Agent for dyeing keratin-based fibers Number:7,393,367 from the United States Patent and Trademark Office (PTO) owispatent An agent for dyeing keratin-containing fibers, especially human hair, is comprised of a cosmetic carrier, and (A) at least one compound of Formula I, ##STR00001## wherein each of R.sup.1, R.sup.2 and R.sup.3 is independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a hydroxyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a hydroxy C.sub.1-C.sub.6 alkyloxy group, a sulfonyl group, a carboxyl group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a hydroxy C.sub.2-C.sub.6 alkyloxycarbonyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a C.sub.2-C.sub.6 acyl group, a formyl group, a nitro group, a carbamoyl group --C(O)--NR.sup.4R.sup.5, or a --(CH.sub.2).sub.nNR.sup.6R.sup.7 group wherein each of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group or a C.sub.2-C.sub.6 hydroxyalkyl group; and n is number from 0 to 6, wherein R.sup.1 and R.sup.2 can form a 5- or 6-membered aromatic or heteroaromatic ring; and (B) at least one CH-acidic compound.<H keratin, fibers, Agent, for, dyein, 7393367.html, Patent, pto, 7393367

Title: Agent for dyeing keratin-based fibers

Abstract: An agent for dyeing keratin-containing fibers, especially human hair, is comprised of a cosmetic carrier, and (A) at least one compound of Formula I, ##STR00001## wherein each of R.sup.1, R.sup.2 and R.sup.3 is independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a hydroxyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a hydroxy C.sub.1-C.sub.6 alkyloxy group, a sulfonyl group, a carboxyl group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a hydroxy C.sub.2-C.sub.6 alkyloxycarbonyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a C.sub.2-C.sub.6 acyl group, a formyl group, a nitro group, a carbamoyl group --C(O)--NR.sup.4R.sup.5, or a --(CH.sub.2).sub.nNR.sup.6R.sup.7 group wherein each of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group or a C.sub.2-C.sub.6 hydroxyalkyl group; and n is number from 0 to 6, wherein R.sup.1 and R.sup.2 can form a 5- or 6-membered aromatic or heteroaromatic ring; and (B) at least one CH-acidic compound.

Patent Number: 7,393,367 Issued on 07/01/2008 to Gross, et al.

Inventors: Gross; Wibke (Dusseldorf, DE), Hoffkes; Horst (Dusseldorf, DE), Oberkobusch; Doris (Dusseldorf, DE), Muller; Helmut (Dusseldorf, DE), Brake; Carsten (Mulheim a.d. Ruhr, DE)
Assignee: Henkel Kommanditgesellschaft auf Aktien (Dusseldorf, DE)

Appl. No.: 11/937,464

Filed: November 8, 2007

Related U.S. Patent Documents


Application Number	Filing Date	Patent Number	Issue Date
PCT/EP2006/002707	Mar., 2006

Foreign Application Priority Data


May 12, 2005 [DE]			10 2005 022 790

Current U.S. Class: 8/405 ; 544/245; 8/406; 8/407; 8/410; 8/435; 8/565; 8/567; 8/573; 8/608; 8/613

Current International Class: A61Q 5/10 (20060101); C07D 239/00 (20060101)

Field of Search: 8/405,406,407,410,435,565,567,573,608,613 544/245

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6099592	August 2000	Vidal et al.
6284003	September 2001	Rose et al.
7105032	September 2006	Gross et al.

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Other References

STIC Search Report dated Mar. 24, 2008. cited by examiner .
H. Moehrle et al., Zum Identitatsnachweis von Coffein im Arzneibuch, 2. Mitt.: Struktur des Farbstoffs aus modifizierter Reaktion Pharmazie, Die, Govi Verlag, Eschborn, DE, Bd. 54 Nr. 4, (1999), Seiten 269-279. cited by other .
H. Baumann et al., Reaktionen der Methylenebasen von Oxazolidinonen und Pyrimidonen Justus Liebigs Annalen der Chemie, Verlag Chemie GmbH, Weinheim, DE, Bd. 717, (1968), pp. 124-136. cited by other .
C. Zviak, The Science of Hair Care, Chapter 7 pp. 248-250 and Chapter 8 pp. 264-267 Marcel Dekker, Inc. New York and Basel, (1986). cited by other.

Primary Examiner: Elhilo; Eisa B
Attorney, Agent or Firm: Drach; John E.

Parent Case Text

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation under 35 U.S.C. .sctn. 365(c) and 35 U.S.C. .sctn. 120 of International Application No. PCT/EP2006/002707, filed Mar. 24, 2006. This application also claims priority under 35 U.S.C. .sctn. 119 of German Patent Application No. DE 10 2005 022 790.2, filed May 12, 2005. Both the International Application and the German Application are incorporated herein by reference in their entireties.

