DE19723912A1 - Enzymatic bleaching of coloured cellulosics, especially indigo-dyed denim - Google Patents

Abstract

Bleaching of coloured, cellulose-containing products such as textiles is effected using an oxidoreductase and a suitable oxidation agent, with the mediator used being an aliphatic, cycloaliphatic, heterocyclic or aromatic NO-, NOH- or HN(R)OH-containing compound.

Description

The invention relates to processes for bleaching colored cellu loose fiber products such. B. textiles.

To achieve a bleached appearance textiles entwe with a general chlorine-containing bleach, such as. B. Hypochlorite (EP 0743391) or treated with chlorine-free processes (WO 95/20643).

In addition to the general methods are also special procedures be wrote. Special methods include mechanical Ver drive like B. Processes in which the textiles in the presence from pumice to a desired lightening of the color in a washing machine to be washed. The procedure has many disadvantages such as damage to the fiber by the pumice, Wear of washing machines, need for stones and to remove the dust, the increased space requirements in the wash machine through the use of pumice, as well as disposal Problems associated with solid waste from pumice. Kom The pumice treatment is usually combined with one subsequent hypochlorite treatment, which at 60 ° C and a pH of 11-12 is performed. After subsequent neutralisa tion, the textile material must be washed out. The usage Hypochlorite is undesirable on the one hand because of hypochlorite itself, because of the high AOX load in the wastewater and on the other hand, because neutralization also causes a large salt load, which must be disposed of.

Special processes also include processes which are used for Achieving a bleached appearance of textile fibers and  Textile products use enzymes. As enzymes have been described Cellulases and oxidoreductases.

In the procedures which belong to the group of oxidoreductases Using peroxidases, the enzymes are used together with What used with hydrogen peroxide or with systems which hydrogen can produce peroxide (WO 92/18683). Hydrogen peroxide must there be very carefully dosed as the system increases through Hydrogen peroxide concentration is inactivated. excess Peroxide must also be removed. The achievable effec te are therefore low and poorly reproducible.

In the procedures which belong to the group of oxidoreductases use oxidizing enzymes, the enzymes together with acid used. The use of reinforcing substances is also described (WO 96/12845). Disadvantage of the described method is that they are not efficient (WO 96/12846, Example 1, Ta belle 2).

A slightly improved process is described in WO 96/12846 in which oxidative enzymes together with a Ver Stronger substance can be used. Become an amplifier substance while compounds from the class of phenothiazines or phenoxa called zine. The synthesis of these compounds is expensive, so that their use in an economic process is only right restricted is possible. The described bleaching effects are low.

The enzymatic bleaching of dyed textile fibers is difficult rig, as many dyes, especially indigo, are not soluble in aqueous Systems are therefore poor substrates for enzymes put. In addition, form the dyes, especially indigo, with the Fiber is a very compact structure, which is very difficult for enzymes only vulnerable.  

Also, a method which microorganisms for decolorization of Indigo dyed textiles used is described (WO 9418312), but a technical commitment is very tedious and with a high microbial load of textiles.

There is therefore a need for effective enzymatic methods to produce a bleached appearance of dyed fiber len.

The present invention relates to processes for bleaching zel lulosehaltigen fiber products such. B. textiles using an oxidoreductase, an oxidoreductase suitable oxidizing agent and a mediator, characterized in that the mediator is selected from the group of aliphatic, cycloaliphatic, heterocyclic or aromatic NO, NOH or

Links.

With the method according to the invention, inter alia, the Pro solved, an economical and efficient procedure be a textile fiber, specially dyed with indigo Denim to give a bleached appearance.

The inventive method is most advantageous to Zel containing lulose fiber products such as. Cotton, Viscose, ramie, linen etc. or mixtures prepared therefrom or Mixtures of any of these fibers together with syntheti fibers or synthetic fibers.

The fibers are ge with various commercially available dyes dyes in particular indigo or indigo-related dyes, like thioindigo.  

Particularly preferred is the application of the method to indioge dyed denim as well as products made from it.

The method can also be applied to other natural fibers, such as B. silk on hair and related structures such as bristles or feathers.

As the oxidizing agent, for example, air, oxygen, ozone, H ₂ O ₂ , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, Perspetersäure, Metachlor peroxibenzosäure, perchloric acid, perborates, peracetates, Persulfa te, peroxides or oxygen species and their radicals such as OH, OOH, singlet oxygen, superoxide (O ₂ ⁻), ozonide, dioxygenyl Ka tion (O ₂ ⁺), dioxiranes, dioxetanes or Fremy radicals are used.

Preferably, such oxidizing agents are used, the ent can not be generated by the corresponding oxidoreductases can z. B. dioxiranes from laccases plus carbonyls or che mix the mediator can regenerate or this directly umset zen. As oxidoreductases are preferably phenol used oxidizing enzymes. Such enzymes use either Hydrogen peroxide or molecular oxygen as an electron acceptor gate.

Examples of such enzymes are enzymes from the group of Per oxidases and oxidases.

Peroxidases (EC 1.11.1.7) may be of different biological systems are obtained, for. B. from plants, animals or Microorganisms. Preferably, they are obtained from mushrooms.

Peroxidases preferably require hydrogen peroxide as cosubstrate oxide.  

This connection can either go directly to the other components can be given in the process of the invention or it can a precursor compound are released. Finally, can Hydrogen peroxide also formed in situ by an auxiliary reaction be, z. B. by the enzymatic conversion of glucose with Glucose oxidase (E.C. 1.1.3.4).

The concentration of hydrogen peroxide added or formed Oxides is preferably in the range of 0.001-25 mmol / l.

Oxidases preferably use acid as an electron acceptor material. Oxygen is usually in sufficient quantity in dissolved aqueous solutions, but can also, if necessary by suitable technical measures such. B. the creation of a Pressure, the use of oxygen gas or an oxygen gas generating auxiliary system are introduced into the system. This may be especially necessary if the procedure is elevated Temperatures should be operated as the solubility of acid substance in aqueous solutions with the increase in temperature takes.

The group of oxidases includes the laccases, which in the En classified under EC 1.10.3.2. The far These include enzymes, which are in the group of catecholoxida sen (1.10.3.1), the bilirubin oxidases (1.3.3.5), or the mono Phenol monooxigenases (1.14.99.1) are classified.

Laccases are in numerous microbial and plant orga described. The microbial laccases are predominantly derived from bacteria or fungi, including the filamentous fungi and yeasts. Laccase or laccase-related enzymes may be included For example, be obtained from the natural organisms or by means of known recombinant DNA technology in suitable  Expression systems produced and according to the state of Technique isolated from the culture medium.

In the process according to the invention are preferably 0.1-100 IU Oxidoreductase per g of dyed fiber (eg denim) particularly before added 0.5-20 IU oxidoreductase per g of dyed fiber (eg denim) used.

The mediator is preferably at least one compound Selects from the group of aliphatic, cycloaliphatic, he terocyclic or aromatic compounds containing at least ei N-hydroxy, oxime, nitroso, N-oxyl or N-oxime function ent holds.

Examples of such compounds are those mentioned below Compounds of formula I, II, III or IV, wherein the Verbindun gene of the formulas II, III and IV are preferred and the compounds of Formula III and IV are particularly preferred.

Compounds of general formula I are:

where X is one of the following groups:
(-N = N-), (-N = CR ⁴ -) _p , (-CR ⁴ = N-) _p , (-CR ⁵ = CR ⁶ ) _p

and p is 1 or 2,
where the radicals R ¹ to R ^{6 may be} identical or different and represent independently of one another the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ -alkyl , C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino-, carbamoyl- and sulfamoyl groups of the radicals R ¹ to R ^{6 may} furthermore be unsubstituted or monosubstituted or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy,
and where the radicals R ² and R ³ can form a common group -A- and -A- represents one of the following groups:
(-CR ⁷ = CR ⁸ -CR ⁹ = CR ¹⁰ -) or (-CR ¹⁰ = CR ⁹ -CR ⁸ = CR ⁷ -).

The radicals R ⁷ to R ¹⁰ may be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 can} furthermore be unsubstituted or monosubstituted or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and where the C ₁ -C ₁₂ -alkyl-, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl groups of the radicals R ⁷ to R ¹⁰ unsubstituted or may be further substituted mono- or polysubstituted by the radical R ¹¹ and wherein the radical R ^{11 may represent} one of the following groups: hydrogen, halogen, hydroxy, for myl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ -alkyl, C C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, and their esters and salts, and wherein the carbamoyl, sulfamoyl, amino groups of the radical R ^{11 are} unsubstituted or furthermore mono- or disubstituted by the radical R ¹² can be substituted and wherein the radical R ^{12 can represent} one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ - alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl.

