Hair dyeing agents containing indigo derivatives Number:7,060,109 from the United States Patent and Trademark Office (PTO) owispatent Compositions and method for coloring keratin fibers consisting of derivatives of benzo[b]furan-3-one and/or benzo-[b]-thiophen-3-one compounds with special reactive components. These compositions form intensely colored compounds when applied to keratin fibers. The compositions may also be used with substantive dyes and/or oxidation colorants.<H derivatives, containing, Hair, dyeing, age, 7060109.html, Patent, pto, 7060109

Title: Hair dyeing agents containing indigo derivatives

Abstract: Compositions and method for coloring keratin fibers consisting of derivatives of benzo[b]furan-3-one and/or benzo-[b]-thiophen-3-one compounds with special reactive components. These compositions form intensely colored compounds when applied to keratin fibers. The compositions may also be used with substantive dyes and/or oxidation colorants.

Patent Number: 7,060,109 Issued on 06/13/2006 to Hoeffkes, et al.

Inventors: Hoeffkes; Horst (Duesseldorf, DE); Nelles; Karin (Monheim, DE); Moeller; Hinrich (Monheim, DE)
Assignee: Henkel Kommanditgesellschaft auf Aktien (Henkel KGa A) (Duesseldorf, DE)

Appl. No.: 380343

Filed: September 11, 2001

PCT Filed: September 11, 2001

PCT NO: PCT/EP01/10480

371 Date: March 12, 2003

PCT PUB.NO.: WO02/22092

PCT PUB. Date: March 21, 2002

Foreign Application Priority Data


Sep 14, 2000 [DE]			100 45 856

Current U.S. Class: 8/405 ; 548/364.7; 549/469; 8/574; 8/575; 8/576; 8/577; 8/607; 8/608

Field of Search: 8/405,575,576,607,608,574,577 548/364.7 549/469

References Cited [Referenced By]

U.S. Patent Documents


4003699	January 1977	Rose et al.
4865774	September 1989	Fabry et al.
4931218	June 1990	Schenker et al.
5061289	October 1991	Clausen et al.
5199954	April 1993	Schultz et al.
5294726	March 1994	Behler et al.
5380340	January 1995	Neunhoeffer et al.
5534267	July 1996	Neunhoeffer et al.
5663366	September 1997	Neunhoeffer et al.
5743919	April 1998	Moeller et al.
5766576	June 1998	Lowe et al.
5769903	June 1998	Audousset et al.
5879412	March 1999	Rondeau et al.
6099592	August 2000	Vidal et al.
6284003	September 2001	Rose et al.
6371993	April 2002	Moeller et al.

Foreign Patent Documents


23 59 399	Jun., 1975	DE
197 45 354	Jan., 1989	DE
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196 30 275	Jan., 1998	DE
196 48 020	Mar., 1998	DE
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197 17 224	Oct., 1998	DE
197 17 280	Oct., 1998	DE
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359 465 A2	Mar., 1990	EP
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WO 94/08969	Apr., 1994	WO
WO 94/08970	Apr., 1994	WO
WO 96/15765	May., 1996	WO

Other References

The Science of Hair Care, Chapter 7, pp. 235-261, published in vol. 7, Dermatology, Marcel Dekker Inc. NY/Basle (1986). cited by other .
The Science of Hair Care, Chapter 8, pp. 263-286, published in vol. 7, Dermatology, Marcel Dekker Inc. NY/Basle (1986). cited by other .
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Primary Examiner: Elhilo; Eisa
Attorney, Agent or Firm: Harper; Stephen D. Hill; Gregory M.

Claims

What is claimed is:

1. A dye precursor composition for coloring keratinous fibers comprising, in a cosmetically acceptable medium, (a) at least one compound selected from the group consisting of 5-carboxymethoxy-benzo[b]thiophen-3-one, 5,6-dihydroxybenzo[b]thiophen-3-one and 6-hydroxy-5-methoxybenzo[b]thiophen-3-one, 5-carboxymethoxybenzo[b]furan-3-one, and 5-(2'-hydroxyethoxy)-benzo[b]-furan-3-one; and (b) at least one reactive compound selected from the group consisting of (b1) reactive carbonyl compounds selected from the group of aromatic, heteroaromatic or unsaturated aldehydes or ketones, dialdehydes or diketones or acetals, semiaminals or imine derivatives of the reactive carbonyl compounds, and (b2) CH-active compounds corresponding to formula (2) or (3): ##STR00016## in which R.sup.10 is a C.sub.1-10 alkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 hydroxyalkyl group, a C.sub.2-4 carboxyalkyl group, a C.sub.2-4 sulfoalkyl group or an aralkyl group, R.sup.7 and R.sup.8 independently of one another represent a hydrogen atom, a C.sub.1-4 alkyl group, a halogen atom, a hydroxy group, a C.sub.1-4 alkoxy group or a nitro group or together form a fused aromatic ring, R.sup.9 is a hydrogen atom, a C.sub.1-4 alkyl group or an aryl group, A is an oxygen or a sulfur atom, the group --CH.dbd.CH-- or >N--R.sup.11, where R.sup.11 is a C.sub.1-4 alkyl group, a C.sub.2-4 carboxyalkyl group, a C.sub.2-4 sulfoalkyl group, a C.sub.2-4 sulfoxyalkyl group, a C.sub.2-4 hydroxyalkyl group or an aralkyl group, and AN.sup.- is an anion selected from halide, C.sub.1-4 alkyl sulfate, C.sub.1-4 alkanesulfonate, arenesulfonate, C.sub.1-4 perfluoroalkanesulfonate, tetrafluoroborate, perhalogenate, sulfate, hydrogen sulfate or carboxylate, ##STR00017## in which R.sup.12 is a C.sub.1-4 acyl group, a C.sub.1-4 alkylsulfonyl group, a C.sub.1-4alkylsulfinyl group, a C.sub.1-4 alkylamino group, a di-C.sub.1-4-alkyamino group, a vinyl carbonyl group, a methineimino group, a nitrile group, an ester or carboxylic acid amide group which may optionally be substituted by a C.sub.1-4 alkyl group, a C.sub.2-4 hydroxyalkyl group or an aryl group, and R.sup.13 represents a C.sub.1-4 acyl group, a C.sub.1-4 alkoxy group, a C.sub.1-4 alkylamino group, a C.sub.1-4 acylamino group or a di-C.sub.1-4-alkylamino group; the substituents R.sup.12 and R.sup.13 together with the rest of the molecule may also form a 5-, 6- or 7-membered ring system from the series of thiazolidine-2,5-diones, thiazolidine-2-thion-5-ones, perhydropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione-4,6-diones, cyclopentane1,3diones, cyclohexane-1,3-diones, indane-1,3-diones, 2-pyrazoline-5-ones, 1,2-dihydro-6-hydroxy-2-hydroxypyridines or enol esters thereof, and AX represents oxygen, sulfur or a dicyanomethylene group.

2. The composition of claim 1 wherein the reactive carbonyl compound is isatin or a derivative thereof.

3. The composition of claim 2 wherein the reactive carbonyl compound is isatin.

4. The composition of claim 1 wherein the reactive carbonyl compound is an aromatic aldehyde or derivative thereof.

5. The composition of claim 4 wherein the reactive carbonyl compound is selected from the group consisting of 4-N,N-dimethylaminobenzaldehyde, 4-N,N-dimethylaminocinnamaldehyde, vanillin and 4-N,N-dimethylamino-1-naphthaldehyde.

6. The composition of claim 1 further comprising at least one oxidation dye precursor of the primary intermediate and/or secondary intermediate type.

7. The composition of claim 1 wherein the dye precursor is of the indole or indoline type.

8. The composition of claim 1 further comprising at least one substantive dye.

9. The composition of claim 1 further comprising an oxidizing agent.

10. The composition of claim 9 wherein the oxidizing agent is hydrogen peroxide.

11. A method for coloring keratinous fibers comprising applying the composition of claim 1 to the keratinous fibers and then rinsing it off the fibers.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 USC 371 of international application PCT/EP01/10480 filed on Sep. 11, 2001, the international application not being published in English. This application also claims priority under 35 USC 119 to DE 100 45 856.4 filed on Sep. 14, 2000.

BACKGROUND OF THE INVENTION

This invention relates to compositions for coloring keratin fibers which contain special derivatives of benzo[b]furan-3-one and/or benzo-[b]-thiophen-3-one and reactive compounds, to a coloring process using this dye precursor combination and to the use of this combination for coloring keratin fibers.

Nowadays, human hair is treated in many different ways with hair-care preparations. Such treatments include, for example, the cleaning of hair with shampoos, the care and regeneration of hair with rinses and treatments and the bleaching, coloring and shaping of hair with coloring and tinting formulations, wave formulations and styling preparations. Among these, formulations for modifying or shading the color of the hair occupy a prominent position.

