JPS5821659B2 - Method for producing asymmetric chromium-containing complex dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of asymmetric chromium-containing complexes.

A large number of monosulfonic acid or monocarboxylated asymmetric chromium-containing complexes are already known.

According to French Patent No. 1,101,955, such a complex consists of a metal-free metallizable monoazo dye and a chromium-containing complex compound of 1/1 of a sulfonic monoazo dye in a ratio of about 1:1. It may also be produced by reacting at molar ratios.

The reaction is advantageously carried out in a neutral or slightly alkaline aqueous medium in an open or closed vessel at ambient temperature or heated, for example from 50°C to 120°C.

Generally, it is recommended to react the 1:1 metal-containing complex and metal-free dye in as equal amounts as possible.

The reaction is very often carried out in the presence of sodium bicarbonate, sodium carbonate or sodium hydroxide.

Under these conditions both dyes combined are 0
-carboxy-〇′-hydroxyazo dye,
The proportion of asymmetric complexes obtained is generally small, even zero.

This result shows that 1/1 complexes of monosulfonated or monocarboxylated 0-carboxy-O'-hydroxyazo dyes react with metal-free 0-carboxy-O'-hydroxyazo dyes rather than symmetrical 1/2 complexes. It is essentially based on the fact that it is rapidly converted to

In this study, the inventor discovered that if the basic organic reagent molecules were to react at a pH
5 to 10 in the presence of a basic organic reagent which, in addition to the amine function capable of forming salts, has one or more water-soluble groups, such as hydroxyl groups or sulfonic or carboxyl groups in the form of alkali metal salts. If so, the proportion of undesired compounds in the final product, i.e. the symmetric 1/2 complex and unreacted metallizable dye, is significantly reduced and a final product consisting essentially of the desired asymmetric chromium-containing complex is obtained. I discovered that it is possible.

The present invention provides a method for producing a monosulfonated or monocarboxylated asymmetric chromium-containing complex dye, in which one is a metallizable monoazo dye that does not contain a sulfonic group or a carboxyl group that does not participate in metalization, and the other is a metalizable monoazo dye that does not participate in metalization. 1/1 with sulfone group or carboxyl group
A monosulfonated or monocarboxylated asymmetric chromium-containing complex characterized by reacting a chromium complex monoazo dye in an aqueous medium in the presence of 1 to 4 equivalents of the above-defined basic organic reagent at a molar ratio of about 1:1. An object of the present invention is to provide a method for producing a dye.

The reaction operation is preferably performed in p) 17 to 11. Temperature 50℃
The temperature is between 100°C and 100°C.

The monoazo dye used in the process of the invention in the unmetallized state or in the form of a 1/1 chromium complex can be prepared by coupling a diazotized derivative of a diazotizable base with a coupling compound, e.g. It can also be manufactured by the following method.

Examples of diazotizable bases are anthranilic acid, substituted derivatives thereof such as 2-amino-5-nitrobenzoic acid, 2-
Amino-3-t4-. 5-1- or 6-chlorobenzoic acid, 2-amino-3,5-dichlorobenzoic acid, 2-amino-4-sulfonamidobenzoic acid, 2-amino-5-sulfonamidobenzoic acid, 2-amino-4( or 5)-(
N-arylsulfonamido)benzoic acid, 2-amino-
4(or 5)-mono- or di-alkyl sulfonamide benzoic acid, 2-amino-5-acetylaminobenzoic acid, 2-amino-4-(or 5)-sulfobenzoic acid, 2-amino-3+,4 −． 5-1 or 6-carboxybenzoic acid, 2-amino-3-sulfo-5-chlorobenzoic acid, 2-amino-5-sulfo-3-chlorobenzoic acid or 2-amino-5-sulfo-4-chlorobenzoic acid acid, 2
-amino-3-(N-phenylcarbonamide)-5-
sulfobenzoic acid and 2-amino-3-naphthoic acid.

Examples of coupling compounds include various pyrazolones, especially 1-phenyl-3-methyl-5-pyrazolones and the following substituents on the phenyl nucleus: 2/, 3/- or 41-chloro, 2/- or 4/- Methyl, 3/- or 4'-nitro, 3'- or 4'-amino, 2'-ethyl, 3'
-cyano, 3'-carbonamide, 3'- or 4'-
Sulfonamide, 41-methoxy, 215'-dichloro-137-sulfonamido-4/-chlor, 3'-amino-4'-methyl, 3'-methoxy-4'-amino, 3
'-Methoxy-41-acetylamino, 2'-methyl-
51-sulfonamide, 3'- or 4'-sulfo, 3
'-carboxy, 2'-sulfo-47-chlor, 2/-
Chlor-5'-sulfo, 2/, 5/-dichlor-4
7-sulfo, 2'-methyl-47-sulfo-6'-chlor, 2'-sulfo-5'-amino and 2'-methyl-
Mention may be made of its homologs having 3'-amino-5'-sulfo.

Other examples of pyrazolones are 1,3-diphenyl-5-py
Zolone, ■-phenyl-3-carboxy-5-pyrazolone, 1-acetyl-3-methyl-5-pyrazolone, 3-
Methyl-5-pyrazolone, 1-phenyl-3-carbonamide? and N-alkyl or aryl)-3-carbonamido-5-pyrazolone and 2/-methyl-4'
-sulfo-1-phenyl-3-methyl-5-pyrazolone.

