EP1606447A1 - Oxidation system containing a macrocyclic metal complex, the production thereof and its use - Google Patents

Abstract

The invention relates to an oxidation system containing a macrocyclic metal complex, an oxidizing agent and an oxidation-increasing compound. This oxidation system is suited for use under diverse reaction conditions for oxidizing oxidizable substances by brining the oxidizable substance into contact with the special oxidation system. It is possible to use this oxidation system, for example, in a method for removing excess unbound dye from textile materials after a dying process.

Description

Oxidation system containing a macrocyclic metal complex, its manufacture and use

The present invention relates to an oxidation system containing a macrocyclic metal complex, an oxidizing agent and an oxidation-enhancing compound and also a method for the oxidation of oxidizable substances by bringing the oxidizable substance into contact with the special oxidation system.

From EP-A-0 918 840, US-A-6,099,586 and WO-A-02/16330 special macrocyclic metal complexes are known which can be used as bleach activators. In combination with a peroxide source, preferably hydrogen peroxide, these bleach activators enable oxidation reactions to be carried out. Such oxidation reactions are carried out, for example, in paper bleaching, in the decolorization of colored wastewater or in the desulfurization of fuels. The use in household detergents to remove or decolorize soiling on the laundry and in the wash liquor is also described. In all of these applications, the use of special macrocyclic metal complexes leads to an improvement in results compared to treatment with only one peroxide source.

Due to the large number of possible oxidation reactions, there is an interest in providing improved oxidation systems which can be used as widely as possible.

Surprisingly, it has now been shown that the addition of special oxidation-reinforcing compounds to a macrocyclic metal complex and an oxidizing agent can unexpectedly significantly improve the oxidizing effect.

The invention relates to an oxidation system containing the three components

1) a macrocyclic metal complex of the general formula (I)

embedded image in which

Yi, Y ₃ and Y ₄ independently of one another represent a single bond or a bridge member which contains 1, 2 or 3 carbon atoms in the bridge,

Y _{2 represents} a bridge member with at least 1 carbon atom in the bridge,

R independently of one another are hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ or two radicals R which are bonded to the same carbon atom together represent a substituted one or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, where the carbon atom to which the two radicals R are attached is in each case part of the benzene, cycloalkyl or cycloalkenyl ring,

M is a transition metal in oxidation states I, II, III, IV, V or VI or is selected from groups 6, 7, 8, 9, 10 and 11 of the Periodic Table of the Elements,

is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis

is another ligand.

2) an oxidizer and

3) an oxidation-enhancing compound.

In the general formula (1) Yi, Y ₃ and Y ₄ independently of one another for a (-CH ₂ -) _X group, where x is 1, 2 or 3 and one or more H atoms in the (-CH ₂ -) group are substituted by a radical R ¹ may be, where R ^{1 is} alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two radicals R ¹ which are attached to two adjacent C atoms of the (-CH ₂ -) _X group are bonded together form a benzene, cycloalkyl or cycloalkenyl ring which can contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

Y ₂ in the general formula (1) is preferably

a bridge member with 1, 2 or 3 carbon atoms in the bridge, preferably for a (-CH ₂ -) _y group, where y is 1 or 2 and one or more H atoms in the (-CH ₂ -) _X group by one R ^u can be substituted, where R "is alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two R ^u radicals attached to two adjacent C atoms of (-CH ₂ -) _X group are bonded, together form an optionally substituted benzene, cycloalkyl or cycloalkenyl ring, which may contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen, preferably a benzene ring, which may be substituted by electron-donating or electron-withdrawing radicals.

The radicals R in the general formula (1) independently of one another are preferably hydrogen, -CC ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₄ -C ₁₂ -cycloalkenyl, C ₂ -C ₃ -alkenyl,

C ₆ -Ci ₄ aryl, C ₂ -C ₂ alkynyl, C C ₂ alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ or two radicals R, which are bonded to the same carbon atom, form together a substituted or unsubstituted benzene, C ₃ -C ₈ cycloalkyl or C ₄ -C ₂ cycloalkenyl ring, the carbon atom to which the two radicals R are attached in each case part of the benzene, cycloalkyl or

Is cycloalkenyl ring.

In the general formula (1), the metal M stands for a transition metal with the oxidation states I, II, III, 3N, V or VI or is selected from groups 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements. The metal M is preferably Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Νi, Pd and / or Pt. Mixtures of metals of the aforementioned oxidation states or of the groups mentioned in the periodic table of the elements are also possible.

In general formula (1), Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis. The metal ligand complex is usually negative, preferably - 1. Accordingly, the counter ion is usually positively charged, with a preferred negative charge of -1 corresponding to +1.

Suitably, Q represents an alkali metal counterion, preferably potassium, lithium or sodium, NR'V and PR'V ^" , where R ^{U1 can} independently represent hydrogen, alkyl, aryl, alkylaryl, alkenyl or together a cycloalkyl, cycloalkenyl or form an aryl ring which optionally contains one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

L is any other ligand that can be coordinated to M. It is preferably a labile ligand, in particular H ₂ O, Cl or CN.

The abovementioned preferred and particularly preferred meanings for the radicals YY ₄ , R, R ¹ , R ^u , R ^∞ , Q and L can be combined with one another as desired.

Macrocyclic metal complexes of the general formula (1A) are preferably used in the oxidation system according to the invention,

wherein

X and Z independently of one another denote hydrogen, electron-donating or electron-withdrawing groups,

R ^iv and R ^v independently of one another are hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy radicals or R ^1V and R ^v together represent a cycloalkyl or form a cycloalkenyl ring which may contain one or more heteroatoms, M represents a transition metal of oxidation states I, II, III, TV, V or VI or is selected from groups 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements,

Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis and

L is another ligand.

In the macrocyclic metal complex of the formula (IA), X and Z can independently represent hydrogen or electron-donating or electron-withdrawing radicals. The electron donating or electron withdrawing residues change the electron density of the metal ligand complex and thus influence its reactivity.

Suitable electron-withdrawing radicals are, for example, halogens, preferably chlorine, bromine or iodine, particularly preferably chlorine, S0 ₃ ^" , OS0 ₃ ^" , OS0 ₃ R ^VI , where "represents hydrogen, alkyl, aryl or alkylaryl, or N0 ^" .

Suitable electron-donating radicals are, for example, Ci-Cg-alkoxy, preferably methoxy, ethoxy, propoxy and butoxy, CC ₈ alkyl, preferably methyl, ethyl, propyl, n-butyl and tert-butyl and hydrogen.

In the macrocyclic metal complex of the formula (IA), R ^1V and R ^v independently of one another denote hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy radicals. R ^w and R ^v are preferably independently of one another alkyl, particularly preferably C 1 -C ₅ -alkyl. R ^1V and R ^v are particularly preferably identical and denote methyl or ethyl. Furthermore, R ^1V and R ^v together preferably form a cycloalkyl, in particular a cyclopentyl or cyclohexyl ring, or a cycloalkenyl ring. This cycloalkyl or cycloalkenyl ring can contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

The preparation of the macrocyclic metal complexes contained in the oxidation system according to the invention is described in EP-A-918 840, US-A-6,099,586 and WO-A-02/16330, to which reference is hereby explicitly made.

The oxidizing agent can be an organic or inorganic oxidizing agent. A peroxy compound is usually used. Suitable are hydrogen peroxide, hydrogen peroxide adducts, compounds which are capable of hydrogen peroxide in to release or produce aqueous solution, organic peroxides, persulfates, perphosphates and persilicates.

The hydrogen peroxide adducts include alkali metal, preferably sodium, lithium or potassium carbonate peroxy hydrate and urea peroxide.

Compounds which are capable of generating hydrogen peroxide in aqueous solution include alkali metal, preferably sodium, potassium or lithium perborate (as mono- or tetrahydrate). Such perborates are commercially available.

Alternatively, the combination of an alcohol oxidase and the corresponding alcohol can be used as the peroxide source.

Organic peroxides include benzoyl and cumene hydroperoxides.

Persulfates include peroxymonosulfate and Carot's acid.

Particularly preferred oxidizing agents are hydrogen peroxide and sodium perborate.

The oxidation-intensifying compounds (“mediator”) are aliphatic, cycloaliphatic ₃ heterocyclic or aromatic compounds with at least one OH, NO, NOH, HRN-OH functionality or mixtures of these compounds.

Such compounds and their preparation are described in EP-A-0 885 868, WO-A-97/06244 and WO-A-96/12845.

Examples of such compounds are the compounds of the formula (I), (II), (III) and (TV) mentioned below, the compounds of the formulas (IT), (III) and (TV) being preferred and the compounds of the formulas (III) and (TV) are particularly preferred.

Compounds of the general formula (I) are:

where X for (-N = N-), (-N = € R ⁴ -) _p , (-CR ⁴ = N-) _P , (-CR ⁵ = CR ⁶ ) _P ,

- stands and p is 1 or 2,

where the radicals R ¹ to R ^{6 may be the} same or different and may mean independently of one another: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C ₂ -alkyl, CC ₆ -alkyloxy, carbonyl- C C ₆ -alkyl, phenyl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and salts and esters thereof, the amino, carbamoyl and sufamoyl groups of the radicals R ¹ to R ^{6 being} unsubstituted or can be mono- or disubstituted with hydroxy, -C ₃ alkyl or C _r C ₃ alkoxy, and the radicals R ² and R ³ can form a common group -A- and -A- (-CR ⁷ = CR ⁸ -CR ⁹ = CR ⁱ⁰ -) or (-CR ¹⁰ = CR ⁹ -CR ⁸ = CR ⁷ -) means.

The radicals R ⁷ to R ¹⁰ can be identical or different and independently of one another are: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C ₂ -alkyl, -Cg-alkyloxy, carbonyl -Cs-alkyl, phenyl, aryl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and salts and esters thereof, the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 being} unsubstituted or can be substituted once or twice with hydroxy, CC ₃ alkyl or C ₁ -C ₃ alkoxy and where the C 1 -C ₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₁ -C ₆ alkyl, Phenyl, aryl groups of the radicals R ⁷ to R ^{10 may be} unsubstituted or substituted one or more times with the radical R ¹¹ and the radical R ^{n represents} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, -CC ₂ alkyl, -C ₆ alkyloxy, carbonyl-C; -C _< s-alkyl, phenyl, aryl, sulfo s or esters and salts thereof, where the carbamoyl, sulfamoyl, amino groups of the radical R ^{π can be} unsubstituted or mono- or disubstituted with the radical R ¹² and the radical R ^{12 can be} one of the following groups: hydrogen, hydroxy, Formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₆ -C ₆ alkyl, phenyl or aryl.

Examples of the compounds of the general formula (I) mentioned are:

1-hydroxy-1, 2,3-triazole-4,5-dicarboxylic acid 1-phenyl-1 Hl, 2,3-triazole-3-oxide 5-chloro-l-phenyl-1 Hl, 2,3-triazole- 3-oxide 5-methyl-l-ρhenyl-1 Hl, 2,3-triazole-3-oxide 4- (2,2-dimethylpropanoyl) -l -hydroxy-1 Hl, 2,3-triazole

4-hydroxy-2-phenyl-2H-l, 2,3-triazole-l-oxide 2,4,5-triphenyl-2H-l, 2,3-triazole-l-oxide 1-benzyl-l Hl, 2 , 3-triazol-3-oxide 1-benzyl-4-chloro-1 H-1, 2,3-triazole-3-oxide 1-benzyl-4-bromo-1 H-1, 2,3-triazole-3-oxide 1-benzyl-4- methoxy-1 H-1, 2,3-triazole-3 oxide

Compounds of the general formula (II) are:

where X for (-N = N-), (-N = CR ⁴ -) _P , (-CR ⁴ = N-) _P , (-CR ⁵ = CR ⁶ ),

O ^" O ^" l ₊ or -N = N - stands

and p is 1 or 2.

The radicals R ¹ and R ⁴ to R ¹⁰ can be the same or different and represent one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C ₂ -alkyl, C 1 - C ₅ alkyloxy, carbonyl -CC ₆ alkyl, phenyl, aryl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and salts and esters thereof, the amino, carbamoyl and sulfamoyl Groups of the radicals R ¹ and R ⁴ to R ^{10 can} furthermore be unsubstituted or mono- or disubstituted with hydroxy, C ₁ -C ₃ -alkyl or CC ₃ -alkoxy and the C 1 -C ₂ -alkyl-, CC ₆ -alkyloxy-, Carbonyl-C ₆ alkyl, phenyl, aryl. and aryl-Cβ-alkyl groups of the radicals R ¹ and R ⁴ to R ^{10 can be} unsubstituted or substituted one or more times with the radical R ¹² and the radical R ^{12 can be} one of the following groups: hydrogen, halogen, Hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C 1 -C ₂ alkyl, C _t -C 6 alkyloxy, carbonyl C ₆ -C ₆ alkyl, phenyl, aryl, sulfo, sulfeno, sulfϊno and esters and Salts thereof, where the carbamoyl, sulfamoyl and amino groups of the radical R ^{12 can be} unsubstituted or mono- or disubstituted with the radical R ¹³ and the radical R ^{13 can be} one of the following groups: hydrogen, hydroxy, formyl , Carboxy and salts and esters thereof, amino, nitro, -CC ₂ alkyl, CC ₆ alkyloxy, carbonyl-C _r C ₆ alkyl, phenyl or aryl.

Examples of the compounds of the general formula (H) mentioned are: 1-hydroxy-benzimidazole

l-hydroxybenzimidazole-2-carboxylic acid 1 -hydroxybenzimidazole 2-methyl-1-hydroxybenzimidazole 2-phenyl-1-hydroxybenzimidazole

1-hydroxyindoles

2-phenyl-1-hydroxyindole

Substances of the general formula (III) are:

where X for (-N = N-), (-N = CR ⁴ -) _m , (-CR ⁴ = N-) _m , (-CR ⁵ = CR ⁶ -) "

O ^' l ₊

-N = N- or -N = N-

and m is 1 or 2.

What has been said above applies to the radicals R ⁷ to R ¹⁰ and R ⁴ to R ⁶ .

R ¹⁴ can mean: -M, where M is hydrogen, alkali, preferably lithium, sodium or potassium, alkaline earth metal, preferably calcium or magnesium, ammonium, C 1 -C ₄ -alkylammonium or CC ₄ - alkanolammonium, Ci-Cio-alkyl, Ci -Cio-alkylcarbonyl, where C 1 -C ₁₀ -alkyl and C 1 -C 8 -alkylearbonyl can be unsubstituted or substituted one or more times with a radical R ¹⁵ , where R ^{15 can represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, Carboxy and salts and esters thereof, amino, nitro, C 1 -C ₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₆ -C ₆ alkyl, phenyl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono , Phosphonooxy and salts and esters thereof, it being possible for the amino, carbamoyl and sulfamoyl groups of the radical R ^{15 to be} unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl or C ₁ -C ₃ alkoxy. Of the substances of the formula (III), derivatives of 1-hydroxybenzotriazole and of the tautomeric benzotriazole-1-oxide and their esters and salts are particularly preferred (compounds of the formula (IV))

M in formula (TV) is hydrogen, alkali, preferably lithium, sodium or potassium, alkaline earth, preferably calcium or magnesium, ammonium, C ₁ -C ₄ -alkylammonium or C ₁ -C ₄ alkanolammonium.

The radicals R ⁷ to R ¹⁰ can be the same or different and represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, - 2-alkyl, Cj-Cö-alkyloxy, carbonyl - -Cg-alkyl, phenyl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and salts and esters thereof, the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 being} unsubstituted or can be substituted once or twice with hydroxy, C ₁ -C ₃ alkyl or - alkoxy and the QC ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl, -Cs alkyl, phenyl, aryl Groups of the radicals R ⁷ to R ^{10 can be} unsubstituted or substituted one or more times with the radical R ¹⁶ and the radical R ^{16 can represent} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino , nitro, Cι-Cι ₂ alkyl, Ci-Cβ-alkyloxy, carbonyl-Ci-Ce-alkyl, phenyl, aryl, sulfo, sulfeno, sulf can be no, and esters and salts thereof, where the carbamoyl, sulfamoyl and amino groups of the radical R ¹⁶ being unsubstituted or mono- or disubstituted by the radical R ¹⁷ and wherein R ¹⁷ may represent one of the following groups: hydrogen , Hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C 1 -C ₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₆ -C ₆ alkyl, phenyl or aryl.