Examples of the compounds mentioned are:
1-hydroxy-1,2,3-triazole-4,5-dicarboxylic acid
1-phenyl-1H-1,2,3-triazol-3-oxide
5-chloro-1-phenyl-1H-1,2,3-triazol-3-oxide
5-methyl-1-phenyl-1H-1,2,3-triazol-3-oxide
4- (2,2-Dimethylpropanoyl) -1-hydroxy-1H-1,2,3-triazole
4-Hydroxy-2-phenyl-2H-1,2,3-triazol-1-oxide
2,4,5-triphenyl-2H-1,2,3-triazol-1-oxide
1-benzyl-1H-1,2,3-triazol-3-oxide
1-benzyl-4-chloro-1H-1,2,3-triazol-3-oxide
1-benzyl-4-bromo-1H-1,2,3-triazol-3-oxide
1-benzyl-4-methoxy-1H-1,2,3-triazol-3-oxide
Compounds of general formula II are:

where X is one of the following groups: (-N = N-), (-N = CR ⁴ -) _p , (-CR ⁴ = N-) _p , (-CR ⁵ = CR ⁶ ) _p

and p is 1 or 2.

The radicals R ¹ and R ⁴ to R ¹⁰ may be identical or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl , C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, sulfono, esters and salts thereof, of sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino , carbamoyl and sulfa moyl groups of the radicals R ¹ and R ⁴ to R ^{10 can} furthermore be unsubstituted or monosubstituted or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy
and wherein the C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₁ -C ₆ alkyl, phenyl, aryl, aryl C ₁ -C ₆ alkyl groups of Radicals R ¹ and R ⁴ to R ¹⁰ unsubstituted or further mono- or polysubstituted with the radical R ¹² may be substituted and wherein the radical R ^{12 may represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₁ -C ₆ alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R ^{12 are} unsubstituted or may further be mono- or disubstituted by the radical R ¹³ and wherein the radical R ^{13 may represent} one of the following groups: hydrogen, hydroxy, formyl , carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl.

Examples of the compounds mentioned are:
1-hydroxy-benzimidazole
1-hydroxy-benzimidazole 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 is one of the following groups: (-N = N-), (-N = CR ⁴ -) _m , (-CR ⁴ = N-) _m , (-CR ⁵ = CR ⁶ -) _m

and m is 1 or 2.

For the radicals R ⁷ to R ¹⁰ and R ⁴ to R ⁶ , the above applies. R ¹⁴ can be: hydrogen, C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkylcarbonyl, their C ₁ -C ₁₀ -alkyl and C ₁ -C ₁₀ -alkylcarbonyl unsubstituted or with one radical R ¹⁵ one or more times wherein R ^{15 may represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, sulfono, their esters and salts, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters,
wherein the amino, carbamoyl and sulfamoyl groups of the radical R ^{15 may} furthermore be unsubstituted or monosubstituted or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ alkoxy.

Of the substances of the formula III, particular preference is given to derivatives of 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide and also their esters and salts (compounds of the formula IV)

The radicals R ⁷ to R ¹⁰ may be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sulfamoyl groups of the radicals R ⁷ to R ^{10 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and where the C ₁ -C ₁₂ -alkyl-, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl groups of the radicals R ⁷ to R ¹⁰ unsubstituted or may be further substituted one or more times with the radical R ¹⁶ and wherein the R ^{16 can represent} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ -alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts, and wherein the carbamoyl, sulfamoyl, amino groups of the radical R ¹⁶ unsubstituted or furthermore monosubstituted or disubstituted by the radical R ¹⁷ and where the radical R ^{17 can represent} one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl C ₁ -C ₆ alkyl, phenyl, aryl.

Examples of the compounds mentioned are:
1H-hydroxybenzotriazoles
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-6-sulfonic acid
1-hydroxybenzotriazole-6-sulfonic acid, monosodium salt
1-hydroxybenzotriazole-6-carboxylic acid
1-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-1-hydroxy-benzo-triazole
2,3-bis (2-bromo-4-methylphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (4-bromo-phenyl) -4,6-dinitro-2,3-dihydro-1-hydroxy-benzotriazole
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-1-hydroxybenzotriazole
4-bromo-6-nitro-1-hydroxybenzotriazole
6-bromo-4-nitro-1-hydroxybenzotriazole
4-chloro-1-hydroxybenzotriazole
5-chloro-1-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-1-hydroxybenzotriazole
4,6-dibromo-1-hydroxybenzotriazole
4,6-dichloro-1-hydroxybenzotriazole
5,6-dichloro-1-hydroxybenzotriazole
4,5-dichloro-1-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-1-hydroxybenzo-triazole
4,6-dinitro-1-hydroxybenzotriazole
4,6-dinitro-2,3-diphenyl-2,3-dihydro-1-hydroxybenzotriazole
4,6-dinitro-2,3-di-p-tolyl-2,3-dihydro-1-hydroxybenzotriazole
5-hydrazino-7-methyl-4-nitro-1-hydroxybenzotriazole
5,6-dimethyl-1-hydroxybenzotriazole
4-methyl-1-hydroxybenzotriazole
5-methyl-1-hydroxybenzotriazole
6-methyl-1-hydroxybenzotriazole
5- (1-methylethyl) -1-hydroxybenzotriazole
4-methyl-6-nitro-1-hydroxybenzotriazole
6-methyl-4-nitro-1-hydroxybenzotriazole
5-methoxy-1-hydroxybenzotriazole
6-methoxy-1-hydroxybenzotriazole
7-Methyl-6-nitro-1-hydroxybenzotriazole
4-nitro-1-hydroxybenzotriazole
6-nitro-1-hydroxybenzotriazole
6-nitro-4-phenyl-1-hydroxybenzotriazole
5-phenylmethyl-1-hydroxybenzotriazole
4-trifluoromethyl-1-hydroxybenzotriazole
5-trifluoromethyl-1-hydroxybenzotriazole
6-trifluoromethyl-1-hydroxybenzotriazole
4,5,6,7-tetrachloro-1-hydroxybenzotriazole
4,5,6,7-tetrafluoro-1-hydroxybenzotriazole
6-tetrafluoroethyl-1-hydroxybenzotriazole
4,5,6-trichloro-1-hydroxybenzotriazole
4,6,7-trichloro-1-hydroxybenzotriazole
6-sulfamido-1-hydroxybenzotriazole
6-N, N-diethyl-sulfamido-1-hydroxybenzotriazole
6-N-methylsulfamido-1-hydroxybenzotriazole
6- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6- (5,6,7,8-tetrahydro-imidazo [1,5-a] -pyridin-5-yl) -1-hydroxy-benzotriazole
6- (phenyl-1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6 - [(5-methyl-1 H -imidazo-1-yl) phenylmethyl] -1-hydroxybenzo-triazo-1
6 - [(4-methyl-1 H -imidazo-1-yl) phenylmethyl] -1-hydroxybenzo-triazo-1
6 - [(2-methyl-1 H -imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6- (1H-imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
5- (1H-imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
6- [1- (1H -imidazol-1-yl) -ethyl] -1-hydroxybenzotriazole monohydrochloride
3H-benzotriazol-1-oxide
3H-benzotriazol-1-oxide
6-Acetyl-3H-benzotriazol-1-oxide
5-ethoxy-6-nitro-3H-benzotriazole-1-oxide
4-ethyl-7-methyl-6-nitro-3H-benzotriazole-1-oxide
6-amino-3,5-dimethyl-3H-benzotriazol-1-oxide
6-amino-3-methyl-3H-benzotriazol-1-oxide
5-bromo-3H-benzotriazole-1-oxide
6-bromo-3H-benzotriazole-1-oxide
4-Bromo-7-methyl-3H-benzotriazol-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-nitro-3H-benzotriazole-1-oxide
4,6-dibromo-3H-benzotriazol-1-oxide
4,6-dibromo-3-methyl-3H-benzotriazol-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-benzotriazol-1-oxide
5,7-dichloro-6-nitro-3H-benzotriazole-1-oxide
3,6-dimethyl-6-nitro-3H-benzotriazole-1-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-1-oxide
7-methyl-6-nitro-3H-benzotriazole-1-oxide
5-chloro-6-nitro-3H-benzotriazole-1-oxide
2H-benzotriazole-1-oxide
2- (4-acetoxy-phenyl) -2H-benzotriazole-1-oxide
6-acetylamino-2-phenyl-2H-benzotriazole-1-oxide
2- (4-ethyl-phenyl) -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-benzotriazole-1-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-benzotriazole-1-oxide
2- (4-bromophenyl) -6-nitro-2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2,4-dibromophenyl) -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 1-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-benzotriazole-1-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-benzotriazole-1-oxide
2- [4- (4-chlorophenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzo-triazole-1-oxide
2- (2-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- {4- [N '- (3-Chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-di-nitro-2H-benzotriazole 1-oxide
2- {4- [N '- (4-Chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole 1-oxide
2- (2-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-picrylazo-2H-benzotriazole-1-oxide
5-chloro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
4,5-dibromo-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dimethyl-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -4,6-dinitro-benzotriazol-1-oxide
2- (2,5-dimethylphenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (2,5-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-Dinitro-2- [3-nitro-4- (N'-phenylhydrazino) -phenyl]-2H-benzotriazole-1-oxide
4,6-Dinitro-2- [4-nitro-4- (N'-phenylhydrazino) -phenyl]-2H-benzotriazole-1-oxide
4,6-dinitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-dinitro-2-o-tolyl-2H-benzotriazole-1-oxide
4,6-dinitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,6-dinitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
2- (4-methoxyphenyl) -2H-benzotriazol-1-oxide
2- (4-methoxyphenyl) -6-methyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-m-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-o-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-Methyl-2-phenyl-2H-benzotriazole-1-oxide
4-methyl-2-m-tolyl-2H-benzotriazole-1-oxide
4-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
4-Methyl-2-p-tolyl-2H-benzotriazole-1-oxide
6-Methyl-2-m-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
6-Methyl-2-p-tolyl-2H-benzotriazole-1-oxide
2- [1] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [1] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- (3-nitrophenyl) -2H-benzotriazole-1-oxide
6-nitro-2-phenyl-2H-benzotriazole-1-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-1-oxide
2-p-tolyl-2H-benzotriazole-1-oxide

