WO1997041177A1

WO1997041177A1 - Process for producing the stable modification of formazan colorants

Info

Publication number: WO1997041177A1
Application number: PCT/EP1997/002042
Authority: WO
Inventors: Claus Marschner; Manfred Patsch; Günther Seybold; Gerhard Wagenblast
Original assignee: Basf Aktiengesellschaft
Priority date: 1996-04-26
Filing date: 1997-04-23
Publication date: 1997-11-06
Also published as: AU2767997A; ID16681A

Abstract

This invention concerns a process for the production of the stable modification of formazan colorants, characterized by the fact that the modification which initially arises from the synthesis of metal complex colorants is converted into a stable modification in the presence of a catalyst which is a chelate ligand for transition metals.

Description

Process for producing the stable modification of formazan dyes

description

The invention relates to a method for producing the stable modification of formazan dyes.

Methods for producing the stable modification are already known from the prior art; e.g. describes an acid treatment in European patent specification 28788 (see the paragraph on pages 2/3) which results in the stable modification, but this is not generally applicable and leads to loss of yield, in particular in the case of hydrolysis-sensitive dyes. Furthermore, a lengthy heat treatment is known from European patent application 321784 (see example 1), which leads to a stable modification but also entails the risk of hydrolysis.

In particular, the known methods are not suitable for dyes with sensitive reactive anchors.

The present invention was therefore based on a gentle process which enables the preparation of stable formazan modifications in a good space-time yield.

Accordingly, a process for producing the stable modification of formazan dyes has been found, which is characterized in that the modification which initially arises in the synthesis of the metal complex dyes is converted into the stable in the presence of a catalyst which is a chelate ligand for transition metals Modification transferred.

Suitable formazan dyes which can be converted into the stable modification according to the invention are both acid and reactive dyes, the method being of particular importance for the latter. The term formazan dye is already to be understood in the present invention as the respective metal complex.

Formazan dyes are described in large numbers in the literature, for example the following patent or published documents may be mentioned:

EP-A 99721 DE-A 3840653 EP-A 592980 EP-A 144766 DE-A 4230095 The process according to the invention is of particular importance for open azane reactive dyes and their precursors which do not yet contain a fiber-reactive group.

The process according to the invention is particularly valuable for formazan dyes which are prepared by coupling diazotized aminophenol derivatives to hydrazones in the presence of the metal-donating compounds; this is, moreover, the customary production method.

Metals for the formazan complexes are preferably copper and nickel. The o-aminophenols suitable for the dyes are known from the extensive patent literature, as are the useful hydrazones.

Preferred formazans are, for example, compounds of the general formulas Ia-Ie

in which

Y is vinyl or a radical of the formula CH ₄ -Q, where Q is a group which can be split off under alkaline reaction conditions and

E is a heterocyclic fiber-reactive radical or a fiber-reactive radical of the formula L-W, where L is a bridge member and w is a fiber-reactive radical from the aliphatic series, and

the rings A and B are optionally substituted and may be benzofused and the ring C is optionally substituted.

The formazans of the formula Ia-Id are dyes with only one fiber-reactive group on ring A, B or C, in contrast to formazans of the formula Ie which carry two fiber-reactive groups.

The rest Q stands for a group which can be split off under alkaline reaction conditions. Such groups are, for example, chlorine, bromine, C 1 -C ₄ -alkylsulfonyl, phenylsulfonyl, OS0 ₃ H, SS0 ₃ H, OP (O) (OH) ₂ , C 1 -C ₄ -alkylsulfonyloxy, phenylsulfonyloxy, C 1 -C ₄ -alkanoyloxy, C 1 -C ₄ -dialkylamino or a radical of the formula

where Z ¹ , Z ² and Z ^{3 are the} same or different and independently of one another each have the meaning of C 1 -C ₄ -alkyl or benzyl and An® each have the meaning of one equivalent of an anion. Anions which can be used here are, for example, fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzene sulfonate or 2- or 4-methylbenzenesulfonate.

Fiber-reactive radicals E are those which react substitutively or additively with the groups of the substrates to be treated which contain hydroxyl groups or nitrogen atoms.