Claims

The invention claimed is:

1. An agent for dyeing keratin-containing fibers, especially human hair, comprising a cosmetic carrier, and (A) at least one compound of Formula I, ##STR00029## wherein each of R.sup.1, R.sup.2 and R.sup.3 is independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a hydroxyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a hydroxy C.sub.1-C.sub.6 alkyloxy group, a sulfonyl group, a carboxyl group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a hydroxy C.sub.2-C.sub.6 alkyloxycarbonyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a C.sub.2-C.sub.6 acyl group, a formyl group, a nitro group, a carbamoyl group --C(O)--NR.sup.4R.sup.5, or a --(CH.sub.2).sub.nNR.sup.6R.sup.7 group wherein each of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group or a C.sub.2-C.sub.6 hydroxyalkyl group; and n is number from 0 to 6, wherein R.sup.1 and R.sup.2 can form a 5- or 6-membered aromatic or heteroaromatic ring; and (B) at least one CH-acidic compound.

2. The agent of claim 1 wherein R.sup.2 and R.sup.3 is a hydrogen atom.

3. The agent of claim 1 wherein the group R.sup.1 is a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a C.sub.1-C.sub.6 alkoxy group, a formyl group, a hydroxyl group, a halogen atom, a carboxy group or a nitro group.

4. The agent of claim 1 wherein the compound of Formula I is selected from the group consisting of: 3-Allyl-4-hydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-methoxybenzaldehyde, 3-Allyl-5-ethoxy-4-hydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-methyl benzaldehyde, 3-Allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-Diallyl-4-hydroxybenzaldehyde, 3-Allyl-4,5-dihydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-nitrobenzaldehyde, 3-Allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-Allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde).

5. The agent of claim 1 wherein Component (B) is selected from the group consisting of a compound of Formula (II) and/or Formula (III) ##STR00030## wherein each of R.sup.8 and R.sup.9 is independently a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy C.sub.1-C.sub.6 alkyl group, a R.sup.IR.sup.IIN--(CH.sub.2).sub.m-- group, wherein each of R.sup.I and R.sup.II is independently a hydrogen atom, a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group, wherein R.sup.I and R.sup.II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m stands for a number 2, 3, 4, 5 or 6, each of R.sup.10 and R.sup.12 is independently a hydrogen atom or a C.sub.1-C.sub.6 alkyl group, wherein at least one of the groups R.sup.10 and R.sup.12 id a C.sub.1-C.sub.6 alkyl group, R.sup.11 is a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkoxy group, a group R.sup.IIIR.sup.IVN--(CH.sub.2).sub.q--, wherein each of R.sup.III and R.sup.IV is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group and q is 1, 2, 3, 4, 5 or 6, wherein the group R.sup.11 together with one of the groups R.sup.10 or R.sup.12 can form a 5- or 6-membered aromatic ring that can be optionally substituted with a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkoxy group, a nitro group, a hydroxy group, a group R.sup.VR.sup.VIN--(CH.sub.2).sub.s--, wherein each of R.sup.V and R.sup.VI is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group and is 0, 1, 2, 3, 4, 5 or 6; Y is an oxygen atom, a sulfur atom or NR.sup.VII, wherein R.sup.VII is a hydrogen atom, an aryl group, a heteroaryl group, a C.sub.1-C.sub.6 alkyl group or a C.sub.1-C.sub.6 arylalkyl group; X.sup.- is a physiologically compatible anion; Het stands for an optionally substituted heteroaromatic group; X.sup.1 is a direct bond or a carbonyl group.

6. The agent of claim 1 wherein Component (B) is 1H-benzimidazol-2-ylacetonitrile [2-(cyanomethyl)benzimidazole] and wherein the agent further comprising a salt is selected from the group consisting of 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3,dipropyl,4-6-dimethyl-2-thioxo-pyrimidinium 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-3,4-dimethyl-2-oxo-quinazolinium and 1,2-Dihydro-3,4-dimethyl-2-thioxo-quinazolinium or a combination thereof wherein the anion of the salt is a physiologically compatible counter ion X.sup.-.

7. The agent of claim 1 further comprising at least one reactive carbonyl compound as Component (C) selected from the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxy-benzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4-hydroxy-2,3-dimethyl-benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2-hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methyl-benzaldehyde, 3,4-dihydroxy-5-methyl-benzaldehyde, 3,4-dihydroxy-6-methyl-benzaldehyde, 3,4-dihydroxy-2-methoxy-benzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodo-benzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-napthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino-benzaldehyde, 4-(1-imidazolyl)-benzaldehyde and piperonal.

8. The agent of claim 1 wherein the amount of each of the compounds of Formula I, the compounds of Component B, and optionally the compounds of Component C is from 0.03 to 65 mmol based on 100 g of the total colorant.

9. The agent of claim 8 wherein the amount is from 1 to 40 mmol, based on 100 g of the total colorant.

10. The agent of claim 1 further comprising color reinforcers selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine and mixtures thereof.

11. The agent of claim 1 further comprising from 0.01 to 6 wt. % of an oxidizing agents based on the application solution.

12. The agent of claim 11 wherein the oxidizing agent is H.sub.2O.sub.2.

13. The agent of claim 1 further comprising at least one developer component as an oxidation dye precursor and optionally at least one coupler component.

14. The agent of claim 1 further comprising at least one substantive dye.

15. The agent of claim 14 the amount of the substantive dye is from 0.01 to 20 wt. % based on the total colorant.

16. The agent of claim 1 further comprising anionic, zwitterionic or non-ionic surfactants.

17. A hair dye comprising a coloration component comprising a compound of Formula I as recited in claim 1 and a compound of Component (B) as recited in claim 1.