The mediator may preferably be further selected from the group of cyclic N-hydroxy compounds having at least one optionally substituted five- or six-membered ring containing the structure mentioned in formula V.

and their salts, ethers or esters, wherein
B and D, the same or different, and O, S, or NR ¹⁸ mean where
R ^{18 is} hydrogen, hydroxy, formyl, carbamoyl, sulfono, ester or salt of the sulfono group, sulfamoyl, nitro, amino, phenyl, arylC ₁ -C ₅ alkyl, C ₁ -C ₁₂ Alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphonooxy, ester or salt of the phosphonooxy radical,
where carbamoyl, sulfamoyl, amino and phenyl radicals unsubstituted or may be mono- or polysubstituted by a radical R ¹⁹ and the aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals may be saturated or unsaturated, branched or unbranched and may be mono- or polysubstituted by a radical R ¹⁹ where
R ^{19 is the} same or different and hydroxy, formyl, carboxy radical, ester or salt of the carboxy, carbamoyl, sulfonic ester or salt of the sulfono, sulfamoyl, nitro, amino, phenyl, C ₁ -C ₅ Alkyl, C ₁ -C ₅ alkoxy.

Preferably, the mediator is selected from the group of compounds of the general formula VI, VII, VIII or IX,

where B, D have the meanings already mentioned and the radicals R ²⁰ -R ^{35 are} identical or different and have halogen, carboxyl, salt or ester of a carboxy radical or the meanings mentioned for R ¹⁸ ,
where R ²⁶ and R ²⁷ or R ²⁸ and R ^{29 may} not simultaneously denote hydroxy or amino, and
if appropriate, two of the substituents R ²⁰ -R ²³ , R ²⁴ -R ²⁵ , R ²⁶ -R ²⁹ , R ³⁰ -R ³⁵ can be linked to a ring -E-, where -E- has one of the fol lowing meanings:
(-CH = CH) - _n where n = 1 to 3, -CH = CH-CH = N- or

and where appropriate, the radicals R ²⁶ -R ^{29 may} also be connected to one another by one or two bridge elements -F-, where -F- is the same or different and has one of the following meanings: -O-, -S, -CH ₂ -, CR ³⁶ = CR ³⁷ -;
wherein 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 my formulas VI, VII, VIII or IX, in which B and D, O or S mean.

Examples of such compounds are N-hydroxy-phthalimide and optionally substituted N-hydroxy-phthalimide derivatives, N-Hydroxymalei mid and optionally substituted N-hydroxymaleimide derivatives, N-hydroxy-naphthalimide and optionally substituted N-hydroxy-naphthalimide Derivatives, N-hydroxysuccinimide and optionally substituted N-hydroxysuccinimide derivatives, preferably sol che, in which the radicals R ²⁶ -R ^{29 are} polycyclic.

Particularly preferred mediators are N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide and 3-amino-N-hydroxyphthalimide.

Mediator suitable compounds of formula VI are example, as:
N-hydroxyphthalimide,
4-amino-N-hydroxyphthalimide,
3-amino-N-hydroxyphthalimide,
N-hydroxy-benzene-1,2,4-tricarbonsäureimid,
N, N'-dihydroxy pyromellitic diimide,
N, N'-dihydroxy-benzophenone-3,3 ', 4,4'-tetracarboxylic diimide.

Mediator suitable compounds of formula VII are for example:
N-hydroxymaleimide,
Pyridine-2,3-dicarboxylic acid N-hydroxyimide.

Mediator suitable compounds of formula VIII are for example:
N-hydroxysuccinimide
N-Hydroxyweinsäureimid,
N-hydroxy-5-norbornene-2,3-dicarboximide,
exo-N-hydroxy-7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-cis-cyclohexane-1,2-dicarboximide,
N-hydroxy-cis-4-cyclohexene-1,2-dicarboximide.

Mediator suitable compound of formula IX is example, as:
N-hydroxynaphthalimide sodium salt.

A mediator suitable compound having a six-membered ring containing the structure mentioned in formula V is, for example:
N-hydroxyglutarimide.

The exemplified compounds are also suitable in the form their salts or esters as mediator.  

Also suitable as a mediator are compounds selected from the group of N-aryl-N-hydroxy amides.

Of these, preference is given to using compounds of the general formula X, XI or XII as mediators

and their salts, ethers or esters, wherein
G monovalent homo- or heteroaromatic mononuclear or dinuclear radical and
L is a bivalent homo- or heteroaromatic mono- or bicyclic radical and
wherein these aromatics are replaced by one or more identical or different radicals R ³⁸ selected from the group consisting of halogen, hydroxy, formyl, cyano, carbamoyl, carboxy radical, esters or salts of the carboxy radical, sulfono radical, ester or salt of the sulfono radical, Sul famoyl, nitro, nitroso, amino, phenyl, aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ -Carbonyl, carbonyl-C ₁ -C ₆ alkyl, phospho, phosphono, phosphono-oxyrest, ester or salt of the phosphonooxy may be substituted and
wherein carbamoyl, sulfamoyl, amino and phenyl unsubstituted or may be mono- or polysubstituted with a radical R ³⁹ and the aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl C ₁ -C ₆ alkyl radicals may be saturated or unge saturated, branched or unbranched and may be mono- or polysubstituted with a radical R ³⁹ , in which
R ^{39 is the} same or different and hydroxy, formyl, cyano, carboxyl, ester or salt of the carboxy, carbamoyl, sulfo no, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl radical and
in each case two radicals R ³⁸ or R ^{39 can be} linked in pairs via a bridge [-CR ⁴⁰ R ⁴¹ -] _m to m equal to 0, 1, 2, 3 or 4, and
R ⁴⁰ and R ⁴¹ are the same or different and are a carboxyl radical, ester or salt of the carboxyl, phenyl, C ₁ -C ₅ alkyl, C ₁ - C ₅ alkoxy, C ₁ -C ₅ -alkylcarbonyl radical, and one or more non-adjacent groups [-CR ⁴⁰ R ⁴¹ -] by oxygen, sulfur or an imino radical optionally substituted by C ₁ to C ₅ alkyl radical and two adjacent groups [-CR ⁴⁰ R ⁴¹ -] by a group [-CR ⁴⁰ = CR ⁴¹ -] can be replaced and
I in amidic form of einbindiger acid radical of acids selected from the group consisting of carboxylic acid having up to 20 carbon atoms, carbonic acid, half esters of carbonic acid or carbamic acid, sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid, diesters of phosphoric acid means and
K in amide form present divalent acid radical of acids selected from the group consisting of mono- and dicarboxylic acids having 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:

and their salts, ethers or esters, wherein
Ar ¹ monovalent homo- or heteroaromatic mononuclear aryl radical and
Ar ^{2 is a} bivalent homo- or heteroaromatic mononuclear aryl radical,
which by one or more, identical or different radicals R ⁴⁴ selected from the group hydroxy, cyano, carboxyl, ester or salt of the carboxy, sulfono, ester or salt of Sul fonorests, nitro, nitroso, amino, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl may be substitu- tuiert,
where amino radicals can be unsubstituted or monosubstituted or polysubstituted by an R ⁴⁵ radical and the C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ - C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and may be monosubstituted or polysubstituted by a radical R ⁴⁵ ,
wherein R ^{45 is the} same or different and hydroxy, carboxy, ester or salt of the carboxy, sulfono, nitro, amino, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C _5- Alkylcarbonylrest means and
in each case two radicals R ^{44 can be} linked in pairs via a bridge [-CR ⁴⁰ R ⁴¹ -] _m to m equal to 0, 1, 2, 3 or 4, and
R ⁴⁰ and R ^{41 have} the meanings already mentioned, and one or more nonadjacent groups [-CR ⁴⁰ R ⁴¹ -] are substituted by oxygen, sulfur or an imino radical optionally substituted by a C ₁ to C ₅ alkyl radical and two adjacent groups CR ⁴⁰ R ⁴¹ -] can be replaced by a group [-CR ⁴⁰ = CR ⁴¹ -],
R ⁴² identical or different monovalent radicals selected from the group consisting of hydrogen, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl radical, where phenyl radicals may be unsubstituted or substituted one or more times with a radical R ⁴⁶ and the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ - Alkoxy, C ₁ -C ₁₀ carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be monosubstituted or polysubstituted with one radical R ⁴⁶ , wherein
R ^{46 is the} same or different and is hydroxy, formyl, cyano, carboxyl, ester or salt of the carboxy, carbamoyl, sulfo no, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy and
R ⁴³ denotes divalent radicals selected from the group ortho, meta, para-phenylene, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkylene, C ₁ -C ₅ -alkylenedioxy radical, where phenylene radicals may be unsubstituted or monosubstituted or polysubstituted by a radical R ⁴⁶ and the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy radicals saturated or unsaturated, can be branched or unbranched nen and with one radical R ⁴⁶ mono- or polysubstituted, where
p is 0 or 1 and
q is an integer from 1 to 3.

Ar ^{1 is} preferably phenyl and Ar ^{2 is} ortho-phenylene, Ar ¹ being up to five and Ar ² being up to four identical or different radicals selected from the group consisting of C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkylcarbonyl -, carboxy, ester or salt of the carboxy, sulfono, ester or salt of the sulfono, hydroxy, cyano, nitro, nitroso and amino may be substituted iert, wherein amino radicals having two different radicals selected from the group hydroxy and C ₁ -C ₃ alkylcarbonyl substituents may be tuiert.

Preferably, R ^{42 is a} monovalent radical selected from the group consisting of hydrogen, phenyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, wherein the C ₁ -C ₁₂ -alkyl radicals and C ₁ -C ₅ -alkoxy radicals saturated or unsaturated, branched or unbranched.

Preferably, R ^{43 is a} divalent radical selected from the group consisting of ortho or para-phenylene, C ₁ -C ₁₂ -alkylene, C ₁ -C ₅ -alkylenedioxy radical, where the aryl-C ₁ -C ₅ -alkyl-, C ₁ C ₁₂ alkyl, C ₁ -C ₅ alkoxy radicals may be saturated or unsaturated, branched or un-branched and may be monosubstituted or polysubstituted with one radical R ⁴⁶ .

Preferably R ^{46 is} carboxy, ester or salt of the carboxyrests, carbamoyl, phenyl, C ₁ - C ₃ alkoxy.

Examples of compounds used as mediators are N-hydroxyacetanilide, N-hydroxypivaloylanilide, N- Hydroxyacrylanilide, N-hydroxybenzoylanilide, N-hydroxy-methylsul fonylanilide, N-hydroxy-N-phenyl-methylcarbamate, N-hydroxy-3-oxo-butyrylanilide, N-hydroxy-4-cyanoacetanilide, N-hydroxy-4-methoxyacetanilide, N-hydroxyphenacetin, N-hydroxy-2,3-dimethylacetanilide, N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, 1-Hydroxy-3,4-dihydroquinoline (1H) -2-one, N, N'-dihydroxy-N, N'-diacetyl-1,3-phenylenediamine, N, N'-dihydroxy succinic acid, N, N'-dihydroxymaleic dianilide, N, N'- Dihydroxy-oxa-dianilide, N, N'-dihydroxy-phosphoric di anilide, N-acetoxyacetanilide, N-hydroxymethyloxalylanilide, N- Hydroxymaleinsäuremonoanilid.  

Preferred mediators are N-hydroxyacetanilide, N- Hydroxyformanilide, N-hydroxy-N-phenyl-methylcarbamate, N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, 1-hydroxy-3,4-dihydroquinoline (1H) -2-one and N-acetoxyacetan lid.

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

Preferred mediators here are compounds of the general formulas (XVIII) or (XIX)

and their salts, ethers or esters used, wherein
M is the same or different and is a monovalent linear or branched or cyclic or polycyclic saturated or unsaturated alkyl radical having 1-24 C atoms and
wherein this alkyl radical is replaced by one or more radicals R ⁴⁸ which are identical or different and are selected from the group hydroxy, mercapto, formyl, carbamoyl, carboxy, ester or salt of the carboxy radical, sulfono radical, ester or salt of the sulfono radicals, sulfamoyl, nitro, nitroso, amino, hydroxylamino, phenyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, phospho-, phosphono, phosphonooxy, esters or salts of Phosphonooxyrests substituted can be and
where carbamoyl, sulfamoyl, amino, hydroxylamino, mercapto and phenyl radicals may be unsubstituted or substituted one or more times with one radical R ⁴⁸ and the C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be mono- or polysubstituted by a radical R ⁴⁸ , where
R ^{48 is the} same or different and hydroxy, formyl, cyano, carboxyl, ester or salt of the carboxy, carbamoyl, sulfo no-, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, C ₁ C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl radical and non-α-methylene groups may be replaced by oxygen, sulfur or an optionally monosubstituted imino radical, and
N in monidary form of einbindiger acid radical of acids selected from the group of aliphatic or mononuclear or mononuclear aromatic or mono- or binuclear heteroaromatic carboxylic acids having up to 20 carbon atoms, carbonic acid, half esters of carbonic acid or carbamic acid, sulfonic acid, phosphonic acid phosphoric acid, monoesters of phosphoric acid, diesters of phosphoric acid and
T in amidic form of divalent acid group of acids selected from the group consisting of aliphatic, mono- or di-nuclear aromatic or mononuclear or dinuclear heteroaromatic dicarboxylic acids containing up to 20 carbon atoms, carbonic acid, sulfonic acid, phosphonic acid, phosphoric acid monoester meaning tet and
wherein alkyl radicals of aliphatic acids N and T present in amide form can be linear or branched and / or cyclic and / or polycyclic saturated or unsaturated and contain 0-24 carbon atoms and are unsubstituted or monosubstituted or polysubstituted by the radical R ⁴⁷ are and
Aryl and heteroaryl radicals of the aromatic or heteroaromatic acids N and T present in amide form by one or more radicals R ⁴⁹ which are identical or different and are selected from the group hydroxyl, mercapto, formyl, cyano, carbamoyl , Carboxy, ester or salt of the carboxy radical, sulfono radical, ester or salt of the sulfono group, sulfamoyl, nitro, nichro, amino, phenyl, aryl-C ₁ -C ₅ alkyl, C ₁ -C _12- alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, phospho, phosphono, phosphonooxy radical, ester or salt of the phosphonooxy may be substituted and
where carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals may be unsubstituted or substituted one or more times with the radical R ⁴⁸ and the aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl-C C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be substituted one or more times with the radical R ⁴⁸ .

Particularly preferred mediators are compounds having the general formulas (XX, XXI, XXII or XXIII):