Colorants or tints containing substantive dyes as their coloring component are normally used for temporary colors. Substantive dyes are based on dye molecules which are directly absorbed onto the hair and do not require an oxidative process for developing the color. Dyes such as these include, for example, henna which has been used since ancient times for coloring the body and hair. Corresponding colors are generally sensitive to shampooing so that an often unwanted change of shade or even a visible "decoloration" can occur.

So-called oxidation colorants are used for permanent, intensive colors with corresponding fastness properties. Oxidation colorants normally contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates under the influence of oxidizing agents or atmospheric oxygen. Oxidation colorants are distinguished by excellent long-lasting coloring results. Natural-looking colors normally require a mixture of a relatively large number of oxidation dye precursors; in many cases, substantive dyes are used for shading.

Finally, a new coloring process has very recently attracted considerable attention. In this process, precursors of the natural hair dye melanin are applied to the hair. These precursors then form "nature-analogous" dyes in the course of oxidative processes. One such process using 5,6-dihydroxyindoline as the dye precursor is described in EP-B1-530 229. Another new coloring system is described, for example, in EP-A2-359 465. In this process, selected isatin derivatives are reacted with aromatic amines in the coloring of keratin fibers.

Nevertheless, there is always an ongoing search for other coloring systems which give intensive colors of the fibers with excellent fastness properties.

SUMMARY OF THE INVENTION

It has now surprisingly been found that special derivatives of benzo[b]furan-3-one and/or benzo[b]thiophen-3-one react with special reactive components to form intenstively colored compounds which are capable of coloring keratinous fibers.

DETAILED DESCRIPTION OF THE INVENTION

In a first embodiment, therefore, the present invention relates to a composition for coloring keratinous fibers which contains as dye precursors in a cosmetically acceptable medium (a) at least one derivative of benzo[b]furan-3-one and/or at least one derivative of benzo[b]thiophen-3-one corresponding to formula (1):

##STR00001## in which X is sulfur or oxygen, Y is hydrogen, a C.sub.1-4 alkyl group or a C.sub.1-4 acyl group, the substituents R.sup.1, R.sup.3 and R.sup.4 independently of one another represent hydrogen, a C.sub.1-4 alkyl group which may optionally be substituted by one or more hydroxy group(s) an optionally substituted amino group, a carboxy group optionally esterified with a C.sub.1-4 alkyl group or a group --SO.sub.2R.sup.5, where R.sup.5 is a hydroxy group, an optionally substituted amino group or a C.sub.1-4 alkyl group, an optionally substituted amino group, a perfluorinated C.sub.1-4 alkyl group, a cyano group, a C.sub.2-5 alkenyl group, a nitro group, a halogen atom, an optionally C.sub.1-4-alkyl-substituted mercapto group, a group --SO.sub.2R.sup.5 or a group --OR.sup.6, an optionally esterified or amidated carboxyl group and R.sup.2 and optionally R.sup.6 independently of one another represent hydrogen, a C.sub.1-4 alkyl group which may optionally be substituted by one or more hydroxy group(s), an optionally substituted amino group, a carboxy group optionally esterified with a C.sub.1-4 alkyl group or a group --SO.sub.2R.sup.5, or a perfluorinated C.sub.1-4 alkyl group, and (b) at least one reactive compound selected from (b1) reactive carbonyl compounds selected from the group of aromatic, heteroaromatic or unsaturated aldehydes or ketones, dialdehydes or diketones or acetals, semiaminals or imine derivatives of such reactive carbonyl compounds and/or (b2) CH-active compounds corresponding to formula (2) or (3):

##STR00002## in which R.sup.10 is a C.sub.1-10 alkyl group, a C.sub.2-4 alkenyl group, a C.sub.2-4 hydroxyalkyl group, a C.sub.2-4 carboxyalkyl group, a C.sub.2-4 sulfoalkyl group or an aralkyl group, R.sup.7 and R.sup.8 independently of one another represent a hydrogen atom, a C.sub.1-4 alkyl group, a halogen atom, a hydroxy group, a C.sub.1-4 alkoxy group or a nitro group or together form a fused aromatic ring, R.sup.9 is a hydrogen atom, a C.sub.1-4 alkyl group or an aryl group, A is an oxygen or a sulfur atom, the group --CH.dbd.CH-- or >N--R.sup.11, where R.sup.11 is a C.sub.1-4 alkyl group, a C.sub.2-4 carboxyalkyl group, a C.sub.2-4 sulfoalkyl group, a C.sub.2-4 sulfoxyalkyl group, a C.sub.2-4 hydroxyalkyl group or an aralkyl group, and AN.sup.- is an anion selected from halide, C.sub.1-4 alkyl sulfate, C.sub.1-4 alkanesulfonate, arenesulfonate, C.sub.1-4 perfluoroalkane-sulfonate, tetrafluoroborate, perhalogenate, sulfate, hydrogen sulfate or carboxylate,

