EP1404289A1

EP1404289A1 - 1-benzopyrane-derivatives and colouring agents containing the salts thereof

Info

Publication number: EP1404289A1
Application number: EP02714147A
Authority: EP
Inventors: Guido Sauter; Hans-Jürgen BRAUN; Raymond Brouillard; André FOUGEROUSSE; Christine Roehri-Stoeckel
Original assignee: Wella GmbH
Current assignee: Procter and Gamble Deutschland GmbH
Priority date: 2001-06-22
Filing date: 2002-02-06
Publication date: 2004-04-07
Also published as: BR0205662A; JP2004521144A; US20030196281A1; DE10130144A1; WO2003000214A1

Abstract

The invention relates to an agent for colouring fibres, said agent being obtained by mixing two components if necessary, by adding an alkalisation agent or an acid. Said agent is characterised in that one of the components (component A2) contains at least one electrophilic compound and the other component (component A1) contains at least one 1-benzopyrane of formula (Ia)/(Ib) or one 1-benzopyrylium-derivative of formula (I). The invention also relates to a method for the temporary colouration of keratin fibres, whereby hair is initially coloured with the above-mentioned known colouring agent and then discoloured by a reducing agent at any later given moment.

Description

1-Benzopyran derivatives and colorants containing their salts

The present invention relates to colorants, in particular for keratin fibers such as human hair, which contain 1-benzopyran derivatives and / or 1-benzopyrylium derivatives with CH-acidic groups in position 2 and / or position 4.

For dyeing fibers, for example hair, wool or furs, either direct dyes or oxidation dyes are generally used, in which the dyeing results from the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color takes place under the influence of oxidizing agents, which in some cases can damage the fibers. Furthermore, some oxidation dye precursors can, in exceptional cases, trigger allergies in people who are appropriately disposed. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties

EP-PS 0 847 749 discloses the use of a combination of diimino-isoindoline derivatives or 3-amino-isoindolone derivatives and compounds with primary or secondary amino groups for coloring keratin fibers without the addition of oxidizing agents. Farther it is known from DE-OS 43 35 623 to use a combination of indolinone derivatives and compounds with primary or secondary amino groups, heterocycles or aromatic hydroxy compounds for coloring keratin fibers. DE-OS 44 09 143 describes the use of isatin derivatives for coloring keratin fibers. DE-OS 197 45 292 discloses the use of a combination of malonaldehyde derivatives, such as malonaldehyde bis-dialkylacetals, and amines or CH-active compounds for coloring hair without the addition of oxidizing agents. Furthermore, DE-OS 197 17 280 discloses the use of a combination of certain heterocyclic aldehydes and amines or CH-active compounds for coloring hair without the addition of oxidizing agents.

However, the means and processes for dyeing fibers known from the prior art are not satisfactory in every respect. There was therefore still a great need for colorants which, under mild conditions, enable both intensive and gentle dyeings with a wide range of shades and, if desired, can be easily decolorized at any later point in time.

It is therefore an object of the present invention to provide a dyeing system which, without the addition of oxidizing agents (such as hydrogen peroxide), gently and at the same time intensively dyeing the fibers in the yellow, brown, green and violet range with good fastness properties (lightfastness , Fastness to washing, fastness to rubbing), which can be easily and gently removed at any time. Surprisingly, it has now been found that when using a combination (a) of certain 1-benzopyran derivatives and / or 1-benzopyrylium derivatives of the formula (l) / (la) / (lb), which are in position 2 and / or position 4 with a CH-acidic group are substituted, and (b) at least one electrophilic compound gently achieves colorations with excellent brilliance and depth of color, which can be completely removed again at any later point in time.

The present invention therefore relates to an agent for dyeing fibers, such as, for example, cotton jute, sisal, linen or modified natural fibers, such as, for example, regenerated cellulose, nitrocellulose, alkyl cellulose, hydroxyalkyl cellulose or acetyl cellulose, or synthetic fibers such as, for example, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers and polyester fibers, and in particular keratin fibers such as wool, silk or hair, in particular human hair, which is obtained by mixing two components, if necessary with the addition of an alkalizing agent or an acid, and is characterized in that the one component ( Component A2) contains at least one electrophilic compound and the other component (component A1) contains at least one 1-benzopyran of the formula (Ia) or formula (Ib) or a 1-benzopyrylium derivative of the formula (I),

(la) (I) (Ib)

where: X is an oxygen atom, sulfur atom or selenium atom; Rx and Ry are independently a hydrogen atom, an aryl group, C1 to C8 alkyl group, a C1 to C8 monohydroxyalkyl group, a C1 to C8 polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 to C8) alkyl group, a halogen atom (F, Cl, Br, J), an -O-COR ^a group, an S-COR ^a group, SR ^a group, a heteroaryl group, a phenyl group, a benzyl group, a - OCH ₂ aryl group or a CH ₂ -Rz group; Rx "and Ry" are independently a CH-Rz group; Rz is equal to a hydrogen atom, an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted aromatic carbocycle or heterocycle, a C1 to C8 alkyl group, a C1 to C8 monohydroxyalkyl group, a C1 to C8 Polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 to C8) alkyl group, a halogen atom (F, Cl, Br, J), a -OCOR ^a group, a nitro group, a cyano group, a -CO-R ^a group , a -CO-OR ^a group, a CO-OCF ₃ group, a CO-NHR ^a group, a CO-N (R ^a ) ₂ group, a SO ₂ -NH ₂ group, a SO ₂ -NHR ^a group, a SO ₂ -N (R ^a ) ₂ or a SO ₂ -OR ^a group, where R ^a is a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group is; with the condition that the tautomeric formula (la) only applies if Rx is equal to a CH ₂ -Rz group and the tautomeric formula (Ib) only applies if Ry is equal to a CH ₂ -Rz group, and Rz in Rx and Rx 'or Ry and Ry' each has the same meaning; R1, R2, R3, R4 and R5 are independently of one another a hydrogen atom, a straight-chain or branched C1 to C4 alkyl group, a C1 to C4 hydroxyalkyl group, a hydroxy group, a methoxy group, a benzyl group, a halogen atom ( F, Cl, Br, J), a nitro group, a nitroso group, a cyano group, a trifluoromethyl group, a -CHO group, a -COR ^b group, a -COOH group, a -CO ₂ R ^b group, one -OCOR ^b group, an -OCH ₂ aryl group, an -SO ₂ NH ₂ group, an -SO ₂ CHF ₂ group, an -SO ₂ CF ₃ group, a SO ₂ NH ₂ group, one SO ₂ NHR ^b group, a SO ₂ N (R ^b ) ₂ group, a SO ₂ R ^b group, an -NH ₂ group, a - (NH ₃ ) ⁺ group, an -NHR ^b group , one - (NH ₂ R ^b ) ⁺ group, one -N (R ^b ) ₂ group, one - (N (R ^b ) ₃ ) ⁺ group, one -NHCOR ^b group, one -NHCOOR ^b - Group, a -CH ₂ NH ₂ group, a -CH ₂ NHR ^b group, a -CH ₂ N (R ^b ) ₂ group, a -CO ₂ CF ₃ group or a -PO (OR ^b ) ₂ group, where R ^b is a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group; and

A ^" is the anion of an organic or inorganic acid, preferably a chloride, bromide, iodide, hydrogen sulfate, sulfate, toluenesulfonate, benzenesulfonate, monomethyl sulfate, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetraphenyl borate, tetraphenyl borate, Formate, acetate or propionate ion, with the chloride ion, tetrafluoroboration, acetate and hydrogen sulfate ion being particularly preferred. The compounds of formula (I) with Rx and / or Ry are preferably CH ₂ -Rz, with Rz are hydrogen.