The respective fiber-creative rest generally has no influence on the process according to the invention and is therefore arbitrary.

Heterocyclic aereactive radicals E are, for example, halogen-substituted radicals of 1,3,5-triazine, quinoxaline, phthalazine, pyrimidine or pyridazone, or the 2-alkylsulfonylbenzothiazole rest. They are familiar to the person skilled in the art and are described, for example, in US Pat. No. 5,446,193.

Fiber-reactive radicals W from the aliphatic series are, for example, acryloyl, mono-, di- or trichloroacryloyl, -C0-CC1 = CH-COOH, -C0-CH = CC1-C00H, 2-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl, 2-chloro-2,3,3-trifluorocyclobut-1-ylcarbonyl, 2,2,3, 3-tetrafluorocyclobut-1-ylcarbonyl, 2,2,3, 3-tetrafluorocyclo but-1-ylsulfonyl, 2- (2,2,3,3-tetrafluorocyclobut-1-yl) acryloyl, 1- or 2-bromoacryloyl, 1- or 2-alkyl- or arylsulfonyl-acryloyl, such as 1- or 2 -Methylsulfonylacryloyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl or a radical of the formula S0 ₂ -Y, where Y has the meaning given above.

Suitable bridge members L, which link the aliphatic anchor residue W with the amino group of the formazan, obey e.g. of the formula

-CO-alk-, alk-,

-CO-N P or -CO — N N— alk-,

U ² U ¹ where

U ^{1 is} hydrogen, C ¹ -C ₄ -alkyl, carboxyl, C 1 -C ₄ -alkoxy, halogen, nitro or hydroxysulfonyl and U ^{2 is} hydrogen, C ¹ -C ₆ -alkyl, which may be substituted by hydroxy,

C ~ ~ C ₄ alkoxy, halogen, cyano, hydroxysulfonyl or a radical of the formula -S0 ₂ -Y> where Y has the meaning given above, is substituted, or optionally substituted phenyl and alk C -C ₆ alkylene.

The phenyl rings A, B and C can, for example, bear those substituents listed in US Pat. No. 5,446,193, to which express reference is made. Preferred substituents are water-solubilizing groups, in particular the hydroxysulfonyl group. The process according to the invention is particularly suitable for forazans of the general formula Ha and b

in which E has the meaning given above.

Furthermore, the process according to the invention is suitable for the production of metal complex formazans which are precursors of the structure types Ib, Id and Ie and which, instead of the fiber-reactive radical E, carry hydrogen or a protective group suitable for the amino group, such as acetyl, and otherwise have the formulas Ib, I and I obey.

Form azanes whose ring B is substituted in the o-position to the phenolic oxygen with hydrogen, amino, a protective group protected amino or a NH-E radical are particularly preferably used in the process according to the invention.

In the production of reactive dyes from the formazan series, it is possible to have the reactive groups already in the starting components, but often they are only introduced after the synthesis of the metal complexes; the corresponding methods are also described in the patent literature.

Compounds suitable for the process according to the invention are those containing transition metals, preferably subgroups VIIIA and IB of the Periodic Table of the Elements, in particular copper and nickel Can form chelate complexes, so-called chelate ligands. The

The term chelate ligand encompasses both bidentate ligands, that is to say those which are coordinated in the complex via two molecular sites to the central atom, and also multidentate ligands, that is to say those which have 3, 4, 5 or 6 coordination sites. Within the scope of the method according to the invention, it is also conceivable that

Complexes with the chelate ligands can be run as reaction stages.

Ligands which are preferred via nitrogen atoms of heterocycles, hydroxyl, amino, alkylamino, phosphonic acid, formyl, alkanone, imino, carboxy, carbonamide, carboxylic acid ester, oxime, hydroxamic acid, hydroxamic acid ester , Mercapto, thiocarbonyl, thioester or thiocarbamate groups are linked to the central atom.

Types of such connections are e.g.

