DE965345C - Process for the production of water-soluble, chromium-containing dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

ISSUED JUNE 6, 1957

GERMAN PATENT OFFICE

PATENT LETTERING

CLASS 22a GROUP 1 INTERNAT. CLASS C 09 b

B 36542 IVb j 22 a

Dr. Otto Kaufmann, Ludwigshafen / Rhine

has been named as the inventor

Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen / Rhein

Process for the production of water-soluble, dirom-containing

Dyes

Patented in the territory of the Federal Republic of Germany on July 21, 1955

Patent application known since December 27, 1956

Patent issued on May 23, 1957

It has been found that new water-soluble, chromium-containing dyes are obtained if sulfonic acid group-free, but azo or azomethine dyes containing carboxyl groups which are based on ι molecule metal-free dye iAtom Chromium in complex bond with organic compounds which can form complex chromium compounds but are not dyes.

As starting materials, azo dyes or azomethine dyes come into consideration, the one for the Complex formation suitable grouping, such as

N = N

and

N = CH

OH

OH

contain, in which A is a hydroxyl, alkoxy, carboxyl or carbalkoxyl group, and which also contain at least one carboxyl group in any position. This can either be immediate to the chromophoric system or externally via a sulfonamide or other group

709 532-98

be bound to an aliphatic or aromatic radical. Other substituents, with the exception of Sulphonic acid groups can be present in the dye molecule.

Diazo components containing carboxy groups are, for example, i-amino-2-methoxybenzene-5 - carboxylic acid, 1-amino - 2-methoxybenzene 4 - carboxylic acid, 1 - aminobenzene - 2, 5 - dicarboxylic acid, ι - aminobenzene - 2, 5 - dicarboxylic acid - dimethyl ester, i- Amino - 2 - methoxybenzene- 5 -sulfonic acid - (2 '- carboxy) - phenylamide, i-amino - 2, 5 - dimethoxybenzene-4-sulfonic acid- (2'-carboxy) -phenylamide and i-amino-2-methoxy-5-methylbenzene-4-sulfonic acid (3'-carboxy) phenylamide.

The three last-mentioned compounds can be obtained in a simple manner by reacting the appropriate ones sulfonic acid group-free acetylamino compounds with chlorosulfonic acid, then reaction the sulfochlorides obtained with an aminobenzoeao acid and finally hydrolysis of the acetylamino group to the free amine (e.g. by boiling with 10% hydrochloric acid).

Instead of the i-amino-2-methoxybenzene compounds one can also use the corresponding i-amino-2-oxybenzene compounds use. In general, however, the i-amino-2-methoxy compounds are preferred, since they are generally more easily accessible and couple with better yield.

Azo components containing carboxyl groups are, for example, i- (3'-carboxy) -phenyl-3-methyl-5-pyrazolone, i-phenyl-s-carboxy-S-pyrazolone, 2-0xynaphthalene-3-carboxylic acid, 2-0xynaphtha-Hn - 6 - carboxylic acid, 2 - oxynaphthalene-6-sulfonic acid- (2 ' - carboxy) - phenylamide, 1 - succinylamino - 7 - oxynaphthalene, 2 - oxyanthracene-3-carboxylic acid.

The conversion into the 1: i chromium complex compound may refer to, for example, those described in patent specification 479,373 or in the Journal of the Chemical Society (London), 1939, pp. 823-835.

Suitable complex-forming compounds are, for example those aromatic compounds, the hydroxyl, carboxyl and / or sulfonic acid groups contain, such as 2-oxybenzoic acid, 1, 2-dioxybenzene, ortho- or peri-dioxynaphthalenes, o-oxynaphthoic acids, Phthalic acid and its derivatives, also o-nitrosonaphthols, 8-oxyquinoline, pyridine-2-sulfone or carboxylic acid, oxalic acid, tartaric acid, citric acid, malic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, Polyglycols or ethanolamine. The implementation of these compounds with those containing carboxyl groups ι: i-chromium complex azo or -AzometHnfarbstoffen can be in water or in organic Solvents, e.g. B. ethylene glycol, bis (/ 3-oxyethyl) ether or ethanol. It is not necessary that the connections are in dissolved form; they can generally be added in finely divided form in water Use temperatures between 60 and 100 °. The dyes thus obtained are suitable for Dyeing of wool, silk, leather, casein wool and synthetic fibers. You're already pulling out weak acid bath on wool.

The dye prepared according to Example 12 of the present application has compared to that according to Example 2 of German patent specification 606 095 by handling the chromium complex compound of the azo dye from diazotized i-oxy-a-amino ^ -nitrobenzene-6-sulfonic acid dye obtained with oxalic acid has significantly improved washfastness, though the wet fastness properties of metal complex dyes that have a sulfonic acid group in the o-position a complex-bound hydroxyl group are known to be particularly well known.