Suitable compounds of the formulas (I), (la) and (Ib) include, in particular, 7-hydroxy-4-methylene-2-phenyl-4H-1-benzopyran, 7-methoxy-4-methylene-2- (3, 4,5-trimethoxyphenyl) -4H-1-benzopyran, 5,7-dihydroxy-4-methylene-2-phenyl-4H-1-benzopyran, 5,7-dimethoxy-4-methylene-2-phenyl-4H-1 -benzopyran, 4-methylene-4H-1-benzopyran, 4-methylene-2-phenyl-4H-1 -benzopyran, 7-amino-4-methylene-2-phenyl-4H-1 -benzopyran, 7-dimethylamino-4 - methylene-2-phenyl-4H-1-benzopyran, 4-methylene-7-nitro-2-phenyl-4H-1-benzopyran, 2-methylene-2H-1-benzopyran, 2-methylene-4-phenyl-2H -1-benzopyran, 2-methylene-4-methyl-2H-1-benzopyran, and 4-methylene-2-methyl-4H-1-benzopyran and their salts; where the 7-hydroxy-4-methyl-2-phenyl-1-benzopyrylium chloride, 7-methoxy-4-methyl-2- (3,4,5-trimethoxyphenyl) -1-benzopyrylium chloride, 5, 7-dihydroxy-4-methyl-2-phenyl-1-benzopyrylium chloride, 5,7-dimethoxy-4-methyl-2-phenyl-1-benzopyrylium chloride, 4-methyl-1-benzopyrylium chloride, 4-methyl-2-phenyl-1-benzopyrylium chloride, 7-amino-4-methyl-2-phenyl-1 - benzopyrylium chloride, 7-dimethylamino-4-methyl-2-phenyl-1 - benzopyrylium chloride, 4-methyl-7-nitro-2-phenyl-1-benzopyrylium chloride, 2-methyl-1-benzopyrylium chloride, 2-methyl-4-phenyl-1-benzopyrylium chloride, 7-hydroxy-2,4- dimethyl-1-benzopyrylium chloride, 5,7-dihydroxy-2,4-dimethyl-1-benzopyrylium chloride, 7-dimethylamino-2,4-dimethyl-1-benzopyrylium chloride and 2,4-dimethyl-1 - benzopyrylium chloride, are particularly preferred. According to the present invention, “electrophilic compounds” are understood to mean compounds which can form unsaturated carbon-carbon bonds by reaction on the nucleophilic carbon of the CH — Rz group in Rx 'or Ry' from formula (la) or formula (Ib). Suitable electrophilic compounds therefore contain an electrophilic reaction center such as, for example, a carbonyl carbon, imine carbon or a sp ² hybridized carbon atom activated by a hetero atom. Examples of suitable electrophilic compounds are in particular carbonyl compounds, imine compounds and substituted 1-alkyl-quinolinium derivatives of the formulas (IIIa) and (Mb),

in which the residual group R6 is a straight-chain or branched C1 to C8 alkyl group, a C1 to C8 monohydroxyalkyl group, a C2 to C8 polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 to C8) alkyl group or is a thio (C1 to C8) alkyl group; the radical groups R7, R8, R9, R10, R11 and R12 independently of one another are equal to a hydrogen atom, a straight-chain or branched C1 to C4 alkyl group, a straight-chain or branched C1 to C4 hydroxyalkyl group, a hydroxy group, a methoxy group, an ethoxy group, a benzyl group, a halogen atom (F, Ci, Br, J), a nitro group, a nitroso group, a cyano group, a trifluoromethyl group, a -CHO group, a -COR ^c group, a -COOH group, a -CO ₂ R ^c group, a -OCOR ^c group, one -O-S0 ₂ CF ₃ group, an -OCH ₂ aryl group, an -SO ₂ NH ₂ group, an -SO ₂ CHF ₂ group, an -SO ₂ CF ₃ group, an SO ₂ NH ₂ Group, a SO ₂ NHR ^c group, a SO ₂ N (R ^c ) ₂ group, a SO ₂ R ^c group, an -NH ₂ group, a - (NH ₃ ) ⁺ group, a - NHR ^C group, a - (NH ₂ R ^C ) ⁺ group, a -N (R ^C ) ₂ group, a - (N (R ^C ) ₃ ) ⁺ group, a -NHCOR ^c group, one -NHCOOR ^c group, a -CH ₂ NH ₂ group, a -CH ₂ NHR ^C group, a -CH ₂ N (R ^C ) ₂ group, a -CO ₂ CF ₃ group or a -PO ( OR ^c ) ₂ group, where R ^c is a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group;

Hai represents an iodine atom, bromine atom, chlorine atom or a methoxy group, ethoxy group, CF ₃ -SO ₂ -O group, aryl-SO ₂ -O group, (SO ₃ ) ^' group, with the chlorine atom and the ethoxy group being preferred are; and A ^"has the meaning given above.

The compounds of the formulas (IIIa) and (IIb) are known from the literature and can be used, for example, using standard synthesis methods known from the literature, as described, for example, in US Pat. No. 3,149,105 and GB Pat. No. 1,102,891 or by T.G. Deligeorgiev et al. in Dyes and Pigments, 1999, pages 49-54 and G.B. Bariin et al. in J. Chem. Soc. Perkin Trans. 2, 1975, pages 298-302.

