DE1129641B - Process for the production of chromium-containing azo dyes - Google Patents

Description

The invention relates to a process for the production of chromium-containing azo dyes.

It has been found that valuable blue to blue-gray azo dyes can be obtained from one Monoazo dye of the formula I

OH

HO ₃ S-

-N =

(I)

and an unsulfated, metallizable monoazo dye of the general formula II

HOOC-B-X-A-N = N-D (II)

wherein A is an optionally further substituted hydroxyphenyl radical which is the hydroxyl group in o-position to the binding site of the azo group contains, X an oxygen-containing divalent bridge member, B an optionally further substituted aryl radical from the benzene and naphthalene series and D a halogenated one 1-Hydroxy-2-naphthyl radical means one of the two monoazo dyes in the one Chromium complex compound, which contains 1 atom of chromium for 1 molecule of the dye, and then attaches to this 1 molecule of the other, metal-free monoazo dye.

Chromium complex compounds which can be used according to the invention and which contain a whole atom of chromium bound per dye molecule are obtained from the corresponding metal-free monoazo dyes by treatment with excess chromium-releasing agent. It is preferably carried out in acidic medium and at temperatures of about 80 to 15O ⁰ C, if necessary under pressure. In the simplest case, the chromating is carried out in an aqueous solution or suspension. Often the addition of organic solvents or working in such as in alcohols, formamide or acetamide is indicated. Optionally, in an organic melt, e.g. B. in that of an alkali salt of a low molecular weight aliphatic monocarboxylic acid, such as sodium acetate, worked. Chromium-releasing agents are mainly chromium salts, e.g. B. chromium chloride, chromium fluoride, chromium sulfate, chromium acetate and chromium formate into consideration. However, chromium complex compounds or salts of hexavalent chromium, e.g. B. Method of Manufacture
of chromium-containing azo dyes

Applicant:
JR Geigy AG, Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority;
Switzerland of April 15, 1959 (No. 72 092)

Dr. Fabio Beffa and Dr. Guido Schetty,

Basel, Switzerland),
have been named as inventors

Alkali dichromates, can be used. When using the latter is the presence of a reducing Substance, e.g. B. a reducing sugar favorable.

As such a chromium complex compound which contains 1 atom of chromium per dye molecule is particularly that of the sulfonic acid group-containing monoazo dye of the formula I easily and as a single compound accessible. It is therefore the preferred so-called 1: 1 chromium complex component in the process according to the invention, to which a metal-free, carboxylic acid group-containing monoazo dye of the general formula II is then attached will.

The sulfonic acid group-free coupling products of are used as monoazo dyes of the formula II o-hydroxydiazobenzene compounds, which are attached to the benzene nucleus via an oxygen-containing bridge member contain a carboxyl group-containing aryl radical bound, with in o-position to the hydroxyl group connectable halogenated 1-hydroxynaphthalenes into consideration. This comes as oxygen-containing bridge links primarily carbonyl, carbonylamino, sulfonyl and sulfonylamino groups in question. Diazo components for Monoazo dyes of the formula II which can be used according to the invention are accordingly for example

209 580/363

wise those from 4-hydroxy-3-nitrobenzoic acid halides by condensation with aminobenzoic acids or aminonaphthalenecarboxylic acids, reduction and 4-Hydroxy-3-diazobenzene-1-carboxylic acid carboxyarylamides obtainable in diazotization. Another group are the sulfonic acid carboxyarylamides corresponding to the abovementioned compounds. You get this for example from 4-chloro-3-nitrobenzenesulfonic acid halides by reacting with aminoaryl carbon very good lightfastness and rubfastness and good waterfastness and seawater resistance. You can use the chromium-containing azo dyes - because of their good water solubility and Acid resistance - also for printing wool using the so-called Vigoureux printing process use. Finally, they can also be used for dyeing and printing artificial fibers, e.g. B. polyamide and polyurethane fibers, as they also have good wet-fastness on these synthetic fibers

acids, exchange of the chlorine atom for the hydroxyl 10 stains.