18. A method for dyeing keratin-containing fibers, especially human hair, comprising the steps of (a) contacting the hair with a composition comprising an agent of claim 1 and a cosmetic ingredient for about 15-30 minutes, and (b) removing the composition by rinsing.

19. The method of claim 18 wherein the composition is removed by washing with a shampoo.

20. The method of claim 18 wherein the keratin-containing fibers are bleached or colored with an oxidation colorant before step (a).

21. A compound of Formula (V) ##STR00031## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.8, R.sup.9, R.sup.11, R.sup.12 and X.sup.- are the same as defined in claim 5.

22. A compound of Formula (VI) ##STR00032## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.8, R.sup.9, R.sup.11 and X.sup.- are the same as defined in claim 5.

Description

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable

INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC

Not Applicable

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The invention relates to an agent for dyeing keratin-based fibers, particularly human hair, which comprises 3-allyl-4-hydroxybenzaldehyde and/or its derivatives in combination with CH-acidic compounds, the use of this combination in agents for dyeing keratin-containing fibers, for refreshing the color or nuancing previously colored keratin-containing fibers as well as a method for dyeing keratin-containing fibers, in particular, human hair.

Generally, either substantive dyes or oxidation dyes that result from oxidative coupling of one or more developer components with each other or with one or more coupler components are used for coloring fibers containing keratin. Coupler components and developer components are also called oxidation dye precursors.

Normally, primary aromatic amines with an additional free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino pyrazole derivatives as well as 2,4,5,6-tetramino pyrimidine and derivatives thereof are employed as the developer components.

Specific exemplary representatives are p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraminopyrimidine, p-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5-diaminophenoxy)ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5,4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

m-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as the coupling components. Particularly suitable coupling substances are .alpha.-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino) anisole (Lehmann's Blue), 1-phenyl-3-methylpyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis(2',4'-diaminophenoxy) propane, 2-chloro resorcinol, 4-chloro resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

(2) Description of Related Art, Including Information Disclosed Under 37 C.F.R. .sctn..sctn. 1.97 and 1.98

In regard to further typical dye components, reference is expressly made to the series "Dermatology", edited by Ch. Culnan and H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, volume 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250 (substantive dyes), and chapter 8, pages 264-267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", published by the European Union, obtainable in disk form from the Bundesverband Deutscher Industrie-und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel e.V., Mannheim.

Indeed, with the oxidation dyes, intensive colorations can be achieved with good fastness characteristics, but the development of the color normally occurs in the presence of oxidizing agents such as, for example H.sub.2O.sub.2, which in some cases can result in damage to the fibers. It still proves problematic to prepare oxidative hair colorations in the red tones having adequate fastness characteristics, especially with very good wash fastness and rubbing fastness. Furthermore, some of the oxidation dye precursors or certain mixtures of oxidation dye precursors sometimes have a sensitizing effect on people with delicate skin. The substantive dyes are applied under more gentle conditions, but their disadvantage is that the resulting colorations often possess only inadequate fastness characteristics.

The object of the present invention is to provide dyes for fibers containing keratin, especially human hair, which in regard to the color depth and fastness characteristics, such as for example light fastness, rubbing fastness and wash fastness as well as fastness to perspiration and to cold waving, are qualitatively at least equivalent to the conventional oxidation hair dyes, without, however being necessarily dependent on oxidizing agents such as for example H.sub.2O.sub.2. Furthermore, the dyes must have no or only a very slight sensitization potential and in no case may have a mutagenic effect. Dyes, comprising 3-allyl-4-hydroxybenzaldehyde and its derivatives according to the following Formula I in combination with CH-acidic compounds, as well as the use of this combination for dyeing fibers containing keratin or for color refreshing or nuancing already dyed fibers containing keratin, are unknown up to now.

CH-acidic 1,2-dihydropyrimidinium derivatives, which are known from the patent application WO A1 2004/022016, when combined with reactive carbonyl compounds, particularly benzaldehyde derivatives, are suitable for dyeing keratin-containing fibers. However, 3-allyl-4-hydroxybenzaldehyde and its derivatives in accordance with the present invention are not mentioned.

BRIEF SUMMARY OF THE INVENTION

Surprisingly, it has now been found that the compounds illustrated in Formula I in combination with CH-acidic compounds are eminently suitable, even in the absence of oxidizing agents, for dyeing fibers containing keratin. They produce colorations with excellent brilliance and depth of color and lead to a wide range of color nuances. In particular, colorations are obtained with improved fastness characteristics over a range of nuances from yellow through orange, brown orange, brown, red, red-violet up to blue-violet and dark blue. However, in principle the use of oxidizing agents should not be excluded. Moreover, the inventive benzaldehyde derivatives are characterized by an increased physiological compatibility.