Examples of suitable carbonyl compounds and imine compounds are: 4-hydroxy-3-methoxy-benzaldehyde (vanillin), 3-hydroxy-4-methoxy-benzaldehyde (isovanillin), 3,4-dihydroxy-benzaldehyde, 4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxy-benzaldehyde, 4-dimethylaminobenzaldehyde, 4-methyl-5-imidazole carboxaldehyde, 4-dimethylamino-cinnamaldehyde, 4-hydroxy-2- methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4'-hydroxy-biphenyl-1-carbaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3 , 4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, indole -3-carbaldehyde, benzene-1,4-dicarbaldehyde, 4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquinone, 4-carboxybenzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4 -hydroxy- cinnamaldehyde, 3-methoxy-4- (1-pyrrolidinyl) -benzaldehy d, 4-diethylamino-3-methoxybenzaldehyde, 1,2-phthalaldehyde, pyrrole-2-aldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde, chromone-3-carboxaldehyde, 6-methyl-4-oxo-1 ( 4H) -benzopyran-3-carbaldehyde, N-methylpyrrole-2-aldehyde, 5-methyl-furfural, 6-hydroxychromene-3-carboxaldehyde, 6-methylindole-3-carboxaldehyde, 4-dibutylamino-benzaldehyde, N-ethylcarbazole -3-aldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde, 5- (4- (diethylamino) phenyl) -2,4-pentadienal, 2,3-thiophene-dicarboxaldehyde, 2,5-thiophene dicarboxaldehyde, 2-methoxy-1-naphthaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde and 4-nitrobenzaldehyde, 4 - (((2-hydroxyethyl) imino) rnethyl ) -2-methoxyphenol, 5 - (((2-hydroxyethyl) imino) methyl) -2-methoxyphenol, 2,6-Dimethoxy-4 - (((2-hydroxyethyl) imino) methyl) phenol, 4 - (((2-hydroxyethyl) imino) methyl) phenol, 1, 2-dihydroxy-4 - (((2nd -hydroxyethyl) imino) - methyl) benzene, N, N-dimethyl-4 - (((2-hydroxyethyl) imino) methyl) aniline, 1, 2-dihydroxy-3 - (((2-hydroxyethyl) imino) methyl ) benzene, 4 - (((3-hydroxypropyl) imino) methyl) phenol, 2,6-dimethoxy-4 - (((3-hydroxypropyl) imino) methyl) phenol, 4 - (((2,3 -Dihydroxypropyl) imino) methyl) phenol, 2,6-dimethoxy-4 - (((2,3-dihydroxypropyl) imino) methyl) phenol, 2 - [(4-hydroxy-benzylidene) amino] propane-1, 3-diol, 2 - [(4-hydroxy-3,5-dimethoxybenzylidene) amino] propane-1,3-diol, 4 - (((2-hydroxy-2-phenylethyl) imino) methyl ) phenol, 2,6-dimethoxy-4 - (((1-phenyl-2-hydroxyethyl) imino) methyl) phenol, 4 - (((2-hydroxyphenyl) imino) methyl) phenol, 2,6-dimethoxy 4 - (((2-hydroxyphenyl) imino) methyl) phenol, 5-guanidino-2- [(4-hydroxybenzylidene) amino] pentanoic acid, 2 - [(4-dimethylamino-naphthalene-1-ylmethylene) - amino] ethanol, 5-guanidino-2 - [(4-hydroxy-3,5-dimethoxybenzylidene) amino] pentanoic acid , 2 - [(4-Hydroxy-3,5-dimethoxybenzylidene) amino] -3- (3H-imidazol-4-yl) propanoic acid, 2 - [(4-hydroxybenzylidene) amino] -3 - (3H-imidazol-4-yl) propanoic acid, 2 - [(4-hydroxy-3,5-dimethoxy-benzylidene) amino] -3- (1H-indol-3-yl) propanoic acid, 2- [ (4-hydroxybenzylidene) amino] -3- (1 - indol-3-yl) propanoic acid, 2 - (((2-hydroxyethyl) imino) methyl) phenol, 1, 2-dihydroxy-3- ( ((2-hydroxyethyl) imino) methyl) benzene, 1,2,3-trihydroxy-4 - (((2-hydroxyethyl) imino) methyl) benzene, 1,2,3,4-tetrahydroxy-5- ( ((2-hydroxyethyl) imino) methyl) benzene and 1, 2,4-trihydroxy-4 - (((2-hydroxyethyl) imino) methyl) benzene.

The carbonyl compounds can also be produced in situ by enzymatic oxidation of corresponding aryl alcohols and benzyl alcohols With the help of one or more suitable oxidation enzymes.

Suitable aryl alcohols and benzyl alcohols include, for example, the following compounds: benzyl alcohol, 4-hydroxy-benzyl alcohol, 4-hydroxy-3-methoxy-benzyl alcohol (vanillyl alcohol), 3-hydroxy-4-methoxy-benzyl alcohol (isovanillyl- alcohol), 3,5-dimethoxy-4-hydroxy-benzyl alcohol, 3,4-dihydroxy-benzyl alcohol, 2-hydroxy-3-methoxy-benzyl alcohol, 4-ethoxy-benzyl alcohol, 4-carboxybenzyl alcohol, 2,5-dihydroxy -benzyl alcohol, 2,4-dihydroxy-benzyl alcohol, 2-hydroxy-benzyl alcohol, 3,5-dimethoxy-4-hydroxy-benzyl alcohol, 4-hydroxy-2-methoxy-benzyl alcohol, 2,4-dimethoxy-benzyl alcohol, 2,3 -Dimethoxy-benzyl alcohol, 2,5-dimethoxy-benzyl alcohol, 3,5-dimethoxy-benzyl alcohol, 3,4-methylenedioxy-benzyl alcohol, 3,4-dimethoxy-benzyl alcohol, 3-ethoxy-4-hydroxy-benzyl alcohol, 3.5 -Dimethyl-4-hydroxy-benzyl alcohol, 3,4-dimethoxy-5-hydroxy-benzyl alcohol, 3,4,5-trimethoxy-benzyl alcohol, 2,4,6-trihydroxy-benzyl alcohol, 3,4,5-trihydroxy-benzyl - alcohol, 2,3,4-trihydroxy-benzyl alcohol, 3,5-di tert-butyl-4-hydroxy-benzyl alcohol, 2-nitro-benzyl alcohol, 3-nitro-benzyl alcohol, 4-nitro-benzyl alcohol, 2-amino-benzyl alcohol, 3-amino-benzyl alcohol, 3-amino-4-methyl-benzyl alcohol , 3,5-diamino-benzyl alcohol, 4-amino-benzyl alcohol, 4-dimethylamino-benzyl alcohol, 4-diethylamino-2-hydroxy-benzyl alcohol, 4-diethylamino-3-methoxy-benzyl alcohol, 4-dimethylamino-2-methoxy-benzyl alcohol , 4-dibutylamino-benzyl alcohol, 3-methoxy-4- (1 - pyrro! Idinyl) benzyl alcohol, (4-methoxy-naphthalen-1-yl) -methanol, (4-dimethylamino-naphthalene-1 - yl) -methanol, 2- (hydroxymethyl) -1-naphtol, 1-naphthalene-methanol, 2-naphthalene-methanol, (2-methoxy-naphtalin-1-yl) -methanol, 4-hydroxymethyl-naphthalene-1 -ol, 4'-hydroxymethyl-biphenyl-4- ol, (4-hydroxymethylphenyl) methanol, 4- (3-hydroxypropenyl) -2-methoxyphenol, 4- (3-hydroxypropenyl) -2,6-dimethoxyphenol, 3- (4th -Dimethylamino-phenyl) -prop-2-en-1-ol, 5- (4- (diethylamino-phenyl) - penta-2,4-dien-1-ol, thiophene-2-yl-methanol, (5- Hydroxymethyl-thiophene-2-yl) methanol, thiophene-3-yl-methanol, (1 f -pyrrol-2-yl) -methanol, (1-methyl-1 H-pyrrol-2-yl) -methanol, 5 -Methyl-furan-2-yl) -methanol, (1H-indol-3-yl) -methanol and (6-methyl-1H-indol-3-yl) -methanol.