group, reduction of the 4-hydroxy- Compared with that from the German interpretation

3-nitrobenzenesulfonic acid carboxyarylamide to the 1: 2 mixed chromium complex compound of the azo dyes 4-chloro-2-amino-1-hydroxybenzene - 5,8-dichloro-1-hydroxynaphthalene and 1-amino-2-hydroxynaphthalene-4- sulfonic acid -> ■ 2-hydroxynaphthalene has the silk coloration of the process obtainable 1: 2 mixed chromium complex compound of the azo dyes 4-hydroxy-3-aminobenzophenone-2'-carboxylic acid -> 5,8-dichloro-1-hydroxynaph- and 1-amino-2 -hydroxynaphthalene-4-sulf on- y 2-hydroxynaphthalene a better washing

tuents in question, e.g. halogen, alkyl, alkoxy, fastness.

Acyl, acylamino, nitro and cyano groups. The following examples serve to illustrate

Halogenated 1-hydroxynaphthalenes which are used in the invention. In these examples mean

Coupling o-position to the hydroxyl group and a total of 25 parts by weight, unless otherwise expressly with the previously defined diazo components that are mentioned. The temperatures are in degrees Celsius

specified.

speaking amines and diazotization of the same. Other diazo components that may be considered are also the diazonium compounds of 2- (3'-amino-4'-hydroxybenzoyl) -benzoic acid and 4-hydroxy-3-aminodiphenylsulphone-3'-carboxylic acid and finally also the descendants of these abovementioned basic p body. The 20 thalin common in azo dyes, non-ionic substituents, are used as further substituents

example 1

HO

Forming dyes of the general formula II are

z. B. 4-chloro-1-hydroxynaphthalene, 5-chloro-1-hydroxynaphthalene, the 5,8-dichloro-l-hydroxynaph-

thalin and the 5.8,: x: -TricUor-l-hydroxynaphthalene. Preferred monoazo dyes of the general

Formula contain the defined carboxyl group attached to an N-phenylsulfonic acid amide radical. It is also advantageous for the properties of the dyes if the carboxyl group in these radicals is bonded in each case in the o-position to the amide nitrogen. In these dyes, the group —SO ₂ —NH— denotes the bridge member X of the formula II. In addition, particularly valuable dyes prepared according to the invention are obtained if the monoazo dyes of the formula II are the coupling products of the aforementioned preferred diazo compounds with di- or trichloro-1-hydroxy -

naphthalene compounds are used. The addition of the 1: 1 chromium complex compounds

fertilize to the metal-free dyes are characterized in that 1 mol each of the two components heated an acid binding agent at moderate temperatures for example from 40 to 95 ⁰ C in an aqueous solution or suspension in the presence. Often the presence of an organic polar solvent, e.g. B. alcohol, glycol monomethyl ether or monoethyl ether, advantageous. As acid-binding agents, for example, sodium acetate, sodium carbonate or sodium hydroxide or the corresponding

Lithium, potassium or ammonium compounds 30 parts by volume are added to 150 parts of water

to serve. The addition occurs under the mentioned 2 η-sodium hydroxide solution and 5.32 parts of the monoazo dyes, Conditions usually quickly and completely. obtained by coupling diazotized 2-amino

The er l-hydroxybenzene-4-sulfonic acid (2'-carboxyphenyl) obtained by the process according to the invention Chromium complex dyes are dark blue 60 amide with 5,8-dichloro-1-hydroxynaphthalene. To this until black powder. They dissolve easily in a hot mixture, if you give the chromium complex compound, drain water and are particularly suitable as textile dyes. containing 1 atom of chromium per molecule of dye, to, As such, they are thanks to their deep hues and which are 0.52 parts of chrome and 3.94 parts of mono thanks very valuable for their good fastness properties. azo dyes from l-diazo ^ -hydroxynaphthalene ^ -sul-man it is used in particular for dyeing acidic acid and 2-hydroxynaphthalene. Man natural materials containing polypeptide groups, such as heating the mixture to 90 to 95 ° until the Wool, silk and leather. The marine starting compounds obtained have disappeared. The chrome blue to gray-blue wool dyeings are particularly containing addition compound is added

NH

precipitated from sodium chloride, filtered off and dried. It is a dark powder made from wool weakly acidic bath colors in true navy blue tones.