Examples of the compounds of the general formula (HI) mentioned are:

1-Hydroxybenzotriazole

1 -hydroxybenzotriazole 1-hydroxybenzotriazole, sodium salt 1 -hydroxybenzotriazole, potassium salt 1-hydroxybenzotriazole, lithium salt

1-hydroxybenzotriazole, ammonium salt

1-hydroxybenzotriazole, calcium salt

1-hydroxybenzotriazole, magnesium salt 1 -hydroxybenzotriazole-4-sulfonic acid

1-Hydroxybenzotriazole-4-sulfonic acid, sodium salt

1-Hydroxybenzotriazole-4-sulfonic acid, potassium salt

1-hydroxybenzotriazole-4-sulfonic acid, ammonium salt

1-hydroxybenzotriazole-5 -sulfonic acid l-hydroxybenzotriazole-5-sulfonic acid, sodium salt

1-Hydroxybenzotriazole-5-sulfonic acid, potassium salt

1-hydroxybenzotriazole-5-sulfonic acid, ammonium salt

1-hydroxybenzotriazole-6-sulfonic acid

1-hydroxybenzotriazole-6-sulfonic acid, sodium salt l-hydroxybenzotriazole-6-sulfonic acid, potassium salt

1-hydroxybenzotriazole-6-sulfonic acid, ammonium salt l-hydroxybenzotriazole-7-sulfonic acid

1-Hydroxybenzotriazole-7-sulfonic acid, sodium salt

1-hydroxybenzotriazole-7-sulfonic acid, potassium salt l-hydroxybenzotriazole-7-sulfonic acid, ammonium salt

1-Hydroxybenzotriazole-6-sulfonic acid, monosodium salt l-hydroxybenzotτiazole-4-carboxylic acid

1-hydroxybenzotriazole-4-carboxylic acid, sodium salt

1-hydroxybenzotriazole-4-carboxylic acid, potassium salt l-hydroxybenzotriazole-4-carboxylic acid, ammonium salt

1-hydroxybenzotriazole-5-carboxylic acid

1-hydroxybenzotriazole-5-carboxylic acid, sodium salt

1-hydroxybenzotriazole-5-carboxylic acid, potassium salt

1-hydroxybenzotriazole-5-carboxylic acid, ammonium salt l-hydroxybenzotriazole-6-carboxylic acid

1-hydroxybenzotriazole-6-carboxylic acid, sodium salt

1-Hydroxybenzotriazole-6-carboxylic acid, potassium salt

1-hydroxybenzotriazole-6-carboxylic acid, ammonium salt

1-hydroxybenzotriazole-7-carboxylic acid l-hydroxybenzotriazole-7-carboxylic acid, sodium salt

1-hydroxybenzotriazole-7-carboxylic acid, potassium salt 1-hydroxybenzotriazole-7-carboxylic acid, ammonium salt l-hydroxybenzotriazole-6-N-phenylcarboxamide

5-ethoxy-6-nitro-1-hydroxybenzotriazole 4-ethyl-7-methyl-6-nitro-1-hydroxybenzotriazole

2,3-bis (4-ethoxy-phenyl) -4,6-dinitro-2,3-dihydro-l-hydroxybenzotriazole 2,3-bis (2-bromo-4-methylphenyl) -4.6 dinitro-2,3-dihydro-l-hydroxybenzotriazole

2,3-bis- (4-bromo-phenyl) -4,6-dinitro-2,3-dihydro-l-hydroxybenzotriazole

2,3-bis (4-carboxy-phenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole

4,6-bis (trifluoromethyl) -1-hydroxybenzotriazole

5-bromo-1-hydroxybenzotriazole 6-bromo-1-hydroxybenzotriazole

4-bromo-7-methyl-1-hydroxybenzotriazole

5-bromo-7-methyl-6-nitro-l-hydroxybenzotriazole

4-bromo-6-nitro-1-hydroxybenzotriazole

6-bromo-4-nitro-1-hydroxybenzotriazole 4-chloro-1-hydroxybenzotriazole

5-chloro-l-hydroxybenzotriazole

6-chloro-1-hydroxybenzotriazole

6-chloro-5-isopropyl-1-hydroxybenzotriazole

5-chloro-6-methyl-1-hydroxybenzotriazole 6-chloro-5-methyl-1-hydroxybenzotriazole

4-chloro-7-methyl-6-nitro-1-hydroxybenzotriazole

4-chloro-5-methyl-1-hydroxybenzotriazole

5-Chloro-4-methyl-1-hydroxybenzotriazole

4-chloro-6-nitro-1-hydroxybenzotriazole 6-chloro-4-nitro-1-hydroxybenzotriazole

7-chloro-1-hydroxybenzotriazole

6-diacetylamino-1-hydroxybenzotriazole

2,3-dibenzyl-4,6-dinitro-2,3-dihydro-l-hydroxybenzotriazole

4,6-dibromo-l-hydroxybenzotriazole 4,6-dichloro-1-hydroxybenzotriazole

5,6-dichloro-l-hydroxybenzotriazole

4,5-dichloro-l-hydroxybenzotriazole

4,7-dichloro-1-hydroxybenzotriazole

5, 7-dichloro-6-nitro-1-hydroxybenzotriazole 5,6-dimethoxy-1-hydroxybenzotriazole

2,3-di- [2] naphthyl-4,6-dinitro-2,3-dihydro-l-hydroxybenzotriazole , 6-dinitro-1-hydroxybenzotriazole, 6-dinitro-2,3-diphenyl-2,3-dihydro-l-hydroxybenzotriazole, 6-dinitro-2,3-di-p-tolyl-2,3-dihydro-l -hydroxybenzotriazole -hydrazino-7-methyl-4-nitro-l-hydroxybenzotriazole, 6-dimethyl-l-hydroxybenzotriazole -methyl-1-hydroxybenzotriazole -methyl-1 -hydroxybenzotriazole -methyl-1 -hydroxybenzotriazole - (l -methylethyl) - 1 -hydroxybenzotriazole -Methyl-6-nitro- 1 -hydroxybenzotriazole -Methyl-4-nitro- 1 -hydroxybenzotriazole -Methoxy- 1 -hydroxybenzotriazole -Methoxy- 1 -hydroxybenzotriazole -Methyl-6-nitro-l-hydroxybenzotriazole -Nitro-l -hydroxybenzotriazole -Nitro- 1 -hydroxybenzotriazole -Nitro-4-phenyl- 1 -hydroxybenzotriazole -Ph6nylmetlryl- 1 -hydroxybenzotriazole -Trifluormetlιyl- 1 -hydroxybenzotriazole -Trifluormethyl-l -hydroxybenzotriazole -Trifluormethyl- 1-Hydroxybenzotriazole-1-Hydroxybenzyl-1-Hydroxybenzotriazole -hydroxybenzotriazole, 5,6,7-tetrafluoro-l-hydroxybenzotriazole-tetrafluoroethyl-1-hydroxybenzotriazole, 5,6-trichloro-l-hydroxybenzotriazole, 6,7-trichloro-1-hyd roxybenzotriazole -sulfamido-1-hydroxybenzotriazole -N, N-diethyl-sulfamido-1-hydroxybenzotriazole -N-methylsulfamido-1-hydroxybenzotriazole - (l Hl, 2,4-triazol-1 -ylmethyl) - 1 -hydroxybenzotriazole - (5, 6,7,8-tetrahydroimidazo- [l, 5-a] pyridin-5-yl) -l-hydroxybenzotriazole - (phenyl-1 H-1, 2,4-triazole-1 -ylmethyl) - 1-hydroxybenzotriazole - [(5-methyl-1 H-imidazol-yl) phenylmethyl] - 1-hydroxybenzotriazole - [(4-methyl-1 H-imidazo-1-yl) -phenylmethyl] - 1-hydroxybenzotriazole - [(2- methyl-1H-imidazo-1-yl) -phenylmethyl] -l-hydroxybenzotriazole - (1H-imidazole-1-yl-phenylmethyl) - 1-hydroxybenzotriazole 5- (1 H-imidazole-1-yl-phenylmethyl) -1-hydroxybenzotriazole

6- [l- (l H-Imidazol-l-yl) ethyl] -l-hydroxybenzotriazole monohydrochloride

H-benzotriazole-1-oxides 3H-benzotriazole-1-oxide

6-acetyl-3H-benzotriazole-1 oxide

5-ethoxy-6-NiOO-3H-benzotriazole-1 oxide

4-ethyl-7-methyl-6-nitro-3H-benzotriazole-1 oxide

6-amino-3,5-dimethyl-3H-benzotriazole-1-oxide 6-amino-3-methyl-3H-benzotriazole-1-oxide

5-bromo-3H-benzotriazole-1 oxide

6-bromo-3H-benzotriazole-1 oxide

4-bromo-7-methyl-3H-benzotriazole-1 oxide

5-bromo-4-chloro-6-nitro-3H-benzotriazole-1 oxide 4-bromo-6-nitro-3H-benzotriazole-1 oxide

6-bromo-4-nitro-3H-benzotriazole-1 oxide

5-chloro-3H-benzotriazole-1 oxide

6-chloro-3H-benzotriazole-1 oxide

4-chloro-6-mtro-3H-benzol-tiazole-1-oxide 4,6-dibromo-3H-benzotriazole-1-oxide

4,6-dibromo-3-methyl-3H-benzotriazole-1 oxide

4,6-dichloro-3H-benzotriazole-1 oxide

4,7-dichloro-3H-benzotriazole-1 oxide

5,6-dichloro-3H-benzotriazole-1-oxide 4,6-dichloro-3-methyl-3H-benzotriazole-1-oxide

5,7-dichloro-6-nitro-3H-benzotriazole-1 oxide

3,6-dimethyl-6-nitro-3H-benzotriazole-l-oxide

3,5-dimethyl-6-nitro-3H-benzotriazole-1 oxide

3-methyl-3H-benzotriazole-1-oxide 5-methyl-3H-benzotriazole-1-oxide

6-methyl-3H-benzotriazole-1 oxide

6-methyl-4-nitro-3H-benzotriazole-l-oxide

7-methyl-6-nitro-3H-benzotriazole-1 oxide

5-chloro-6-nitro-3H-benzotriazole-l-oxide H-benzotriazol-l-oxide

2- (4-acetoxy-phenyl) -2H-benzotriazole-1 oxide

6-acetylamino-2-phenyl-2H-benzotriazole-1 oxide

2- (4-ethylphenyl) -4,6-dinitro-2H-benzotriazole-1 oxide 2- (3-aminophenyl) -2H-benzotriazole-1 oxide

2- (4-aminophenyl) -2H-benzotriazole-1 oxide

6- amino-2-phenyl-2H-benzotriazole-1 oxide

5-bromo-4-chloro-6-nitro-2-phenyl-2H-benzotriazol-l-oxide

2- (4-bromophenyl) -2H-benzotriazole-1-oxide 5-bromo-2-phenyl-2H-benzotriazole-1-oxide

6-bromo-2-phenyl-2H-benzotriazole-1 oxide

2- (4-bromophenyl) -4,6-dinitro-2H-benzotτiazol-1-oxide

2- (4-bromophenyl) -6-nitro-2H-benzotriazole-1 oxide

5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-l-oxide 5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-l-oxide

5-chloro-2- (2-chlorophenyl) -2H-benzotriazol-l-oxide

5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1 oxide

5-chloro-2- (2,4-dϊbromphenyl) -2H-benzotriazole-1-oxide

5-chloro-2- (2,5-dimethylphenyl) -2H-benzotriazole-1-oxide 5-chloro-2- (4-nitrophenyl) -2H-benzotriazole-1-oxide

5-Chloro-6-nitro-2-phenyl-2H-benzotriazole-1 oxide

2- [4- (4-chloro-3-nitro-phenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-l-oxide

2- (3-chloro-4-nitro-phenyl) -4,6-dinitro-2H-benzotriazole-1 oxide

2- (4-chloro-3-nitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide 4-chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide

5-Chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1 oxide

6-Chloro-4-nitro-2-p-tolyl-2H-benzotriazol-l-oxide

2- (2-chlorophenyl) -2H-benzotriazole-1 oxide

2- (3-chlorophenyl) -2H-benzotriazole-1-oxide 2- (4-chlorophenyl) -2H-benzotriazole-1-oxide

5-chloro-2-phenyl-2H-benzotriazol-l-oxide

2- [4- (4-chlorophenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-l-oxide

2- (2-chlorophenyl) -4,6-Dmitro-2H-benzotriazol-l-oxide

2- (3-chloro-henyl) -4,6-dinitro-2H-benzotriazole-l-oxide 2- (4-chloro-phenyl) -4,6-dinitro-2H-benzotriazole-l-oxide

2- {4- [N ^l - (3-chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-l-oxide - {4-psf ^, - (4-chloroenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-l-oxide - (2-chlorophenyl) -6-methyl-2H-benzotriazole-l -oxide - (3-chlorophenyl) -6-methyl-2H-benzotriazole-l-oxide - (4-chlorophenyl) -6-methyl-2H-benzotriazole-l-oxide - (3-chlorophenyl) -6-mtro-2H -benzotriazole-1-oxide - (4-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide - (4-chlorophenyl) -6-picrylazo-2H-benzotriazole-1-oxide -chloro-2- (2, 4,5-trimethylphenyl) -2H-benzotriazole-l-oxide, 5-dibromo-6-nitro-2-p-tolyl-2H-benzotriazole-l-oxide, 5-dichloro-6-nitro-2-phenyl-2H -benzotriazole-l-oxide, 5-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-l-oxide, 7-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-l-oxide , 7-Dimethyl-6-nitro-2-phenyl-2H-benzotriazole-1-oxide - (2,4-dimethylphenyl) -4,6-dinitro-benzotriazole-1-oxide - (2,5-dimethylphenyl) -4 , 6-dinitro-2H-benzotriazole-1-oxide - (2,4-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide - (2,5-dimethylphenyl) -6-nitro-2H-benzotriazole-1 -oxide, 6-dmitro-2- [3-ni1xo-4- (N'-phenylhydrazino) phenyl -] - 2H-benzotriazole-l-oxide, 6-Dinitro-2- [4-nitro-4- (N ^, -phenylhydrazino) phenyl -] - 2H-benzotriazole-1-oxide, 6-dinitro-2-phenyl-2H-benzotriazole-1-oxide - (2nd , 4-dinitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide - (2,4-dinitrophenyl) -6-nitro-2H-benzotriazole-1-oxide, 6-dinitro-2-o-tolyl- 2H-benzotriazole-1-oxide, 6-dinitro-2-p-tolyl-2H-benzotriazole-1-oxide, 6-dinitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide - (4-methoxyphenyl) -2H-benzotriazole-l-oxide - (4-methoxyphenyl) -6-methyl-2H-benzotriazole-1-oxide-methyl-6-nitro-2-m-tolyl-2H-benzotriazole-l- oxide-methyl-6-nitro-2-o-tolyl-2H-benzotriazole-l-oxide-methyl-6-nitro-2-p-tolyl-2H-benzotriazole-l-oxide-methyl-4-nitro-2- p-tolyl-2H-benzotriazole-l-oxide-methyl-2-phenyl-2H-benzotriazole-l-oxide-methyl-2-m-tolyl-2H-benzotriazole-l-oxide-methyl-2-o-tolyl- 2H-benzotriazole-l-oxide-methyl-2-p-tolyl-2H-benzotriazole-l-oxide-methyl-2-m-tolyl-2H-benzotriazole-l-oxide 6-methyl-2-o-tolyl-2H-benzotriazol-l-oxide

6-Methyl-2-p-tolyl-2H-benzotriazol-l-oxide

2- [l] naphthyl-4,6-dinitro-2H-benzotriazole-l-oxide

2- [2] Naρhthyl-4,6-dinitro-2H-benzotriazole-l-oxide 2- [l] Naρhthyl-6-nitro-2H-benzotriazole-l-oxide

2- [2] naphthyl-6-nitro-2H-benzotriazole-1 oxide

2- (3-nitrophenyl) -2H-benzotriazol-l-oxide

6-nitro-2-phenyl-2H-benzotriazol-l-oxide

4-nitro-2-p-tolyl-2H-benzotriazole-1 oxide 6-nitro-2-o-tolyl-2H-benzotriazole-1 oxide

6-nitro-2-p-tolyl-2H-benzotriazole-1 oxide

6-nitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1 oxide

2-phenyl-2H-benzotriazole-1 oxide

2-o-tolyl-2H-benzotriazole-l-oxide 2-p-tolyl-2H-benzotriazole-l-oxide

The mediator can preferably also be selected from the group of cyclic N-hydroxy compounds with at least one optionally substituted five- or six-membered ring containing the structure mentioned in the general formula (V)

and their salts, ethers or esters, where

B and D are the same or different and are oxygen, sulfur, or NR ¹⁸ , where

R ¹⁸ for hydrogen, hydroxyl, formyl, carbamoyl, sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl, aryl -CC ₅ -alkyl-, -CCC- ₂ alkyl-, -C ₅ -alkoxy - Cι-Cι ₀ -carbonyl, carbonyl-C _ö -alkyl, phospho, phosphono or Phosphonooxyrest, and esters or salts thereof is, where the carbamoyl, sulfamoyl, amino and phenyl unsubstituted or can be substituted one or more times with a radical R ¹⁹ and the aryl, -Cs-alkyl, C _r C ₂ alkyl, CC ₅ alkoxy, Cio carbonyl and carbonyl C ₆ alkyl Residues may be saturated or unsaturated, branched or unbranched and may also be substituted one or more times with a radical R ¹⁹ , where R ^{19 is} identical or different and is a hydroxyl, formyl or carboxy radical and also esters or salts thereof, a carbamoyl or Sulforest, ester or salts thereof, sulfamoyl, nitro, amino, phenyl, C 1 -C ₅ alkyl or C ₅ -C ₅ alkoxy radical.