##STR00003## in which R.sup.12 is a C.sub.1-4 acyl group, a C.sub.1-4 alkylsulfonyl group, a C.sub.1-4alkylsulfinyl group, a C.sub.1-4 alkylamino group, a di-C.sub.1-4-alkyamino group, a vinyl carbonyl group, a methineimino group, a nitrile group, an ester or carboxylic acid amide group which may optionally be substituted by a C.sub.1-4 alkyl group, a C.sub.2-4 hydroxyalkyl group or an aryl group, and R.sup.13 represents a C.sub.1-4 acyl group, a C.sub.1-4 alkoxy group, a C.sub.1-4 alkylamino group, a C.sub.1-4 acylamino group or a di-C.sub.1-4-alkylamino group; the substituents R.sup.12 and R.sup.13 together with the rest of the molecule may also form a 5-, 6- or 7-membered ring system from the series of thiazolidine-2,5-diones, thiazolidine-2-thion-5-ones, perhydropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1,3-diones, indane-1,3-diones, 2-pyrazoline-5-ones, 1,2-dihydro-6-hydroxy-2-hydroxypyridines or enol esters thereof, and AX represents oxygen, sulfur or a dicyanomethylene group.

Keratinous fibers in the context of the present invention are understood to be pelts, wool, feathers and, in particular, human hair.

Examples of the C.sub.1-4 alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups. Preferred C.sub.1-4 hydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group. According to the invention, the other terms used are derived from the definitions given here. According to the invention, a particularly preferred perfluorinated C.sub.1-4 alkyl group is the trifluoromethyl group. According to the invention, a particularly preferred carboxy-C.sub.1-4-alkyl group is the carboxymethyl group. According to the invention, examples of a halogen atom are an F, a Cl or a Br atom. A Cl atom is particularly preferred. Preferred amino-C.sub.1-4-alkyl groups are the aminomethyl, aminoethyl, diethylaminomethyl and dimethylaminomethyl groups. Preferred substituted amino groups are the amino-C.sub.1-4-alkylamino groups, among which the aminoethylamino group is particularly preferred. A preferred acyl group is the acetyl group. Preferred alkenyl groups are the vinyl group and the allyl group.

According to the invention, compounds of formula (1) in which the substituent Y is hydrogen are particularly preferred. In the case of these compounds, which are present in a keto-enol equilibrium in accordance with formula (1a):

##STR00004## all statements in the present specification apply both to the keto form of these compounds and to the enol form.

Compounds of formula (1) where R.sup.1 and/or R.sup.4 are hydrogen have proved to be particularly advantageous.

Other preferred compounds of formula (1) can be those where at least one of the substituents R.sup.1, R.sup.3 or R.sup.4 is not hydrogen.

In a particularly preferred embodiment, the substituent --OR.sup.2 is selected from a hydroxy group, a methoxy group, a carboxymethyl group and a 2-hydroxyethoxy group.

In a first variant of the present invention, preferred compounds of formula (1) are those where X is an oxygen atom such as, for example, the compounds 5-carboxymethoxy benzo[b]furan-3-one, 5-hydroxybenzo[b]furan-3-one or 5-(2'-hydroxyethoxy)-benzo[b]furan-3-one.

In a second variant of the present invention, preferred compounds are those where X is a sulfur atom such as, for example, the compounds 5-hydroxybenzo[b]thiophen-3-one, 5-carboxymethoxybenzo[b]thiophen-3-one, 5,6-dihydroxybenzo[b]thiophen-3-one or 6-hydroxy-5-methoxybenzo[b]thiophen-3-one.

Particularly preferred compositions according to the invention contain at least one compound corresponding to formula (1) and at least one reactive carbonyl compound selected from the group of aromatic, heteroaromatic or unsaturated aldehydes or ketones, the dialdehydes or diketones or the acetals, semiaminals or imine derivatives of such reactive carbonyl compounds.

Suitable reactive carbonyl compounds of the aromatic aldehyde type are described, for example, in German patent applications DE 196 30 274 A1 and DE 196 30 275 A1. Other suitable arylaldehydes are known from U.S. Pat. No. 5,199,954. According to the invention, particularly suitable compounds are: benzaldehyde and benzaldehyde derivatives thereof such, as for example, 2-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 3,4-dihydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaidehyde, 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, 4-ethoxybenzaldehyde, 4-carboxybenzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dibutylaminobenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, biphenyl-4-carbaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde und 4-nitrobenzaldehyde, 1-naphthaldehyde and derivatives thereof such as, for example, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde and 2-methoxy-1-naphthaldehyde and cinnamaldehyde and derivatives thereof such as, for example, 4-hydroxy-3-methoxycinnamaldehyde (coniferyl aldehyde), 4-dimethylaminocinnamaldehyde and 3,5-dimethoxy-4-hydroxy-cinnamaldehyde.