Other coupling compounds that may be mentioned are, for example, β
- Amides of acetocarboxylic acids, such as acetoacetanilide groups and phenyl nuclei with the following substituents 2- or 4-
methoxy, 2- or 4-chloro, 2- or 4-methyl, 2,4-dimethyl, 2,5-dichlor, 2-methyl-4-(or 5)-chlor, 2-chloro-4-nitro, 4-acetyl-2-13-1 or 4-sulfo, 2-
．． Acetanilides with 3-1 or 4-carboxy, 2-methoxy-5-carboxy and 2-methoxy-4-sulfo-5-methyl.

Barbyric acid and functional derivatives of malonic acid, acetylacetate and benzoylacetate, such as alkylmalonates, alkyl acetylacetates, alkylbenzoylacetates, acetoacetamides.

Also suitable are N-monoalkyl and N,N-dialkyl acetamides.

A large number of amines whose molecules have hydroxyl groups or acid groups in the form of salts can be used as basic organic reagents in the process of the invention.

Amines that are particularly useful from an economic and practical point of view are alkanolamines, such as mono-, di- and triethanolamine, and the alkali metal salts of taurine or glycine, the use of which allows the reduction of 1/1 chromium in slightly alkaline aqueous medium. Asymmetric complex dyes can be obtained by hot condensation of the complex with dyes that are normally insoluble under condensation conditions.

It is noted that the dye thus obtained has a proportion of 1/2 symmetric complexes of less than 20% of the separated dye.

These dyes have excellent coloring power on natural or synthetic polyamide fibers.

The invention is illustrated in the following examples, in which parts are parts by weight.

Example 1 5-nitro-anthranilic acid and 1-phenyl-3-
The monoazo dye obtained from methyl-5-pyrazolone is separated in an acidic medium and 102 parts of dye paste, corresponding to 0.095 mol of dye, are taken up in 1000 parts of boiling water containing 20 parts of monoethanolamine.

Diazotized derivatives of anthranilic acid and 4'-sulfo-1-
55 parts (i.e. 0.1 mol) of the 1/1 chloro-mediated complex dye obtained by metallization in an acidic medium of the azo dye obtained by coupling with phenyl-3-methyl-5-pyrazolone are added to the above mixture at 15 parts. Add sequentially for minutes, mix well, and hold at 99°C.

After stirring at 95-100°C for 30 minutes, the reaction is terminated.

The resulting brown solution is cooled, acidified to pH 5 and salted out with 100 parts of sodium chloride to precipitate the dye.

After passing through the mouth, the precipitate is dried to obtain 83 parts of a dye containing 80% or more of a dye consisting of an asymmetric complex having the formula.

The quality of the product can also be evaluated by thin layer chromatography on silica gel using a developing solution of butanol saturated with concentrated ammonia.

The dyes obtained are very soluble in water and in many organic solvents and can dye wool and nylon in a neutral bath in reddish-yellow colors of excellent general fastness.

If monoethanolamine is replaced by an equimolar amount of sodium hydroxide or sodium carbonate, the proportion of asymmetric complex dye of formula (I) in the dye obtained is 50%.
smaller.

Example 2 20 parts of monoethanolamine to 30 parts of jetanolamine
If carried out as in Example 1, substituting 45 parts of triethanolamine or 45 parts of triethanolamine, a product identical to the dye of Example 1 is obtained.

Example 3 Example 1 is carried out replacing 20 parts of monoethanolamine by 25 parts of 2-amino-ethanesulfonic acid (taurine) and the product mixture is neutralized to pH 9.5 with an equivalent of aqueous sodium hydroxide solution.

Formation of the asymmetric complex is rapid.

At the end of the reaction it is necessary to adjust the pH to 8 to 10 by adding a small supplementary amount of aqueous sodium hydroxide solution.

The separated dye is the same as that of Example 1.

Example 4 Working as in Example 3, replacing taurine with 20 parts of glycine, a dye of good quality is obtained, consisting essentially of an asymmetric complex of formula (1).

Examples 5 to 16 Further examples of the method according to the invention are summarized in the following table.

Starting from the 1/1 chromium-containing complex of the azo dye shown in the second column and the unmetallized azo dye shown in the third column, the procedure is as in Example 1.

The present invention is a method for producing a chromium complex dye as described in the claims, and includes the following embodiments.

(1) The production method described in the claims is characterized in that the basic organic reagent has one or more hydroxyl groups or sulfonic or carboxyl groups in the form of their salts with alkali metals. A method for producing an asymmetric chromium-containing complex dye.

(2. A method for producing an asymmetric chromium-containing complex dye as claimed in the claims, characterized in that the reaction is carried out at a temperature of 50°C to 100'C.

(3) A method for producing an asymmetric chromium-containing complex dye as claimed in the claims, characterized in that the reaction is carried out at pH 7 to 11.

(4) In the manufacturing method described in the claims, the metallizable monoazo dye and the monoazo dye used in the form of a 1/1 chromium-containing complex are each 0-carboxy-α-
A method for producing an asymmetric chromium-containing complex dye, which is a hydroxy-azo dye.

Claims (1)

[Claims] 1 A metalizable monoazo dye that does not contain a sulfonic group or carboxyl group that does not participate in metallization on one side, and a 1/1 chromium complex monoazo dye that has a sulfonic group or carboxyl group that does not participate in metallization on the other hand in a molar ratio of about 1:
In the method for producing a monosulfonated or monocarboxylated asymmetric chromium-containing complex dye, which comprises reacting in an aqueous medium in step 1, mono-, di- or triethanolamine, or an alkali metal salt of taurine or glycine, A method for producing a monosulfonated or monocarboxylated asymmetric chromium-containing complex dye, which comprises reacting in the presence of 4 equivalents.