Di- or polycarboxylic acids, di- or polycarboxamides,

Di- or polycarboxylic acid esters,

Di- or polyhydroxy compounds,

Di- or polycarbonyl compounds,

Nitrogen heterocycles which carry complexes in the vicinity of the heteroatom, in particular carboxyl, formyl, hydroxy or amino groups, dipyridines, amino and hydroxycarboxylic acids, amino and hydroxycarboxamides, amino and hydroxycarboxylic acid esters, amino alcohols or Polyether compounds.

Individual active compounds are, for example, oxalic acid, malonic acid, succinic acid, mandelic acid, lactic acid, tartaric acid, citric acid, salicylic acid, salicylaldehyde, anthranilic acid, N-methylanthranilic acid, glycine, phenylglycine, alanine, iminodiacetic acid, nitrilotriacetic acid, EDTA, and tetraethylene glycol

PhNHC NH - Ph or

Nitrogen heterocycles such as pyridines and quinolines which are substituted with complexing groups such as carboxyl, formyl, hydroxy or amino are preferred.

Compounds which can form bidentate chelate complexes are particularly preferred. Pyridine and quinoline carboxylic acids are especially preferred, especially 2-carboxypyridines.

The process according to the invention is generally carried out in aqueous solution or aqueous suspension. An aqueous solution is also to be understood to mean solutions which, in addition to water, contain up to 20% by weight of a water-miscible organic solvent such as C 1 -C ₄ -alkanols, in particular methanol, ethanoi, isopropanol or a cyclic ether such as tetrahydrofuran. However, water is preferably used as the sole solvent.

The process according to the invention can generally be carried out under very mild conditions, for example at temperatures between 0 and 80 ° C., in particular 20 to 60 ° C. The pH Of values ^"for the transformation are not critical, however, are those 1-7 preferable, and in the more acidic range, such as aqueous sulfuric acid, the reaction proceeds faster. The inventive method can both be performed in a continuous or discontinuous manner.

The catalysts are generally used in amounts of 0.5 to 25, preferably 1 to 10, mol%, based on 1 mol of formazan dye.

The method according to the invention enables the production of stable formazan modifications in a good space-time yield.

The method according to the invention is illustrated by the following representative examples, in which information about

Unless stated otherwise, parts and percentages are by weight.

Example 1:

a) 78.7 g of the aminophenol of the formula

were dissolved in 600 ml of water, cooled to 0 to 5 ° C and the pH with conc. Hydrochloric acid set to 2. Then was added by adding 51 g of 23 wt. -% aqueous sodium nitrite solution diazotized at 0 to 5 ° C.

The resulting diazo suspension was left at 10 to 15 ° C. to a mixture of 75.8 g of the hydrazone of the formula which had been brought to a pH of 6.5 to 7.0

and 44.9 g of copper sulfate pentahydrate run in 750 ml of water, the pH being kept between 6.5 and 7.0 by sprinkling in sodium hydrogen carbonate. After the end of the feed, the mixture was left to stir at 15 to 20 ° C. for a further 12 hours. The precipitated dye was suction filtered and 20 wt. - Washed% aqueous saline solution.

The moist filter material obtained, which dissolves in water with a bluish green color and shows characteristic absorptions at 400 and 633 nm in the UV spectrum, was stirred in 820 ml of water for conversion to the more stable complex form. The pH was adjusted to 5 with 10% hydrochloric acid, then 1.0 g of 2-pyridinecarboxylic acid was added and the mixture was stirred at 60 ° C. for one hour until the complex was largely converted (according to HPLC 95%).

The pH was adjusted to 6.5 to 7.0 by adding soda. The resulting reactive dye was salted out by adding 150 g of sodium chloride. A dye of the formula was obtained

dyes the cotton in a strong reddish blue shade with very good fastness properties. λm _ax = 599 nm

Example 2:

The moist filter material obtained in Example la, which dissolves in water with a bluish green color, was stirred in 820 ml of water for conversion into the more stable complex form. The pH was adjusted to 3 with 10% hydrochloric acid, then 1.0 g of 2-pyridinecarboxylic acid was added and the mixture was stirred for one hour at 20-25 ° C. until the complex was largely converted (according to HPLC "=" 95%). The dye was isolated as described in Example 1b.