Derivatives of the aromatic aldehydes which carry an optionally substituted hydroxy or amino group in the para position to the substituent bearing the aldehyde function are particularly preferred. The free hydroxy group and the di-(C.sub.1-4-alkyl)-amino group, for example the dimethylamino group, is particularly preferred.

Suitable reactive carbonyl compounds of the heteroaromatic aldehyde type are described, for example, in German patent application DE 197 172 806. Particularly suitable dyes are, for example, trans-.beta.-(2-furyl)-acrolein, 1-methylindole-3-carbaldehyde, 2-(1,3,3-trimethyl-2-indolinylidene)-acetaldehyde, 4-methylimidazole-5-carbaldehyde, 3-methoxy-4-(1-pyrrolidinyl)-benzaldehyde, pyrrole-2-carbaldehyde, thiophene-2-carbaldehyde, thiophene-3-carbaldehyde, chromone-3-carbaldehyde, 6-methylchromone-3-carbaldehyde, N-methylpyrrole-2-carbaldehyde, 5-methylfurfural, 6-hydroxychromene-3-carbaldehyde, N-ethylcarbazole-3-carbaldehyde, indole-3-carbaldehyde, 6-methylindole-3-carbaidehyde, thiophene-2,3-dicarbaldehyde, thiophene-2,5-dicarbaldehyde oder antipyrine-4-carbaldehyde. Special products of this type containing a pyridinium group are described in German patent application DE 197 45 356, for example the eminently suitable 4-formyl-1-methylpyridinium benzenesulfonate and 4-formyl-1-methylquinolinium methanesulfonate or methylsulfate or p-toluenesulfonate and 2-formyl-1-methylquinolinium-p-toluenesulfonate hydrate.

Suitable reactive carbonyl compounds of the unsaturated aldehyde type are described, for example, in German patent application DE 197 17 224. Glutaconaidehyde in the form of its salts, for example its alkali metal or tetrabutyl ammonium salt, or 2-chloro-3-hydroxymethylene-1-cyclohexene-1-carbaldehyde is particularly suitable for the purposes of the present invention. Another aldehyde suitable for the purposes of the invention is 5-(4-diethylamino)-phenyl)-2,4-pentadienal.

Dialdehydes and diketones and derivatives thereof which are suitable as reactive carbonyl compounds for the purposes of the invention are, for example, alicyclic and cyclic 1,2-, 1,3- or 1,4-dicarbonyl compounds, such as isatin, 1-H-quinoline-2,3,4-trione, ninhydrin, alloxan, isobarbituric acid, benzene-1,4-dicarbaldehyde, 1,2-phthaldialdehyde, 1,2-cyclohexandione, 1,3-cylcohexanedione, 1,4-cyclohexanedione, dimedone, 1,2-cyclopentadione, 1,3-cyclopentadione, p- and o-quinones, 2-methyl-1,4-naphthoquinone, 1,3-indanediones and derivatives thereof. Such dyes can be found, for example, in German Offenlegungsschrift DE 43 35 627 A1. Suitable compounds are, for example, malondialdehyde, preferably in the form of its dimethylacetal, 1,3-indanedione or 2-acetyl-1,3-cyclohexanedione. Another suitable 1,2-dicarbonyl compound is the potassium salt of isatic acid.

Diketones suitable in accordance with the invention as a reactive carbonyl compound also include cyclic dicarbonyl compounds such as, for example, the isatin and isatin derivatives described, for example, in German Offenlegungsschrift DE 44 09 143 A1. According to the invention, isatin, isatin-5-sulfonic acid potassium salt, N-allyl isatin, 1-piperidinomethyl isatin, 1-hydroxymethyl isatin and 1-diethylaminomethyl isatin are preferred.

Another cyclic dicarbonyl compound suitable as a reactive carbonyl compound is, for example, dehydroascorbic acid of which the suitability as a hair dye is known from German patent application DE 197 45 354.

Finally, acetals, imine derivatives and semiaminals of the reactive carbonyl compounds mentioned are also suitable for the purposes of the invention. Such compounds are obtained by reaction of the carboxyl group with primary alcohols or amines and optionally elimination of water.