The mediator is preferably selected from the group of the compounds of the general formula (VI), (VH), (VIII) or (IX),

where B and D have the meanings already mentioned and the radicals R ²⁰ -R ^{35 are} identical or different and have a halogen radical, carboxy radical, salts or esters of a carboxy radical or the meanings mentioned for R ¹⁸ , where R ²⁶ and R ²⁷ and R ²⁸ and R ^{29 must} not simultaneously denote hydroxy or amino radicals and, if appropriate, two of the substituents each R ²⁰ -R ²³ , R ²⁴ -R ²⁵ , R ²⁶ -R ²⁹ , R ³⁰ -R ³⁵ can be linked to form a ring -E-, where -E- has one of the following meanings:

(-CH = CH) _n with n = 1 to 3, -CH = CH-CH = N- or

B D

II II

- C— N— C - (V)

I OH

and where appropriate the radicals R ²⁶ -R ^{29 can} also be connected to one another by one or two bridge elements -F-, where -F- is identical or different and has one of the following meanings: -0-, -S, -CH ₂ - , -CR ³⁶ = CR ³⁷ -, where R ³⁶ and R ^{37 are the} same or different and have the meaning of R ²⁰ .

Particularly preferred mediators are compounds of the general formulas (VI), (VII), (VIII) or (IX) in which B and D are oxygen or sulfur.

Examples of such compounds are N-hydroxy-phthalimide and optionally substituted N-hydroxy-phthalimide derivatives, N-hydroxymaleimide and optionally substituted N-hydroxymaleimide derivatives, N-hydroxy-naphthalimide and optionally substituted N-hydroxy-naphthalenimide derivatives, N Hydroxysuccinimide and optionally substituted N-hydroxysuccinimide derivatives, preferably those in which the radicals R ²⁶ -R ^{29 are} polycyclically linked.

Compounds of the formula (VI) which are suitable as mediators are, for example:

N-hydroxyphthalimide 4-amino-N-hydroxyphthalimide 3-amino-N-hydroxyphthalimide

N-hydroxy-benzene-1, 2,4-tricarboximide

N, N'-dihydroxy-pyromellitic acid diimide

N ^ '- dihydroxybenzophenone-S ^' ^^ '- tetracarboxylic.

Compounds of the formula (VTI) which are suitable as mediators are, for example:

N-hydroxymaleimide

Pyridine-2,3-dicarboxylic acid N-hydroxyimide. Compounds of the formula (VHI) which are suitable as mediators are, for example:

N-hydroxysuccinimide N-hydroxy tartarimide N-hydroxy-5-norbornene-2,3-dicarboximide exo-N-hydroxy-7-oxabicyclo [2.2. l] hept-5-ene-2,3-dicarboximide

N-hydroxy-cis-cyclohexane-1, 2-dicarboximide N-hydroxy-cis-4-cyclohexene-1, 2-dicarboximide.

A compound of formula (IX) suitable as a mediator is, for example:

N-hydroxynaphthalimide sodium salt

A suitable compound with a six-membered ring containing the structure mentioned in formula (V) is, for example:

N-hydroxyglutarimide

The compounds mentioned by way of example are also suitable as mediators in the form of their salts or esters.

Compounds selected from the group of N-aryl-N-hydroxyamides are also suitable as mediators.

Of these, the compounds of the general formula (X), (XI) or (XII) are preferably used as mediators

OH I G— N— I (X)

OH OH I I

G— N— K— N— G (XI)

OH / N s

L— K (xπ)

and their salts, ethers or esters, where

G is a monovalent homo- or heteroaromatic mono- or dinuclear radical and L is a double-bonded homo- or heteroaromatic mono- or dinuclear radical and these aromatic radicals can be substituted by one or more, identical or different radicals R ³⁸ , where R ^{38 can} stand for a halogen, hydroxyl, formyl or cyano -, Carbamoyl, carboxy, esters or salts thereof, a sulforest, esters or salts thereof, a sulfamoyl, nitro, nitroso, amino, phenyl, aryl -CC ₅ -alkyl, C _r Cι ₂ Alkyl, CC ₅ alkoxy, C Cι ₀ - carbonyl, carbonyl-Ci-Cβ-alkyl, phospho-, phosphono-, phosphonooxy, esters or salts thereof, the carbamoyl, sulfamoyl, amino and phenyl residues in turn can be unsubstituted or substituted one or more times with a radical R ³⁹ and the aryl-C ₅ -C ₅ -alkyl-, CC ₁₂ -alkyl-, C ₁ -C ₅ -alkoxy-, C ₁ -C ₅ -carbonyl-, carbonyl- C ₁ -C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and may also be substituted one or more times with a radical R ³⁹ , where R ^{39 is the} same or different and is a hydroxyl, formyl, cyano, carboxy radical, ester or salt thereof, a carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, C 1 -C ₅ -Alkyl-, CC ₅ -alkoxy, -C-C ₅ alkylcarbonyl radical and two radicals R ³⁸ or R ^{39 in} pairs over a bridge [-CR ⁴⁰ R ⁴¹ -] _m , with m equal to 0.1, 2, 3 or 4 can be linked and R ⁴⁰ and R ^{41 are the} same or different and are a carboxy radical, ester or salt thereof, a phenyl, -CC ₅ alkyl, CC ₅ -alkoxy or d-Cs-alkylcarbonyl radical and one or more non-adjacent groups [-CR ^4o R ⁴¹ -] replaced by O, S or an imino residue optionally substituted with a CC ₅ alkyl radical and two adjacent groups [-CR ⁴⁰ R ⁴¹ -] replaced by a group [-CR ⁴⁰ = CR ⁴¹ ] and can be a monovalent acid residue of acids present in amidic form selected from the group of carboxylic acids with up to 20 carbon atoms, carbonic acid, half-ester of carbonic acid or it means carbamic acid, sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid and diesters of phosphoric acid and K is an amidic form of a double-bonded acid residue of acids selected from the group of mono- and dicarboxylic acids with up to 20 carbon atoms, carbonic acid, Sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid means.

Particularly preferred mediators are compounds of the general formula (XIII), (XIV), (XV), (XVI) or (XVII)

^HO s,

N - C

Λ CRVH

and their salts, ethers or esters, where

Ar ^{1 is} a monovalent homo- or heteroaromatic mononuclear aryl radical and

Ar ² denotes a double-bonded homo- or heteroaromatic mononuclear aryl radical, each of which can be substituted by one or more, identical or different radicals R ⁴⁴ , where R ^{44 is} a hydroxyl, cyano, carboxy radical, ester or salt thereof, a sulfor radical, ester _ö represent alkyl, or salt thereof, an nitro, nitroso, amino, Cι-Cj ₂ alkyl, Cι-C ₅ alkoxy, Cι-C ₁₀ -carbonyl, carbonyl or Ci-C, wherein the amino radicals can be unsubstituted or substituted one or more times with a radical R ⁴⁵ and the C ₅ -C ₅ alkyl ₅ C ₅ C alkoxy, C 1 -C ₀ carbonyl and carbonyl Ci-Cg-alkyl Radicals may be saturated or unsaturated, branched or unbranched and may also be substituted one or more times with a radical R ^4S , where R ^{45 is} identical or different and is a hydroxyl, carboxy radical, ester or salt thereof, a sulfo, nitro , Amino, -CC ₅ - alkyl, CC ₅ -alkoxy or -CC ₅ alkylcarbonyl radical and two radicals R ^{44 can be} linked in pairs over a bridge [-CR ⁴⁰ R ⁴¹ -] _m with m equal to 0, 1, 2, 3 or 4 and

R ⁴⁰ and R ^{41 have} the meanings already mentioned and one or more non-adjacent groups [-CR ⁴⁰ R ⁴¹ -] by O, S or an imino radical optionally substituted by a CC ₅ alkyl radical and two adjacent groups [-CR ⁴⁰ R ⁴¹ -] can be replaced by a group [-CR ⁴⁰ = CR ⁴¹ -],

R ^{42 is the} same or different and is hydrogen, phenyl, aryl -CC ₅ alkyl, -C ₂ alkyl, -C ₅ alkoxy or a Ci-Cio-carbonyl radical, the phenyl radicals being unsubstituted or can be substituted one or more times with a radical R ⁴⁶ and the aryl-C ₅ -C ₅ -alkyl,

C _r C ₂ alkyl, Cj-Cs alkoxy, C ₅ -C ₅ carbonyl radicals saturated or unsaturated, branched or can be unbranched and can also be substituted one or more times with a radical R ⁴⁶ , where

R ^{46 is the} same or different and is a hydroxyl, formyl, cyano, carboxy radical, ester or salt thereof, a carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, C 1 -C ₅ -Alkyl-, -C-C ₅ alkoxy radical and R ^{43 is} the divalent radicals ortho-, meta-, para-phenylene, aryl-Cι-C ₆ alkyl, Q-Cπ-alkylene or C ₁ -C ₅ -Alkylendioxy means, where the phenylene radicals can be unsubstituted or substituted one or more times with a radical R ⁴⁶ and the aryl -CC-C ₅ alkyl, -C-C ₁₂ alkyl, Ci-Cs-alkoxy radicals saturated or can be unsaturated, branched or primary branched and can be substituted one or more times with a radical R ⁴⁶ , where

p represents 0 or 1 and

q represents an integer from 1 to 3.

Ar is preferably a phenyl radical and Ar ^{2 is} an ortho-phenylene radical, Ar ¹ by up to five and Ar ² by up to four identical or different radicals C _r C ₃ alkyl, C _r C ₃ alkylcarbonyl, carboxy, ester or salts thereof, sulfo, esters or salts thereof, hydroxyl, cyano, nitro, nitroso or amino may be substituted, it being possible for amino radicals to be substituted with two different radicals selected from the group consisting of hydroxy and -Cs alkylcarbonyl.

R ⁴² preferably represents a monovalent radical selected from the group consisting of hydrogen, phenyl, C 1 -C ₂ alkyl and Cs alkoxy, the CC ₁₂ alkyl and C 1 -C ₅ alkoxy being saturated or unsaturated, branched or can be unbranched.

R ⁴³ preferably represents a double-bonded radical ortho- or para-phenylene, C 1 -C ₂ -alkylene or CC ₅ -alkylenedioxy, the aryl-C 1 -C ₅ -alkyl-, C _r Ci ₂ -alkyl- and Q. -Cs-alkoxy radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁴⁶ .

R ⁴⁶ preferably denotes a carboxy radical, esters or salts thereof, a carbamoyl, phenyl or C ₁ -C ₃ alkoxy radical.

Examples of compounds that can be used as mediators are:

N-hydroxyacetanilide, N-hydroxypivaloylanilide, N-Hydroxyacrylanilid,

N-Hydroxybenzoylanilid,

N-hydroxy-methylsulfonylanilid,

N-hydroxy-N-phenylmethyl carbamate, N-hydroxy-3-oxobutyrylanilide,

N-hydroxy-4-cyanoacetanilide, N-hydroxy-4-methoxyacetanilide,

N-Hydroxyphenacetin,

N-hydroxy-2,3-dimethylacetanilide,

N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, l-hydroxy-3,4-dihydrochmolin- (lH) -2-one,

N, N'-dihydroxy-N, N'-diacetyl-l, 3-phenylenediamine,

N, N'-dihydroxy-bernsteinsäuredianilid,

N, N'-dihydroxy-maleic acid dianilide, N, N'-dihydroxy-oxalic acid dianilide,

N, N'-dihydroxy-phosphorsäuredianilid,

N-acetoxiacetanilide,

N-Hydroxymethyloxalylanilid,

N-Hydroxymaleinsäuremonoanilid.

Preferred mediators are

N-hydroxyacetanilide, N-hydroxyformanilide, N-hydroxy-N-phenylmethylcarbamate, N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, l-hydroxy-3,4-dihydroquinoline- (lH) -2- on and N-acetoxyacetanilide.

The mediator can also be selected from the group of N-alkyl-N-hydroxy amides.

Preferred mediators are compounds of the general formula (XVEOf) or (XIX)

OH IM— N— N "(XVHI) OH OH II

M— N— T— N— M (XIX)

as well as their salts, ethers or esters, where

M is the same or different and is a monovalent linear or branched, cyclic or polycyclic, saturated or unsaturated C ₁ -C ₂ -alkyl radical and where this alkyl radical can be substituted by one or more radicals R ⁴⁸ , where R ^{48 are} identical or different and hydroxyl -, Mercapto, formyl, carbamoyl, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, hydroxylamino, phenyl, C 1 -C ₅ alkoxy -, C Cι ₀ carbonyl, phospho-, phosphono- or phosphonooxy as well as esters or salts thereof and wherein the carbamoyl, sulfamoyl, amino, hydroxylamino, mercapto and phenyl radicals are unsubstituted or one or more times with a radical R ⁴⁸ can be substituted and the -CC ₅ alkoxy, -Ci _o -carbonyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁴⁸ , where R ^{48 is the} same or is different and hydroxy , Formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, CC ₅ - alkyl, -Cs alkoxy or Ci-Cs-alkylearbonyl means and non-permanent methylene groups can be replaced by oxygen or sulfur or an optionally, simply substituted imino radical and

N '"denotes a monovalent acid residue of acids present in amidic form, the acids being aliphatic, mono- or dinuclear aromatic or mono- or dinuclear heteroaromatic carboxylic acids having 1-20 C atoms, carbonic acid, half-esters of carbonic acid or carbamic acid, Sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid or diesters of phosphoric acid are and

T is a double-bonded acid residue of acids present in amidic form, the acids being aliphatic, mono- or dinuclear aromatic or mono- or dinuclear heteroaromatic dicarboxylic acids with 1-20 C atoms, carbonic acid, sulfonic acid, phosphonic acid, phosphoric acid or monoesters of phosphoric acid and where alkyl radicals of the aliphatic acids N '"and T present in amidic form can be linear or branched, cyclic and / or polycyclic, saturated or unsaturated and contain 1-24 carbon atoms and are unsubstituted or one or more times with the radical R ^{47 are} substituted and furthermore aryl and heteroaryl radicals of the aromatic or heteroaromatic acids N '"and T present in amidic form can be substituted by one or more radicals R ⁴⁹ , where R ^{49 are} identical or different and hydroxyl, mercapto, formyl -, cyano, carbamoyl, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl, -Cs-alkyl, C 1 -C ₂ -alkyl, CC ₅ -alkoxy, C 1 -C ₀ Carbonyl, phospho-, phosphono- or phosphonooxy as well as esters or salts thereof and wherein carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with the radical R ⁴⁸ and the aryl C ₅ -C ₅ alkyl, C 1 -C 10 -carbonyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with the radical R ⁴⁸ .