In principle, any enzyme which can catalyze the oxidation of the alcohol to an aldehyde or ketone can be used as the "oxidation enzyme". Examples of such enzymes, without being limited to them, are: alcohol dehydrogenases (EG Classification 1.1.1.-), alcohol oxidases (EG Classification 1.1.2.- and 1.1.3.- and 1.1.99.-), Flavin oxidases (EC Classification 1.2.-), laccases (EC Classification 1.4 .--), peroxidases (EC Classification 1.11.1.-), hydroxylases and monooxygenases (EC Classification 1.13.12.- and 1.13.99.-), whereby Enzymes optimized (for example genetically modified) for the oxidation of the alcohols used are particularly preferred.

The enzyme is preferably used in an amount of 5-100 units per millimole of substrate (alcohol), where one unit of enzyme activity indicates the amount of enzyme required to catalyze the oxidation of 1 micromole of alcohol per minute.

As suitable substituted 1-alkyl-quinolinium compounds of the formulas

(lla) and (Mb) can be specifically called:

4-chloro-1-ethyl-quinolinium salts, 4,7-dichloro-1-ethyl-quinolinium salts, 4-chloro-1-ethyl-7-trifluoromethyl-quinolinium salts, 4-chloro-1-ethyl-6-nitroquinolinium salts, 4-chloro-1-methyl-quinolinium salts, 4-methoxy-1-methyl-quinolinium salts, 4-ethoxy 1-methyl-quinolinium salts, 4-ethoxy-1-ethyl-quinolinium salts, 4-iodo-1-methyl-quinolinium salts, 4-chloro-1 - methyl-2-phenyl-quinolinium salts, 4-chloro-1-methyl-3- [(methylphenylamino) sulfonyl] quinolinium salts, 4-chloro-2 - [[[4- (dimethylamino) phenyl] imino] methyl] -6-methoxy-1-methylquinolinium salts, 4-chloro-1-ethyl -3- [(phenylamino) sulfonyl] quinolinium salts, 4-chloro-6-dimethylcarbamoyl-1-methyl-quinolinium salts, 4-chloro-1-ethyl-6-sulfamoyl-quinolinium salts, 4-chloro-1-ethyl-6- 6- formyl-quinolinium salts, 4-chloro-1-ethyl-7-nitro-quinolinium salts, 4-chloro-1-ethyl-7-methoxy-quinolinium salts, 2-chloro-1-methyl-quinolinium salts, 2,6-dichloro-1 - methyl-quinolinium salts and 2-chloro-1-methyl-4-trifluoromethanesulfonyloxy-quinolinium salts, the 4-chloro-1-ethyl-quinolinium tetrafluoroborate, 4 , 7-dichloro-1-ethyl-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-7-trifluoromethyl-quinolinium, 4-chloro-1-ethyl-6-nitroquinolinium tetrafluoroborate, 4-chloro-1-methyl-quinolinium -chloride, 4-methoxy-1-methyl-quinolinium tetrafluoroborate, 4-iodo-1-methyl-quinolinium iodide, 4-chloro-1-methyl-2-phenyl-quinolinium tetrafluoroborate, 4-chloro-1-methyl-3 - [(methylphenylamino) sulfonyl] quinolinium methyl sulfate, 4-chloro-2 - [[[4- (dimethylamino) phenyl] imino] methyl] -6-methoxy-1-methylquinolinium chloride, 4 -Chloro-1-ethyl-3 - [(phenylamino) sulfonyl] quinolinium tetrafluoroborate, 4-chloro-6-dimethylcarbamoyl-1-methyl-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-6-sulfamoyl-quinolinium- tetrafluoroborate, 4-chloro-1-ethyl-6-formyl-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-7-nitro-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-7-methoxy-quinolinium tetrafluoroborate, 2-chloro-1-methyl-quinolinium-tetrafluoroborate, 2,6-dichloro-1-methyl-quinolinium tetrafluoroborate and 2-chloro-1-methyl-4-trifluoromethanesulfonyloxy-quinolinium tetrafluoroborate are particularly preferred.

The compounds of the formulas (I) / (Ia) / (Ib) are kept separate from the electrophilic compounds until shortly before use. The colorant according to the invention therefore generally consists of two components, namely a colorant (A1) which contains the compounds of the formula (I) / (la) / (Ib) and, where appropriate, substantive dyes, and a further colorant (A2) which contains the electrophilic compounds and optionally substantive dyes. These two components are mixed into a ready-to-use dye immediately before use and then applied to the fiber to be dyed. Of course, it is also possible for one or both components to consist of several individual components which are mixed together before use. However, a two-component kit consisting of an agent of component (A1) and an agent of component (A2) is particularly preferred.

Although the use of the aforementioned agent without the addition of oxidizing agents is preferred because of the better protection of the fiber, use of the aforementioned coloring agent in conjunction with oxidizing agents is readily possible, for example if simultaneous bleaching of the fiber is desired or if customary oxidation dye precursors are added to the coloring agent should be. The compounds of the formulas (I) / (Ia) / (Ib) and the electrophilic compound are in the respective color carrier composition (component (A1) or component (A2)) in a total amount of about 0.02 to 20 percent by weight, preferably 0, 2 to 10 percent by weight, wherein in the ready-to-use colorant obtained by mixing components (A1) and (A2), the compounds of the formulas (I) / (Ia) / (Ib) and the electrophilic compound in each case in a total amount of about 0 , 01 to 10 percent by weight, preferably 0.1 to 5 percent by weight, are included.

Furthermore, the colorant according to the invention can optionally additionally contain customary, physiologically acceptable, direct dyes from the group of acidic or basic dyes, nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes.

The substantive dyes can be used in component (A1) and / or component (A2) in a total amount of about 0.02 to 20 percent by weight, preferably 0.2 to 10 percent by weight, the total amount of substantive dyes in the ready-to-use colorants obtained by mixing components (A1) and (A2) is about 0.01 to 10 percent by weight, preferably 0.1 to 5 percent by weight.

The preparation form for the ready-to-use colorant and components (A1) and (A2) can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. Other suitable forms of preparation are a cream, a gel Foam or an emulsion. Their composition represents a mixture of the compounds of the formulas (I) / (Ia) / (Ib) and / or the electrophilic compounds with the additives customary for such preparations.

Customary additives used in colorants in solutions, creams, emulsions, gels or foams are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, n-propanol and isopropanol or glycols such as glycerol and 1,2-propanediol, and also wetting agents or emulsifiers the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, oxyethylamides, oxyethylamides, ethoxylated fatty acid fatty acids higher fatty alcohols, starch or cellulose derivatives, perfumes, hair pretreatment agents, conditioners, hair swelling agents, preservatives, petroleum jelly, paraffin oil and fatty acids as well as care products such as katio African resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The constituents mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight (based on the colorant), the thickeners in an amount of about 0.1 to 30 percent by weight ( based on the colorant) and the care substances in a concentration of about 0.1 to 5 percent by weight (based on the colorant). The pH of the ready-to-use colorant is generally about 3 to 11, preferably about 1 to 6, with a pH of 1 to 3 being particularly preferred. The pH of the ready-to-use colorant is obtained when the component (A1) containing the compounds of the formula (I) and / or (la) / (lb) containing the compounds of the formula (I) is mixed with the electrophilic component (A2) as a function of the pH of the components (A1) and (A2) and the mixing ratio of these two components. If necessary, after mixing components (A1) and (A2), the pH of the ready-to-use coloring agent can be adjusted to the desired value by adding an alkalizing agent or an acid.