The group of merocyanine and cyanine or azomethine dyes are obtainable from the unsaturated dialdehydes and diketones. Suitable imine derivatives of gutacondialdehyde are, for example, the mono-N-methylaniline derivative of glutaconaldehyde (5-N-methylanilinopentadienal) or N-(5-anilino-2,4-pentadien-1-ylidene)-anilinium chloride. Another suitable vinylogous cyanine dye is 7-dimethylamino-2,4,6-heptatrienylidene dimethyl ammonium perchlorate. Such compounds are known as hair colorant components, for example from German patent application DE 197 17 223.

The following are mentioned as examples of preferred compounds of formula (2): 1,4-dimethylquinolinium, 1,2-dimethylquinolinium, 1,4-dimethylpyridinium, 1,2-dimethylpyridinium, 2,4,6-trimethylpyrilium, 2-methyl-1-ethylquinolinium, 2,3-dimethylisoquinolinium, 1,2,3,3-tetramethyl-3H-indolium, 2,3-dimethylbenzothiazolium, 2,3-dimethyl-6-nitrobenzothiazolium, 3-benzyl-2-benzothiazolium, 2-methyl-3-propylbenzothiazolium, 2,4-dimethyl-3-ethylthiazolium, 3-(2-carboxyethyl)-2,5-dimethylbenzothiazolium, 1,2,3-trimethylbenzimidazolium, 5,6-dichloro-1,3-diethyl-2-methylbenzimidazolium, 3-ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylnaphtho[1,2-d]thiazolium, 5-chloro-3-ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylbenzoxazolium salts which may be present, for example as chlorides, bromides, iodides, methanesulfonates, benzenesulfonates, p-toluenesulfonates, trifluoromethanesulfonates, methylsulfates, tetrafluororborates and 2-methyl-3-(3-sulfopropyl)-benzothiazolium hydroxide (inner salt), 4-methyl-1-(3-sulfopropyl)-pyridinium hydroxide (inner salt, 4-methyl-1-(3-sulfopropyl)-quinolinium hydroxide (inner salt), 5-methoxy-2-methyl-3-(3-sulfopropyl)-benzothiazolium hydroxide (inner salt) and mixtures of the above.

According to the invention, the compounds of formula (2) may also be present in the form of their bases or the enamines, depending on the pH of the particular composition.

Examples of compounds corresponding to formula (3) are rhodamine, rhodamine-3-acetic acid, barbituric acid, thiobarbituric acid, 1,3-dimethyl and 1,3-diethyl thiobarbituric acid, oxindole, 3-indoxyl acetate, coumaranone, 1-methyl-3-phenylpyrazolinone, indane-1,3-dione, cyclopentane-1,3-dione, 1,2-dihydro-1-ethyl-6-hydroxy-4-methyl-2-oxo-3-pyridine carbonitrile, 1-dicyanomethylene indane and mixtures of the above.

The variety of shades obtainable with the coloring system according to the invention can be further increased by combination with one or more compounds containing a primary or secondary amino or hydroxy group selected from the group of amino acids and peptides, aromatic amines, phenols, aminophenols and nitrogen-containing heterocycles. In many cases, darker shades are also obtained.

Suitable amino acids are, in particular, the naturally occurring and synthetic amino acids, for example arginine, histidine, phenylalanine, dihydroxy phenylalanine, ornithine, lysine. Suitable peptides are, above all, oligo- and polypeptides which have sufficient solubility in water for use in the preparations according to the invention for reducing keratin. Examples include glutathione and the oligopeptides present in the hydrolyzates of collagen, keratin, elastin, casein or vegetable proteins, such as soya protein, wheat protein, algal protein or almond protein.

Suitable aromatic amines and aminophenols are N,N-dimethyl-, N,N-diethyl-, N-(2'-hydroxyethyl)-N-ethyl-, N,N-bis-(2'-hydroxyethyl)-, N-(2'-methoxyethyl)-, 2-chloro-, 2,3-, 2,4- and 2,5-dichloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3- and 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o- and p-phenylenediamine, o- and m-toluylenediamine, 2,5-diaminophenol, -toluene and -phenethol, 4-amino-3-methylphenol, 2-(2',5'-diaminophenyl)-ethanol, 2,4-diaminophenoxyethanol, 2-(2',5'-diaminophenoxy)-ethanol, 4-methylamino-, 3-amino-4-(2'-hydroxyethyloxy)-, 3,4-methylenediamino- and 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5-(2'-hydroxyethylamino)-, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy-, 5-(2'-hydroxyethylamino)-4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraminobenzene, 2,4,5-triaminophenol, pentaminobenzene, hexaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminopyrocatechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxypyrocatechol, aromatic anilines and phenols containing another aromatic radical corresponding to formula (4):