One aspect of the invention pertains to an agent for dyeing keratin-containing fibers, especially human hair, comprising a cosmetic carrier, and

(A) at least one compound of Formula I,

##STR00002## wherein each of R.sup.1, R.sup.2 and R.sup.3 is independently a hydrogen atom, a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a hydroxyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a hydroxy C.sub.1-C.sub.6 alkyloxy group, a sulfonyl group, a carboxyl group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a hydroxy C.sub.2-C.sub.6 alkoxycarbonyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a C.sub.2-C.sub.6 acyl group, a formyl group, a nitro group, a carbamoyl group --C(O)--NR.sup.4R.sup.5, or a --(CH.sub.2).sub.nNR.sup.6R.sup.7 group wherein each of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is independently a hydrogen atom, a C.sub.1-C.sub.6 alkyl group or a C.sub.2-C.sub.6 hydroxyalkyl group; and n is a number from 0 to 6, wherein R.sup.1 and R.sup.2 can form a 5- or 6-membered aromatic or heteroaromatic ring; and (B) at least one CH-acidic compound.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Not Applicable

DETAILED DESCRIPTION OF THE INVENTION

Keratin-containing fibers are understood to mean wool, furs, feathers and particularly human hair. However, the inventive dyes can, in principle, also be used for dyeing other natural fibers, such as e.g., cotton, jute, sisal, linen or silk, modified natural fibers, such as e.g., cellulose regenerate, nitrocellulose, alkyl cellulose or hydroxyalkyl cellulose or acetyl cellulose.

Examples of C.sub.1-C.sub.6 alkyl groups are the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert.-butyl, n-pentyl and n-hexyl groups. Propyl, ethyl and methyl are preferred alkyl groups. Examples of suitable cyclic alkyl groups are cyclopentyl and cyclohexyl groups. Examples of preferred C.sub.2-C.sub.6 alkenyl groups are vinyl and allyl groups.

Furthermore, preferred examples of a C.sub.1-C.sub.6 hydroxyalkyl group can be a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyethyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a C.sub.2-C.sub.6 polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

Inventively preferred C.sub.1-C.sub.6 alkoxy groups are a methoxy or ethoxy group, for example.

The methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl groups, n-pentyloxycarbonyl and n-hexyloxycarbonyl are examples of C.sub.1-C.sub.6 alkoxycarbonyl groups; the methoxycarbonyl and the ethoxycarbonyl groups are particularly preferred.

The acetyl, n-propanoyl, n-butanoyl groups and n-hexanoyl groups are examples of a C.sub.2-C.sub.6 acyl group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and the methoxyhexyl group are examples of the inventive C.sub.1-C.sub.6 alkoxy C.sub.2-C.sub.6 alkyl groups.

A preferred hydroxy (C.sub.1-C.sub.6) alkoxy group is the 2-hydroxyethoxy group.

A preferred hydroxy (C.sub.2-C.sub.6) alkoxycarbonyl group is the 2-hydroxyethoxycarbonyl group.

Exemplary halogen atoms are F, Cl, Br or I atoms, Cl atoms being quite particularly preferred.

The aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl, bis(2-hydroxyethyl)amino and the amino group are examples of a R.sup.6R.sup.7N--(CH.sub.2).sub.n-- group, wherein the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and the amino group are particularly preferred.

The N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-bis(2-hydroxyethyl)carbamoyl and the carbamoyl group are exemplary carbamoyl groups R.sup.4R.sup.5NC(O)--. The other terms used are derived according to the invention from the definitions given here.

In a preferred embodiment, the inventive composition comprises at least one compound according to Formula (I), which carry a hydrogen atom as the substituent R.sup.2 and R.sup.3. Furthermore, representatives of the compounds corresponding to Formula (I) are preferred, in which the R.sup.1 group carries a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group (especially an allyl group), a C.sub.1-C.sub.6 alkoxy group (especially a methoxy group), a formyl group, a hydroxyl group, a halogen atom, a carboxy group or a nitro group. Once again, in this embodiment, the groups R.sup.2 and R.sup.3 particularly preferably stand for a hydrogen atom.

It is particularly preferred if at least one of the following compounds corresponding to Formula (I) is comprised in the inventive composition: 3-Allyl-4-hydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-methoxybenzaldehyde, 3-Allyl-5-ethoxy-4-hydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-methylbenzaldehyde, 3-Allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-Diallyl-4-hydroxybenzaldehyde, 3-Allyl-4,5-dihydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-nitrobenzaldehyde, 3-Allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-Allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde).

Quite particularly preferably, the inventive compositions comprise at least one compound from the group 3-Allyl-4-hydroxybenzaldehyde, 3-Allyl-4-hydroxy-5-methoxybenzaldehyde, 3-Allyl-4-hydroxy-5-methylbenzaldehyde, 3-Allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-Diallyl-4-hydroxybenzaldehyde, 3-Allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-Allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde).

Moreover, according to the invention, such compounds corresponding to Formula (I) can also be used as Component A, in which the reactive carbonyl group is protected or derivatized in such a manner that the carbon atom of the derivatized carbonyl group is still reactive towards the CH-acidic compounds of the compound B. These derivatives are preferably addition compounds a) of amines and their derivatives forming imines or oximes as the addition compound b) of alcohols forming acetals as the addition compound c) of water, forming hydrates as the addition compound onto the carbon atom of the formyl group --CHO in compounds corresponding to Formula (I).