To adjust the pH of the ready-to-use agent and component (A1) or (A2), alkalizing agents such as, for example, alkanolamines, alkylamines, alkali metal hydroxides or ammonium hydroxide and alkali metal carbonates or ammonium carbonates or acids such as, for example, lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid , Citric acid, ascorbic acid and boric acid can be used.

The ready-to-use colorant is obtained immediately before use by mixing the component (A1) containing the compounds of the formulas (I) and / or (la) / (lb) with the component (A2) containing the electrophilic compound (optionally with the addition of an alkalizing agent or an acid) and then applied to the fiber. Depending on the desired depth of color, this mixture is left for 5 to 60 minutes, preferably 15 to 30 minutes, at a temperature of 20 to 50 degrees Celsius, in particular at 30 to 40 degrees Celsius act. The fiber is then rinsed with water and, if necessary, washed with a shampoo.

The colorant according to the invention enables a wide range of color shades in the range from yellow-red to blue and brown-black with excellent fastness properties, with a gentle, uniform and permanent coloring of the fibers, in particular of keratin fibers, such as human hair, for example, even without the addition of oxidizing agents becomes.

Surprisingly, the dyeings obtained in this way can be completely and gently removed again at any time using reducing agents.

Another object of the present invention is therefore a process for dyeing and later decolorizing keratin fibers, such as wool, silk or hair and in particular human hair, in which the fiber is dyed with a dyeing agent (A) according to the invention and at any later point in time the coloring is removed again with a decolorizing agent (B), component (B) containing at least one sulfite, for example an ammonium sulfite, alkali sulfite or alkaline earth sulfite, in particular sodium sulfite or ammonium sulfite, as the decolorizing agent.

The total amount of sulfites in component (B) is about 0.1 to 10 percent by weight, preferably about 2 to 5 percent by weight. The agent for decolorizing the fibers dyed with the colorant (A) (hereinafter referred to as "decolorizing agent") can be in the form of an aqueous or aqueous-alcoholic solution, as a gel, cream, emulsion or foam, the decolorizing agent both in the form of a one-component preparation and also In addition to the powder form to protect against dust formation, the decolorizing agent can also be made up as a tablet - also as an effervescent tablet or granulate - before use with cold or warm water, optionally with the addition of one or more of the The additives and auxiliaries mentioned below, the decolorizing agent, but it is also possible that these additives and auxiliaries (if they are in solid form) are already contained in the decolorizing powder or decolorizing granulate or the effervescent tablet. By wetting the powder with oils or waxes erfor if necessary, the formation of dust can be reduced.

The decolorizing agent can additionally contain additives and auxiliaries, such as, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, n-propanol and isopropanol, glycol ethers or glycols such as glycerol and in particular 1,2-propanediol, and also wetting agents or emulsifiers from the classes of the anionic , cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyltrimethylammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, oxyethylated fatty alcohols, fatty acids, higher fatty alcohol alcohols, fatty acid alcohols, fatty acid alcohols, higher fatty alcohol alcohols, fatty acid alcoholic fatty acids, higher fatty alcohol alcohols, fatty acid alcoholic fatty acids, higher fatty alcohol alcohols, fatty acid alcoholic fatty acids, higher fatty alcohol alcohols, fatty acid alcoholic fatty acids, higher fatty alcohol alcohols, furthermore or cellulose derivatives, Perfumes, hair pretreatment agents, conditioners, hair swelling agents, preservatives, petroleum jelly, paraffin oil and fatty acids as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine.

The pH of the decolorizing agent is about 3 to 8, in particular about 4 to 7. If necessary, the desired pH can be adjusted by adding suitable acids, for example α-hydroxycarboxylic acids such as lactic acid, tartaric acid, citric acid or malic acid, phosphoric acid, acetic acid, glycolic acid, salicylic acid , Glutathione or gluconic acid lactone, or else alkalizing agents such as alkanolamines, alkylamines, alkali hydroxides, ammonium hydroxide, alkali carbonates, ammonium carbonates or alkali phosphates.

The exposure time of the decolorizing agent is 5 to 60 minutes, in particular 15 to 30 minutes, depending on the color and temperature to be decolorized (about 20 to 50 degrees Celsius), the decolorization process being accelerated by the application of heat. After the exposure time of the decolorizing agent has ended, the hair is rinsed with water and, if necessary, washed with a shampoo.

Although component (B) is particularly well suited for decolorizing keratin fibers dyed with the colorant (A), in particular human hair, component (B) can in principle also be used for decolorizing other natural or synthetic fibers dyed with the colorant (A) such as cotton, viscose, nylon, cellulose acetate can be used. The following examples are intended to explain the subject in more detail without restricting it to these examples.

B e i s p i e l e

Example 1.1 to 7.2 hair dye

Component A1

Compound of the formula (l) / (la) / (lb) amounts given in Table 1-7 cetylstearyl alcohol 12.0 g

Polyethylene glycol octadecyl ^ether (Brij® 78 P from Fluka) 2.8 g

Ethanol 24.8 g

Water, fully desalinated ad 100.0 g

The cetylstearyl alcohol is melted at 80 ° C. The compound of the formula (I) / (Ia) / (Ib) is added to a hot (70 ° C.) mixture of polyethylene glycol octadecyl ether, water and ethanol and dissolved by stirring. This hot mixture is then added to the melted cetylstearyl alcohol and stirred until a cream is obtained. If necessary, the pH of the cream can be adjusted to 2-3 with 90% lactic acid.

Component A2

Carbonyl compound / imine compound or

Compound of the formula (Ila) / (IIb) amounts given in Table 1-7

Cetylstearyl alcohol 12.0 g

Polyethylene glycol octadecyl ^ether (Brij® 78 P from Fluka) 2.8 g

Ethanol 24.8 g

Water, fully desalinated ad 100.0 g

Variant 1: carbonyl / imine compounds

The cetylstearyl alcohol is melted at 80 ° C. The polyethylene glycol octadecyl ether is heated to 80 ° C. with the water and the carbonyl compound dissolved in the ethanol. This mixture is added to the melted cetylstearyl alcohol and stirred until a cream is obtained. At room temperature, the pH of the cream is optionally adjusted to pH = 9-10 by adding 20% aqueous monoethanolamine solution (preparation of the in situ imine compound).

Variant 2: compounds of the formula (IIa) / (IIb)

The cetylstearyl alcohol is melted at 80 ° C. The polyethylene glycol octadecyl ether is heated to 80 ° C. with 95% of the water and added to the molten cetylstearyl alcohol and stirred until one

Cream results. At room temperature the compound of the formula

(lla) / (llb) added together with the ethanol and the remaining water.

Component A1 and component A2 are mixed together in a ratio of 1: 1. The pH of the mixture thus obtained is adjusted if necessary by adding a 90% lactic acid solution or a 20% monoethanolamine solution adjusted to the pH _m given in the examples. The ready-to-use hair dye thus obtained is applied to the hair and evenly distributed with a brush. After an exposure time of 30 minutes at 40 ° C, the hair is washed with a shampoo, then rinsed with lukewarm water and then dried.

