hydroxides, carbonates or -bicarbonate neutralized.

The dyes of the formula (1) are distinguished by red shades, high substantivity and good lightfastness and sewage fastness.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, super polyamide fibers and super-polyurethanes, but especially cellulosic materials with a fibrous structure, such as Linen, cellulose, regenerated cellulose, cotton and especially paper. They are suitable for both the exhaust process as well as for dyeing by the padder dyeing process, after which the goods with aqueous and optionally is also impregnated with salt-containing dye solutions.

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

In the following examples, the parts are parts by weight and the temperatures are in degrees Celsius specified.

90 98 19/074 7

example 1

A solution of 9.3 parts of cyanuric chloride in 50 parts of acetone is added to an ice-cold, neutral solution of 23.9 parts of I-acid in 350 parts of water, and the temperature is allowed to rise slowly to room temperature. After about 2 hours, warm the E.eaktionsgemisch to 40-45 ⁰ C and then allowed over the course of about 5 hours uniformly 100 parts of 1-n sodium hydroxide solution are added dropwise, raising the pH-value of about 2 to 7 increases . A clear solution is produced and only traces of I-acid can be detected. The solution is then cooled to room temperature and 16.8 parts of sodium bicarbonate are added.

In the meantime, an ice-cold, neutral solution of 20.3 parts of 4-methoxy-aniline-2-sulfonic acid in 250 parts 25 parts of 4N sodium nitrite solution and 30 parts of 10N hydrochloric acid are added to water. After the diazotization is complete the pH of the suspension is adjusted to 7 by the dropwise addition of approx. 10 parts of 10N sodium hydroxide solution.

The diazo compound thus obtained is then poured into the solution of the coupling component described above and stir overnight at room temperature.

The next day is added to the coupling mixture with 15 parts of diethanolamine and heated to 95 ⁰ C. A clear solution and after 6 hours, the dye formed is salted out in the heat with 5 Vol .-% saline. After cooling, the dyestuff is filtered off and ^{dried in vacuo at 90 °} C. The dyestuff of the formula thus obtained

OCH,

SO ₃ H

9 0 9 8 19

N (CH ₀ CH ₀ OH)

/ 074 ² 7 ² ■

- r-

dyes cotton and paper in red tones.

Similar dyes are obtained if, instead of 4-methoxy-aniline- 2- sulfonic acid, one of the aromatic amines listed below or mixtures thereof are used as diazo components: 2-amino-naphthalene-6-sulfonic acid, 2-amino-naphthalene-1-sulfonic acid , 4-methoxy-aniline-3-sulfonic acid, 4-ethoxy-aniline-3-sulfonic acid, aniline-4-sulfonic acid, 2-methylaniline-4-sulfonic acid, 2,5-dimethyl-aniline-4-sulfonic acid, aniline-2 sulfonic acid, 4-chloroaniline-2-sulfonic acid, 2-methy1-5-chloroaniline-4-sulfonic acid.

90 9819/074 7

-yr-%

Example 2

An ice-cold, neutral slurry of 11.3 parts of the aminomonoazof arb substance "4-methoxy-aniline-2-sulfonic acid - * - J acid "in 600 parts of water is mixed with a solution of 4.7 parts of cyanuric chloride in 25 parts of acetone Hydrochloric acid released is neutralized by adding dropwise about 25 parts of 1N sodium hydroxide solution. After a short time a clear solution results and no free amino group can be detected any more.

The solution of dichlorotriazine dye thus obtained is then treated with a neutral slurry of 11.8 parts of the monoazo dye ^ir 2-naphthylamine-1-sulfonic acid "s * I-acid" in 300 parts of water. The reaction mixture is heated for a few hours to 50-55 ° C. and during this 2nd condensation the pH is kept between 5 and 7 by adding 1N sodium hydroxide solution.

After completion of the reaction is added to the reaction mixture with 7.5 parts of diethanolamine and heated for 6 hours at 95 ⁰ C.

After a clarifying filtration, the dye formed is salted out at 90 ⁰ C with 5 Vol .-% saline. It is allowed to cool, filtered and the dye is dried in vacuo at 90.degree.

The dye of the formula thus obtained

NH-C, C-NH
NN

N = N

^S0 3 ^H

N (CH ₂ CH ₂ OH).

dyes cotton and paper in red tones.

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Similar dyes are obtained if 2 are the same or 2 different aminoazo dyes of the below Table are linked to one another via cyanuric chloride according to the information in Example 2 and the 3rd chlorine atom on the triazine ring is reacted with diethanolamine:

6-amino-1-hydroxy-2,2'-azonaphthalene-3,6'-disulfonic acid, 6-amino-1-hydroxy-2- (4'-methoxy-2'-sulfophenylazo) -naphthalene-3-sulfonic acid,

6-Amino-1-hydroxy-2,2'-azonaphthalenes, 1'-disulfonic acid, 6-amino-1-hydroxy-2- (2 ', 5'-dimethyl-4 ¹ -sulfophenylazo) -naphthalene-3-sulfonic acid ,

6-amino-1-hydroxy-2- (4'-sulfophenylazo) -naphthalene-3-sulfonic acid,

6-Amino-1-hydroxy-2- (4'-ethoxy-3'-sulfophenylazo) -naphthalene-3-sulfonic acid,

6-methylamino-1-hydroxy-2- (4'-methoxy-2'-sulfophenylazo) -naphthalene-3-sulfonic acid.