In general, those compounds that possess a hydrogen atom bonded to an aliphatic carbon atom, wherein the carbon-hydrogen bond is activated due to electron-withdrawing substituents, are recognized as CH-acidic compounds. In principle there are no limits to the choice of the CH-acidic compounds, as long as a compound that is colored to the human eye is obtained after the aldol condensation with the inventive benzaldehyde derivatives of Formula (I). According to the invention, they are preferably CH-acidic compounds that comprise an aromatic and/or a heterocyclic group. Once again, the heterocyclic group can be aliphatic or aromatic in nature.

The 3-allyl-4-hydroxybenzaldehyde compounds of Formula (I) combined with at least one CH-acidic compound selected from Formulas (II) and/or (III) are preferred

##STR00003## in which R.sup.8 and R.sup.9 independently of one another stand for a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy C.sub.1-C.sub.6 alkyl group, a R.sup.IR.sup.IIN--(CH.sub.2).sub.m-- group, in which R.sup.I and R.sup.II stand independently of one another for a hydrogen atom, a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group, wherein R.sup.I and R.sup.II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m stands for a number 2, 3, 4, 5 or 6, R.sup.10 and R.sup.12 independently of one another stand for a hydrogen atom or a C.sub.1-C.sub.6 alkyl group, wherein at least one of the groups R.sup.10 and R.sup.12 means a C.sub.1-C.sub.6 alkyl group, R.sup.11 stands for a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkoxy group, a R.sup.IIIR.sup.IVN--(CH.sub.2).sub.q-- group, in which R.sup.III and R.sup.IV independently of one another stand for a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group and q stands for a number 1, 2, 3, 4, 5 or 6, wherein the group R.sup.11 together with one of the groups R.sup.10 or R.sup.12 can form a 5- or 6-membered aromatic ring that can be optionally substituted with a halogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 hydroxyalkoxy group, a nitro group, a hydroxy group, a R.sup.VR.sup.VIN--(CH.sub.2).sub.s-- group, in which R.sup.V and R.sup.VI independently of one another stand for a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.6 alkyl group and s stands for a number 0, 1, 2, 3, 4, 5 or 6, Y stands for an oxygen atom, a sulfur atom or a group NR.sup.VII, in which R.sup.VII stands for a hydrogen atom, an aryl group, a heteroaryl group, a C.sub.1-C.sub.6 alkyl group or a C.sub.1-C.sub.6 arylalkyl group, X.sup.- stands for a physiologically compatible anion,

Het stands for an optionally substituted heteroaromatic group,

X.sup.1 stands for a direct bond or a carbonyl group.

The enamine forms act in the same way as the compounds of Formula II. Here, reference is expressly made to the publication WO A1 2004/022016, which is incorporated in its entirety.

At least one group R.sup.10 or R.sup.12 of Formula II stands imperatively for a C.sub.1-C.sub.6 alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its .alpha.-carbon atom. Particularly preferred alkyl groups are the methyl-, ethyl-, propyl-, n-butyl-, iso-butyl, n-pentyl-, neo-pentyl-, n-hexyl groups. R.sup.10 and R.sup.12 independently of one another stand quite particularly preferably for hydrogen or a methyl group, wherein at least one of the groups R.sup.10 or R.sup.12 means a methyl group.

In a preferred embodiment, Y stands for an oxygen atom or a sulfur atom, particularly preferably for an oxygen atom.

The group R.sup.8 is preferably selected from a (C.sub.1-C.sub.6) alkyl group (particularly preferably a methyl group), a C.sub.2-C.sub.6 alkenyl group (especially an allyl group), a hydroxy (C.sub.2- to C.sub.6) alkyl group or an optionally substituted benzyl group.

R.sup.11 preferably stands for a hydrogen atom.

The groups R.sup.9, R.sup.10 und R.sup.12 particularly preferably stand for a methyl group, the group R.sup.11 for a hydrogen atom, Y for an oxygen atom or a sulfur atom and the group R.sup.8 is selected from a (C.sub.1-C.sub.6) alkyl group (particularly preferably a methyl group), a C.sub.2-C.sub.6 alkenyl group (especially an allyl group), a hydroxy (C.sub.2- to C.sub.6) alkyl group or an optionally substituted benzyl group.

Preferably, the compounds according to Formula II are selected from one or a plurality of compounds of the group of salts with physiologically compatible counter ions X.sup.-, said group being formed from salts of 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-oxo-pyrimidinium 1,2-Dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-di(2-hydroxyethyl)-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidinium, 1,2-Dihydro-3,4-dimethyl-2-oxo-quinazolinium and 1,2-Dihydro-3,4-dimethyl-2-thioxo-quinazolinium.

Quite particularly preferable compounds according to Formula II are selected from one or a plurality of compounds of the group of salts with physiologically compatible counter ions X.sup.-, said group being formed from salts of 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1,3,4-trimethyl-2-oxo-pyrimidinium, 1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-Dihydro-1-(2-hydroxyethyl)-3,4,6-trimethyl-2-oxo-pyrimidinium and 1,2-Dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium.

X.sup.- in Formula (II) as well as in the above lists preferably stands for halide, benzenesulfonate, p-toluenesulfonate, C.sub.1-C.sub.4 alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogen sulfate or p-toluenesulfonate are particularly preferably employed as X.sup.-.