##STR00005## in which R.sup.1 is a hydroxy group or an amino group which may be substituted by C.sub.1-4 alkyl, C.sub.1-4 hydroxyalkyl or C.sub.1-4-alkoxy-C.sub.1-4-alkyl groups, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent hydrogen, a hydroxy group or an amino group, which may be substituted by C.sub.1-4 alkyl, C.sub.1-4 hydroxyalkyl, C.sub.1-4 aminoalkyl or C.sub.1-4-alkoxy-C.sub.1-4-alkyl groups, a carboxylic or sulfonic acid group and X is a direct bond, a saturated or unsaturated, optionally hydroxy-substituted carbon chain containing 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom or a group corresponding to formula (5): Z-(CH.sub.2--Y--CH.sub.2-Z').sub.o (5) in which Y is a direct bond, a CH.sub.2 or CHOH group, Z and Z' independently of one another represent an oxygen atom, an NR.sup.7 group, where R.sup.7 is hydrogen, a C.sub.1-4 alkyl or a hydroxy-C.sub.1-4-alkyl group, the group --O--(CH.sub.2).sub.p--NH or NH--(CH.sub.2).sub.p'--O, where p and p'=2 or 3, and o is a number of 1 to 4, such as for example 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid monosodium or disodium salt, 4,4'-diaminodiphenyl methane, -sulfide, -sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3',4,4'-tetraminodiphenyl, 3,3'4,4'-tetraminobenzophenone, 1,3-bis-(2,4-diaminophenoxy)-propane, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 1,3-bis-(4-aminophenylamino)-propane, -2-propanol, 1,3-bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-bis-[2-(4-aminophenoxy)-ethyl]-methylamine, N-phenyl-1,4-phenylenediamine.

The compounds mentioned above may be used both in free form and in the form of their physiologically compatible salts, more especially as salts of inorganic acids, such as hydrochloric acid or sulfuric acid.

Suitable phenols are, for example, 2-, 3- or 4-methoxyphenol, 3-dimethylaminophenol, 2-(2'-hydroxyethyl)- and 3,4-methylenedioxyphenol, resorcinol and 2-, 4- and 5-methylresorcinol, 2- and 4-chlororesorcinol, 2,5-dimethylresorcinol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2,4- or 3,4-dihydroxybenzoic or phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid or 2,4,5-trihydroxyacetophenone, 1-naphthol, 1,5-, 2,3- and 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid or 3,6-dihydroxy-2,7-naphthalene-disulfonic acid.

Suitable nitrogen-containing heterocyclic compounds are, for example, 2-, 3-, 4-amino-, 2-amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-triamino- and 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methylpyrimidine, 3-amino-, 3-amino-5-hydroxy- and 3,5-diaminopyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5- and 7-aminobenzimidazole and -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6- and 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The compounds mentioned above may be used both in free form and in the form of their physiologically compatible salts, for example as salts of inorganic acids, such as hydrochloric acid or sulfuric acid.

These coloring systems may be further strengthened by suitable nitrogen-containing heterocycles such as, for example, piperidine, piperidine-2-, -3- or -4-carboxylic acid, pyridine, 2-, 3- or 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazine and physiologically compatible salts thereof.

Several dye precursors of the reactive compound (b) type may be simultaneously present in the colorant preparations according to the invention. Similarly, several benzo[b]furan-3-one and/or benzo[b]thiophen-3-one derivatives may also be present in the compositions according to the invention. Several of the other compounds from the group of amino acids, peptides, aromatic amines, aminophenols, phenols and nitrogen-containing heterocycles may also be present together should this be necessary for obtaining the required shade.

The benzo[b]furan-3-one and/or benzo[b]thiophen-3-one derivatives are present in the compositions according to the invention in quantities of preferably 0.02 to 8% by weight, more preferably 0.05 to 5% by weight and most preferably 0.1 to 2% by weight, based on the composition as a whole. The reactive compounds (b) are present in the compositions according to the invention in quantities of preferably 0.02 to 8% by weight, more preferably 0.05 to 5% by weight and most preferably 0.1 to 2% by weight, based on the composition as a whole.

In another embodiment, however, the color-changing compositions according to the invention may also contain other dyes and/or dye precursors.

The present invention is not limited in any way in regard to the dye precursors suitable for use in the compositions according to the invention. The compositions according to the invention may contain as dye precursors oxidation dye precursors of the primary and secondary intermediate type and precursors of "nature-analogous" dyes, such as indole and indoline derivatives and mixtures of representatives of these groups.