Compounds with the general formulas (XX), (XXI), (XXII) or (XXIH) are particularly preferred as mediators:

and their salts, ethers or esters, where

Alk ^{1 is the} same or different and means a monovalent linear or branched, cyclic or polycyclic, saturated or unsaturated C 1 -C ₄ -alkyl radical,

wherein this alkyl radical can be substituted by one or more radicals R ⁵⁰ , where R ^{50 are the} same or different and hydroxyl, formyl, carbamoyl, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro -, nitroso, amino, hydroxylamino, phenyl,

.C _r C ₅ - alkoxy or -Cs carbonyl and where the carbamoyl, sulfamoyl, amino, Hydroxylamino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁵¹ and the C 1 -C ₅ -alkoxy-, -Cio-carbonyl radicals can be saturated or unsaturated, branched or unbranched and with a radical R ⁵¹ one or can be substituted several times, wherein

R ^{51 is} identical or different and is hydroxy, formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, amino, phenyl, benzoyl, -Cs alkyl, -Cs-alkoxy- or C _r C ₅ -alkylcarbonyl means and non-α-methylene groups can be replaced by oxygen or sulfur or an optionally monosubstituted imino radical, and wherein

R ^{52 is the} same or different monovalent radicals hydrogen, phenyl, pyridyl, furyl, pyrrolyl, thienyl, aryl C 1 -C ₅ -alkyl, C _r C ₂ -alkyl, -Cio-alkoxy or C _r C ₁₀ -carbonyl, the phenyl -, Pyridyl, furyl, pyrrolyl and thienyl radicals can be unsubstituted or substituted one or more times with a radical R ⁵³ and the aryl-Ci-Cs-alkyl, Cι-Ci ₂ alkyl, -Cι-C ₅ - Alkoxy and Q-Cio-carbonyl radicals can be saturated or unsaturated, branched or unbranched and can also be substituted one or more times with a radical R ⁵³ , where

R ^{53 is the} same or different and hydroxyl, formyl, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, amino, phenyl, Ci-C ₅ alkyl or Ci-C ₅ -Alkoxy means and

R ^{54 is} divalent radicals phenylene, pyridylene, thienylene, furylene, pyrrolylene, aryl -CC ₅ alkyl, -C ₂ alkylene, -C ₅ alkylene dioxy, the phenylene, pyridylene, thienylene, furylene or pyrrolylene radical can be unsubstituted or substituted one or more times with a radical R ⁵³ and the aryl-CrC ₅ alkyl, C _r C ₂ alkyl, Q-Cs alkoxy radicals can be saturated or unsaturated, branched or unbranched and can also be substituted one or more times with a radical R ⁵³ , where p is 0 or 1.

Particularly preferred mediators are compounds of the general formula (XX), (XXI), (XXH) and (XXIII), in which

Alk ^{1 is the} same or different and means a monovalent, linear, branched or cyclic, saturated or unsaturated C 1 -C 8 -alkyl radical, where this alkyl radical can be substituted by one or more radicals R ⁵⁰ , which are identical or different and hydroxyl, carbamoyl -, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, amino, phenyl, C _r C ₅ alkoxy or -Cs carbonyl and where the carbamoyl, sulfamoyl, amino and phenyl radicals unsubstituted or one or more times with a radical R ⁵¹ may be substituted and the QC ₅ alkoxy, Q-Cio-carbonyl radicals may be saturated or unsaturated, branched or unbranched and may also be substituted one or more times with a radical R ⁵¹ , where R ^{51 is the} same or different and Hydroxy, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, amino, phenyl, benzoyl, C ₁ -C 5 alkyl, CC ₅ alkoxy or C ₁ -C ₅ alkyl carbonyl means and

where R ^{52 is the} same or different monovalent radicals hydrogen, phenyl, furyl, aryl -CC-C ₅ alkyl, -Cπ-alkyl, -Cio-alkoxy or -C-C ₁₀ carbonyl, the phenyl and furyl radicals being unsubstituted or a - Or can be substituted several times with a radical R ⁵³ and the aryl -CC ₅ alkyl, -C ₁₂ alkyl, -Cs-alkoxy and C -C ₀ carbonyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁵³ , where

R ^{53 is the} same or different and means carboxy, esters or salts thereof, carbamoyl, phenyl, -C ₅ - alkyl or CC ₅ alkoxy and

R ^{54 is} a double-bonded radical phenylene, furylene, C 1 -C ₂ -alkylene and -Cs-alkylenedioxy, where the phenylene and furylene radical may be unsubstituted or substituted one or more times with a radical R ⁵³ and the aryl-Ci-Cs- alkyl, Cl-C ₁₂ -alkyl, -Cs-alkoxy radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁵³ ,

where p is 0 or 1.

Examples of compounds that can be used as mediators are

N-hydroxy-N-methyl acid amide,

N-hydroxy-N-methyl-benzenesulfonamide,

N-hydroxy-N-methyl-p-toluene-sulfonic acid amide,

N-hydroxy-N-methyl-furan-2-carboxamide, N-hydroxy-N-methyl-thiophene-2-carboxamide,

N, N'-dihydroxy-N, N'-dimethyl-phthalic acid diamide,

NjN'-dihydroxy-NjN'-dimethyl-isophthalsäurediamid,

N, N'-dihydroxy-N, N'-dimethyl-terephthalic acid diamide,

N ^ '- dihydroxy-NjN'-dimethyl-benzene-ljS-disulfonic acid diamide, N, N'-dihydroxy-N, N'-dimethyl-furan-3, 4-dicarboxylic acid diamide,

N-Hydroxy-N-tert-butyl-benzoic acid amide,

N-Hydroxy-N-tert-butyl-benzenesulfonamide, N-Hydroxy-N-tert-butyl-p-toluenesulfonamide,

N-Hydroxy-N-tert-butyl-furan-2-carboxamide,

N-Hydroxy-N-tert-butyl-thiophene-2-carboxamide,

N, N ^, -dihydroxy-N, N'-di-tert-butyl-phthalic acid diamide, N, N'-dihydroxy-N, N'-di-tert-butyl-isophthalic acid diamide,

N _j N'-dihydroxy-N _j N'-di-tert-butyl-terephthalic acid diamide,

N, N'-dihydroxy-N, N'-di-tert-butyl-benzene-l, 3-disulfonsäurediamid,

N, N'-dihydroxy-N, N'-di-tert-butyl-furan-3,4-dicarboxylic acid diamide,

N-hydroxy-N-cyclohexylbenzoic acid amide, N-hydroxy-N-cyclohexylbenzenesulfonic acid amide,

N-Hydroxy-N-cyclohexyl-p-toluene sulfonic acid amide,

N-Hydroxy-N-cyclohexyl-furan-2-carboxamide,

N-Hydroxy-N-cyclohexyl-thiophene-2-carboxamide,

N, N'-dihydroxy-N, N'-dicyclohexyl-phthalic acid diamide, N, N'-dihydroxy-N, N'-dicyclohexyl-isophthalic acid diamide,

N, N'-dihydroxy-N, N'-dicyclohexyl-terephthalic acid diamide,

N, N'-dihydroxy-N, N'-dicyclohexyl-benzene-l, 3-disulfonsäurediamid,

N, N'-dihydroxy-N, N'-dicyclohexyl-furan-3,4-dicarboxylic acid diamide ₅

N-hydroxy-N-isopropylbenzoic acid amide, N-hydroxy-N-isopropylbenzene sulfonic acid amide,

N-hydroxy-N-isopropyl-p-toluenesulfonamide,

N-hydroxy-N-isoρropyl-furan-2-carboxamide,

N-hydroxy-N-isopropyl-thiophene-2-carboxamide,

N, N'-dihydroxy-N, N'-diisopropyl-phthalic acid diamide, N ^ '- dihydroxy-N _j N'-diisopropyl-isophthalic acid diamide,

N _j N'-dihydroxy-NjN'-diisopropyl-terephthalic acid diamide,

N, N'-dihydroxy-N, N'-diisopropyl-benzene-1,3-disulfonic acid diamide,

N, N'-dihydroxy-N, N'-di-isopropyl-furan-3,4-dicarboxylic acid diamide,

N-hydroxy-N-methyl-acetamide, N-hydroxy-N-tert-butyl-acetamide,

N-hydroxy-N-isopropyl-acetamide,

N-Hydroxy-N-cyclohexyl-acetamide,

N-hydroxy-N-methyl-pivalinsäureamid,

N-hydroxy-N-isopropyl-pivalic acid amide, N-hydroxy-N-methyl-acrylamide,

N-Hydroxy-N-tert-butyl-acrylamide, N-hydroxy-N-isopropyl-acrylamide, N-hydroxy-N-cyclohexyl-acrylamide, N-hydroxy-N-methyl-methanesulfonamide, N-hydroxy-N-isopropyl methanesulfonamide, N-hydroxy-N-isopropyl-methylcarbamate,

N-hydroxy-N-methyl-3-oxo-butyric acid amide, N _j N'-dihydroxy-N _j N'-dibenzoyl-ethylenediamine, N, N'-dihydroxy-N, N'-dimethylsuccinic acid diamide, N, N'-dihydroxy -N, N'-di-tert-butyl-maleic acid diamide, N-hydroxy-N-tert. butyl-maleic,

N _j N'-dihydroxy-HN'-di-tert-butyl-oxalic acid diamide, N, N'-dihydroxy-N, N'-di-tert-butyl-phosphoric acid diamide.

Preferred mediators are compounds selected from the group

N-hydroxy-N-methylbenzoic acid amide, N-hydroxy-N-methylbenzenesulfonic acid amide,

N-hydroxy-N-methyl-p-toluenesulfonamide,

N-hydroxy-N-methyl-furan-2-carboxamide,

N, N'-dihydroxy-N, N'-dimethyl-phthalic acid diamide,

N, N'-dihydroxy-N, N'-dimethyl-terephthalic acid diamide, N, N'-dihydroxy-N ₅ N'-dimethylbenzene-1,3-disulfonic acid diamide,

N-Hydroxy-N-tert-butyl-benzoic acid amide,

N-Hydroxy-N-tert-butyl-benzenesulfonamide,

N-Hydroxy-N-tert. butyl-p-toluenesulfonamide,

N-Hy (koxy-N-tert-butyl-furan-2-carboxamide, N, N'-dihydroxy-N, N'-di-tert-butyl-terephthalic acid diamide,

N-hydroxy-N-isopropyl-benzoic acid amide,

N-hydroxy-N-isopropyl-p-toluenesulfonamide,

N-hydroxy-N-isopropyl-furan-2-carboxamide,

HN'-dihydroxy-NjN'-diisopropyl-terephthalic acid diamide, N, N'-dihydroxy-N, N'-diisopropyl-benzqH, 3-disulfonic acid diamide,

N-hydroxy-N-methyl-acetamide,

N-Hydroxy-N-tert. butyl-acetamide,

N-hydroxy-N -isopropylacetamide,

N-hydroxy-N-cyclohexyl-acetamide, N-hydroxy-N-methyl-pivalic acid amide, N-Hydroxy-N-tert-butyl-acrylamide,

N-hydroxy-N-isopropyl-acrylamide,

N-hydroxy-N-methyl-3-oxo-butyric acid,

NjN' dihydroxy NjN'-dibenzoyl-ethylenediamine,

N, N'-dihydroxy-N, N'-di-tert-butyl-maleic acid diamide,

N-Hydroxy-N-tert-butyl-maleamic acid,

N.N'-dihydroxy-N, N'-di-tert-butyl-oxalic acid diamide.

The mediator can also be selected from the group of oximes of the general formula (XXTV) or (XXV)

and their salts, ethers, or esters, where

U is the same or different and means oxygen, sulfur or NR ⁵⁵ , where

R ^{55 is} hydrogen, hydroxy, formyl, carbamoyl, sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl, aryl-CrCs-alkyl, CC ₁₂ -alkyl, -C-C ₅ -alkoxy, Cι-Cι ₀ -carbonyl, Means carbonyl-Ci-Cβ-alkyl, phospho, phosphono or phosphonooxy and also esters or salts thereof,

wherein may be unsubstituted carbamoyl, sulfamoyl, amino and phenyl or mono- or polysubstituted by a radical R ⁵⁶ and the aryl Cι-C ₅ alkyl, Cι-Cι ₀ - alkyl, Cι-C ₅ Alkoxy, Cj-Cio-carbonyl and carbonyl-Q-Cö-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁵⁶ , where R is the same or different and is hydroxy, formyl, carboxy, esters or salts thereof, carbamoyl, sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl-, C ₁ -C ₅ -alkyl or C ₁ -C ₅ -alkoxy means and

the radicals R ⁵⁷ and R ^{58 are} identical or different and are halogen or carboxy and also esters or salts thereof, or have the meanings given for R ⁵⁵ , or to form a ring [-CR ^δl R ⁶² ] _n with n equal to 2, 3 or 4 are linked and

R and R have the meanings given for R and

R ⁶¹ and R ^{62 are} identical or different and are halogen or carboxy and also esters or salts thereof, or have the meanings given for R ⁵⁵ .

Particularly preferred mediators are compounds of the general formula (XXTV) in which U is oxygen or sulfur and the other radicals have the meanings given above. An example of such a compound is 2-hydroxyiminomalonic acid dimethyl ester.

Also particularly preferred as mediators are isonitroso derivatives of eyelise-like ureidea of the general formula (XXV). Examples of such compounds are 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid, alloxane-4,5-dioxime.

Particularly preferred as mediator is alloxan-5-oxime hydrate (violuric acid) and / or its esters, ethers or salts.

The mediator can also be selected from the group of vicinal nitroso-substituted aromatic alcohols of the general formulas (XXVI) or (XXVII)

(XXVI) (XXVII)

and their salts, ethers or esters, where

R> 6 ⁰ 3 ^J , R τ> 6 ⁰ 4 ⁴ , τ R.6 ⁰ 5 ³ and R ^{66 are the} same or different and are hydrogen, halogen, hydroxy, formyl, carbamoyl or carboxy as well as esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, _R nitro, nitroso, cyano, amino, phenyl, aryl-Cι-C ₅ -alkyl, Cι ₂ alkyl, QC ₅ alkoxy, C Cι ₀ -carbonyl, carbonyl-C _r C ₆ -alkyl, phospho, phosphono or phosphonooxy and esters or salts thereof, where the carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁶⁷ and the aryl-C _r C ₅ -alkyl, C _r Ci ₂ -Alkyl-, Q-Cs-alkoxy, Q-Cio-carbonyl, carbonyl-C] -C ₆ -alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁶⁷ can, whereby

R ^{67 is the} same or different and means hydroxyl, formyl or carboxy and also esters or salts thereof, carbamoyl, sulfo and salts or esters thereof, sulfamoyl, nitro, nitroso, amino, phenyl, Q-Cs-Al 1, Q-Cs-alkoxy or the radicals R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are linked in pairs to form a ring [-CR ⁶⁸ R ⁶⁹ -] _m , where m is an integer and has a value from 1 to 4, or to form a ring [-CR ⁷⁰ = CR ⁷¹ -] “, where n is an integer and means a value from 1 to 3, and

R ⁶⁸ , R ⁶⁹ , R ⁷⁰ and R ^{71 are the} same or different and have the meanings given for R ⁶³ to R ⁶⁶ .

Aromatic alcohols are preferably to be understood as meaning phenols or higher-condensed derivatives of phenol.

Preferred mediators are compounds of the general formula (XXVI) or (XXVII), the synthesis of which can be attributed to the nitrosation of substituted phenols.

Examples of such connections are:

2-nitrosophenol,

3-methyl-6-nitrosophenol,

2-methyl-6-nitrosophenol,

4-methyl-6-nitrosophenol, 3-ethyl-6-nitrosophenol,

2-ethyl-6-nitrosophenol,

4-ethyl-6-nitrosophenol,

4-isopropyl-6-nitrosophenol,

4-tert-butyl-6-nitrosophenol, 2-phenyl-6-nitrosophenol,

2-Benzyl-6-nitrosophenol,

4-Benzyl-6-nitrosophenol, 2-hydroxy-3-nitrosobenzyl alcohol,

2-hydroxy-3-nitrosobenzoic acid,

4-hydroxy-3-nitrosobenzoic acid,

2-methoxy-6-nitrosophenol, 3,4-dimethyl-6-nitrosophenol,

2,4-dimethyl-6nitrosophenol,

3, 5-dimethyl-6-nitrosophenol,

2,5-dimethyl-6-nitrosophenol,

2-nitrosoresorcinol, 4-nitrosoresorcinol,

2-Nitrosoorcin,

2-Nitrosophloroglucin

4-Nitrosopyrogallol,

4-nitroso-3-hydroxyaniline, 4-nitro-2-nitrosophenol.

Also preferred as mediators are o-nitroso derivatives of highly condensed aromatic alcohols.

Examples of such connections are:

2-nitroso-l-naphthol, 1-methyl-3-nitroso-2-naphthol,

9-hydroxy-10-nitroso-phenanthrene.

Particularly preferred mediators are:

1 -nitτoso-2-naphthol, 1 -nitroso-2-naphthol-3, 6-disulfonic acid, 2-nitroso-1-naphthol-4-sulfonic acid,

2,4-dinirroso-1,3-dihydroxybenzene

as well as esters, ethers or salts of the compounds mentioned.