The group Het according to Formula (III) preferably stands for the molecule fragment with the following Formula (IV),

##STR00004## in which R.sup.13 and R.sup.14 stand independently of one another for a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethyl carbonyl group, an optionally substituted heteroaryl group, an aryl C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a C.sub.1-C.sub.6 alkoxy C.sub.2-C.sub.6 alkyl group, a C.sub.1-C.sub.6 sulfoalkyl group, a C.sub.1-C.sub.6 carboxyalkyl group, a R.sup.VIIR.sup.IXN--(CH.sub.2).sub.m-- group, in which R.sup.VIII and R.sup.IX stand independently of one another for a hydrogen atom, a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.4 alkyl group, wherein R.sup.VIII and R.sup.IX together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m stands for a number 0, 1, 2, 3 or 4, wherein R.sup.13 and/or R.sup.14 can form an annulated, optionally substituted aromatic or heteroaromatic 5- or 6-membered ring on the ring of the residual molecule X.sup.2 and X.sup.3 stand independently of one another for a nitrogen atom or a CR.sup.15 group, wherein R.sup.15 stands for a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethyl carbonyl group, an optionally substituted heteroaryl group, an aryl C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 alkoxycarbonyl group, a C.sub.1-C.sub.6 alkoxy C.sub.2-C.sub.6 alkyl group, a C.sub.1-C.sub.6 sulfoalkyl group, a C.sub.1-C.sub.6 carboxyalkyl group and a R.sup.XR.sup.XIN--(CH.sub.2).sub.n-- group, in which R.sup.X and R.sup.XI stand independently of one another for a hydrogen atom, a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.4 alkyl group, wherein R.sup.X and R.sup.XI together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n stands for a number 0, 1, 2, 3 or 4, wherein at least one of the substituents X.sup.2 and X.sup.3 can form an annulated, optionally substituted aromatic 5- or 6-membered ring together with the residual molecule, X.sup.4 stands for an oxygen atom, a sulfur atom, a vinylene group or an N--H group, wherein the last two groups, independently of one another, can be optionally substituted with a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 hydroxyalkyl group, a C.sub.2-C.sub.6 polyhydroxyalkyl group, a C.sub.1-C.sub.6 alkoxy C.sub.2-C.sub.6 alkyl group, a C.sub.1-C.sub.6 sulfoalkyl group, a C.sub.1-C.sub.6 carboxyalkyl group, a group R.sup.XIIR.sup.XIIIN--(CH.sub.2).sub.p--, in which R.sup.XII and R.sup.XIII stand independently of one another for a hydrogen atom, a linear or cyclic C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, a C.sub.1-C.sub.6 hydroxyalkyl group or an aryl C.sub.1-C.sub.4 alkyl group, wherein R.sup.XII and R.sup.XIII together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p stands for a number 0, 1, 2, 3 or 4, with the proviso that when X.sup.4 stands for a vinylene group, at least one of the groups X.sup.2 or X.sup.3 means a nitrogen atom.

The bond between the heterocyclic ring of Formula (IV) and the molecule fragment --X.sup.1--CH.sub.2--C.ident.N with retention of the inventive compound of Formula (III) occurs on the ring of the heterocycle and substitutes a hydrogen atom bonded to this ring. Consequently, it is imperative that the substituents R.sup.13, R.sup.14, X.sup.2, X.sup.3 and X.sup.4 are selected such that at least one of these substituents permits the formation of a corresponding bond. Consequently, it is imperative that at least one of the groups R.sup.13 or R.sup.14 forms the bond to the molecule fragment --X.sup.1--CH.sub.2--C.ident.N, when X.sup.4 is an oxygen atom or a sulfur atom and X.sup.2 and X.sup.3 mean a nitrogen atom.

The group Het of Formula (IV) is particularly preferably derived from the heteroaromatics furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnolin, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, benzothiazole, phenazine, benzocinnolin, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine and cumarine, wherein the above-cited heteroaromatics can be substituted with at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C.sub.1-C.sub.6) alkyl group, a heteroaryl group, an aryl group, a (C.sub.1-C.sub.6) alkyl group, a (C.sub.1-C.sub.6) alkoxy group, a hydroxy group, a (C.sub.2-C.sub.6) hydroxyalkyl group, a (C.sub.2-C.sub.6) polyhydroxyalkyl group, a (C.sub.1-C.sub.6) alkoxy (C.sub.1-C.sub.6) alkyl group, an aryl (C.sub.1-C.sub.6) alkyl group, an amino group, a (C.sub.1-C.sub.6) monoalkylamino group, a (C.sub.1-C.sub.6) dialkylamino group, a dialkylaminoalkyl group --(CH.sub.2).sub.n--NR'R'', in which n is a whole number from 2 and 6 and R' and R'' independently of one another means a linear or branched alkyl group that can together optionally form a ring.