and their salts, ethers or esters, wherein
Alk ^{1 is the} same or different and is a monovalent linear or branched or cyclic or polycyclic saturated or unsaturated alkyl radical having 1-10 C atoms, this alkyl radical being replaced by one or more radicals R ⁵⁰ which are identical or different and are selected from the group Hydroxy, formyl, carbamoyl, carboxy, ester or salt of the carboxyrest, sulfono, ester or salt of the sulfono, sulfo moyl, nitro, nitroso, amino, hydroxylamino, phenyl, C ₁ -C _5- alkoxy, C ₁ -C ₅ -carbonyl radicals may be substituted and wherein carbamoyl, sulfamoyl, amino, hydroxylamino and Phenylre ste unsubstituted or mono- or polysubstituted with a radical R ⁵¹ may be substituted and the C C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be mono- or polysubstituted by a radical R ⁵¹ , where
R ^{51 is the} same or different and hydroxy, formyl, cyano, carboxyl, ester or salt of the carboxy, carbamoyl, sulfo no-, sulfamoyl, nitro, amino, phenyl, benzoyl, C ₁ -C ₅ -Alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₅ -alkylcarbonyl radical and
non-α-methylene groups can be replaced by oxygen, sulfur or an optionally monosubstituted imino radical and
where R ^{53 represents} identical or different monovalent radicals selected from the group consisting of hydrogen, phenyl, pyridyl, furyl, pyrrolyl, thienyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₁₀ -carbonyl,
where phenyl, pyridyl, furyl, pyrrolyl and thienyl radicals may be unsubstituted or substituted mono- or polysubstituted by an R ⁷ radical and the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl -, C ₁ -C ₅ alkoxy and C ₁ -C ₁₀ carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be mono- or polysubstituted by a radical R ⁵³ and
R ^{53 is the} same or different and is hydroxy, formyl, carboxy, ester or salt of the carboxy, carbamoyl, sulfono, sulfamoyl, nitro, amino, phenyl, C ₁ -C ₅ alkyl, C C ₁ -C ₅ alkoxy radical and
R ⁵⁴ divalent radicals selected from the group consisting of phenylene, pyridene, thienylene, furylene, pyrrolylene, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkylene, C ₁ -C ₅ - Alkylenedioxy radical, where phenylene, pyridylene, thienylene, furylene, pyrrolylene unsubstituted or mono- or polysubstituted with an R ⁵³ may be substituted and the aryl-C ₁ -C ₅ alkyl, C ₁ - C ₁₂ alkyl, C ₁ -C ₅ alkoxy radicals may be saturated or unsaturated, branched or unbranched and may be mono- or polysubstituted by a radical R ⁵³ , where
p is 0 or 1.

Very particular preference is given as mediators to compounds of the general formula (XX-XXIII) in which Alk ^{1 is the} same or different and is a monovalent linear or branched or cyclic saturated or unsaturated alkyl radical having 1-10 C atoms,
wherein this alkyl group by one or more radicals R ⁵⁰ , which are identical or different and are selected from the group hydroxy, carbamoyl, carboxy, ester or salt of the carboxy, sulfono, ester or salt of the sulfono, sulfamoyl, Ami no -, phenyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ carbonyl radicals may be substituted and
where carbamoyl, sulfamoyl, amino and phenyl unsubstituted or may be mono- or polysubstituted with a radical R ⁵¹ and the C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl radicals saturated or unsaturated, branches or may be unbranched and may be monosubstituted or polysubstituted with a radical R ⁵¹ , wherein R ^{51 is} identical or different and hydroxy, carboxyl, ester or salt of the carboxy, carbamoyl, sulfono, sulfamoyl, Ni tro-, amino -, phenyl, benzoyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl radical and
where R ⁵² denotes identical or different monovalent radicals selected from the group consisting of hydrogen, phenyl, furyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₀ -alkoxy, C ₁ -C ₁₀ -carbonyl radical, where phenyl and furyl radicals can be unsubstituted or monosubstituted or polysubstituted with an R ⁵³ radical and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl- , C ₁ -C ₅ -alkoxy and C ₁ -C ₁₀ -carbonyl radicals may be saturated or unsaturated, branched or unbranched and may be monosubstituted or polysubstituted with one radical R ⁵³ , where
R ^{53 is the} same or different and is carboxy, ester or salt of the carboxy, carbamoyl, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy and
R ^{54 is a} divalent radical selected from the group phenylene, Fury len, C ₁ -C ₁₂ alkylene, C ₁ -C ₅ alkylenedioxy radical, where phenylene, furanylene unsubstituted or one or more times with a radical R ⁵³ may be substituted and the aryl C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy radicals may be saturated or unsaturated, branched or unbranched and with a radical R ^{53 may be} mono- or polysubstituted, where
p is 0 or 1.

Examples of compounds that can be used as mediators are
N-hydroxy-N-methyl-benzoic acid amide, N-hydroxy-N-methylbenzenesulfonic acid amide, N-hydroxy-N-methyl-p-toluenesulfonic 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,
N, N'-dihydroxy-N, N'-dimethyl-isophthalic acid diamide, N, N'-dihydroxy-N, N'-dimethyl-terephthalic diamide,
N, N'-dihydroxy-N, N'-dimethyl-benzene-1,3-disulfonsäurediamid,
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-isophthalsäurediamid,
N, N'-dihydroxy-N, N'-di-tert-butyl-terephthalic acid diamide,
N, N'-dihydroxy-N, N'-di-tert-butyl-benzene-1,3-disulfonsäuredi-amide,
N, N'-dihydroxy-N, N'-di-tert-butyl-furan-3,4-dicarboxylic acid diamide,
N-hydroxy-N-cyclohexylbenzoic acid amide, N-hydroxy-N-cyclohexylbenzenesulfonamide,
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-isophthalsäurediamid,
N, N'-dihydroxy-N, N'-dicyclohexyl-terephthalic acid diamide,
N, N'-dihydroxy-N, N'-dicyclohexylbenzene-1,3-disulfonic acid diamide,
N, N'-dihydroxy-N, N'-dicyclohexyl-furan-3,4-dicarboxylic acid di amide,
N-hydroxy-N-isopropylbenzoic acid amide, N-hydroxy-N-isopropylbenzene-sulfonic acid amide, N-hydroxy-N-isopropyl-p-toluenesulfonic acid amide, N-hydroxy-N-isopropyl-furan-2-carboxamide, N-hydroxy-N-isopropylthiophene-2-carboxylic acid amide, N, N'-dihydroxy-N, N'-diisopropylphthalic diamide, N, N'-dihydroxy-N, N'-diisopropylisophthalic acid diamide, N, N'-dihydroxy-N, N'-diisopropyl prope-terephthalic acid diamide, N, N'-dihydroxy-N, N'-diisopropyl p-benzene-1,3-disulfonic acid diamide, N, N'-dihydroxy-N, N 'diisopropyl p-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-methane sulfonamide, N-hydroxy-N -isopropyl-methanesulfonamide, N-hydroxy-N-isopropyl-methylcarbamate,
N-hydroxy-N-methyl-3-oxobutyric acid amide, N, N'-dihydroxy-N, N'-dibenzoylethylenediamine, N, N'-dihydroxy-N, N'-dimethylsuccinic acid diamide,
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,
N, N'-dihydroxy-N, N'-di-tert-butyl-phosphorus-säurediamid.

Preferred mediators are compounds selected from the group consisting of N-hydroxy-N-methylbenzoic acid amide, N-hydroxy-N-methylbenzenesulfonamide, N-hydroxy-N-methyl-p-toluenesulfonic acid amide, N-hydroxy-N-methyl -furan-2-carboxylic acid amide, N, N'-dihydroxy-N, N'-dimethylphthalic diamide, N, N'-dihydroxy-N, N'-dimethyl-terephthalic diamide,
N, N'-dihydroxy-N, N'-dimethyl-benzene-1,3-disulfonsäurediamid,
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, N'-dihydroxy-N, N'-di-tert-butyl-terephthalic acid diamide, N-hydroxy-N-isopropyl-benzoic acid amide, N-hydroxy-N-isopropyl-p-to-luolsulfonic acid amide,
N-hydroxy-N-isopropyl-furan-2-carboxylic acid amide, N, N'-dihydroxy-N, N'-diisopropyl terephthalic acid diamide, N, N'-dihydroxy-N, N'-diisopropylbenzene-1 , 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-pivalinamide, N-hydroxy-N-tert-butyl-acrylamide, N-hydroxy-N-propyl-acrylamide, N-hydroxy-N-methyl-3-oxobutyramide,
N, N'-dihydroxy-N, N'-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 furthermore be selected from the group of oximes of the general formula I or II

and their salts, ethers, or esters, wherein
U, the same or different and O, S, or NR ⁵⁵ mean
R ⁵⁵ hydrogen, hydroxy, formyl, carbamoyl, sulfono, ester or salt of the sulfono, sulfamoyl, nitro, amino, phenyl, aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ Alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphonooxy, ester or salt of the phosphonooxy radical,
where carbamoyl, sulfamoyl, amino and phenyl radicals unsubstituted or may be mono- or polysubstituted by a radical R ⁵⁶ and the aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals may be saturated or unge saturated, branched or unbranched and may be monosubstituted or polysubstituted with one radical R ⁵⁶ , in which
R ^{56 is the} same or different and hydroxy, formyl, carboxy radical, ester or salt of the carboxy, carbamoyl, sulfonic ester or salt of the sulfono, sulfamoyl, nitro, amino, phenyl, C ₁ -C ₅ Alkyl, C ₁ -C ₅ alkoxy and
the radicals R ⁵⁷ and R ^{58 are} identical or different and are halogen, carboxyl, ester or salt of the carboxy radical, or have the meanings given for R ⁵⁵ , or a ring [-CR ⁶¹ R ⁶² ] _n 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 are halogen, carboxy radical, ester or salt of the carboxy group, or have the meanings given for R ⁵⁵ .