The hair can be completely decolorized at any time (for example after several days or weeks) within 20 minutes at 40 ° C. with an acidic (pH = 5) 5% sodium sulfite solution (component B).

The dyeing and bleaching results are summarized in Tables 1 to 7 below.

The L * a * b * color measurement values given in the present examples were determined using a color measuring device from Minolta, type Chromameter II. Here, the L-value stands for the brightness (i.e. the lower the L-value, the greater the color intensity), while the a-value is a measure of the red component (i.e. the larger the a-value, the greater the red component is larger). The b-value is a measure of the blue component of the color, the more negative the b-value, the greater the blue component.

Unless stated otherwise, all percentages in the present application represent percentages by weight. Table 1: Coloring results no. Component A1) pH = 2-3 color shade measured values component A2) pH = 4-5 after the

Coloring / decoloring

1.1 A1) 7-hydroxy-4-methyl-2-phenyl-1 - untreated hair: 63.30; -0.48; +10.40 benzopyrylium chloride: 3.14 g brown-red After staining: 26.64; +21.25; +13.13

A2) 4-hydroxy-3-methoxybenzaldehyde: 1.75 g after pH _m = 2.3 decolorization: light orange

1.2 A1) 7-hydroxy-4-methyl-2-phenyl-1 ■ untreated hair 63.30; -0.48; +10.40 benzopyrylium chloride: 3.14 g brown After staining: 24.06; +9.79; +7.89 A2) 3,5-dimethoxy-4-hydroxybenzaldehyde: 2.10 g after pH _m = 2.8 discoloration: light orange

Table 1: (photo replacement) no. Component A1) pH = 2-3 color shade measured values component A2) pH = 4-5 according to L a b

Coloring / decoloring

1.3 A1) 7-hydroxy-4-methyl-2-phenyl-1 - untreated hair 63.30; -0.48; +10.40 benzopyrylium chloride: 3.14 g green After staining: 26.54; +4.58; +13.39

A2) 4- (Dimethylamino) benzaldehyde:

1.72 g after pH _m = 2.6 decolorization: pale yellow

1.4 A1) 7-hydroxy-4-methyl-2-phenyl-1 ■ untreated hair: 63.30; -0.48; +10.40 benzopyrylium chloride: 3.14 g dark red After staining: 22.55; +33.09; +2.02 A2) 4-chloro-1-ethyl-quinolinium; tetrafluoroborate: 3.21 g pH _m = 7.9

Table 1: (continued) No. Component A1) pH = 2-3 hue Color measurement values component A2) pH = 4-5 after the L a b staining

1.5 A1) 7-hydroxy-4-methyl-2-phenyl-1 - untreated hair: 63.30; -0.48; +10.40 benzopyrylium chloride: 3.14 g brown After staining: 38.88; +12.12; +22.80

A2) 4-Dimethylamino-1-naphthaldehyde: 2.29 g pH _m = 2.4

Table 2: (continued) No. Component A1) pH = 2-3 hue Color measurement values Component A2) pH = 9-10 after coloration

2.3 A1) 7-methoxy-4-methyl-2- (3,4,5- untreated hair: 63,30; -0,48; +10.40 trimethoxy-phenyl) -1-benzopyτylium- green after dyeing: 44.24; -26.15; +13.38 chloride: 4.33 g

A2) 4- (Dimethylamino) benzaldehyde 1.72 g pH _m = 2.6

Table 6: (continued) No. Component A1) pH = 2-3 hue Color measurement values Component A2) pH = 4-5 after the color L from

6.4 A1) 7-hydroxy-2,4-dimethyl-1 - untreated hair: 63.30; -0.48; +10.40 benzopyrylium chloride: 2.42 g brown After staining: 46.81; +3.22; +38.83 A2) 3,5-dimethoxy-4-hydroxybenzaldehyde: 4.19 g pH _m = 7.0

6.5 A1) 7-hydroxy-2,4-dimethyl-1 - untreated hair: 63.30; -0.48; +10.40 benzopyrylium chloride: 2.42 g dark red After staining: 30.24; +54.22; +15.23 A2) 4-chloro-1-ethyl-quinolinium tetrafluoroborate; 6.43 g pH _m = 7.9

Claims

Patent claims

1. Agent for dyeing fibers, which is obtained by mixing two components, if necessary with the addition of an alkalizing agent or an acid, characterized in that one component (component A2) contains at least one electrophilic compound and the other component (component A1) contains at least one 1-benzopyran of the formula (Ia) / (Ib) or a 1-benzopyrylium derivative of the formula (I),

where: X is an oxygen atom, sulfur atom or selenium atom; Rx and Ry are independently a hydrogen atom, an aryl group, C1 to C8 alkyl group, a C1 to C8 monohydroxyalkyl group, a C1 to C8 polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 to C8) alkyl group, a halogen atom, an -O-COR ^a group, an S-COR ^a group, SR ^a group, a heteroaryl group, a phenyl group, a benzyl group, an -OCH ₂ aryl group or a CH ₂ RZ group; Rx ^* and Ry ^* are independently a CH-Rz group; Rz is equal to a hydrogen atom, an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted aromatic carbocycle or Heterocycle, a C1 to C8 alkyl group, a C1 to C8 mono-hydroxyalkyl group, a C1 to C8 polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 to C8) alkyl group, a halogen atom, an -OCOR ^a group, a nitro group, a cyano group, a -CO-R ^a group, a -CO-OR ^a group, a -CO-OCF ₃ group, a -CO-NHR ^a group, a -CO- N (R ^a ) ₂ group, an -SO ₂ -NH ₂ group, an -SO ₂ -NHR ^a group, an -SO ₂ -N (R ^a ) ₂ or an -SO ₂ -OR ^a group where R ^{a is} equal to a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group; with the condition that the tautomeric formula (la) only applies if Rx is equal to a CH ₂ -Rz group and the tautomeric formula (Ib) only applies if Ry is equal to a CH ₂ -Rz group, and Rz in Rx and Rx 'or Ry and Ry' each has the same meaning; R1, R2, R3, R4 and R5 independently of one another are equal to a hydrogen atom, a straight-chain or branched C1 to C4 alkyl group, a C1 to C4 hydroxyalkyl group, a hydroxy group, a methoxy group, a benzyl group, a halogen atom, one Nitro group, a nitroso group, a cyano group, a trifluoromethyl group, a -CHO group, a -COR ^b group, a -COOH group, a -CO ₂ R ^b group, a -OCOR group, a -OCH ₂ aryl Group, an -SO ₂ NH ₂ group, an -SO ₂ CHF ₂ group, an -SO ₂ CF ₃ group, an -SO ₂ NH ₂ group, an -SO ₂ NHR ^b group, an - SO ₂ N (R ^b ) ₂ group, an -SO ₂ R ^b group, an -NH ₂ group, an -NH ₃ ⁺ group, an -NHR ^b group, an -NH ₂ R ^{b +} group , an -N (R ^b ) ₂ group, an -N (R ^b ) ₃ ⁺ group, an -NHCOR group, an -NHCOOR ^b group, a -CH ₂ NH ₂ group, a -CH ₂ NHR ^b group, a -CH ₂ N (R ^b ) ₂ group, a -CO ₂ CF ₃ group or one -PO (OR ^b ) ₂ group, where R is a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group; and A ^" is the anion of an organic or inorganic acid.