The compounds according to Formula (III) are advantageously selected from the group consisting of 2-(2-furoyl)-acetonitrile, 2-(5-bromo-2-furoyl)-acetonitrile, 2-(5-methyl-2-trifluormethyl-3-furoyl)-acetonitrile, 3-(2,5-dimethyl-3-furyl)-3-oxopropanitrile, 2-(2-thenoyl)-acetonitrile, 2-(3-thenoyl)-acetonitrile, 2-(5-fluoro-2-thenoyl)-acetonitrile, 2-(5-chloro-2-thenoyl)-acetonitrile, 2-(5-bromo-2-thenoyl)-acetonitrile, 2-(5-methyl-2-thenoyl)-acetonitrile, 2-(2,5-dimethylpyrrol-3-oyl)-acetonitrile, 2-(1,2,5-trimethylpyrrol-3-oyl)-acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2-(pyrid-2-yl)-acetonitrile, 2,6-bis(cyanomethyl)-pyridine, 2-(indol-3-oyl)-acetonitrile, 2-(2-methyl-indol-3-oyl)-acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcumarine, 2-(2-isopropyl-5,6-benzoquinolin-4-oyl)-acetonitrile, 2-(2-phenyl-5,6-benzoquinolin-4-oyl)-acetonitrile, 2-(quinoxalin-2-yl)-acetonitrile, 2-(cumaron-2-yl)-acetonitrile, 6,7-dichloro-5-(cyanoacetyl)-2,3-dihydro-1-benzofuran-2-carboxylic acid tert.-butyl ester, 2-(6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl)-acetonitrile and 2-(1-phenyl-1,4-dihydrothiochromeno[4,3-c]pyrazol-3-oyl)-acetonitrile. 1H-Benzimidazol-2-yl acetonitrile [2-(cyanomethyl)benzimidazole] is particularly preferred.

In another aspect of the invention, it can be advantageous for broadening the color spectrum to add at least one further compound as Component C in addition to at least one compound corresponding to Formula (I) as Component A and at least one compound of Component B. The compound of Component C is preferably selected from at least one reactive carbonyl compound that is different from the compounds of Formula (I).

In the context of the invention, reactive carbonyl compounds as Component C possess at least one carbonyl group as the reactive group that reacts with the CH-acidic compound corresponding to Component B to form a carbon-carbon bond. Preferred reactive carbonyl compounds are the aldehydes and ketones, particularly aromatic aldehydes. Moreover, according to the invention, such compounds are also applicable as Component C, in which the reactive carbonyl group is derivatized or protected in such a manner that the reactivity of the carbon atom of the derivatized carbonyl group remains towards the CH-acidic compounds of Component B. These derivatives are preferably addition compounds a) of amines and their derivatives forming imines or oximes as the addition compounds b) of alcohols forming acetals or ketals as the addition compounds c) of water forming hydrates as the addition product (in this case c), Component C is derived from an aldehyde) on the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of Component C are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde, N-ethylcarbazol-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),2-indole aldehyde, 3-indole aldehyde, 1-methylindol-3-aldehyde, 2-methylindol-3-aldehyde, 2-(1',3',3'-trimethyl-2-indolinylidene)-acetaldehyde, 1-methylpyrrole-2-aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromone-3-aldehyde, 3-(5'-nitro-2'-furyl)-acrolein, 3-(2'-furyl)-acrolein and imidazol-2-aldehyde, 5-(4-dimethylaminophenyl)penta-2,4-dienal, 5-(4-diethylaminophenyl)penta-2,4-dienal, 5-(4-methoxyphenyl)penta-2,4-dienal, 5-(3,4-dimethoxyphenyl)penta-2,4-dienal, 5-(2,4-dimethoxyphenyl)penta-2,4-dienal, 5-(4-piperidinophenyl)penta-2,4-dienal, 5-(4-morpholinophenyl)penta-2,4-dienal, 5-(4-pyrrolidinophenyl)penta-2,4-dienal, 5-(4-dimethylamino-1-naphthyl)penta-3,5-dienal, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1-methylpyridinium-, 2-formyl-1-methylpyridinium-, 4-formyl-1-ethylpyridinium-, 2-formyl-1-ethylpyridinium-, 4-formyl-1-benzylpyridinium-, 2-formyl-1-benzylpyridinium-, 4-formyl-1,2-dimethylpyridinium-, 4-formyl-1,3-dimethylpyridinium-, 4-formyl-1-methylquinolinium-, 2-formyl-1-methylquinolinium-, 5-formyl-1-methylquinolinium-, 6-formyl-1-methylquinolinium-, 7-formyl-1-methylquinolinium-, 8-formyl-1-methylquinolinium-, 5-formyl-1-ethylquinolinium-, 6-formyl-1-ethylquinolinium-, 7-formyl-1-ethylquinolinium-, 8-formyl-1-ethylquinolinium-, 5-formyl-1-benzylquinolinium-, 6-formyl-1-benzylquinolinium-, 7-formyl-1-benzylquinolinium-, 8-formyl-1-benzylquinolinium-, 5-formyl-1-allylquinolinium-, 6-formyl-1-allylquinolinium-, 7-formyl-1-allylquinolinium- and 8-formyl-1-allylquinolinium benzenesulfonate, -p-toluenesulfonate, -methanesulfonate, -perchlorate, -sulfate, -chloride, -bromide, -iodide, -tetrachlorozincate, -methylsulfate, -trifluoromethanesulfonate, -tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methylquinisatin, as well as any mixture of the above compounds.

