DE1238134B - Process for the production of dyes - Google Patents

Description

UNDESREPUBLIC OF GERMANY

UTSCHES

PATENT OFFICE

EDITORIAL

Int. a .: C 09 b

German class: 22 a -1

Number:
File number:
Registration date:
Display day:

1 238 134
B75729IVc / 22a

March 5, 1964

April 6, 1967

It has been found that valuable dyes are obtained by using compounds of the general formula

Z - A - (CH ₂ ) * - C

Shark

N ^/

in which Z is a radical capable of reacting with a phenolic hydroxyl group or preferably a radical capable of reacting with an acylatable amino group, A an aromatic radical with six ring members, Hal a chlorine or bromine atom, but preferably a chlorine atom, and η denotes the number 0 or 1, with phenolic or acylatable hydroxyl groups Reacts amino groups containing dyes or dye precursors and, in the case of the use of dye precursors, the reaction products are supplemented by combination with the remaining component to form dyes. Residues capable of reacting with phenolic hydroxyl groups or acylatable amino groups are, for example, carboxylic acid halide, sulfonic acid halide, isocyanate or urethane radicals.

Starting compounds of the general formula 1 in which Z is a carboxylic acid or sulfonic acid chloride group means is obtained, for example, from the corresponding carboxyphenyl- or sulfophenylthiodiazoles in a manner known per se by the action of acid chlorides, such as phosphorus pentachloride, Phosphorus oxychloride, phosphorus trichloride, thionyl chloride or phosgene, optionally under Addition of tertiary bases such as pyridine, dimethylformamide, N-methylpyrrolidone, diethylaniline or Tripropylamine. But they can also be obtained if you look at compounds of the general formula

N
Η - Α— (CH ₂ ) * - C

= C - shark

II Process for the preparation of dyes

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Werner Ball, Heidelberg;

Dr. Erwin Hahn, Viernheim (Hess.)

Amines of the formula

N ===== C - shark
H ₂ N - A - (CH ₂ ) "- CS III

in which A, Hai and η have the meaning given above, by reaction with phosgene or chloroformic acid esters.

Examples of compounds of the formula I are the compounds of the formulas IV to VI called:

ClOC

C-Cl

in which A, Hal and η have the meaning given above, introduces sulfonic acid halide groups or carboxylic acid halide groups in the usual way. Compounds of the formula 1 in which Z is an isocyanate or urethane group are obtained, for example, by known methods from the reaction of the compounds of the formula I with dyes or dye precursors containing phenolic hydroxyl groups or amino groups, B. in aqueous solution or suspension, in organic solvents or mixtures of water

709 548/347

and organic solvents, expediently in the presence of acid-binding agents, such as alkali hydroxides, carbonates, hydrogen carbonates, acetates or tertiary bases, such as dimethylformamide and pyridine.

The dyes which can be prepared according to the invention can contain the remainder of the general formula

C - shark

- A - (CH ₂ ) "- C

VII

once or several times, e.g. B. two to three times included. Dyes with one or two residues of the general formula VII, however, are preferred.

Dyes containing primary or secondary amino groups which can be acylated are particularly suitable Dyes of the azo, anthraquinone and tetrazaporphin series into consideration, which advantageously at least a water-solubilizing group, e.g. B. a sulfonic acid, carboxylic acid or sulfatooxäthylgruppe, contain.

Monoazo dyes in particular are dyes of the azo series to be acylated according to the invention technically important, but polyazo dyes such as disazo and trisazo dyes can also be used. Metal complexes of azo dyes are also used in the preparation of the dyes according to the invention into consideration.

Azo dyes which correspond in that of the diazo component and / or in that of the coupling component Part of the molecule containing acylatable amino groups are in the usual manner by coupling made of diazo components with coupling components. Instead of a free acylatable amino group At least one of the components can also have an amino group which can be converted into an acylatable amino group Group, e.g. B. an acetylamino or a nitro group, which after the coupling in an acylatable amino group is converted.

Diazo components which, in addition to the diazotizable amino group, have at least one further acylatable Amino group are, for example, 1,3-diaminobenzene - 4 - sulfonic acid, 1,4 - diaminobenzene-3-sulfonic acid, 1,4-diaminobenzene and 1,4-diamino-3-nitrobenzene.

Examples of compounds which can be converted into diazo components with acylatable amino groups are called: l-amino-4-nitrobenzene, 1-amino-3-nitrobenzene, 1 - amino-4-formylaminobenzene, I-amino-3-fromylaminobenzene, l-amino-4-nitrobenzene - 6 - sulfonic acid, 1 - amino - 3 - nitrobenzene-6 - sulfonic acid, 1 - methylamino - 4 - nitrobenzene-6 - sulfonic acid, 1 - methylamino - 3 - nitrobenzene-6-sulfonic acid and 1,2-diamino-4-nitrobenzene.