2. Composition according to claim 1, characterized in that the compound of formula (I), (la) and (Ib) is selected from 7-hydroxy-4-methylene-2-phenyl-4H-1-benzopyran, 7-methoxy -4-methylene-2- (3,4,5-trimethoxyphenyl) -4H-1-benzopyran, 5,7-dihydroxy-4-methylene-2-phenyl-4H-1-benzopyran, 5,7-dimethoxy-4 -methylene-2-phenyl-4H-1-benzopyran, 4-methylene-4H-1-benzopyran, 4-methylene-2-phenyl-4H-1-benzopyran, 7-amino-4-methylene-2-phenyI-4H -1-benzopyran, 7-dimethylamino-4-methylene-2-phenyl-4H-1-benzopyran, 4-methylene-7-nitro-2-phenyl-4H-1-benzopyran, 2-methylene-2H-1-benzopyran , 2-methylene-4-phenyl-2H-1-benzopyran, 2-methylene-4-methyl-2H-1-benzopyran and 4-methylene-2-methyl-4H-1-benzopyran and their salts.

3. Composition according to claim 1, characterized in that the compound of formula (I), (la) and (Ib) is selected from 7-hydroxy-4-methyl-2-phenyl-1-benzopyrylium chloride, 7-methoxy -4-methyl-2- (3,4,5-trimethoxy-phenyl) -1-benzopyrylium chloride, 5,7-dihydroxy-4-methyl-2-phenyl-1-benzopyrylium chloride, 5,7-dimethoxy -4-methyl-2-phenyl-1 - benzopyrylium chloride, 4-methyl-1-benzopyrylium chloride, 4-methyl-2-phenyl-1-benzopyrylium chloride, 7-amino-4-methyl-2 -phenyl-1-benzopyrylium chloride, 7-dimethylamino-4-methyl-2-phenyl-1 - benzopyrylium chloride, 4-methyl-7-nitro-2-phenyl-1-benzopyrylium chloride, 2-methyl-1 -benzopyrylium chloride, 2-methyl-4-phenyl-1 -benzopyrylium- Chloride, 7-hydroxy-2,4-dimethyl-1-benzopyrylium chloride, 5,7-dihydroxy-2,4-dimethyl-1-benzopyrylium chloride, 7-dimethylamino-2,4-dimethyl-1 - benzopyrylium and 2,4-dimethyl-1-benzopyrylium chloride.

4. Agent according to one of claims 1 to 3, characterized in that the electrophilic compound is selected from carbonyl compounds, imine compounds and substituted 1-alkyl-quinolinium derivatives of the formula (Ila) and (IIb),

(lla) ( ^{| lb} > in which the residual group R6 is a straight-chain or branched C1 to C8 alkyl group, a C1 to C8 monohydroxyalkyl group, a C2 to C8 polyhydroxyalkyl group, a C1 to C8 alkoxy (C1 - to C8) alkyl group or a thio (C1 to C8) alkyl group; the residual groups R7, R8, R9, R10, R11 and R12 independently of one another are equal to a hydrogen atom, a straight-chain or branched C1 to C4 alkyl group, a straight-chain or branched C1 to C4 hydroxyalkyl group, a hydroxy group, a methoxy group, an ethoxy group, a benzyl group, a halogen atom, a nitro group, a nitroso group, a cyano group, a trifluoromethyl group, a -CHO group, a -COR ^c group , a -COOH group, a -CO ₂ R ^c group, an -OCOR ^c group, an -O-SO ₂ CF ₃ group, an -OCHgAryl group, an -SO ₂ NH ₂ group, one -SO ₂ CHF ₂ group, an -SO ₂ CF ₃ group, an SO ₂ NH ₂ group, a SO ₂ NHR ^c group, a SO ₂ N (R ^G ) ₂ group, a SO ₂ R ^c group, an -NH ₂ group, a - (NH ₃ ) ⁺ group, a -NHR ^C - Group, one - (NH ₂ R °) ⁺ group, one -N (R °) ₂ group, one - (N (R °) ₃ ) ⁺ group, one -NHCOR ⁰ group, one -NHCOOR ⁰ Group, a -CH ₂ NH ₂ group, a -CH ₂ NHR ° group, a -CH ₂ N (R ^C ) ₂ group, a -CO ₂ CF ₃ group or a -PO (OR °) ₂ group, where R ° is a hydrogen atom, an optionally substituted aromatic carbocycle or heterocycle or a C1 to C6 alkyl group;

Hai represents an iodine atom, bromine atom, chlorine atom or a methoxy group, ethoxy group, CF ₃ -SO ₂ -O group, aryl-SO ₂ -O group, (SO ₃ ) ^" group, with the chlorine atom and the ethoxy group being preferred and A ^* is the anion of an organic or inorganic acid.

5. Composition according to claim 4, characterized in that the carbonyl compound or imine compound is selected from 4-hydroxy-3-methoxy-benzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 3,4-dihydroxy-benzaldehyde, 4-hydroxy benzaldehyde , 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-methyl-5-imidazole carboxaldehyde, 4-dimethylamino-cinnamaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4 -hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4'-hydroxy-biphenyl-1-carbaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4, 6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, indole-3-carbaldehyde, benzene-1,4-dicarbaldehyde, 4-ethoxybenzaldehyde, 2-methyl-1, 4-naphthoquinone, 4-carboxy-benzaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 3-methoxy-4- (l-pyrrolidinyl ) -benzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 1,2-phthalaldehyde, pyrrole-2-aldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde, chromone-3-carboxaldehyde, 6-methyl-4-oxo 1 (4H) -benzopyran-3-carbaldehyde, N-methylpyrrole-2-aldehyde, 5-methyl-furfural, 6-hydroxychromene-3-carboxaldehyde, 6-methylindole-3-carboxaldehyde, 4-dibutylamino-benzaldehyde , N-ethylcarbazole-3-aldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde, 5- (4- (diethylamino) phenyl) -2,4-pentadienal, 2,3- Thiophene dicarboxaldehyde, 2,5-thiophene dicarboxaldehyde, 2-methoxy-1-naphthaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobene zaldehyde and 4-nitrobenzaldehyde, 4 - (((2-hydroxyethyl) imino) methyl) -2-methoxyphenol, 5 - (((2-hydroxyethyl) imino) methyl) -2-methoxyphenol, 2,6-dimethoxy-4- (((2-hydroxyethyl) imino) methyl) phenol, 4 - (((2-hydroxyethyl) imino) methyl) phenol, 1,2-dihydroxy-4 - (((2-hydroxyethyl) imino) - methyl) benzene, N, N-dimethyl-4 - (((2-hydroxyethyl) imino) methyl) aniline, 1,2-dihydroxy-3 - (((2-hydroxyethyl) imino) methyl) benzene, 4 - ((( 3-hydroxypropyl) imino) methyl) phenol, 2,6-dimethoxy-4 - (((3-hydroxypropyl) imino) methyl) phenol, 4 - (((2,3-dihydroxypropyl) imino) methyl) phenol , 2,6-Dimethoxy-4 - (((2,3-dihydroxypropyl) imino) methyl) phenol, 2 - [(4-hydroxybenzylidene) amino] propane-1,3-diol, 2 - [( 4-Hydroxy-3,5-dimethoxy-benzylidene) amino] propane-1,3-diol, 4 - ((((2-hydroxy-2-phenylethyl) imino) methyl) phenol, 2,6-dimethoxy -4 - (((1-phenyl-2-hydroxyethyl) imino) methyl) phenol, 4 - (((2-hydroxyphenyl) imino) methyl) phenol, 2,6-Dimethoxy-4 - (((2-hydroxyphenyl) imino) methyl) phenol, 5-guanidino-2- [(4-hydroxybenzylidene) amino] pentanoic acid, 2 - [(4-dimethylamino-naphthalene -1-y! Methylene) amino] ethanol, 5-guanidino-2 - [(4-hydroxy-3,5-dimethoxybenzylidene) amino] pentanoic acid, 2 - [(4-hydroxy-3,5 -dimethoxy-benzylidene) amino] -3- (3H-imidazol-4-yl) propanoic acid, 2 - [(4-hydroxybenzylidene) amino] -3- (3H-imidazol-4-yl) propanoic acid , 2 - [(4-Hydroxy-3,5-dimethoxy-benzylidene) aminp] -3- (1H-indol-3-yl) propanoic acid, 2 - [(4-hydroxy-benzylidene) amino] -3 - (1H-indol-3-yl) propanoic acid, 2 - (((2-hydroxyethyl) imino) methyl) phenol, 1, 2-dihydroxy-3 - (((2-hydroxyethyl) imino) methyl) benzene, 1 , 2,3-trihydroxy-4 - (((2-hydroxyethyl) imino) methyl) benzene, 1,2,3,4-tetrahydroxy-5 - (((2-hydroxyethyl) - imino) methyl) benzene and 1, 2,4-trihydroxy-4 - (((2-hydroxyethyl) imino) methyl) benzene.