Instead of pyridinecarboxylic acid-2 there were others

Catalysts for converting metal formazan complex dyes into the more stable complex form can be used. Table I:

Other metal complex formazan dyes which can be converted into the stable complex form in neutral, weakly acidic or weakly alkaline solution using the catalysts listed in Table 1, e.g. :

Example: "49

a) 88 g of acetamino-o-phenolic acid are dissolved in 500 ml of water by adding 16.5 ml of sodium hydroxide solution (50% at) to 0-5 ° C. After acidification with 150 ml of hydrochloric acid (M 200), diazotization was carried out by adding 90 ml of sodium nitrite solution (M 300). After a subsequent stirring time of 2 hours at 0-5 ° C., the resulting diazo suspension was left at 10-15 ° C. to give a mixture of 99.9 g of the hydrazone of the formula set to a pH of 6.5 to 7.0

and 81 g of copper sulfate -5 ^ 0 in 500 ml of water, the pH being kept between 6.5 and 7.0.

After the feed had ended, the mixture was left to stir at 15 to 20 ° C. for a further 2 hours. The solution of the copper formazan precomplex obtained showed a characteristic absorption band in the UV spectrum:

λ _m ax = 637 nm

To convert to the more stable complex form, the pH of the solution was concentrated with. Hydrochloric acid reduced to 6 and the reaction mixture heated to 60 ° C. After adding 4.0 g of pyridinecarboxylic acid-2, the mixture was stirred at 60 ° C. for 3 hours.

The copper formazan dye of the formula in solution

now showed an absorption maximum in the UV spectrum at 608 nm. b) 185 ml of sodium hydroxide solution (50% strength) were added to the saponification of the acetylamino group and the mixture was then heated to 90.degree took.

After adding 500 g of ice, the pH was then set to 5 at 63 ° C. with 635 ml of hydrochloric acid (M 200) and the dye was salted out by adding 95 g of potassium chloride and 285 g of sodium chloride. After drying, 167 g of the electrolyte-containing compound of the formula were obtained

The following compounds were treated analogously:

let

Example: 54

66 g of cyanuric chloride were added to the compound obtained in Example 49b before salting out. The pH of the reaction mixture was kept at 4.0 to 4.5 until the end of the acylation by adding sodium hydrogen carbonate. After 2 hours, 62 g of 3-aminobenzenesulfonic acid, dissolved in 150 ml of water, were introduced. The suspension was heated to 40 ° C. and the pH was kept at 6.0 to 6.5 by adding sodium hydrogen carbonate.

After 6 hours the formazan dye became the formula

isolated by salting out.

The formazan dyes of the formula listed in Table 2 below are used in an analogous manner

receive: Table 2

Example 62

Example 59 was repeated, but 38 g of 4-amino-2-methylaminobenzenesulfonic acid, dissolved in 100 ml of water, were added instead of 3-amino-benzenesulfonic acid.

The suspension was heated to 60 ° C. and the pH was kept at 7.0 to 7.5 by adding sodium hydrogen carbonate. After 6 hours, the electrolyte-containing formazan dye, which corresponds to the following formula in the form of the free acid, was isolated by spray drying:

Claims

claims

1. A process for the preparation of the stable modification of azane dyes, characterized in that the modification which initially arises in the synthesis of the metal complex dyes is converted into the stable modification in the presence of a catalyst which is a chelating ligand for transition metals.

Process according to Claim 1, characterized in that reactive dyes of the formazan series are produced.

3. The method according to claim 1, characterized in that the catalyst in amounts of 0.5 to 25, preferably

1 to 10 mol%, based on formazan dyes.

4. The method according to claim 1, characterized in that di- or polycarboxylic acids, di- or polycarbonate acid amides, di- or polycarboxylic acid esters, di- or poly-hydroxy compounds, di- or polycarbonyl compounds, nitrogen heterocycles which complex in the vicinity of the heteroatom as a catalyst Bearing groups, amino or hydroxy carboxylic acids, amino or hydroxy carboxamides, amino or hydroxy carboxylic acid esters, amino alcohols or polyether compounds are used.

5. The method according to claim 1, characterized in that pyridines or quinolines which are substituted with complexing groups are used as the catalyst.