Coupling components which contain one or more acylatable amino groups are for example Aminohydroxybenzenes, aminohydroxynaphthalenes, aminophenylmethylpyrazolones and the N-alkyl or N-aryl, N-aralkyl and N-cycloalkyl derivatives of these compounds as well as the corresponding sulfonic acids, sulfonic acid amides and sulfones.

Anthraquinone dyes to be reacted according to the invention with compounds of the formula I which contain at least one advantageously carry up to three water-solubilizing groups and the at least one expediently contain up to two primary and / or secondary amino groups are, for example, 1,5-diaminoanthraquinone - 2 - sulfonic acid, 1,4 - diaminoanthraquinone-2,5- and 2,6-disulfonic acid, 1-amino-4- (3-amino-4,6-disulfophenylamino) -anthraquinone- 2-sulfonic acid, 1-amino-4- (4-aminosulfothiophenyl) -anthraquinone-2-sulfonic acids, the reaction products of 1 mole each of 1-amino-4-bromoanthraquinone-2 - sulfonic acid, 1 - amino - 4 - bromoanthraquinone-2-carboxylic acid or l-AmineHt-bromoanthraquinone ^ S- or -2,6-disulfonic acid with 1 mole each of an aromatic diamine, such as 1,3- or 1,4-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid or 1,4-diaminobenzene - 2 - sulfonic acid, 2,6 - diaminotoluene - 4 - sulfonic acid, 2,5-diaminobenzene-1,3-disulfonic acid, 1-amino-3-N-methylaminobenzene-4-sulfonic acid, 1-Amino-4-N-methylaminobenzene-3-sulfonic acid, 4,4-diaminodiphenyl sulfide - 2,2 '- disulfonic acid, 4,4' - diaminostilbene - 2,2 '- disulfonic acid, 4,4' - diaminodiphenyl-2,2'-disulfonic acid, 4,4'-diaminodiphenylamine and 4,4'-diaminodiphenyl-3-sulfonic acid or one aliphatic diamine, such as ethylene diamine or propylene diamine.

Dye precursors containing amino groups are, for example, the acylatable ones already mentioned Diazo and coupling components containing amino groups. By diazotization of the invention acylated diazo components and coupling with any coupling components or by coupling any diazo components with coupling components acylated according to the invention, the new dyes are then likewise produced obtain. The diazo components acylated according to the invention can be mixed with acylated according to the invention Relocate coupling components. If necessary, metallizable azo dyes can be used after coupling be metallized.

According to the invention, acylated dye precursors which still contain free amino groups can also be used, e.g. B. with phthalocyanine or anthraquinone polyacid, partially or fully implement and hydrolyze the unreacted acid halide groups.
Insofar as the new dyes contain water-solubilizing groups, such as carboxylic acid, sulfonic acid or sulfato groups, they are suitable for dyeing and printing textile material made of wool, silk, synthetic polyamides and polyurethanes and leather. In particular, as reactive dyes on structures made of native or regenerated cellulose with a high degree of fixation, they provide very uniform block dyeings in continuous dyeing using the one-bath or two-bath process, when using steam or hot air, with different fixing times and temperatures, types of alkali and amounts of alkali. They are also well suited for the exhaust process at low temperatures, e.g. B. the known from the documents of the Belgian patent 619 274 a 2-chlorobenzothiazole group-containing dyes by a significantly higher color strength of the dyeings available on cotton, and result in deep dyeings after relatively short fixing times after the cold pad process.

The parts and percentages given in the examples are weight units. Behave parts of the room to parts by weight like the liter to the kilogram.

example 1

7 parts of acid chloride of 3- (3'-carboxy) -phenyI-5-chloro-1,2,4-thiodiazole (from S-phenyl-S-chloro-1,2,4-thiodiazole by carboxylation in an aluminum chloride urea -Melt with phosgene and treatment of the carboxylic acid obtained with thionyl chloride obtainable) are dissolved in 150 parts by volume of benzene. This solution is added to a neutral aqueous solution which contains 13 parts of the dye which is obtained by coupling diazotized 1-amino-4-acetylamino-2-benzenesulfonic acid with 1 - (2,5-dichloro-4'-sulfo) -phenyl- 3-methylpyrazolone-5 and subsequent saponification of the acetyl group was prepared. The mixture is heated to 35 to 50 ⁰ C and the pH value of the mixture by dropwise addition of aqueous sodium carbonate solution between 6.5 and 7.5. As soon as the pH value remains constant, the dye is salted out with saturated aqueous sodium chloride solution. It is filtered off with suction and the dye is dried at 50 ^° C. in vacuo. It dyes cotton in brilliant yellow shades using the methods customary for reactive dyes.