Particularly preferred mediators are compounds with the all common formula XXIV in which U is O or S and the  other radicals have the meanings given above. On Example of such a connection is 2-hydroxyiminomalonate.

Particularly preferred mediators are isonitrosoderi vate of cyclic ureides of the general formula XXV. Examples for such compounds are 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid, alloxan-4,5-dioxime.

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

The mediator can furthermore be selected from the group of vicinal nitrososubstituted aromatic alcohols of the general formulas XXVI or XXVII

and their salts, ethers or esters, wherein
R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ^{66 are} identical or different and hydrogen, halogen, hydroxy, formyl, carbamoyl, carboxyl, ester or salt of the carboxy, sulfono, ester or salt of the sulfono, sulfamoyl , Nitro, nitroso, cyano, amino, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ - Carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphono-oxyrest, ester or salt of the phosphonooxy radical,
wherein carbamoyl, sulfamoyl, amino and phenyl unsubstituted or may be mono- or polysubstituted with a radical R ⁶⁷ and the aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals may be saturated or unge saturated, branched or unbranched and may be monosubstituted or polysubstituted with one radical R ⁶⁷ , in which
R ^{67 is} identical or different and hydroxy, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ - Alkyl, C ₁ - C ₅ alkoxy means or
the radicals R ⁶³ -R ⁶⁶ are linked in pairs to form a ring [-CR ⁶⁸ R ⁶⁹ -] _m , where m is an integer and has a value of 1 to 4, or a ring [-CR ⁷⁰ = CR ⁷¹ -] _n where n is integer and has a value of 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 .

Among aromatic alcohols are preferably phenols or hö to understand condensed derivatives of phenol.

Preferred mediators are compounds of the general formula XXVI or XXVII, the synthesis of which is based on nitrosation recycled phenols can be traced. Examples of such verbin compounds 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-6-nitrosophenol, 3,5-dimethyl-6-nitrosophenol, 2,5-dimethyl-6-nitrosophenol, 2-nitrosoresorcinol, 4-nitrosoresorcinol, 2-nitrosoorcin, 2-nitrosophloroglucinol and 4-nitrosopyrogallol, 4-nitroso-3-hydroxyaniline, 4-nitro-2-nitrosophenol.

Further preferred mediators are o-nitrosated derivatives condensed aromatic alcohols. Examples of such verbin compounds are 2-nitroso-1-naphthol, 1-methyl-3-nitroso-2-naphthol and 9-hydroxy-10-nitroso-phenanthrene.

Particularly preferred mediators are 1-nitroso-2-naphthol, 1-nitroso-2-naphthol-3,6-disulfonic acid, 2-nitroso-1-naphthol-4-sulfonic acid, 2,4-dinitroso-1,3-dihydroxybenzene and esters, ethers or salts said compounds.

The mediator can also be selected from the group Hydroxypyridines, aminopyridines, hydroxyquinolines, aminoquinolines, Hydroxyisoquinolines, aminoisoquinolines, with to the hydroxy or Amino groups ortho or para nitroso or mercapto substituents, tautomers of the compounds mentioned and their Salts, ethers and esters.

Preferred mediators are compounds of the general formula (XXVIII), (XXIX) or (XXX)

and tautomers, salts, ethers or esters of the compounds mentioned, where in the formulas XXVIII, XXIX or XX two mutually ortho or para radicals R ^{72 are} hydroxyl and Ni trosorest or hydroxy and mercapto radical or nitroso radical and amino radical
and the remaining radicals R ^{72 are the} same or different and are selected from the group consisting of hydrogen, halogen, hydroxyl, mercapto, formyl, cyano, carbamoyl, carboxy, esters and salt of the carboxy, sulfono, esters and salt of the sulfono group, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphono-oxyrest, esters and salt of Phasphonooxyrests and
wherein carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals may be unsubstituted or monosubstituted or polysubstituted with a radical R ⁷³ and tuiert
the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl radicals saturated or unge saturated, branched or unbranched and may be mono- or polysubstituted with a radical R ⁷³ , where R ^{73 is the} same or different and hydroxy, formyl, cyano, carboxyl, ester or salt of the carboxy, carbamoyl, Sulfo no, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy or C ₁ -C ₅ alkylcarbonyl radical and each 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 ³ and R ^{4 are the} same or different and are carboxy, ester or salt of the carboxy, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy or C ₁ -C ₅ alkylcarbonyl and one or more nonadjacent groups [-CR ⁷⁴ R ⁷⁵ -] by oxygen, sulfur or an imino radical optionally substituted by C ₁ -C ₅ -alkyl and two adjacent groups [-CR ⁷⁴ R ⁷⁵ -] by a group [-CR ⁷⁴ = R ⁷⁵ -] can be replaced.

Particularly preferred mediators are compounds of the general formula (XXVIII) or (XXIX) and their tautomers, salts, ethers or esters, where in the formulas (XXVIII) and (XXIX) particularly preferably two mutually ortho R ⁷² radicals and nitroso or hydroxy and mercapto or nitroso and amino and
the remaining radicals R ^{72 are} identical or different and are selected from the group consisting of hydrogen, hydroxyl, mercapto, formyl, carbamoyl, carboxy radical, esters and salts of the carboxy radical, sulfo norest, esters and salt of the sulfono radical, sulfamoyl, Nitro, nitroso, amino, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₅ -carbonyl- , Carbonyl-C ₁ -C ₆ -alkyl, phospho, phosphono, phosphono-oxyrest, esters and salt of Phosphonooxy residue where
Carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals unsubstituted or mono- or polysubstituted by a radical R ⁷³ can be substituted and
the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₅ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl radicals may be saturated or unge saturated, branched or unbranched and may be mono- or polysubstituted with a radical R ⁷³ , wherein R ^{73 has} the meanings already mentioned, and
in each case two radicals R ⁷³ can be linked in pairs via a bridge [-CR ⁷⁴ R ⁷⁵ -] _m to m equal to 2, 3 or 4, and
R ⁷⁴ and R ^{75 have} the meanings already mentioned and one or more nonadjacent groups [-CR ⁷⁴ R ⁷⁵ -] may be replaced by oxygen or an optionally C ₁ -C ₅ alkyl-substituted imino radical.

Examples of compounds used as mediators can, are 2, 6-dihydroxy-3-nitrosopyridine, 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-nitroso-pyridine-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-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline, 3-hydroxy-4-nitroso-isoquinoline, 4-hydroxy-3-nitroso-isoquinoline, 8-hydroxy-5-nitroso-isoquinoline and tautomers of these compounds.

As mediators are preferably 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, 2,4-dihydroxy-3-nitrosoquinoline, 8-hydroxy-5-nitrosoquinoline, 2,3-dihydroxy-4-nitrosoquinoline, see above as tautomers of these compounds.

The mediator can also be selected from the group sta biler nitroxyl radicals (nitroxides), d. H. these free radicals can be obtained in a pure form, characterized and preserved become.  

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

in which
Ar is monovalent homo- or heteroaromatic mononuclear or dinuclear radical and
wherein this aromatic radical is replaced by one or more, identical or different radicals R ⁷⁷ selected from the group of halogen, formyl, cyano, carbamoyl, carboxy, ester or salt of Car boxyrests, sulfono, ester or salt of the sulfono, sulfa moyl, nitro, nitroso, amino, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ - Carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphonooxy, esters or salt of Phos phonooxyrests can be substituted and
where phenyl, carbamoyl and sulfamoyl radicals may be unsubstituted or monosubstituted or polysubstituted by a radical R ⁷⁸ , the amino radical may be monosubstituted or disubstituted by R ⁷⁸ and the aryl-C ₁ -C ₅ -alkyl, C ₁ - C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl C ₁ -C ₆ alkyl radicals may be saturated or unsaturated, branched or unbranched and having one radical R ^{78 may be} monosubstituted or polysubstituted,
where R ^{78 may be} mono- or polysubstituted and is the same or different and is hydroxy, formyl, cyano, carboxy, esters or salts of the carboxy, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino -, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl radical and
R ^{76 is} identical or different and is halogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy, esters or salts of the carboxy, sulfono, ester or salt of the sulfono, Sul famoyl-, nitro-, nitroso- , Amino, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl-,
C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono, phosphono-oxyrest, ester or salt of Phosphonooxy residue means
and R ⁷⁶ in the case of bicyclic stable nitroxyl radicals (structure XXXIII) can also be hydrogen and
where carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁷⁹ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl- , C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and substituted one or more times by a radical R ⁷⁹ where R ^{79 is the} same or different and is hydroxy, formyl, cyano, carboxy, esters or salts of the carboxy, carbamoyl, sulfo no, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ - C ₅ alkoxy, C ₁ -C ₅ -alkylcarbonyl radical and two radicals R ⁷⁸ or R ⁷⁹ in pairs via a bridge [-CR ⁸⁰ R ⁸¹ -] _m with m equal to 0 , 1, 2, 3 or 4 can be linked and
R ⁸⁰ and R ^{81 are the} same or different and are halogen, carboxy, ester or salt of the carboxy, carbamoyl, sulfamoyl, phenyl, benzoyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ -Alkylcarbonylrest be interpreted and
one or more nonadjacent groups [-CR ⁸⁰ R ⁸¹ -] by oxygen, sulfur or an optionally C ₁ -C ₅ -alkyl-substituted 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) -].