Benzaldehyde, cinnamaldehyde and naphthaldehyde together with their derivatives, in particular, with one or more hydroxyl, alkoxy or amino substituents, are quite particularly preferred as the reactive carbonyl compound of Component C. Again, the compounds according to Formula (Ca-1) are preferred.

##STR00005## in which R.sup.1*, R.sup.2* and R.sup.3* independently of each other stand for a hydrogen atom, a halogen atom, a C.sub.1-C.sub.6 alkyl group, a hydroxyl group, a C.sub.1-C.sub.6 alkoxy group, a C.sub.1-C.sub.6 dialkylamino group, a di(C.sub.2-C.sub.6 hydroxyalkyl)amino group, a di(C.sub.1-C.sub.6 alkoxy C.sub.1-C.sub.6 alkyl)amino group, a C.sub.1-C.sub.6 hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C.sub.2-C.sub.6 acyl group or a nitro group, Z' stands for a direct bond or a vinylene group, R.sup.4* and R.sup.5* stand for a hydrogen atom or together form a 5- or 6-membered aromatic or aliphatic ring with the rest of the molecule.

The derivatives of benzaldehyde, naphthaldehyde or cinnamaldehyde of the reactive carbonyl compound according to Component C are particularly preferably selected from 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxy-benzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2-hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methyl-benzaldehyde, 2,4-dihydroxy-5-methyl-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methyl-benzaldehyde, 3,4-dihydroxy-5-methyl-benzaldehyde, 3,4-dihydroxy-6-methyl-benzaldehyde, 3,4-dihydroxy-2-methoxy-benzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodo-benzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iod-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-napthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino-benzaldehyde, 4-(1-imidazolyl)-benzaldehyde and piperonal. Together, these representatives are the particularly preferred additional reactive carbonyl compounds of Component C.

In another aspect of the invention, the colorant additionally comprises at least one reaction product (hereafter named reaction product RP) as the substantive dye from a compound of Formula (I) and a compound of Component B. These types of reaction products RP can be obtained by e.g., heating both reactants in a neutral to weakly alkaline aqueous medium, wherein the reaction products RP either precipitate out of the solution as a solid or are isolated by evaporating the solution. The reaction products can also be prepared according to the literature method H. Mohrle et al, Pharmazie, 1999, 54(4), 269-279.

For the synthesis of the reaction products RP, molar ratios of Component B to the compound according to Formula (I) of about 1:1 to about 1:2 can be reasonable.

Particularly preferred reaction products RP are selected from compounds of Formulas (V), (VI) and (VII),

##STR00006##

##STR00007## in which the groups R1, R2, R3, R8, R9, R11, R12 and X.sup.- are as previously defined for Formulas (I) and (II). All the previously cited embodiments of the above-mentioned groups are also applicable.

In Formula (V), R12 is quite particularly preferably a hydrogen atom.

The compounds of Formulas (V) and (VI) are preferred reaction products RP in accordance with the invention.

The above-mentioned compounds of Formula I, the compounds of Component B, Component C as well as the reaction products RP are preferably used in each case in an amount of 0.03 to 65 mmol, in particular, from 1 to 40 mmol, based on 100 g of the total colorant.

In addition, the inventive agents can comprise at least one developer component and optionally at least one coupler component as the oxidation dye precursors.

According to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically compatible salts as the developer component. Particular preference is given to p-phenylenediamine derivatives of Formula (E1)

##STR00008## wherein G.sup.1 is a hydrogen atom, a C.sub.1- to C.sub.4 alkyl group, a C.sub.1- to C.sub.4 monohydroxyalkyl group, a C.sub.2- to C.sub.4 polyhydroxyalkyl group, a (C.sub.1- to C.sub.4) alkoxy (C.sub.1- to C.sub.4) alkyl group, a 4'-aminophenyl group or a C.sub.1- to C.sub.4 alkyl group that is substituted by a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group; G.sup.2 is a hydrogen atom, a C.sub.1- to C.sub.4 alkyl group, a C.sub.1- to C.sub.4 monohydroxyalkyl group, a C.sub.2- to C.sub.4 polyhydroxyalkyl group, a (C.sub.1- to C.sub.4) alkoxy (C.sub.1- to C.sub.4) alkyl group or a C.sub.1- to C.sub.4 alkyl group that is substituted by a nitrogen-containing group; G.sup.3 is a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C.sub.1- to C.sub.4 alkyl group, a C.sub.1- to C.sub.4 monohydroxyalkyl group, a C.sub.2- to C.sub.4 polyhydroxyalkyl group, a (C.sub.1- to C.sub.4) hydroxyalkoxy group, a C.sub.1- to C.sub.4 acetylamino group, a C.sub.1- to C.sub.4 mesylamino alkoxy group or a C.sub.1- to C.sub.4 carbamoylamino alkoxy group; G.sup.4 stands for a hydrogen atom, a halide atom or a C.sub.1- to C.sub.4 alkyl group or if G.sup.3 und G.sup.4 are in the ortho position relative to one another, they can together form a bridging a,.omega.-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the C.sub.1- to C.sub.4 alkyl groups specified as substituents in the compounds according to the invention are t