4 parts of this chromium-containing dye are dissolved in 4,000 parts of water and, at 40 ° to 50 °, with 100 parts of well-moistened wool, they are added to the dyebath. One adds thereto 2 parts 40% acetic acid added, the dyebath is heated within ¹ hour to ₂ J boiling and maintained at boiling temperature for% hour. The wool is then rinsed with cold water and dried. The navy blue wool dye has good fastness properties.

Dyes with similar properties are obtained if, instead of the monoazo, diazotized 2 - Amino -1 - hydroxybenzene - 4 - sulfonic acid (2'-carboxyphenyl) amide and 5,8-dichloro-1-hydroxynaphthalene made 5.32 parts of the monoazo dye diazoated 2-amino-1-hydroxybenzene-4-sulfonic acid (3'-carboxyphenyl) amide or 2-amino-1-hydroxy-4-sulfonic acid (4'-carboxyphenyl) -amide and 5,8-dichloro-1-hydroxynaphthalene used.

example

HO

-Cl

Example 2

HO ₃ Sf

30th

35

45

COOH

4.81 parts of the monoazo dye from diazotized 4-hydroxy-3-aminobenzophenone-2'-carboxylic acid are suspended in 150 parts of water and 5,8-dichloro-1-hydroxynaphthalene, also 4.44 parts of the chromium complex compound, Contains 1 atom of chromium per 1 molecule of dye, which is 0.52 parts of chromium and 3.94 parts of monoazo dye from l-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene, and 2.4 parts of sodium carbonate. The mixture is heated to 80 to 85 ° and held for so long at this temperature until the starting compounds have disappeared. The chromium-containing dye will precipitated by adding sodium chloride, filtered off and dried. It's a dark powder that Dyes wool from a weakly acidic bath in navy blue tones. The dyeings show good fastness properties.

SO,

NH

Cl

COOH

30 parts by volume of 2η sodium hydroxide solution and 5.67 parts of the monoazo dye are added to 150 parts of water, obtained by coupling diazotized 2 - amino -1 - hydroxybenzene - 4 - sulfonic acid - (2 '- carboxyphenyty amide with S ^ x -trichloro-1-hydroxynaphthalene. The chromium complex compound containing 1 atom of chromium per 1 molecule is added to this mixture Dye, to which 0.52 parts of chromium and 3.94 parts of the monoazo dye from l-diazo-2-hydroxynaphthalene-4-sulfonic acid and corresponds to 2-hydroxynaphthalene. The mixture is heated to 90 bis 95 ° until the starting compounds have disappeared. The chromium-containing addition compound is through Addition of sodium chloride precipitated, filtered off and dried. It is a dark powder that is made of wool weakly acidic bath colors in navy blue tones.

Example 4

5.45 parts of crystallized sodium acetate are added to 150 parts of aqueous 50% ethanol 4.96 parts of the monoazo dye obtained by coupling diazotized 2-amino-1-hydroxybenzene-4-carboxylic acid (2'-carboxyphenyl) amide with 5,8-dichloro-1-hydroxynaphthalene. One passes the Chromium complex compound containing 1 atom of chromium per 1 molecule of dye, to which 0.52 parts of chromium and 3.94 parts of the monoazo dye from 1-diazo-2-hydroxynaphthalene-4-sulfonic acid and corresponds to 2-hydroxynaphthalene. The mixture is heated to 60 to 65 ° until the starting compounds

disappeared, the alcohol drives off by distillation and salts the resulting chromium complex compound the end. After filtering off and drying, a dark powder is obtained, the wool from weak acid bath colors in blue tones.