The parts mentioned in the examples are parts by weight.

example 1

A slurry of 26 parts of the 1: i-chromium complex compound of the azo dye from diazotized 2-aminobenzene-3, 5-dichlorobenzoic acid and i- (2'-carboxy) -phenyl-3-methyl-5-pyrazolone in 1000 parts of water is mixed with 15, 5 parts of 2-oxybenzoic acid-5-sulfonic acid phenylamide are added. The mixture was heated with stirring for 2 hours at 80 to 90 ⁰ and adds, to complete the dye excretion, 100 parts of sodium chloride were added. The dye dyes wool from a weakly acidic bath in greenish yellow tones.

Example 2

20 parts of the 1: i-chromium complex compound des Azomethine dye from i-amino-2-methoxybenzene-5-carboxylic acid and 2-oxy-3,5-dichlorobenzaldehyde dissolved in 400 parts of ethanol and refluxed with 7.5 parts of 2-oxybenzoic acid. The after Distilling off the alcohol remaining dye dyes wool from a weakly acidic bath in yellow tones.

Example 3

30 parts of the monoazo from diazotized i-amino-2,5-dimethoxybenzene-4-sulfonic acid- (2'-carboxy) -phenylamide and i-oxynaphthalene-4-sulfonic acid are in 100 parts of bis (/ 3-oxyethyl) ether after the process of German Patent 931 061 with elimination of the sulfonic acid group in the ι: i-chromium complex azo dye transferred. In addition The product obtained is given 15.5 parts of 2-oxybenzoic acid-5-sulfonic acid-phenylamide at 80 °, the solution holds ι hour at this temperature and carries it no then in 2000 parts of 2% sodium carbonate solution. By adding 300 parts of sodium chloride is the dye deposited. He dyes wool from a weakly acidic bath in blue tones.

Example 4

19 parts of the 1: i-chromium complex compound des Azo dye from diazotized i-amino-2-methoxybenzene-5-carboxylic acid and 2-oxynaphthalene are treated in the manner described in Example 1. A mixed complex dye is obtained which dyes wool from a weakly acidic bath in bordeaux red shades.

In the same way, the 1: i-chromium complex compounds of the following azo dyes reacted with 2-oxybenzoic acid-5-sulfonic acid phenylamide will.

at
games Diazo component Azo component Hue of
- mixed
Chromium complex
link
on WoUe 5 i-aminobenzene-2, 5-dicarbon-
acid i-phenyl-3-methyl-5-pyrazolone yellow 6th i-amino ^ -methoxy-s-methyl-
benzene-4-sulfonic acid
(3'-carboxy) phenylamide i, 3-Diphenyl-5-pyrazolone Red 7th i-amino ^ -methoxy-s-chloro-
benzene 2-oxynaphthalene-6-sulfonic acid-N- (carboxy-
methyl) amide violet 8th i-amino-2-ethoxynaphthalene 2-oxynaphthalene-6-carboxylic acid blue 9 i-amino ^ -methoxy ^ -nitro-
benzene 2-oxynaphthalene-3-carboxylic acid blue IO i-amino-2,5-dimethoxy-benzene
4-sulfonic acid amide 2-oxyanthracene-3-carboxylic acid Blue green II i-amino-2-methoxy-benzene-
4-carboxylic acid 4'-Oxy-4, 5,1 ', 2'-naphtho-i, 3-thiooxol-
S-dioxide of the formula blue O-CH ₂
I. SUN ₈
in Il
V \
( J
)H

Example 12

A slurry of 21 parts of the 1: i-chromium complex compound of the azo dye from diazotized ι - oxy - 2 - amino - 4 - nitrobenzene - 6 - carboxylic acid and 2-oxynaphthalene in 1000 parts of water is mixed with 7 parts of oxalic acid dihydrate. The mixture is heated with stirring for 2 hours at 80 to 90 ⁰ and adds, to complete the dye excretion, 100 parts of sodium chloride thereto. The dye obtained dyes wool from a weakly acidic bath in violet-brown shades.

Claims (1)

Claim H. method for the production of water-soluble, chromium-containing dyes by handling Chromium-containing dyes with organic compounds that are themselves complex chromium compounds can form, but are not dyes, characterized in that they are chromium-containing Starting dyes Azo or azomethine dyes which are free from sulfonic acid groups but contain carboxyl groups used that on 1 molecule of metal-free dye 1 atom of chromium in complex Binding included. Considered publications: German patent specifications No. 606 095, 846142, 725; German patent application B 26 999 IVd / 22a (Patent 932445).