The mediator can also be selected from the group hydroxypyridines, aminopyridines, hydroxyquinolines, aminoquinolines, hydroxyisoquinolines, aminoisoquinolines, with nitroso or amino substituents ortho or para to the hydroxyl or amino groups, tautomers of the compounds mentioned and their salts, ethers and esters , Preferred mediators are compounds of the general formula (XXVHI), (XXLX) or (XXX)

(XXVIII)

as well as tautomers, salts, ethers or esters of the compounds mentioned, where in the formulas (XXVTΠ), (XXIX) and (XXX) two mutually ortho or para radicals R ^{72 are} a hydroxyl and nitroso radical or a hydroxyl and mercapto radical or denote a nitroso radical and amino radical and the other radicals R ^{72 are} identical or different and are hydrogen, halogen, hydroxy, mercapto, formyl, cyano, carbamoyl or carboxy and also esters and salts thereof, sulfo, esters and salts thereof, sulfamoyl, nitro, nitroso, Amino, phenyl, aryl -CC ₅ alkyl, C ₂ alkyl, Ci-Cs-alkoxy, Q-cio-carbonyl, carboryl-C ₆ alkyl, phospho, phosphono or phosphonooxy as well as esters and salts thereof mean and where the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷³ and the aryl-C C ₅ alkyl, C 1 -C ₂ alkyl, CC ₅ alkoxy, -C-Cιo-carbonyl, carbonyl-Cι-C ₆ alkyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁷³ , where R ^{73 is} identical or different and hydroxyl, formyl, cyano or carboxy and also esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino , Phenyl, C 1 -C ₅ -alkyl, C 1 -C ₅ -alkoxy or Q-Cs-alkylcarbonyl and two radicals R ⁷² or two radicals R ⁷³ or R ⁷² and R ^{73 in} pairs over a bridge [-CR ⁷⁴ R ⁷⁵ -] _{m can be} linked to m equal to 1, 2, 3 or 4 and R ⁷⁴ and R ^{75 are} identical or different and carboxy, esters or salts thereof, Phenyl, -CC ₅ alkyl, Ci-Cs-alkoxy or Ci-Cs-alkylcarbonyl mean and one or more non-adjacent groups [-CR ⁷⁴ R ⁷⁵ -] by oxygen or sulfur or an optionally substituted with QC ₅ alkyl Imino residue and two neighboring groups [-CR ⁷⁴ R ⁷⁵ -] can be replaced by a group [-CR ⁷⁴ = R ⁷⁵ -].

Particularly preferred mediators are compounds of the general formula (XXVIII) or (XXIX) and their tautomers, salts, ethers or esters, wherein in the formulas (XXVHI) and (XXLX), two radicals R ^{72 which} are ortho to one another are particularly preferably a hydroxy group. and mean a nitroso radical or a hydroxyl and a mercapto radical or a nitroso radical and an amino radical and the other radicals R ^{72 are} identical or different and are hydrogen, hydroxyl, mercapto, formyl, carbamoyl or carboxy and also esters and salts thereof, sulfo, esters and Salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl, Q-Cs-alkyl, QC ₅ -alkoxy, Cι-C ₅ -carbonyl, carbonyl-Q-Ce-alkyl, phospho, phosphono or phosphonooxy and esters and salts thereof, where the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷³ and the aryl-C 1 -C ₅ -alkyl, Cι-C ₅ alkyl, QC ₅ - alkoxy, Q-Cs carbonyl, Car bonyl-QC ₆ - alkyl radicals may be saturated or unsaturated, branched or unbranched and may be substituted one or more times with a radical R ⁷³ , where R ^{73 has} the meanings already mentioned and two radicals R ^{73 in} pairs over a bridge [ -CR ^{/ 4} R ⁷⁵ -] _{m can be} linked to m equal to 2, 3 or 4 and R ⁷⁴ and R ^{75 have} the meanings already mentioned and one or more non-adjacent groups [-CR ⁷⁴ R ⁷⁵ -] by O or one can optionally be replaced with Q-Cs-alkyl-substituted imino radical.

Examples of compounds that can be used as mediators are

2,6-dihydroxy-3-nitrosopyτidin,

2,3-dihydroxy-4-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid,

2,4-dihydroxy-3-nitrosopyridine,

3-hydroxy-2-mercaptopyridine,

2-hydroxy-3-mercaptopyridine,

2,6-diamino-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine-4-carboxylic acid,

2-hydroxy-3-nitrosopyridine,

3-hydroxy-2-nitrosopyridine,

2-mercapto-3-nitrosopyridine,

3-mercapto-2-nitrosopyridine, 2-amino-3-nitrosopyridine, 3-amino-2-nitrosopyridine, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitroisoquinoline, 2,3-dihydroxy-4-nitτosoquinoline,

3-hydroxy-4-nitrosoisoquinoline, 4-hydroxy-3-nitrosoisoquinoline, 8-hydroxy-5-nitrosoisoquinoline

as well as tautomers of these compounds.

Preferred mediators are

2,6-dihydroxy-3-nitrosopyridine, 2,6-diamino-3-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyridine-4-carboxylic acid, 2,4-dihydroxy-3-nitrosopyridine, 2-hydroxy-3 - mercaptopyridine,

2-mercapto-3-pyridinol, 2 ₅ 4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline

as well as tautomers of these compounds.

The mediator can also be selected from the group of stable nitroxyl radicals (nitroxides), i.e. these free radicals can be obtained, characterized and stored in pure form.

Compounds of the general formula (XXXI), (XXXII) or (XXXIII) are preferably used as mediators,

(XXXIII)

in which

Ar represents a monovalent homo- or heteroaromatic one- or two-core radical and wherein this aromatic radical can be substituted by one or more identical or different radicals R ⁷⁷ , where R ^{77 is} halogen, formyl, cyano, carbamoyl, carboxy, ester or salts thereof , Sulfo, ester or salt thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Cio-carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy and esters or salts thereof and

where the phenyl, carbamoyl and sulfamoyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷⁸ , the amino radical can be substituted once or twice with R ⁷⁸ and the aryl-QC ₅ -alkyl, QQ ₂ -alkyl- QQ-alkoxy, Q-Qo-carbonyl, carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁷³ ,

where R ⁷⁸ can be present one or more times and is identical or different and hydroxyl, formyl, cyano, carboxy and esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl means and

R ^{76 is the} same or different and is halogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy and esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-QQ-alkyl, QQ _2- alkyl, QQ-alkoxy, Q-10-carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy and also esters or salts thereof and

R ⁷⁶ in the case of bicyclic stable nitroxyl radicals (structure XXXπi) can also mean hydrogen and

the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals unsubstituted. or can be substituted one or more times with a radical R ⁷⁹ and the aryl-QQ-alkyl, QQ ₂ - alkyl, QQ-alkoxy, QC ₁₀ -carbonyl, carbonyl-QQ-alkyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁷⁹ , where R ^{79 is} identical or different and hydroxyl, formyl, cyano, carboxy radical, esters or salts thereof, carbamoyl, sulfo, esters and salts thereof , Sulfamoyl, nitro, nitroso, amino, phenyl, Q-Cs-alkyl, QQ-alkoxy, QQ-alkylcarbonyl and two each Residues R ⁷⁸ or R ⁷⁹ can be linked in pairs via a bridge [-CR ⁸⁰ R ⁸¹ -] _m with m equal to 0.1, 2, 3 or 4 and

R ⁸⁰ and R ^{81 are} identical or different and represent halogen, carboxy and esters or salts thereof, carbamoyl, sulfamoyl, phenyl, benzoyl, Q-Cs-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and one or more non-adjacent groups [- CR ⁸⁰ R ⁸¹ -] by oxygen or sulfur or an imino residue optionally substituted with QQ-alkyl and two neighboring groups [-CR ⁸⁰ R ⁸¹ -] by one group [-CR ⁸⁰ = CR ⁸¹ -], [-CR ⁸⁰ = N- ] or [-CR ⁸⁰ = N (O] can be replaced.

Particularly preferred mediators are nitroxyl radicals of the general formulas (XXXIV) and (XXXV),

(XXXIV)

in which

R is identical or different and is phenyl, aryl-Q-Cs-alkyl, QQ ₂ -alkyl, C _r Cs-alkoxy, QQ ₀ -carbonyl or carbonyl-QQ-alkyl, the phenyl radicals being unsubstituted or one or more times with one R ⁸⁴ can be substituted and the aryl-Q-Cs-alkyl, QQ ₂ -alkyl, Q-Cs-alkoxy, Ci-Cio-carbonyl and carbonyl-QQ-alkyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁸⁴ , where R ⁸⁴ can be present one or more times and is identical or different and hydroxyl, formyl or carboxy and esters or salts thereof, carbamoyl, sulfo, esters and Salts thereof means sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and R ^{83 is the} same or different and is hydrogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy and esters or salts thereof, sulfo and esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl , QQ ₂ -alkyl, QQ-alkoxy, QQ ₀ -carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy and also esters or salts thereof means, the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals being unsubstituted or can be substituted one or more times with a radical R ⁷⁸ and the aryl-QC ₅ -alkyl, QQ ₂ -alkyl, QQ-alkoxy, QQ ₀ -carbonyl and carbonyl-QQ-alkyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁷⁸ and a [-CR ⁸³ R ⁸³ -] group by oxygen, an imino radical optionally substituted with CrCs-alkyl, a (hydroxy) imino radical, a carbonyl function or a vinylidene function optionally substituted with R ⁷⁸ or disubstituted in and two neighboring groups [-CR ⁸³ R ⁸³ -] can be replaced by a group [-CR ⁸³ -CR ⁸³ -] or [-CR ⁸³ = N-] or [-CR ⁸³ = N (0) -] ,

Examples of compounds that can be used as mediators are

2,2,6,6-tetramethyl-piperidine-l-oxyl (TEMPO),

4-hydroxy-2 ₉ 2 _s 6,6-tetramethyl-piperidine-l-oxyl,

4-oxo-2,2,6,6-tetramethyl-piperidin-l-oxyl,

4-acetamido-2,2,6,6-tetramethyl-piperidin-l-oxyl,

4- (ethoxyfluorophosphinyloxy) -2,2,6,6-tetramethyl-piperidine-1 -oxyl 4- (isothiocyanato) -2,2,6,6-tetramethyl-piperidine-l-oxyl,

4-maleimido-2,2,6,6-tetramethyl-piperidine-1 -oxyl,

4- (4-nitrobenzoyloxy) -2,2,6,6-tetramethyl-piperidine-l-oxyl,

4- (phosphonooxy) -2,2,6,6-tetramethyl-l-oxyl-ρiperidin,

4-cyano-2,2,6,6-tetramethyl-piperidine-l-oxyl, 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-l-oxyl,

4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-l-oxyl,

4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-l-oxyl,

4-phenacylidene-2,2,5,5-tetramethyl-imidazole idin- 1 -oxyl,

3 - (aminomethyl) -2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-carbamoyl-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl,

3-carboxy-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl,

3-Cyano-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,

3-maleimido-2,2,5,5-tetτamethyl-pyrrolidine-N-oxyl and

3- (4-nitrophenoxycarbonyl) -2,2,5,5-tetramethyl-pyrrolidin-N-oxyl Preferred mediators are

2,2,6,6-tetramethyl-piperidine-1 -oxy (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1 -oxy, 4-oxo-2,2,6,6 tetramethyl-piperidine-l-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-l-oxyl,

4- (isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1 -oxyl, 4-maleimido-2,2,6,6-tetramethyl-piperidine-l-oxyl, 4- (4-nitrobenzoyloxy) - 2,2,6,6-tetramethyl-piperidine-1 -oxy, 4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1 -oxy, 4-cyano-2,2,6,6- tetramethyl-piperidin-1 -oxyl,

3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-l-oxyl, 4-phenyl-2,2,5,5-tetramethyl-3-imidazolin-3-o) -l-oxyl, 4 Carbamoyl-2,2,5,5-tetramethyl-3-imidazolin-3-o) -l-oxyl and 4-phenacylidene-2,2,5,5-tetramethyl-imidazolidine-1 -oxyl.

Are particularly preferred as mediators

2,2,6,6-tetramethyl-piperidine-l-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethyl-piperidine-l-oxyl.

Compounds of the general formula (XXXVI) can also be used as mediators:

(XXXVI)

in which

A represents a group -D, -CH = CH-D, -CH = CH-CH = CH-D, -CTN -D, or -N = CH-D, where D represents a group -CO-E, -S0 ₂ -E, -N-XY or -N ⁺ ~ XYZ, where E is either hydrogen, hydroxyl, a radical -R or -OR and X, Y and Z are identical or different and hydrogen or a radical -R, where R is a QQ ₆ alkyl, preferably a QQ alkyl radical, and alkyl is in each case saturated or unsaturated, straight-chain or branched and is optionally substituted by a carboxy, sulfo or amino group; and

B and C are the same or different and represent a G ppe C _m H _{2m +} ι with 1 <m <5. In a preferred embodiment, in the general formula (XXXVI) A stands for a group —CO-E, in which E is hydrogen, hydroxyl, a radical -R or -OR, in which R is a QQ ₆ -alkyl, preferably a QQ-alkyl radical is, and alkyl is in each case saturated or unsaturated, straight-chain or branched and optionally substituted by a carboxy, sulfo or amino group and B and C are identical or different and represent a group C _m H _{2m +} ι with 1 <m <5.

In the general formula (XXXVI), A can also be in the meta position to the hydroxy group instead of the arrangement in the para position as listed in formula (XXXVI).

Mediators of the general formula (XXXVI), which are acetosyringone (3,5-dimethoxy-4-hydroxyacetophenone), methylsyringate, ethylsyringate, propylsyringate, butylsyringate, hexylsyringate or octylsyringate, are particularly preferred.

In summary, the following mediators are particularly preferred:

3-amino-N-hydroxyphthalimide,

4-amino-N-hydroxyphthalimide, N-hydroxyphthalimide,

3-hydroxy-N-hydroxyphthalimide,

3-methoxy-N-hydroxyphthalimide,

3,4-dimethoxy-N-hydroxyphthalimide,

4 ₃ 5-dimethoxy-N-hydroxyphthalimide, 3,6-dihydroxy-N-hydroxyphthalimide,

3,6-dimethoxy-N-hydroxyphthalimide,

3-methyl-N-hydroxyphthalimide,

4-methyl-N-hydroxyphthalimide,

3,4-dimethyl-N-hydroxyphthalimide, 3,5-dimethyl-N-hydroxyphthalimide,

3,6-dimethyl-N-hydroxyphthalimide,

3-isopropyl-6-methyl-N-hydroxyphthalimide,

3-nitro-N-hydroxyphthalimide,

4-nitro-N-hydroxyphthalimide, 1-hydroxybenzotriazole and its salts l-hydroxybenzotriazole-4-sulfonic acid and its salts l-hydroxybenzotriazole-5-sulfonic acid and its salts l-hydroxybenzotriazole-6-sulfonic acid and its salts lrHydroxybenzotriazol-7-sulfonic acid and its salts l-hydroxybenzotriazole-4-carboxylic acid and its salts l-hydroxybenzotriazole-5-carboxylic acid and its salts l-hydroxybenzotriazol-6-carboxylic acid and its salts l-hydroxybenzotriazole-7-carboxylic acid and its salts

Violuric acid, N-hydroxyacetanilide, 3-nitrosoquinoline-2,4-diol, 2,4-dihydroxy-3-nitrosopyridine, 2,6-dihydroxy-3-nitrosopyrdine,

2,4-dinitroso-l, 3-dihydroxybenzene,

2-nitroso-l-naphthol-3-sulfonic acid,

1 -Nϊtroso-2-naphthol-3, 6-disulfonic acid and

Methylsyringate.

Particularly preferred mediators are:

N-hydroxyphthalimide, 1-hydroxybenzotriazole, l-hydroxybenzotτiazol-6-sulfonic acid and its salts methylsyringate violuric acid,

N-hydroxyacetanilide,

nitrosonaphthols,

Nitrosopyridinols and their derivatives mentioned above.

The macrocyclic metal complex is used in the oxidation system according to the invention in an amount in the range from 0.01 μM to 1000 μM. An amount in the range of 0.1 μM to 100 μM is preferred.

The oxidizing agent is used in the oxidation system according to the invention in an amount in the range from 0.01 to 1000 mM. An amount in the range of 0.1-100 ppm is preferred.

The oxidation-enhancing compound is used in the oxidation system according to the invention in an amount in the range from 0.1 μM - 50 mM. The range from 1 μM to 1 mM is preferred. The range of 10 μM - 0.5 mM is particularly preferred. The invention further relates to a method for the oxidation of oxidizable substances, which is characterized in that the oxidizable substance is brought into contact with a special oxidation system, the special oxidation system containing a macrocyclic metal complex, an oxidizing agent and an oxidation-enhancing compound as defined above.

The oxidation system according to the invention is used, for example, in the following oxidation reactions:

For removing colored contaminants from industrial wastewater, preferably from wastewater from the paper or textile processing industry,

For lightening colored impurities on solid materials, preferably on textiles,

Paper or leather,

For decolorization of dyes which are excess on textile materials after dyeing in unbound form,

o when washing differently colored textiles to prevent unwanted, counter-soapy color transfer during the washing process.