909819/0747

Staining examples example 1

Printing paper

800 kg of sulphate cellulose, bleached and 200 kg of sulphite cellulose, are added in the form supplied to a pulper in which 14 cbm of fabrication water are placed and whipped until there are no specks. The whipping process takes 30 minutes. The opened cellulose is then transferred to a discharge chute. From the dump chest the pulp suspension is milled using media mills to a freeness of 25 ⁰ SR (Schopper-Riegler) and then passes into a blend chest. In the mixing vat, 250 kg of kaolin Ia (as filler) and 1% dye calculated on absolutely dry fibers (in the form of an aqueous solution of 20 g / l) are added as further additions. After an absorption time of 15 minutes, 2% resin glue (absolutely dry) and after 10 minutes 4% alum (both calculated on absolutely dry cellulose) are added. pH of the pulp suspension: 5.3. This paper stock reaches the paper machine via the usual process sequence in this industry.

Example 2 Tissue paper

1000 kg of sulphate cellulose are bleached in the delivered form in a bag in which 14 cbm Manufacturing water are presented, entered and opened until there are no specks. The process of serving takes 30 minutes. The opened material is then transferred to an emptying chute. From the dump the pulp is ground with pulp mills to a freeness of 25 ° SR and then reaches a

909819/0747

-p-

Mixing vat. In the mixing vat, 1% dye is added, calculated on the absolutely dry fiber, in Form of an aqueous solution of 20 g / l. pH of the pulp suspension: 7. After 15 minutes of absorption time, this arrives Paper stock to the paper machine via the usual process flow in this industry.

Example 3 Sizepress application

In 1000 ltr. a 10% anionic starch solution

Then 5 kg of dye are dissolved and applied using a size press

2 adorns. The application of the above solution is 1.5 g / m absolutely dry per side.

909819/0747

Claims (17)

Claims 1. Nouns disazo dyes of the formula - N = N-, N - c 'C-N N N r; = N-D (D, where D, and D ^ independently of one another are each a radical of a Diazo component, R- and R2 independently of one another are hydrogen or methyl, R "hydrogen or hydroxyethyl and R. is hydroxyethyl. 2. Nouns azo dyes according to claim 1, in which D and D _{9 are} identical radicals. 3. Nouns azo dyes according to claim 1 or 2, in which D 1 and D ₉ are each independently a radical of a diazo component of the benzene or naphthalene series and R ₁ j R ₉ , R 1 and R 1 have the meanings given in claim 1. 4. nouns azo dyes according to claim 3, wherein D-. and D ₂ independently of one another is phenyl, which can be substituted by sulfo, methyl, methoxy, ethoxy and chlorine, or naphthyl, which can be substituted by sulfo ", R, and R ₉ independently of one another are hydrogen or methyl and R and R, hydroxyethyl . 909819/0747 OFHGJNAL -χζ - 5. The substantive azo dye according to claim 4, the formula NH-C / C-NH I Il N N N (CH ₂ GH ₂ OH) ₂ ^S0 3 ^H SO ₃ H 6. The substantive azo dye according to claim 4, the formula OH OH N (CH ₂ CH ₂ OH) ₂ 7. Process for the preparation of nouns disazo dyes formula of 4 (D, where D, and D "are each independently a radical of a diazo component, R. and R _{2 are} independently hydrogen or methyl, R" is hydrogen or hydroxyethyl and R, is hydroxyethyl, characterized in that diazotized amino compounds of the formulas 909819/0747 (4) and Coupling components of the formulas GH HO ₃ S NH
R ₁ (6) and ^ 4,6-trihalo-s-triazine of the formula X - C C I Il N N - X 1
X OH NH ι wherein X is fluorine, chlorine or bromine, and an amino compound of the formula HNC (9) by coupling and condensation in any order to give a noun disazo dye of the formula (1). 8. The method according to claim 7, characterized in that amino compounds of the formulas (4) and (5) are used, in which D-, and D _? are the same R.este. 9. The method according to claim 7 or 8, characterized in that starting materials of the formulas (4), (5), (6), (7) and (9) are used, in which D, and D, -, independently of one another, are used Is a residue of a diazo component of the benzene or naphthalene series and R-,, R _? , R-, and R, have the meanings given in claim 7. 909819/0747 10. The method according to claim 9, characterized in that starting materials of the formulas (4), (5), (6), (7) and (9) are used, wherein D, and D "independently of one another phenyl, which is replaced by SuIfο, Methyl, methoxy, ethoxy and chlorine can be substituted, or naphthyl, which can be substituted by SuIfο, R- and R _{2 are} independently hydrogen or methyl and R ₃ and R ^ are hydroxyethyl. 11. The method according to claim 10, for the production of the substantive Azo dye of the formula (2), 'characterized in that that 2-amino-5-hydroxynaphthalene-7-sulfonic acid is condensed with cyanuric chloride in a molar ratio of 2: 1 the secondary condensation product obtained couples 2 equivalents of diazotized 4-methoxy-aniline-2-sulfonic acid and the obtained disazo compound is condensed with diethanolamine, so that the substantive disazo dye of the formula (2) is obtained will. 12. The method according to claim 10, for the production of the substantive Azo dye of the formula (3), characterized in that 4-methoxyaniline-2-sulfonic acid is diazotized and couples to 2-amino-5-hydroxynaphthalene-7-sulfonic acid and the monoazo compound formed condenses with cyanuric chloride, also diazotized 2-aminonaphthalene-1-sulfonic acid and couples to 2-amino-5-hydroxynaphthalene-7-sulfonic acid, the obtained monoazo compound with the above Intermediate product condenses and the disazo compound formed is condensed with diethanolamine, so that the substantive Disazo dye of formula (3) is obtained. 13. The azo dyes obtainable by the process according to claims 7 to 12. 14. Procedure according to the examples given. 909819/0747. 15. Azo dyes according to the examples given. 16. Use of the azo dyes according to Claims 1 to 6 or according to the method according to claims 7 up to 12 azo dyes available for dyeing paper. 17. The paper colored according to claim 16. 909819/0747