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

in which
R ^{82 is} identical or different and is phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl C ₁ -C ₆ alkyl
where phenyl radicals can be unsubstituted or mono- or polysubstituted by a radical R ⁸⁴ and the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and may be monosubstituted or polysubstituted with one radical R ⁸⁴ ,
where R ⁸⁴ may be monosubstituted or polysubstituted and identical or different, and hydroxy, formyl, carboxy, esters or salts of the carboxy, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, Benzoyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl and
R ^{83 is} identical or different and is hydrogen, hydroxy, capro to, formyl, cyano, carbamoyl, carboxy, esters or salts of the carboxy, sulfono, ester or salt of the sulfono, sulfamoyl, nitro, nitroso , Amino, phenyl, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ - C ₆ alkyl, phospho, phosphono, phosphonooxy, esters or salt of Phos phono-oxyrests means
where carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or monosubstituted or polysubstituted with one radical R ⁷⁸ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl- , C ₁ -C ₅ -alkoxy, C ₁ -C ₁₀ -carbonyl, carbonyl-C ₁ -C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and substituted one or more times by a radical R ⁷⁸ and a [-CR ⁸³ R ⁸³ -] - group by oxygen, an optionally substituted with C ₁ -C ₅ alkyl-substituted imino, a (hydroxy) imino, a Car bonylfunktion or optionally with R ⁷⁸ mono- substituted or disubstituted vinylidene function and two adjacent groups [-CR ⁸³ R ⁸³ -] by a group [-CR ⁸³ = CR ⁸³ -] or [-CR ⁸³ = N-] or [-CR ⁸³ = N (O) - ] can be replaced.

Examples of compounds that can be used as mediators are
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO),
4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-oxo-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (Ethoxyfluorphosphinyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl
4- (Isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-maleimido-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (4-nitrobenzoyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-Cyano-2,2,6,6-tetramethyl-piperidine-1-oxyl,
3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-oxyl,
4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl,
4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl,
4-Phenacyliden-2,2,5,5-tetramethyl-imidazolidin-1-oxyl,
3- (aminomethyl) -2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,
3-carbamoyl-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,
3-carboxy-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,
3-Cyano-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,
3-maleimido-2,2,5,5-tetramethyl-pyrrolidin-N-oxyl,
3- (4-nitrophenoxycarbonyl) -2,2,5,5-tetramethyl-pyrrolidin-N-oxyl.

As mediators are preferred
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO),
4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-oxo-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (Isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-maleimido-2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (4-nitrobenzoyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl,
4-Cyano-2,2,6,6-tetramethyl-piperidine-1-oxyl,
3-carbamoyl-2,2,5,5-tetramethyl-3-pyrroline-1-oxyl,
4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl,
4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl,
4-Phenacyliden-2,2,5,5-tetramethyl-imidazolidin-1-oxyl.

As mediators are particularly preferred 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO), and 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl.

The mediator is preferably used in amounts of from 0.005 to 1000 μmol per g of dyed fiber (eg denim), more preferred in amounts of 0.05 to 500 mmol per g of dyed fiber, esp in particular from 0.05 to 100 μmol per g of dyed fiber.  

Usually, the inventive method at temperature ren between 40 and 90 ° C, preferably between 45 and 65 ° C, in particular ders preferably carried out between 45 and 55 ° C.

Depending on the temperature stability of the enzymes used can also other temperatures be optimal. According to the stability of the The process can also be used at elevated temperatures be carried out.

Depending on the choice of mediator and the enzyme may be different optimal reaction conditions are set. Generally leave achieve good bleaching results in the range pH 3 to pH 10. Particularly preferred is the range pH 4.5 to 7.

Depending on the mediator and enzyme used as well as the selected Reak tion conditions, the process can vary at different speeds be designed fend. The usual reaction time is between 10 min and 4 hours, more preferably between 30 min and 2 hours.

The inventive method is typically in industri ellen machines used to bleach Texti lien. The procedure can also be combined with each the other method, which makes it possible Material to be treated with the described components, the Enzyme and the mediator are brought into contact.

The inventive method has over known methods the following advantages. It has better efficiency, one faster bleaching effect through the new mediators. This made possible Furthermore, a lower enzyme dose. In addition, it does not happen Strength losses. All this also leads to an increased host The efficiency of the method compared to known Verfah ren.  

The invention will be further described in the following examples:
In the examples, mediators were purchased from the companies Aldrich, Merck or Janssen or synthesized according to literature references. The mediators used are listed in Tab. 1.

The laccase used in the examples was fermentative from Tra won verses verses.

Laccase activity was determined by the oxidation of 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonate), ABTS, Boehringer Mannheim, under aerobic conditions. The green color resulting from the enzymatic reaction was measured photometrically at 420 nm. The reaction temperature was 25 ° C, the pH 4.5. A laccase unit is the amount of enzymes that catalyzes the conversion of 1 M ABTS / min under the given conditions. To calculate the conversion, an extinction coefficient of 36,000 M ^-1 cm ^{-1 is} used.

example 1 Bleaching denim with different mediator substances from different classes experimental approach

Square cut pieces of dyed denim (9 g / 160 cm ² ) were incubated in a closed 500 ml jar in a total volume of 11.5 ml of liquid at 45 ° C together with Lacca se and one mediator substance each. The pH of the batches was 4.5 (100 mmol / l citrate / phosphate buffer). The additions contained in each case equal molar amounts (each 331 μmol) of the respective mediator substance. 17.8 IU of laccase were added per gram of fabric. After 3 hours of incubation (without stirring), the pieces of fabric were rinsed under running water until the washings showed no coloration. The pieces of cloth were dried in a sheet dryer, then pressed and visually evaluated with a suitable spectrophotometer. The evaluation was carried out as follows:
The degree of bleaching and the color was determined with a suitable for the colorimetric evaluation of reflective objects spectrophotometer CM 3700d Minolta according to the manufacturer's instructions. Measured without gloss and without UV. The brightness of the samples was determined as a percentage of the total reflection compared to a white standard (R 457), the color data was expressed by the coordinates in the color space as CIE standards (L *, a *, b *). L * is the measure of brightness (white = 100, black = 0). + a * means an increase of red (= decrease of green), -a * means a decrease of red (= increase of green), + b * means an increase of yellow (= decrease of blue), -b * means a decrease of yellow (= increase of blue).

The standard illuminant used was C / 2 °.

For the evaluation the software PP2000 of the company Opticontrol was used used.

The values of the treated fabrics became untreated with the values compared with reference substances. All given in the examples Measurements of brightness and color values are averaged values off three measurements each. The change in brightness (L *) and the change of the color coordinates (a *, b *) of the samples in Ver equal to untreated controls was calculated. The result se are reproduced in Tab.

Table 1

Change in brightness L * and color values (a *, b *) of indigo dyed denim using different mediators

A change in the brightness value (L *) of 5 is with the Au already readily recognizable as lightening, d. H. all tested compounds show significant bleaching action.

Example 2 Dependence of the bleaching of denim on the duration of the procedure

To show the time dependence of the bleaching process, the Bleaching effect assessed at different times.

Square cut pieces of dyed denim (9 g / 160 cm ² ) were placed in a closed 500 ml jar in a total volume of 11.5 ml at 45 ° C together with Lacca se and 331 μmol N-phenyl-N-hydroxy-acetamide ( NHA) for various periods of time. The pH of the batches was 4.5 (100 mmol / l citrate / phosphate buffer). 3.5 grams of laccase were added per gram of fabric. After incubation (without stirring), the pieces of fabric were rinsed under running water until the wash water no longer showed any coloration. The fabric pieces were dried in a sheet dryer, then pressed and evaluated optically be described with a ge suitable spectrophotometer as in Ex.

Table 2 shows the change of the brightness (L *) in dependency from the incubation period.

Time course of the bleaching of denim with NHA as media torsubstanz

Time course of the bleaching of denim with NHA as media torsubstanz

The brightness increases significantly over time. After 20 Min is already reached the final state, a continuation of Bleaching no longer brings improvement.

Example 3 Dependence of the bleaching of denim on the enzyme dose

To the dose-dependency of the textile bleach of the used Enzyme quantity to show the following approaches were made.