6. Composition according to claim 4 or 5, characterized in that the carbonyl compound is produced in situ by enzymatic oxidation of corresponding aryl alcohols and benzyl alcohols with the aid of one or more suitable oxidation enzymes.

7. Composition according to claim 4, characterized in that the substituted 1-alkyl-quinolinium compound of the formula (IIa) and (IIb) is selected from 4-chloro-1-ethyl-quinolinium salts, 4,7-dichloro-1- ethyl quinolinium salts, 4-chloro-1-ethyl-7-trifluoromethyl-quinolinium salts, 4-chloro-1-ethyl-6-nitroquinolinium salts, 4-chloro-1-methylquinolinium salts, 4-methoxy-1-methyl quinolinium salts, 4-ethoxy-1-methyl-quinolinium salts, 4-ethoxy-1-ethyl-quinolinium salts, 4-iodo-1-methyl-quinolinium salts, 4-chloro-1-methyl-2-phenyl-quinolinium salts, 4-chloro- 1-methyl-3 - [(methylphenyl-amino) sulfonyl] -quinoliniumsalzen, 4-chloro-2 - [[[4- (dimethylamino) phenyl] imino] methyl] -6-methoxy-1-methylquinolinium salts, 4-chloro-1-ethyl-3 - [(phenylamino) sulfonyl] - quinolinium salts, 4-chloro-6-dimethylcarbamoyl-1-methyl-quinolinium salts, 4-chloro-1-ethyl-6-sulfamoyl-quinolinium salts, 4-chloro-1-ethyl-6-formyl-quinolinium salts, 4-chloro 1-ethyl-7-nitro-quinolinium salts, 4-chloro-1-ethyl-7-methoxy-quinolinium salts, 2-chloro-1-methyl-quinolinium salts, 2,6-dichloro-1-methyl-quinolinium salts and 2-chloro 1-methyl-4-trifluoromethanesulfonyloxy-quinolinium salts.

8. Composition according to claim 7, characterized in that the substituted 1-alkyl-quinolinium compound of the formula (IIa) and (IIb) is selected from 4-chloro-1-ethyl-quinolinium tetrafluoroborate, 4,7-dichloro- 1-ethyl-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-7-trifluoromethyl-quinolinium, 4-chloro-1-ethyl-6-nitroquinolinium tetrafluoroborate, 4-chloro-1-methyl-quinolinium chloride, 4- Methoxy-1-methyl-quinolinium tetrafluoroborate, 4-iodo-1-methyl-quinolinium iodide, 4-chloro-1-methyl-2-phenyl-quinolinium tetrafluoroborate, 4-chloro-1 - methyl-3 - [( methylphenylamino) sulfonyl] quinolinium methyl sulfate, 4-chloro-2 - [[[4- (dimethylamino) phenyl] imino] methyl] -6-methoxy-1-methylquinolinium chloride, 4-chloro 1-ethyl-3 - [(phenylamino) sulfonyl] quinolinium tetrafluoroborate, 4-chloro-6-dimethylcarbamoyl-1-methylquinolinium tetrafluoroborate, 4-chloro-1-ethyl-6-sulfamoyl-quinolinium tetrafluoroborate, 4 -Chloro-1-ethyl-6-formyl-quinolinium tetrafluoroborate, 4-chloro-1-ethyl-7-nitro-qu inolinium tetrafluoroborate, 4-chloro-1-ethyl-7-methoxy-quinolinium tetrafluoroborate, 2-chloro-1-methyl-quinolinium tetrafluoroborate, 2,6-dichloro-1-methyl-quinolinium tetrafluoroborate and 2-chloro- 1-methyl-4-trifluoromethanesulfonyloxy-quinolinium tetrafluoroborate.

9. Composition according to one of claims 1 to 8, characterized in that the ready-to-use preparation (A) has a pH of 3 to 11.

10. Composition according to one of claims 1 to 9, characterized in that the compound of formula (l) / (la) / (lb) in component (A1) in a total amount of 0.02 to 20 percent by weight and the electrophilic compound is contained in component (A2) in a total amount of 0.02 to 20 percent by weight.

11. Agent according to one of claims 1 to 10, characterized in that it contains the compound of formula (l) / (la) / (lb) and the electrophilic compound, based on the ready-to-use preparation, in each case in a total amount of 0.01 contains up to 10 percent by weight.

12. Composition according to one of claims 1 to 11, characterized in that the ready-to-use agent (A) and the components (A1) and (A2) are each in the form of a solution, an emulsion, a foam, a cream or a gel.

13. Composition according to one of claims 1 to 12, characterized in that component (A1) and / or (A2) additionally contains at least one substantive dye from the group of acidic or basic dyes, nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes.

14. Composition according to one of claims 1 to 13, characterized in that component (A1) and / or (A2) consists of several individual components.

15. Agent according to one of claims 1 to 14, characterized in that it is a hair dye.

16. A process for the temporary dyeing of keratin fibers, in which the keratin fiber is dyed with an agent according to one of claims 1 to 15 and the dyeing thus obtained is removed again at any later time by a sulfite-containing preparation (decolorizing agent).