The invention thus furthermore relates to a process for removing excess, unbound dye from textile materials after dyeing, preferably reactive dyeing, which is characterized in that the dyed textile material in at least one of the rinsing steps following the dyeing with the inventive Oxidation system is brought into contact.

With this method, it is advantageously possible to remove the excess, unbound dye from the textile without, however, decolourization of the dyed textile itself.

The coloring of the textile material can be done by dyeing or staining and is referred to below as "dyeing" or "dyeing".

The dyed textile material is preferably brought into contact with the oxidation system according to the invention in at least one of the rinsing steps following the dyeing, by either at least one of the rinsing liquors

1) the three components of the oxidation system are added individually in any order one after the other or individually and simultaneously or 2) first the two components of the macrocyclic metal complex and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the oxidizing agent or

3) first the two components of the oxidizing agent and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the macrocyclic metal complex.

According to variant 1 mentioned above, at least one of the rinsing liquors, preferably a rinsing liquor, all three components of the oxidation system are added individually in any order one after the other or else individually and simultaneously.

In variant 2 mentioned above, at least one of the rinsing liquors, preferably a rinsing liquor, is first added to the two components of the macrocyclic metal complex and the oxidation-enhancing compound either individually and simultaneously or else as a joint formulation and then the oxidizing agent.

In this variant 2, after the addition of the two components of the macrocyclic metal complex and the oxidation-enhancing compound, it is advantageously ensured that the system is thoroughly mixed. The oxidative decolorization is then started by adding the oxidizing agent. After the decolorization is complete, the rinsing liquor is drained off and the textile is washed again with water if necessary.

According to variant 3 mentioned above, the two components of the oxidizing agent and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the macrocyclic metal complex.

Here, too, a short mixing phase has proven itself before the macrocyclic metal complex is added.

If the macrocyclic metal complex is added individually in the three variants mentioned above, this is usually done in the form of an aqueous solution, which may be 0.5-40% by weight, based on the total solution, of a pH stabilizer and of a water-soluble or at least partially water-soluble solvent can be added. Suitable water-soluble solvents are ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide, solvent, or mixtures of these, or sulfolane. Suitable pH stabilizers are phosphate, citrate, carbonate or borate buffers, or mixtures thereof.

If hydrogen peroxide is used as the oxidizing agent, this is used in the form of commercially available aqueous solutions with a content of 3-50%.

If the oxidation-enhancing compound is added individually in the three variants mentioned above, it can be added to the washing liquor in solid form. However, it is possible and preferred to add the oxidation-enhancing compound in the form of a dispersion or solution, particularly preferably in the form of an aqueous solution, which may contain 0.5-40% by weight, based on the entire solution, of a pH stabilizer and a water-soluble or at least partially water-soluble solvent can be added. Suitable water-soluble solvents are ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethylformamide and solvent mixtures or sulphanes. Suitable pH stabilizers are phosphate, citrate, carbonate or borate buffers, or mixtures thereof.

If, according to variant 2, the macrocyclic metal complex and the oxidation-enhancing compound are used in a common, preferably aqueous formulation, this aqueous formulation contains the macrocyclic metal complex in a concentration of 0.01-100 mM and the oxidation-enhancing compound in a concentration of 1-1000 mM ,

If, according to variant 3, the oxidizing agent and the oxidation-enhancing compound are used in a common, preferably aqueous formulation, this aqueous formulation contains the oxidizing agent in a concentration of 0.1-20% by weight and the oxidation-enhancing compound in a concentration of 0.1-20% by weight.

These aqueous formulations of macrocyclic metal complex and oxidation-enhancing compound (variant 2) or of oxidizing agent and oxidation-enhancing compound (variant 3) are prepared by mixing the two respective components of the oxidation system according to the invention and optionally one or more of the additives mentioned below in any order using of water as a solvent.

Wash-active substances, preferably surfactants, sequestering agents, defoamers, enzymes, such as amylases, pectinases, proteases, peroxidase, laccases or lipases, water conditioning agents, such as water softeners, pH stabilizers, such as phosphate, citrate, carbonate, or borate buffers, or their mixtures or solvents, which are water-soluble or at least partially water-soluble. Suitable water-soluble solvents are ethanol, methanol, isopropanol, ethylene glycol, diethylene glycol, polyethylene glycols, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, acetonitrile, acetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, dimethyl formamide or solvent, sulfolane.

Such additives are used in an amount of 0-50% by weight, preferably 0.01-30% by weight, based on the total formulation.

The oxidation system according to the invention is particularly preferably brought into contact with the textile according to one of the three variants mentioned above in one of the rinsing steps following the dyeing.

The treatment time with the oxidation system according to the invention depends on the type and amount of the excess dye to be decolorized. As a rule, 2-60 min is sufficient. If appropriate, a further addition of either individual components or all components of the oxidation system according to the invention may be advantageous during the treatment.

The dyed textile materials are cotton, viscose, rayon, lyocell, wool, silk, polyester, polyamide, polyacrylonitrile and elastane, or their mixtures. It is particularly preferably cotton, viscose and lyocell or their mixtures with polyester, polyamide or elastane.

The coloration can be a coloration with all commercially available dyes. These include reactive dyes, direct dyes, noun dyes, acid dyes, metal complex dyes, disperse dyes, vat dyes and sulfur dyes.

It is preferably dyeings with water-soluble dyes, particularly preferably dyeings with reactive dyes.

The process for removing the excess, unbound dye is usually carried out at a temperature of 25-95 ° C, preferably 40-80 ° C. The pH in the rinsing liquor is in the range of 4-13, preferably 5-12 and particularly preferably 7-11.

The invention further relates to a process for removing colored impurities from industrial waste water, preferably from waste water from the paper or textile processing industry, which is characterized in that the industrial waste water is brought into contact with the oxidation system according to the invention. The industrial waste water is preferably brought into contact with the oxidation system according to the invention by either treating the industrial waste water

1) the three components of the oxidation system are added individually in any order one after the other or individually and simultaneously or

2) first the two components of the macrocyclic metal complex and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the oxidizing agent or

3) first the two components of the oxidizing agent and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the macrocyclic metal complex.

In principle, the same applies to the addition of the oxidation system to the wastewater as to variants 1-3 of the method for removing the excess, unbound dye from textile materials after dyeing described above.

The treatment time for industrial wastewater depends on the type and strength of the contamination. As a rule, 2-60 min is sufficient. If appropriate, a further addition of either individual components or all components of the oxidation system according to the invention can be helpful during the treatment.

The process for removing colored impurities in industrial waste water is usually carried out at a temperature of 25-95 ° C., preferably 40-80 ° C. The pH in the wastewater is in the range of 4-13, preferably 5-12 and particularly preferably 7-11.

The invention further relates to a process for lightening colored impurities on solid materials, preferably textiles, paper or leather, which is characterized in that the solid materials are brought into contact with the oxidation system according to the invention.

These colored contaminants are contaminants and stains that are not due to dye as described for the above process for removing excess dye from dyed fabrics.

The solid material is preferably brought into contact with the oxidation system according to the invention by introducing the solid material into an aqueous liquor and either 1) the three components of the oxidation system are added individually in any order one after the other or individually and simultaneously or

2) first the two components of the macrocyclic metal complex and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the oxidizing agent or

3) first the two components of the oxidizing agent and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the macrocyclic metal complex.

In principle, the same applies to the addition of the oxidation system to the aqueous liquor which contains the material to be lightened as in the previously described variants 1-3 of the process for removing the excess, unbound dye from textile materials after dyeing.

The treatment time of the material to be lightened in the fleet depends on the type and strength of the contamination to be lightened. As a rule, 2-60 min is sufficient. If appropriate, a further addition of either individual components or all components of the oxidation system according to the invention can be helpful during the treatment.

The process for lightening colored impurities on solid materials is usually carried out at a temperature of 25-95 ° C, preferably 40-80 ° C. The pH in the aqueous liquor is in the range 4-13, preferably 5-12 and particularly preferably 7-11.

Examples

The macrocyclic metal complex used in the examples

is produced according to the method described in Examples 1-6 of WO-A-02/16330. This connection is referred to below as lb.

Seis ^' 1-7:

The advantageous effect of the oxidation system according to the invention is shown using the example of decolorization of various dyes. The "decolorization" is given in the examples by the percentage decrease in extinction (= color) measured at the extinction maximum. The higher this percentage, the better the decolorization. To carry out the tests, the aqueous dye solution is introduced and added in succession with stirring the macrocyclic metal complex, the oxidizing compound and the oxidizing agent.

The dye solution contains 30 mg / 1 dye, the pH is adjusted with a phosphate or borate buffer. The decolorization is followed by a spectrophotometer. The different types of dyes in the Remazol ^® and Levafix ^® range are dyes from DyStar GmbH Deutschland Co & KG.

The following concentrations are used for the oxidation system, based on the solution to be decolorized:

Compound lb_- 1 μM hydrogen peroxide = 2 mM oxidation-enhancing compound = 100 μM Example 1:

Decolorization of Levafix Brillantrot E-BA after 10 min at pH = 9.0 and 25 ° C

Example 2:

Decolorization of Levafix Brillantrot E-BA after 10 min at pH = 8.3 and 25 ° C

Example s:

Decolorization of Remazol Brillantgelb 4GL after 10 min at pH = 7.0 and 25 ° C

Example 4:

Decolorization of Remazol Brillantgelb 4GL after 10 min at pH = 8.3 and 25 ° C

Example 5:

Decolorization of Remazol Brillantgelb 4GL after 10 min at pH = 9.0 and 25 ° C

Example 6:

Decolorization of Remazol Brillantrot 3BS at pH = 8.3 and 25 ° C after various times

Example 7:

Decolorization of Remazol Brilliant Red 3BS at pH = 8.3 and 50 ° C after various times

Examples 8

The following examples describe the use of the oxidation system according to the invention in a preferred application, the decolorization of rinsing liquors following textile dyeing in the presence of the dyed textile.

A boiled and bleached cotton knitwear is used, which is dyed in a laboratory dyeing machine (eg Mathis Spectradye) at a liquor ratio of 1:10 according to the following recipe: 10 g of cotton are made up in a fleet

0.4 g / 1 RESPUMIT ^® NF 0.5 g / 1 PERSOFTAL ^® L and 55 g / 1 sodium chloride

Pretreated for 10 minutes at 25 ° C. After heating to 30 ° C, the addition of

4% by weight LEVAFIX ^® Brillantrot E-RN, based on the textile material to be decolored

in 2 servings after 10 or 20 minutes. Then the addition of

9.5 g / 1 sodium carbonate

in three portions at 5 minute intervals. After heating to 60 ° C at 1 ° C / min, the treatment is then carried out at 60 ° C for 60 minutes.

Immediately after the dyeing, the dyed cotton knitwear is rinsed in a liquor ratio of 1:10 in the following way:

(1) Drain the dye liquor

(2) Add fresh water, rinse at 60 ° C for 10 minutes, drain the liquor

(3) Add fresh water, rinse at 95 ° C for 10 minutes, drain the liquor

(4) Add fresh water, rinse at 90 ° C for 10 minutes, drain the liquor

(5) adding fresh water along with

1 μM compound lb and

130 μM 1 -hydroxybenzotriazole (HOBT)

Treatment for 5 minutes at 60 ° C, adding

4.4 mM hydrogen peroxide

Treatment for 10 minutes at 60 ° C, draining the liquor.

(6) Add fresh water, rinse at 40 ° C for 10 minutes, drain the liquor and

(7) Spin the cotton knitwear and drying. In a comparative experiment, the 5th rinsing step is carried out without the addition of HOBT. Otherwise, all steps are carried out in the same way.

The following table shows the color of the individual washing liquors (determined as extinction E at 550 nm; the lower the extinction, the lower the color):

One can clearly see the much better decolorization of the washing liquor in bath 4 in the presence of HOBT and the associated lower color of the last washing liquor for the process according to the invention.

To assess the washout effect, the waterfastness of the dyeing is determined in accordance with DIN 54006 (waterfastness of dyeings, severe stress). Cotton serves as an accompanying fabric. The assessment runs from grade 1 to 5, 5 being the best authenticity.

The method according to the invention accordingly provides a waterfastness that is significantly improved by one grade.

Claims

claims

1. Oxidation system containing the three components

1) a macrocyclic metal complex of the general formula (T)

wherein

Yi, Y ₃ and Y ₄ independently of one another represent a single bond or a bridge member which contains 1, 2 or 3 carbon atoms in the bridge,

Y _{2 represents} a bridge member with at least 1 carbon atom in the bridge,

R independently of one another hydrogen, alkyl, cycloalkyl, cycloalkenyl,

Alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ or two radicals R which are bonded to the same carbon atom together form a substituted or unsubstituted benzene, cycloalkyl or cycloalkenyl ring, the carbon atom to which the two radicals R are attached is in each case part of the benzene, cycloalkyl or cycloalkenyl ring,

M is a transition metal in oxidation states I, II, III, IV, V or VI or from groups 6, 7, 8, 9, 10 and 11 of the Periodic Table of the Elements,

Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis L is another ligand.

2) an oxidizer and

3) an oxidation-enhancing compound.

2. Oxidation system according to claim 1, characterized in that in the general formula (1)

Yi, Y ₃ and Y ₄ independently of one another for a (-CH ₂ -) _X group, where x is 1, 2 or 3 and one or more H atoms in the (-CH ₂ -) _X group by a radical R ¹ may be substituted, wherein R ^{1 is} alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two radicals R ¹ which are attached to two adjacent C atoms of the (-CH ₂ -) _X Group are bonded together form a benzene, cycloalkyl or cycloalkenyl ring which may contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen

3. Oxidation system according to claim 1 or 2, characterized in that in the general formula (1)

Y _{2 stands} for a bridge member with _{1, 2} or 3 carbon atoms in the bridge, preferably for a (-CH ₂ -) _y group, where y is 1 or 2 and one or more H atoms in the (-CH ₂ -) _X groups can be substituted by a radical R ", where R" represents alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy, or two radicals R "which are attached to two adjacent C atoms of the (-CH ₂ -) _X group are bonded together to form an optionally substituted benzene, cycloalkyl or cycloalkenyl ring which can contain one or more heteroatoms, preferably oxygen, sulfur or nitrogen, preferably a benzene ring, which can be substituted by electron-donating or electron-withdrawing radicals can.

4. Oxidation system according to one or more of claims 1-3, characterized in that in the general formula (1)

the radicals R independently of one another for hydrogen, QC ₈ -alkyl, QQ-cycloalkyl, C ₄ -Q ₂ -cycloalkenyl, C ₂ -Q-alkenyl, C ₆ -Q ₄ -aryl, C ₂ -Q ₂ -alkynyl, QQ ₂ -Alkylaryl, halogen, alkoxy, phenoxy, CH ₂ CF ₃ or CF ₃ or two radicals R which are bonded to the same carbon atom, together a substituted or unsubstituted

Form benzene, Q.-Q-cycloalkyl or C ₄ -Q ₂ -cycloalkenyl ring, the carbon Atom to which the two radicals R are bound is in each case part of the benzene, cycloalkyl or cycloalkenyl ring.

Oxidation system according to one or more of claims 1-4, characterized in that in the general formula (1) M for Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and / or Pt or mixtures of metals of the aforementioned oxidation levels or from the groups mentioned in the periodic table of the elements.

Oxidation system according to one or more of claims 1-5, characterized in that in the general formula (1) Q stands for an alkali metal counterion, preferably for potassium, lithium or sodium, NR'V and PR ^m ₄ ⁺ , where R is independent represent hydrogen, alkyl, aryl, alkylaryl, alkenyl from one another or together form a cycloalkyl, cycloalkenyl or an aryl ring which optionally contains one or more heteroatoms, preferably oxygen, sulfur or nitrogen.

7. Oxidation system according to one or more of claims 1-6, characterized in that in the general formula (1) L is a labile ligand, preferably H ₂ 0, Cl or CN.

8. Oxidation system according to claim 1, characterized in that a macrocyclic metal complex of the general formula (IA) is used,

embedded image in which

X and Z independently of one another denote hydrogen, electron-donating or electron-withdrawing groups,

R ^1V and R ^v independently of one another are hydrogen, alkyl, cycloalkyl, cycloalkenyl, alkenyl, aryl, alkynyl, alkylaryl, halogen, alkoxy or phenoxy Represent radicals or R ^1V and R ^v together form a cycloalkyl or cycloalkenyl ring which may contain one or more heteroatoms,

M is a transition metal of oxidation states I, II, πi, TV, V or VI or from groups 6, 7, 8, 9, 10 or 11 of the Periodic Table of the Elements,

Q is a counter ion that balances the charge of the macrocyclic metal complex on a stoichiometric basis and

L is another ligand.