The dyes mentioned in the table below are obtained in the same way:

H ₃ C

R-HN

R-HN

SO:, H

OH

R-HN

H ₃ C

N = N

SO ₃ H

OH

R-HN

SO ₃ H

OH

R-HN

SO ₃ H

SO ₃ H

yellow

yellow

yellow

yellow

yellow

SO ₃ H yellow

yellow

continuation

/ \ N = N

V / HO ₃ S

SO ₃ H

Cu

O'

HO ₃ S

HO ₃ S

SO ₃ H

O'

HO ₃ S

HO ₃ S

orange

ruby

ruby

SO ₃ H

continuation

ß / au

Brown

Brown

continuation

example

R - ■

hue
on cotton

22nd

R-HN

Blue violet

SO ₃ H

If the acylation indicated for the preparation of the dyes mentioned does not take place with the acid chloride of 3- (3'-carboxy) -phenyl-5-chloro-1,2,4-thiodiazole, but with the acid chloride of 3- (4'-carboxyl) -phenyl-5-chloro-1,2,4- thiodiazoles carried out, dyes with the same properties and hues are obtained.

Example 23

To a neutral solution of 16 parts of 1,8-aminonaphthol-3,6-disulfonic acid 8 parts of sodium bicarbonate and a solution of 14 parts of acid chloride of 3- (3'-carboxy) phenyl-5-chloro-1,2,4-thiodiazole are in 400 parts of water given in 300 parts by volume of benzene. This mixture is stirred for 100 hours at room temperature. After that, the benzene layer severed. 12 parts of sodium bicarbonate are added to the aqueous suspension and then added dropwise an aqueous solution containing 11 parts of diazotized 4-chloro-3-toluidine-6-sulfonic acid. The dye is salted out with sodium chloride, filtered off with suction and dried in vacuo at 50 ° C. It stains Cotton in red shades using the methods customary for reactive dyes.

When using the components listed in the following table, the same procedure is used obtained the corresponding dyes.

example

Coupling component

Diazo component

hue
on cotton

SO3H

Red

SO ₃ H red

COHN OH

SO ₃ H SO ₃ H

Red

HO ₃ S

If instead of the acid chloride used in Examples 23 to 26, the acid chloride des 3 - (4 '-carboxy) -phenyl-5-chloro-1,2,4-thiodiazoles used, dyes with the same hues and properties are obtained.

SO ₃ H

27

example

1,3 - Diaminobenzene - 4 - sulfonic acid in 800 parts is added to a neutral solution of 18.8 parts Water 16 parts of sodium bicarbonate and a solution

of 28 parts of 3- (3'-carboxy) -phenyl-5-chloro-1,2,4-thiodiazole acid chloride in 500 parts by volume of benzene and this mixture is stirred for 40 hours at room temperature. The failed product will Sucked off, suspended in glacial acetic acid and after the addition of 25 parts by volume of 35% hydrochloric acid at 8 to 10 C. diazotized with an aqueous sodium nitrite solution. The diazonium salt is filtered off with suction and suspended in water and in an alkaline sodium carbonate medium with 1- (2'.5'-disulfo) -phenyl-3-methylpyrazolone-5 coupled. The dye is salted out with potassium chloride, filtered off with suction and at 50 ° C. in a vacuum dried. It dyes cotton in yellow tones using the usual door reactive dyes.

Claims (2)

Patent claims: 1. Process for the preparation of dyes, characterized in that one Compounds of the general formula N
I.
Z - A - (CH ₂ ) * - C C - shark group or with an acylatable amino group reactive radical. A is an aromatic radical with six ring members, Hal is a chlorine or bromine atom and η is the number 0 or 1, with phenolic hydroxyl groups or acylatable amino groups-containing dyes or dye precursors and in the case of the use of dye precursors the reaction products are supplemented by combination with the remaining dye component to form dyes. 2. The method according to claim 1, characterized in that compounds of the general formula = C-CI Z - A - (CH ₂ ) ,, -C used in the Z, A and /; in claim 1 have mentioned meaning. in the Z one with a phenolic hydroxyl-Considered publications:
Announced documents of the Belgian patent No. 619 274. When the application was announced, a coloring table with explanations was laid out. 70 »548/347 3. 67 Q Bundesdruckerei BerUn