Square cut pieces of dyed denim (9 g / 160 cm ² ) were placed in a closed 500 ml vessel in a total volume of 11.5 ml at 45 ° C together with different enzyme dose laccase and 331 μmol N-phenyl-N-hydroxy Acetamid (NHA) incubated for 1 hour. The pH of the batches was 4.5 (100 mmol / l citrate / phosphate buffer). After incubation (without stirring), the pieces of fabric were rinsed under running water until the washings showed no coloration. The fabric pieces were dried in a sheet dryer, then pressed and visually evaluated with a suitable spectrophotometer (as in Ex. 1).

Table 3 shows the change of the brightness (L *) in dependency the Laccase dose.

Change in brightness (L *) depending on the laccase dose

Change in brightness (L *) depending on the laccase dose

A clear lightening is already with very little Laccase dose of 0.18 IU / g. Already from a dose of 0.9 IU / g is the maximum brightness value under the selected reaction conditions reached.

Example 4 Dependence of the bleaching of denim on the median dose

To the dose-dependency of the textile bleach of the used To show mediator standards, the following approaches were taken.

Square cut pieces of colored denim (9 g / 160 cm ² ) were placed in a closed 500 ml vessel in a total volume of 11.5 ml at 45 ° C together with 16 IU / g laccase and different amounts of mediator substance N-phenyl- N-hydroxy-acetamide (NHA) incubated for 2 hours. The pH of the batches was 4.5 (100 mmol / l citrate / phosphate buffer).

After incubation (without stirring), the pieces of fabric were submerged washed out running water until the wash water your coloring showed more. The pieces of fabric were in a sheet dryer ge dried, then pressed and with a suitable spectral Optically evaluated photometer (as in Ex. 1).

Table 4 shows the change in brightness (L *) a control depending on the median dose

Change in brightness (L *) depending on the media tordosis

Change in brightness (L *) depending on the media tordosis

Under the conditions shown is a direct relationship between mediator dose and bleaching effect in the dose range up to 10 mg NHA in the neck to see. Higher dosage does not help part. The required dosages are very low.

Example 5 Change of color location by treatment of denim with N- Phenyl-N-hydroxy-acetamide (NHA) as mediator substance and laccase

By treating denim with Laccase and Mediatorsub The substance can not only change in brightness (ΔL *) but it can also have a changed color impression  (Δa *, Δb *) are achieved. To demonstrate this effect was following approach.

Rectangular cut pieces of dyed denim (20 g / 355 cm ² ) were incubated in a closed 500 ml jar in a total volume of 23 ml of liquid at 45 ° C together with laccase and N-phenyl-N-hydroxy-acetamide (NHA). The pH of the batches was 4.5 (100 mmol / l citrate / phosphate buffer). The mixtures each contained 1.32 mmol NHAA. Per gram of fabric, 16.25 IU of laccase was added. After 2 hours of incubation (without stirring), the pieces of fabric were rinsed under running water until the washings no longer showed any coloration. A piece of fabric was additionally subjected to an alkaline extraction. For this purpose, the substance was incubated for 1 hour in 200 ml of a 40 mmol / l NaOH solution at 60 ° C. in a shaking water bath and then rinsed out under running water. The pieces of fabric were dried in a sheet dryer, then pressed and visually evaluated with a suitable spectrophotometer. Table 5 shows, in addition to the change of the brightness (ΔL *), the change of the color locus (Δa *, Δb *).

Table 5

Change in color location (a *, b *) by treatment of denim with N-phenyl-N-hydroxy-acetamide (NHA) and laccase.

The treatment changes the color of the fabric in the direction "more yellow" and shifted in the direction of "more green". The influence An additional extraction is significant.

Example 6 Bleaching and changing the color of hair by treatment with laccase and the mediator substance violuric acid

The ability to change the color of hair and the hair to bleach by treatment with laccase and a mediatorub Stanz was in the following experiment with violuric acid (Vio) as Me diatorsubstanz shown in principle.

1 g dark brown mane hair was in a closable 500 ml reaction vessel in a total volume of 40 ml together with Laccase and violuric acid are incubated. The batch contained 80 IU Lac case and 10 mg of violuric acid. After 30 min incubation at pH 4.5 (with 100 mmol / l citrate / phosphate buffer pH 4.5) and 45 ° C taken the hair, ge on a round filter three times with water Wash, air dry and with a suitable spit tralphotometer optically evaluated (as in Ex. 1). The hair samples was in a visually tight pack between two Measure glass plates in the beam path of the device. Table 6 shows the changes in the color location and the brightness of the treated Hair sample compared to an equal treated hair sample without Enzyme and mediator. The effect is clearly visible to the naked eye see. The used dark brown hair was after the treatment brunette.

Changes in the color location and the brightness of the treated Hair sample compared to an equal treated hair sample without Enzyme and mediator

Changes in the color location and the brightness of the treated Hair sample compared to an equal treated hair sample without Enzyme and mediator

The color of the hair becomes "more" by the treatment Red "and shifted towards" more yellow ".

Example 7 Decolorization of an aqueous indigo carmine solution with laccase under Using different mediators

To demonstrate the potential, indigo and related dyes To bleach was a suitably water-soluble indigo derivative, the indigo carmine (C.I. 73015, Sigma) with laccase and under different mediator substances (see Example 1) incubated.

Bleaching of the blue solution became photometric at 608 nm kinetically measured at 25 ° C. The evaluation was carried out by Be Calculation of the time which was necessary, the initial extinction (E. 608 nm = 0.35) of the dye solution. <01689 00070 552 001000280000000200012000285910157800040 0002019723912 00004 01570PAR <The batches were composed of 2 ml of buffer (100 mmol / l Citrate / phosphate pH 4.5), 200 μl of an indole carmine solution (23 mmol / L) and 20 μl of Laccase solution (0.3 IU, in water). Laccase and Dye showed no reaction under the measurement conditions at the. The bleaching reaction was started by adding 100 μl Mediator solution (11.3 μmol / ml, aqueous). Table 7 shows the ge measure half-lives of indigo carmine bleach.

Table 7

Bleaching a blue-colored (E 608 nm = 0.35) solution Indigo carmin by means of laccase and different mediator substances. The half lives (t 1/2) of the bleach are indicated.

mediator Half-life Control without mediator Fade (min) 1-hydroxybenzotriazole (HOBT) 44.4 N-hydroxyphthalimide (HPI) 198 N-phenyl-N-hydroxy-acetamide (NHA) 3.2 Violuric Acid (Vio) 23.8 2,2,6,6-tetramethylpiperidine-N-oxyl (Tempo) 11.7 N-methyl-N-hydroxy-benzamide 5.6 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt 1.3 3-nitroso-2,4-dihydroxy-quinoline (NC) 0.7

Mediator-free reference shows no decrease in absorbance. With all mediator substances used could be Hours incubation, the blue solution completely decolorized. This clearly shows that the indigo chromophore of the Lac case mediator system can be bleached.

Claims (8)

1. A process for bleaching dyed cellulosic fiber products such. As textiles using an oxidoreductase, an oxidoreductase suitable oxidizing agent and egg nes mediator, characterized in that the mediator is selected from the group of aliphatic, cycloaliphatic, heterocyclic or aromatic NO, NOH or
Links. 2. The method according to claim 1, characterized in that the Mediator at least one compound selected from the group of aliphatic, cycloaliphatic, heterocyclic or aromati compounds which contain at least one N-hydroxy, oxime, nitro So, N-oxyl or N-oxi function contains. 3. The method according to claim 1 or 2, characterized in that as an oxidizing agent air, oxygen, ozone, H ₂ O ₂ , organic peroxides, peracids such as peracetic acid, performic acid, per sulfuric acid, persaltic acid, Metachlorperoxibenzosäure, perchloric acid, perborates, peracetates, persulfates, Peroxides or oxygen species and their radicals such as OH, OOH, Singulettsauer fabric, superoxide (O ₂ ⁻), ozonide, dioxygenyl cation (O ₂ ⁺), Dioxira ne, dioxetanes or Fremy radicals are used. 4. The method according to one or more of claims 1 to 3, since characterized in that as oxidoreductase phenol-oxidizing Enzymes are used. 5. The method according to claim 4, characterized in that as phenol-oxidizing enzyme at least one enzyme from the group of Peroxidases and oxidases is used.   6. The method according to one or more of claims 1 to 5, since characterized in that the mediator in amounts of 0.005 to 1000 .mu.mol per g dyed fiber is used. 7. The method according to one or more of claims 1 to 6, since characterized in that it is at temperatures between 40 and 90 ° C is performed. 8. The method according to one or more of claims 1 to 7, since characterized in that it is at a pH in the range of pH 3 until pH 10 is carried out.