9. Oxidation system according to claim 8, characterized in that X and Z are independently> in the general formula (IA) halogen, preferably chlorine, bromine or iodine,

S0 ₃ ^" , OS0 ₃ ^" , OS0 ₃ R ^vi , where R ^ represents hydrogen, alkyl, aryl or alkylaryl, N0 ₂ ^_ , QQ-alkoxy, preferably methoxy, ethoxy, propoxy and butoxy, QQ-alkyl, preferably methyl, ethyl , Propyl, n-butyl and tert-butyl, or hydrogen.

10. Oxidation system according spoke 8 or 9, characterized in that in the macrocyclic metal complex of the general formula (IA) R ^1V and R ^v independently of one another hydrogen, alkyl, preferably QQ-alkyl, particularly preferably both identically methyl or ethyl, cycloalkyl -, Cycloalkenyl, alkenyl, aryl, alkynyl, halogen, alkoxy or phenoxy radicals or together form a cycloalkyl, in particular a cyclopentyl or cyclohexyl, or a cycloalkenyl ring, the cycloalkyl or cycloalkenyl Ring one or more if necessary

Contains heteroatoms, preferably oxygen, sulfur or nitrogen.

11. Oxidation system according to one or more of claims 1-10, characterized in that the oxidizing agent is hydrogen peroxide, hydrogen peroxide adducts, preferably alkali metal, in particular sodium, lithium or potassium carbonate peroxyhydrate, urea peroxide or compounds which in are able to release or generate hydrogen peroxide in aqueous solution, preferably alkali metal, especially sodium, potassium or lithium perborate (as mono- or tetrahydrate), organic peroxides, preferably benzoyl or cumene hydroperoxides, persulfates, preferably peroxymonosulfate and carot ' acid, perphosphates or persilicates.

12. Oxidation system according to one or more of claims 1-11, characterized in that the oxidation-enhancing compounds ("mediator") are aliphatic, cycloaliphatic, heterocyclic or aromatic compounds with at least one OH, NO, NOH, HRN -OH functionality or mixtures of these compounds.

13. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (T),

where X for

O ^" O ^"

- _N ⁺ = _N - or - N = N— _M

and p is 1 or 2,

wherein the radicals R ¹ to R ^{6 are the} same or different and are independently hydrogen, halogen, hydroxyl, formyl, carboxy and salts and

Esters thereof, amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QC ₆ alkyl,

Phenyl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho,

Phosphono, phosphonooxy and salts and esters thereof, mean, the

Amino, carbamoyl and sufamoyl groups of the radicals R ¹ to R ^{6 can be} unsubstituted or mono- or di-substituted with hydroxy, QQ-alkyl or QQ-alkoxy, and the radicals R ² and R ^{3 can be} a common group -A - Can form and -A- means (-CR ⁷ = CR ⁸ -CR ⁹ = CR ¹⁰ -) or (-CR ¹⁰ = CR ⁹ -CR ⁸ = CR ⁷ -), the radicals R ⁷ to R ^{10 being the} same or are different and are independently hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl,

Phenyl, aryl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl,

Phospho, phosphono, phosphonooxy and salts and esters thereof, mean where the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 can be} unsubstituted or mono- or disubstituted with hydroxy, QQ-alkyl or QQ-alkoxy and where the QQ ₂ -alkyl, QQ-alkyloxy- , Carbonyl-QQ-alkyl, phenyl, aryl groups of the radicals R ⁷ to R ^{10 can be} unsubstituted or substituted one or more times with the radical R ¹¹ and where the radical R ^{π is} hydrogen, halogen, hydroxy, formyl, carboxy as well as salts and esters thereof, amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl, phenyl, aryl, sulfo and esters and salts thereof, the carbamoyl, sulfamoyl, amino groups of the radical R ^{π may be} unsubstituted or mono- or disubstituted with the radical R ¹² and where the

R ^{12 is} hydrogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, QQ ₂ -alkyl, QQ-alkyloxy, carbonyl-QQ-alkyl, phenyl or aryl.

14. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (II)

where X for (-N = N-), (-N = CR ⁴ -) _P , (-CR ⁴ = N-) _P , (-CR ⁵ = CR ⁶ ) _P ,

O ^"

- N = N— or - N l * = N— ^

and p is 1 or 2

wherein the radicals R ¹ and R ⁴ to R ^{10 are the} same or different and

Hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl, phenyl, aryl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho , Phosphono, phosphonooxy and their salts and esters, where the amino, carbamoyl and sulfamoyl groups of the radicals R ¹ and R ⁴ to R ^{10 are} unsubstituted or one or two times with hydroxy, QQ-alkyl or QQ-alkoxy can be substituted, and the QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl, phenyl, aryl and aryl QQ alkyl groups of the radicals R ¹ and R ⁴ to R ^{10 may be} unsubstituted or substituted one or more times with the radical R ¹² and where the radical R ^{12 is} hydrogen, halogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, QQ ₂ -alkyl, QQ- alkyloxy,

Carbonyl-QQ-alkyl, phenyl, aryl, sulfo, esters and salts thereof, sulfeno, sulfino means, the carbamoyl, sulfamoyl, amino groups of the radical R ^{12 being} unsubstituted or mono- or disubstituted by the radical R ¹³ can be and the radical R ^{13 is} hydrogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl, phenyl or aryl.

15. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (III)

where X is for (-N = N-), (-N = CR -) _m , (-CR ⁴ = N-) _m , (-CR ⁵ = CR ⁶ -) _n

O ^" O ^"

- N ⁺ = N— or - N ⁺ = N— _stands

and m is 1 or 2

wherein the radicals R ⁷ to R ¹⁰ and R ⁴ to R ^{6 have} the meanings given for the formula (II) and

R ¹⁴ denotes -M, where M denotes hydrogen, alkali, preferably lithium, sodium or potassium, alkaline earth, preferably calcium or magnesium, ammonium, QQ-alkylammonium or QQ-alkanolammonium, QQ ₀ -alkyl, QQ ₀ -alkylcarbonyl , where QQ ₀ alkyl and Q-Qo-alkylcarbonyl may be unsubstituted or substituted one or more times with a radical R ¹⁵ , where R ¹⁵

Hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, Amino, nitro, QQ ₂ -alkyl, QQ-alkyloxy, carbonyl-QQ-alkyl, phenyl, sulfo, and their esters and salts, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters, where the amino , Carbamoyl and sulfamoyl groups of the radical R ^{15 may be} unsubstituted or mono- or di-substituted with hydroxy, QQ-alkyl or QQ-alkoxy.

16. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (TV)

in which

M denotes hydrogen, alkali, preferably lithium, sodium or potassium, alkaline earth, preferably calcium or magnesium, ammonium, QQ-alkylammonium or QC ₄ alkanolammonium and

the radicals R ⁷ to R ^{10 are} identical or different and are hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, Q-Qr alkyl, QQ-

Alkyloxy, carbonyl-QQ-alkyl, phenyl, sulfo and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and salts and esters thereof, mean, the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 can be} unsubstituted or mono- or disubstituted with hydroxy, QQ-alkyl or QQ-alkoxy and where the QQ ₂ -alkyl-, QQ-alkyloxy-, carbonyl-QQ-alkyl-, phenyl-,

Aryl groups of the radicals R ⁷ to R ^{10 can be} unsubstituted or substituted one or more times with the radical R ^lδ and the radical R ^{16 can be} hydrogen, halogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, QQ ₂ -Alkyl, QQ-alkyloxy, carbonyl-QQ-alkyl, phenyl, aryl, sulfo, salts or esters thereof, sulfeno, sulfϊno means, the carbamoyl, sulfamoyl and amino groups of the radical R ^{16 being} unsubstituted or mono- or disubstituted can be substituted by the radical R ¹⁷ and where the radical R ^{17 is} hydrogen, hydroxyl, formyl, carboxy and salts and esters thereof, Amino, nitro, QQ ₂ alkyl, QQ alkyloxy, carbonyl QQ alkyl, phenyl or aryl.

17. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are cyclic N-hydroxy compounds with at least one five- or six-membered ring containing the structure mentioned in the general formula (V)

B D

II II

- C— N— C - (V)

OH

and their salts, ethers or esters, where

B and D are the same or different and are oxygen, sulfur or NR ¹⁸ , where

R ¹⁸ for hydrogen, hydroxy, formyl, carbamoyl, sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl, aryl-QQ-alkyl-, QQ ₂ -alkyl-, Ci-Cs- alkoxy-, Q-Qo- Carbonyl, carbonyl-QQ-alkyl, phospho-, phosphono- or phosphonooxy, as well as esters or salts thereof, the carbamoyl, sulfamoyl, amino and phenyl radicals being unsubstituted or substituted one or more times with a radical R ¹⁹ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl and carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and also with a radical R ¹⁹ can be substituted one or more times, where R ^{19 is} identical or different and is hydroxy, formyl or carboxy and esters or salts thereof, carbamoyl or sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl, QQ-alkyl or QQ- Alkoxy means.

18. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (VT), (VTT), (VTTT) or (TX),

where B and D have the meanings already given for the general formula (V) and the radicals R ²⁰ -R ^{35 are} identical or different and are halogen, carboxy and salts or esters thereof or have the meanings mentioned for R ¹⁸ , where R ²⁶ and R ²⁷ or R ²⁸ and R ^{29 must} not simultaneously denote hydroxy or amino radicals and, if appropriate, two of the substituents R ²⁰ -R ²³ , R ⁴ -R ²⁵ , R ²⁶ -R ²⁹ , R ³⁰ -R ³⁵ to form a ring -E- can be linked, where -E- for

(-CH = CH) _n with n = 1 to 3, -CH = CH-CH = N- or

B D

II II

-C— N— C- (V)

I

OH stands

and where appropriate the radicals R ^2δ -R ^{29 can} also be connected to one another by one or two bridge elements -F-, where -F- is identical or different and has one of the following meanings: -0-, -S, -CH ₂ - , -CR ³⁶ = CR ³⁷ -, where R ³⁶ and R ^{37 are the} same or different and have the meaning of R ²⁰ .

19. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (VI), (VII),. (VIII) or (LX), in which B and D are oxygen or sulfur.

20. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (X), (XI) or (XII),

OH I G— - I

P9

OH OH I I

G— N — K— N— G (XI)

OH I L Λ— K (XII)

and their salts, ethers or esters, where

G is a monovalent homo- or heteroaromatic one- or two-core residue and

L is a double-bonded homo- or heteroaromatic one- or two-core residue _. and wherein these aromatic radicals can be substituted by one or more, identical or different radicals R ³⁸ , where R ^{38 can} stand for halogen, hydroxy, formyl, cyano, carbamoyl, carboxy, ester or salts thereof, sulfo, esters or salts thereof . Sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl, CrQ _2- alkyl, QQ-alkoxy, Q-Qo-carbonyl, carbonyl-QQ-alkyl, phospho, phosphono, phosphonooxy ,. Esters or salts thereof, it being possible for the carbamoyl, sulfamoyl, amino and phenyl radicals to be unsubstituted or substituted one or more times with an R ³⁹ radical and the aryl-Q-Cs-alkyl, QQ ₂ -alkyl, QQ Alkoxy, QQ ₀ carbonyl, carbonyl QQ alkyl radicals may be saturated or unsaturated, branched or unbranched and may also be substituted one or more times with a radical R ³⁹ , where R ^{39 is} identical or different and is hydroxy, Formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl, QQ-alkoxy, QQ-alkylcarbonyl and two radicals R ³⁸ or R ^{39 in} pairs over a bridge

[-CR ⁴⁰ R ⁴¹ -] _m , can be linked to m equal to 0.1, 2, 3 or 4 and R ⁴⁰ and R ^{41 are} identical or different and carboxy, esters or salts thereof, phenyl, QQ-alkyl, QQ -Alkoxy or QQ-alkylcarbonyl and one or more non-adjacent groups [-CR ^4o R ⁴¹ -] by O, S or an imino radical optionally substituted with a QQ-alkyl radical and two adjacent groups [-CR ⁴⁰ R ⁴¹ -] by one

Gmppe [-CR ⁰ = CR ⁴¹ ] can be replaced and a monovalent acid residue present in amidic form of acids selected from the group of carboxylic acids with up to 20 C atoms, carbonic acid, half-ester of carbonic acid or carbamic acid, sulfonic acid, phosphonic acid, phosphoric acid , Monoesters of phosphoric acid and diesters of phosphoric acid and K means a double-bonded amidic form

Acid residue of acids selected from the group of mono- and dicarboxylic acids with up to 20 carbon atoms, carbonic acid, sulfonic acid, phosphonic acid, phosphoric acid or monoesters of phosphoric acid.

21. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (XIH), (XIV), (XV), (XVI) or (XVII)

Ar ¹ - NC— (R ⁴² ) _p -C— N- -Ar ¹

OH OH (xrv)

and their salts, ethers or esters, where

Ar ^{1 is} a monovalent homo- or heteroaromatic mononuclear aryl radical and

Ar ² denotes a double-bonded homo- or heteroaromatic mononuclear aryl radical, which can each be substituted by one or more, identical or different radicals R ⁴⁴ , where R ^{44 is} hydroxyl, cyano, carboxy, esters or salts thereof, sulfo, esters or salts thereof, Represents nitro, nitroso, amino, Q-C ₂ alkyl, QQ-alkoxy, QQ ₀ -carbonyl, carbonyl or QQ-alkyl, where the amino radicals can be unsubstituted or substituted one or more times with a radical R ⁴⁵ and the QQ- Alkyl, QQ-alkoxy, Q-Qo-carbonyl and carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and can also be substituted one or more times with a radical R ⁴⁵ , where R ^{45 is the} same or is different and denotes hydroxyl, carboxy, esters or salts thereof, sulfo, nitro, amino, Q-Cs-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and two residues R ^{44 in} pairs over a bridge [-CR ⁴⁰ R ⁴¹ - ] _{m can be} linked to m equal to 0, 1, 2, 3 or 4 and where

R ⁴⁰ and R ^{41 have} the meanings already mentioned in claim 19 and one or more non-adjacent groups [-CR ⁴⁰ R ⁴¹ -] by O, S or an imino radical which may be substituted by a QQ-alkyl radical and two adjacent groups [-CR ⁴⁰ R ⁴¹ -] can be replaced by a group [-CR ⁴⁰ = CR ⁴¹ -], and wherein R ^{42 is the} same or different and is hydrogen, phenyl, aryl-QQ-alkyl, CrQ ₂ -alkyl, QC ₅ -alkoxy or Q-Qo-carbonyl, the phenyl radicals being unsubstituted or substituted one or more times by a radical R ⁴⁶ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, QQ-carbonyl radicals can be saturated or unsaturated, branched or unbranched and can also be substituted one or more times with a radical R ⁴⁶ , where

R ^{46 is} identical or different and denotes hydroxyl, formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl or QQ-alkoxy and R ^{43 is} ortho, Meta, para-phenylene, aryl-QQ-alkyl-, QQ ₂ -alkylene- or QQ-alkylenedioxy means, where the phenylene radicals can be unsubstituted or substituted one or more times with a radical R ⁴⁶ and the aryl-QQ-alkyl -, QQ ₂ -alkyl, QQ-alkoxy radicals may be saturated or unsaturated, branched or primary branched and may be substituted one or more times with a radical R ⁴⁶ , where

p represents 0 or 1 and

q represents an integer from 1 to 3.

22. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formula (XVIII) or (XIX),

OH I MNN ^m (xyxπ)

OH OH I I

M— N— T— N— M (XIX)

as well as their salts, ethers or esters, where

M is identical or different and denotes a monovalent linear or branched, cyclic or polycyclic, saturated or unsaturated QQ alkyl radical and where this alkyl radical can be substituted by one or more radicals R ⁴⁸ , where R ^{48 are} identical or different and hydroxyl, mercapto, Formyl, carbamoyl, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, hydroxylamino, phenyl, QQ-alkoxy, QQ ₀ carbonyl, phospho, phosphono or Phosphonooxy and esters or salts mean and wherein the carbamoyl, sulfamoyl, amino, hydroxylamino, mercapto. and phenyl radicals can be unsubstituted or mono- or polysubstituted by a radical R ^4S and the QQ-alkoxy, QQ _o -carbonyl radicals can be saturated or unsaturated, branched or unbranched and can be mono- or polysubstituted by a radical R ⁴⁸ where R ^{48 is the} same or different and hydroxyl, formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, salts or esters thereof, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, QQ-alkyl, QQ- Alkoxy or QQ-alkylcarbonyl means and non-α-methylene groups can be replaced by O, S or an optionally monosubstituted imino radical and

N '"denotes a monovalent acid residue of acids present in amidic form, which are aliphatic, mono- or di-core aromatic or mono- or di-core heteroaromatic carboxylic acids with 1-20 C atoms, carbonic acid, half-ester of carbonic acid or carbamic acid, Sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid or diesters of phosphoric acid and

T is a double-bonded acid residue of acids present in amidic form, which are aliphatic, mono- or di-core aromatic or mono- or di-core heteroaromatic dicarboxylic acids with 1-20 C atoms, carbonic acid, sulfonic acid, phosphonic acid, phosphoric acid or monoesters of phosphoric acid is and wherein alkyl radicals of the aliphatic acids N " ^e and present in amidic form

T can be linear or branched, cyclic and / or polycyclic, saturated or unsaturated and contain 1-24 carbon atoms and are unsubstituted or substituted one or more times with the radical R ⁴⁷ and furthermore aryl and heteroaryl radicals of the aromatic or heteroaromatic acids N '"and T can be substituted by one or more radicals R ⁴⁹ , where R ⁴⁹ can be substituted, where R ^{49 are} identical or different and hydroxyl, mercapto, formyl, cyano, carbamoyl, carboxy, esters or salts thereof, Sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Cio-carbonyl, phospho, phosphono or phosphonooxy as well as esters or salts thereof mean and where the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with the radical R ⁴⁸ and the aryl-Q-Cs-alkyl, QQ ₂ -alkyl-C Q- Alkoxy-, Q-Qo-Carbonyl-R este can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with the radical R ⁴⁸ .

3. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XX), (XXI), (XXII) or (XXIII),

(XXIII)

and their salts, ethers or esters, where

Alk 'is identical or different and denotes a monovalent linear or branched, cyclic or polycyclic, saturated or unsaturated QQ ₀ alkyl radical,

where this alkyl radical can be substituted by one or more radicals R ⁵⁰ , where R ^{50 are} identical or different and hydroxyl, formyl, carbamoyl, carboxy, esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, Hydroxylamino, phenyl, QQ-alkoxy, QQ-carbonyl and where the

Carbamoyl, sulfamoyl, amino, hydroxylamino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁵¹ and the QQ-alkoxy, Q-Qo-carbonyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁵¹ , where

R ^{51 is the} same or different and is hydroxy, formyl, cyano, carboxy, esters or salts thereof, carbamoyl, sulfo, salts or esters thereof, sulfamoyl, nitro, amino, phenyl, Benzoyl, Q-Cs-alkyl, QQ-alkoxy or QQ-alkylcarbonyl means and non-α-methylene groups can be replaced by O, S or an optionally monosubstituted imino radical, and wherein

R ^{52 is the} same or different monovalent radicals hydrogen, phenyl, pyridyl, furyl, pyrrolyl, thienyl, aryl, QQ-alkyl, QQ ₂ -alkyl, QQ ₀ -alkoxy or Q-Qo-carbonyl, the phenyl, pyridyl, furyl -, Pyrrolyl and thienyl radicals can be unsubstituted or substituted one or more times with a radical R ⁵³ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy and QQ ₀ -carbonyl radicals saturated or unsaturated, can be branched or unbranched and can also be substituted one or more times with a radical R ⁵³ , where

R ^{53 is the} same or different and denotes hydroxyl, formyl, carboxy, esters or salts thereof, carbamoyl, sulfo, esters and salts thereof, sulfamoyl, nitro, amino, phenyl, QQ-alkyl or QQ-alkoxy and

R ⁵⁴ denotes divalent radicals phenylene, pyridylene, thienylene, furylene, pyrrolylene, aryl-QQ-alkyl, Q-Cι ₂ -alkylene, QQ-alkylenedioxy, phenylene, pyridylene,

Thienylene, furylene and pyrrolylene can be unsubstituted or substituted one or more times with a radical R ⁵³ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy radicals can be saturated or unsaturated, branched or unbranched and likewise can be substituted one or more times with a radical R ⁵³ , where p is 0 or 1.

24. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXTV) or (XXV)

and their salts, ethers, or esters, where

U is the same or different and means oxygen, sulfur or NR ⁵⁵ , where

R ^{55 is} hydrogen, hydroxyl, formyl, carbamoyl, sulfo, ester or salts thereof, sulfamoyl, nitro, amino, phenyl, aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl,

Means carbonyl-Q-Q-alkyl, phospho, phosphono or phosphonooxy and also esters or salts thereof,

where the carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁵⁶ and the aryl-QQ-alkyl, Q-Qo-alkyl, QQ-alkoxy, QQ ₀ - Carbonyl and carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁵⁶ , where

R ^{56 is} identical or different and denotes hydroxyl, formyl, carboxy, esters or salts thereof, carbamoyl, sulfo, esters or salts thereof, sulfamoyl, nitro, amino, phenyl, Q-Cs-alkyl or QQ-alkoxy and

the radicals R ⁵⁷ and R ^{58 are} identical or different and are halogen or carboxy and also esters or salts thereof, or have the meanings given for R ⁵⁵ , or to form a ring [-CR ⁶¹ R ⁶² ] _π with n equal to 2, 3 or 4 are linked and

R ⁵⁹ and R ^{60 have} the meanings given for R ⁵⁵ and

R ⁶¹ and R ^{62 are the} same or different and halogen or carboxy and ester or

Salts thereof mean, or have the meanings given for R ⁵⁵ .

25. Oxidation system according to one or more of claims 1-12,

characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXVI) or (XXVII)

(xxvπ) (XXVII)

and their salts, ethers or esters, where

R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} identical or different and are hydrogen, halogen, hydroxy, formyl, carbamoyl or carboxy and also esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, cyano, amino, Phenyl, aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, QQ ₀ -carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy and also esters or salts thereof, where the carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁶⁷ and the aryl-CrQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Ci-Qo-carbonyl, carbonyl-QQ-aϊkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁶⁷ , where

R is identical or different and denotes hydroxyl, formyl or carboxy and also esters or salts thereof, carbamoyl, sulfo, salts or esters thereof, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl or QQ-alkoxy or the radicals R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are linked in pairs to form a ring [-CR ⁶⁸ R ⁶⁹ -] _m , where m is an integer and has a value from 1 to 4, or to form a ring [-CR ⁷⁰ = CR ^7I -] _{n are} linked, where n is an integer and has a value from 1 to 3, and

R, R, R and R are the same or different and have the meanings given for R to R.

26. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXNlTf), (XXTX) or (XXX), (XXVIII)

as well as tautomers, salts, ethers or esters of the compounds mentioned, where in the formulas (XXVIII), (XXTX) and (XXX) two mutually ortho or para radicals R ^{72 are} a hydroxyl and nitroso radical or a hydroxyl and mercapto radical or denote a nitroso radical and amino radical and the other radicals R ^{72 are} identical or different and are hydrogen, halogen, hydroxy, mercapto, formyl, cyano, carbamoyl or carboxy and also esters and salts thereof, sulfo, esters and salts thereof, sulfamoyl, nitro, nitroso, Amino, phenyl, aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl, carboryl-QQ-alkyl, phospho, phosphono or. Phosphonooxy and esters and salts thereof mean and where the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷³ and the aryl-QQ-alkyl, QQ ₂ -alkyl -, QQ-alkoxy, QQ ₀ -carbonyl, carbonyl-QQ-alkyl radicals may be saturated or unsaturated, branched or unbranched and may be substituted one or more times with a radical R ⁷³ , where R ^{73 is the} same or different and is hydroxy , Formyl, cyano or carboxy as well as esters or salts thereof, carbamoyl, sulfo, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and each represents two radicals R ⁷² or two radicals R ⁷³ or R ⁷² and R ⁷³ can be linked in pairs via a bridge [-CR ⁷⁴ R ⁷⁵ -] _m with m equal to 1, 2, 3 or 4 and R ⁷⁴ and R ^{75 are} identical or different and carboxy, esters or salts thereof, phenyl , QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and one or more non-adjacent ones Groups [-CR ⁷⁴ R ⁷⁵ -] by O, S or a possibly Imino residue substituted with QQ-alkyl and two adjacent groups [-CR R -] can be replaced by one group [-CR ⁷⁴ = R ⁷⁵ -].

27. Oxidation system according to one or more of claims 1-12, characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXXI), (XXXII) or (XXXIII)

(XXXIII)

in which

Ar represents a monovalent homo- or heteroaromatic one- or two-core radical and wherein this aromatic radical can be substituted by one or more identical or different radicals R ⁷⁷ , where R ^{77 is} halogen, formyl, cyano, carbamoyl, carboxy, ester or salts thereof , Sulfo, ester or salt thereof, sulfamoyl,

Nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy as well as esters or salts thereof means and

where the phenyl, carbamoyl and sulfamoyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷⁸ , the amino radical can be substituted once or twice with R ⁷⁸ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl, carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁷⁸ ,

where R ⁷⁸ can be present one or more times and is the same or different and

Hydroxy, formyl, cyano or carboxy as well as esters or salts thereof, carbamoyl, sulfo and also esters and salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and

R ^{76 is the} same or different and halogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy and esters or salts thereof, sulfo, esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-Q-Cs-alkyl , QQ ₂ alkyl, QQ alkoxy,

Q-10-carbonyl, carbonyl-Q-Q-alkyl, phospho, phosphono or phosphonooxy and esters or salts thereof means and

R ⁷⁶ in the case of bicyclic stable nitroxyl radicals (structure XXXIII) can also mean hydrogen and

where the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷⁹ and the aryl, QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, QQ _0- carbonyl, carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁷⁹ , where R ^{79 is} identical or different and is hydroxy, fornryl, cyano, carboxy, Esters or salts thereof, carbamoyl, sulfo, esters and

Salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl and two residues R ⁷⁸ or R ^{79 in} pairs over a bridge [-CR ⁸⁰ R ⁸¹ -] _m with m being the same 0,1,2,3 or 4 can be linked and

R ⁸⁰ and R ^{81 are the} same or different and are halogen, carboxy and esters or salts thereof, carbamoyl, sulfamoyl, phenyl, benzoyl, QQ-alkyl, QQ-alkoxy or QQ-

Mean alkylcarbonyl and one or more non-adjacent groups [-CR ⁸⁰ R ⁸¹ -] by O, S or one optionally substituted with QQ-alkyl-imino radical and two adjacent groups [-CR ⁸⁰ R ⁸¹ -] by a group [-CR ⁸⁰ = CR ⁸¹ -], [-CR ⁸⁰ = N-] or [-CR ⁸⁰ = N (O) -] can be replaced.

28. Oxidation system according to one or more of claims 1-12,

characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXXIV) and (XXXV), (XXXIV)

in which

R is identical or different and means phenyl, aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl or carbonyl-QQ-alkyl, the phenyl radicals being unsubstituted or one or more times with a radical R ⁸⁴ can be substituted and the aryl

QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl and carbonyl-QQ-alkyl radicals can be saturated or unsaturated, branched or unbranched and substituted by one or more R ⁸⁴ radicals can be, where R ⁸⁴ can be present one or more times and is identical or different and hydroxyl, formyl or carboxy and esters or salts thereof, carbamoyl, sulfo and esters and salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl , QQ-alkyl, QQ-alkoxy or QQ-alkylcarbonyl means and

R ^{83 is the} same or different and is hydrogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy and esters or salts thereof, Sύlfo and esters or salts thereof, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-QQ-alkyl, QQ ₂ -Alkyl, QQ-alkoxy, Q-Qo-carbonyl, carbonyl-QQ-alkyl, phospho, phosphono or phosphonooxy as well as esters or salts thereof, the carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals being unsubstituted or a - Or can be substituted several times with a radical R ⁷⁸ and the aryl-QQ-alkyl, QQ ₂ -alkyl, QQ-alkoxy, Q-Qo-carbonyl and carbonyl-QQ-alkyl radicals saturated or unsaturated, branched or can be unbranched and can be substituted one or more times with a radical R ⁷⁸ and a [-CR ⁸³ R ⁸³ -] group by O, an optionally substituted with QQ-alkyl imino residue, a (hydroxy) imino residue, a carbonyl function or one can optionally be substituted with R ⁷⁸ mono- or disubstituted vinylidene function and two adjacent Gmppen [-CR ⁸³ R ⁸³ -] can be replaced by a group [-CR ⁸³ -CR ⁸³ -] or [-CR ⁸³ = N-] or [-CR ⁸³ = N (0) -].

29. Oxidation system according to one or more of claims 1-12,

characterized in that the oxidation-enhancing compounds are compounds of the general formulas (XXXVI):

(XXXVI)

in which

A represents a Grappe -D, -CH = CH-D, -CH = CH-CH = CH-D, -CH = ND, or -N = CH-D, where D represents a group -CO-E, -S0 ₂ -E, -N-XY or -N XYZ, in which E denotes either hydrogen, hydroxy, a radical -R or -OR and X,

Y and Z are the same or different and are hydrogen or likewise a radical - R, where R is a QQ ₆ alkyl, preferably a QQ alkyl residue, and alkyl in each case saturated or unsaturated, straight-chain or branched and optionally by a carboxy, sulfo - or amino group is substituted; and

B and C are the same or different and represent a Grappe C _ra H _{2ra + 1} with 1 <m <5.

30. Oxidation system according to one or more of claims 1-12,

characterized in that the oxidation-enhancing compounds are one of the following compounds:

3-amino-N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide,

N-hydroxyphthalimide,

3-hydroxy-N-hydroxyphthalimide,

3-methoxy-N-hydroxyphthalimide,

3,4-dimethoxy-N-hydroxyphthalimide, 4,5-dimethoxy-N-hydroxyphthalimide,

3,6-dihydroxy-N-hydroxyphthalimide,

3,6-dimethoxy-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide,

4-methyl-N-hydroxvphthalimid,

3, 4-dimethyl-N-hydroxyphthalimide,

3, 5-dimethyl-N-hydroxyphthalimide, 3,6-dimethyl-N-hydroxyphthalimide,

3-isopropyl-6-methyl-N-hydroxyphthalimide,

3-nitr o-N-hydroxy phthalimide,

4-nitro-N-hydroxyphthalimide,

1-hydroxybenzotriazole and its salts l-hydroxybenzotriazole-4-sulfonic acid and its salts l-hydroxybenzotriazole-5-sulfonic acid and its salts l-hydroxybenzotriazole-6-sulfonic acid and its salts l-hydroxybenzotriazole-7-sulfonic acid and its salts l-hydroxybenzotriazole 4-carboxylic acid and its salts l-hydroxybenzotriazole-5-carboxylic acid and its salts l-hydroxybenzotriazole-6-carboxylic acid and its salts l-hydroxybenzotriazole-7-carboxylic acid and its salts

violuric acid,

N-hydroxyacetanilide, 3-nitrosoquinoline-2,4-diol,

2,4-dihydroxy-3-nitrosopyridine,

2,6-dihydroxy-3-nitrosopyrdin,

2,4-dinitroso-1,3-dihydroxybenzene,

2-nitroso-l-naphthol-3-sulfonic acid, l-nitroso-2-naphthol-3,6-disulfonic acid and

Methylsyringate.

31. A method for the oxidation of oxidizable substances, which is characterized in that the oxidizable substance is brought into contact with an oxidation system according to one or more of claims 1-30.

32. A method for removing excess, unbound dye from textile materials after dyeing, preferably reactive dyeing, which is characterized in that the colored textile material in at least one of the rinsing steps following the dyeing with an oxidation system according to one or more of claims 1 -30 is brought into contact.

3. The method according spoke 32, characterized in that the dyed textile material is brought into contact with the oxidation system in at least one of the rinsing steps following the dyeing, by using at least one of the rinsing liquors either

1) the three components of the oxidation system are added individually in any order one after the other or individually and simultaneously or

2) first the two components of the macrocyclic metal complex and the. oxidation-enhancing compound either individually and simultaneously or as a common formulation and then the oxidizing agent or

3) first the two components of the oxidizing agent and the oxidation-enhancing compound are added either individually and simultaneously or else as a common formulation and then the macrocyclic metal complex.

34 Dyed textile material obtainable by the process according to claim 32 or 33.

35. A method for removing colored impurities from industrial waste water, preferably from waste water from the paper or textile processing industry, which is characterized in that the industrial waste water is brought into contact with an oxidation system according to one or more of claims 1 to 30.

36. Wastewater, preferably wastewater from the paper or textile processing industry, obtainable by the process according to 35.

37. A method for lightening colored impurities on solid materials, preferably on textiles, paper or leather, which is characterized in that the solid materials are brought into contact with an oxidation system according to one or more of claims 1 to 30.

38. Solid materials, preferably textiles, paper or leather, obtainable by the process according to approach 37.