Further dyes according to the invention of similar properties are obtained according to the method described in FIGS Examples 1 to 4 indicated method, if one of 0.52 parts of chromium and the in the following The parts given in the table of monoazo dye I produce the 1: 1 chromium complex compound and this Reacts with the specified parts of dye II.

No. Monoazo dye I. Monoazo dye II coloring
on wool 1 l-diazo ^ -hydroxynaphthalene ^ -sulfone-
acid -> 2-hydroxynaphthalene (3.94 parts 2-amino-1-hydroxybenzene-4-sulfonic acid
(2'-carboxy-5'-chlorophenyl) -amide -> 5,8-dichloro-
1-hydroxynaphthalene (5.67 parts) marine
blue 2 the same 2-Amino-1 -hydroxybenzene-4-sulfonic acid
(2'-carboxy-5'-chlorophenyl) -amide - * - 5.8, x-tri-
chloro-1-hydroxynaphthalene (6.01 parts) the same 3 the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(2'-carboxyphenyl) -amide -> 5-chloro-l-hydroxy-
naphthalene (4.98 parts) the same 4th the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(2'-carboxy-5'-chlorophenyl) -amide -> ■ 5-chloro-
1-hydroxynaphthalene (5.32 parts) the same 5 the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(3 ^/ -carboxynaphthyl- (2)) - amide -> 5,8-dichloro-
1-hydroxynaphthalene (5.82 parts) the same 6th the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(3'-carboxynaphthyl- (2)) - amide - * ■ 5.8, x-trichloro-
1-hydroxynaphthalene (6.17 parts) the same 7th the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(3'-carboxynaphthyl- (2)) - amide - »5-chloro-
1-hydroxynaphthalene (5.48 parts) the same 8th the same 2-amino-1-hydroxybenzene-4-sulfonic acid
(3'-carboxynaphthyl- (2)) - amide -> 4-chloro-
1-hydroxynaphthalene (5.48 parts) the same 9 the same 2-amino-1-hydroxyberlZol-4-carboxylic acid
'2'-carboxyphenyl) amide - ^ - 5.8, x-trichloro
1-hydroxynaphthalene (5.31 parts) the same 10 the same 3-amino-4-hydroxybenzophenone-2'-carbon
acid - ^ S ^^ - trichloro-l-hydroxynaphthalene
(5.2 parts) the same 11 the same 3-amino-4-hydroxybenzophenone-2'-carbon
acid -> 5-chloro-l-hydroxynaphthalene
(4.47 parts) plumb line
marine-
blue

Claims (4)

PATENT CLAIMS: 1. A process for the preparation of chromium-containing azo dyes, characterized in that a monoazo dye of the formula I Co OH OH HO ₃ S- (I) and an unsulfated, metallizable monoazo dye of the general formula II HOOC-B-X-A-N = N-D (II) wherein A is an optionally further substituted hydroxyphenyl radical which represents the hydroxyl group contains bonded in the o-position to the azo group, X is an oxygen-containing divalent bridge member, B an optionally further substituted aryl radical from the benzene and naphthalene series and D a halogenated l-hydroxy-2-naphthyl radical means one of the two monoazo dyes in the one Chromium complex compound, which contains 1 atom of chromium for 1 molecule of the dye, and then attaches to this 1 molecule of the other, metal-free monoazo dye. 2. The method according to claim 1, characterized in, that you first of the sulfonic acid group-containing monoazo dye I the one Produces a chromium complex compound which contains 1 atom of chromium for 1 molecule of the dye, and the metal-free monoazo dye II containing carboxylic acid groups is added to these. 3. The method according to claim 1 and 2, characterized in that the monoazo dyes 10 general formula II used, in which the bridge member X is a sulfonic acid amide group. 4. The method according to claim 1 to 3, characterized in that the monoazo dyes general formula II used, in which the carboxyl group is in the o-position to the bridge member X is bound. Considered publications:
German patent specification No. 1 012 007. A coloring table was displayed when the application was announced. © 209 580/363 5.62