The primary intermediates used are normally primary aromatic amines containing another free or substituted hydroxy or amino group in the para- or ortho-position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraminopyrimidine and derivatives thereof.

According to the invention, it can be preferable to use a p-phenylenediamine derivative or a physiologically compatible salt thereof as primary intermediate. Particularly preferred p-phenylenediamine derivatives correspond to formula (6):

##STR00006## in which G.sup.1 stands for a hydrogen atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a (C.sub.1-4)-alkoxy-(C.sub.1-4)-alkyl radical, a 4'-aminophenyl radical or a C.sub.1-4 alkyl radical substituted by a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group; G.sup.2 stands for a hydrogen atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a (C.sub.1-4)-alkoxy-(C.sub.1-4)-alkyl radical or a C.sub.1-4 alkyl radical substituted by a nitrogen-containing group; G.sup.3 stands for a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.1-4 hydroxyalkoxy radical, a C.sub.1-4 acetylaminoalkoxy radical, a C.sub.1-4 mesylaminoalkoxy radical or a C.sub.1-4 carbamoylaminoalkoxy radical; G.sup.4 is a hydrogen atom, a halogen atom or a C.sub.1-4 alkyl radical or if G.sup.3 and G.sup.4 are in the ortho position to one another, they may together form a bridging .alpha.,.omega.-alkylenedioxo group such as, for example, an ethylenedioxy group.

Examples of the C.sub.1-4 alkyl radicals mentioned as substituents in the compounds according to the invention are the methyl, ethyl, propyl, isopropyl and butyl groups. Ethyl and methyl radicals are preferred alkyl radicals. According to the invention, preferred C.sub.1-4 alkoxy radicals are, for example, methoxy or ethoxy radicals. Other preferred examples of a C.sub.1-4 hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyalkyl group is particularly preferred. According to the invention, examples of a halogen atom are the F, Cl or Br atom. A Cl atom is most particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups corresponding to formula (6) are, in particular, the amino groups, C.sub.1-4 monoalkylamino groups, C.sub.1-4 dialkylamino groups, C.sub.1-4 trialkylammonium groups, C.sub.14 monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines corresponding to formula (6) are selected from p-phenylenediamine, p-toluylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)-aniline, N,N-bis-(.beta.-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis-(.beta.-hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis-(.beta.-hydroxyethyl)-amino-2-chloroaniline, 2-(.beta.-hydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(.beta.-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl-.beta.-hydroxyethyl)-p-phenylene-diamine, N-(.beta.,.gamma.-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(.beta.-hydroxyethyloxy)-p-phenylenediamine, 2-(.beta.-acetylaminoethyloxy)-p-phenylenediamine, N-(.beta.-methoxyethyl)-p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and physiologically compatible salts thereof.

According to the invention, most particularly preferred p-phenylenediamine derivatives corresponding to formula (6) are p-phenylenediamine, p-toluylenediamine, 2-(.beta.-hydroxyethyl)-p-phenylene-diamine and N,N-bis-(.beta.-hydroxyethyl)-p-phenylenediamine

In another preferred embodiment of the invention, compounds containing at least two aromatic nuclei substituted by amino and/or hydroxyl groups may be used as primary intermediates.

The binuclear primary intermediates which may be used in the coloring compositions according to the invention include in particular compounds corresponding to formula (7) and physiologically compatible salts thereof:

##STR00007## in which Z.sup.1 and Z.sup.2 independently of one another stand for a hydroxyl or NH.sub.2 radical which is optionally substituted by a C.sub.1-4 alkyl radical, by a C.sub.1-4 hydroxyalkyl radical and/or by a bridging group Y or which is optionally part of a bridging ring system, the bridging group Y is a C.sub.1-14 alkylene group such as, for example, a linear or branched alkylene chain or an alkylene ring which may be interrupted or terminated by one or more nitrogen-containing groups and/or one or more hetero atoms, such as oxygen, sulfur or nitrogen atoms, and may optionally be substituted by one or more hydroxyl or C.sub.1-8 alkoxy radicals, G.sup.5 and G.sup.6 independently of one another stand for a hydrogen or halogen atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a C.sub.1-4 aminoalkyl radical or a direct bond to the bridging group Y, G.sup.7, G.sup.8, G.sup.9, G.sup.10, G.sup.11 and G.sup.12 independently of one another stand for a hydrogen atom, a direct bond to the bridging group Y or a C.sub.1-4 alkyl radical, with the proviso that the compounds of formula (7) contain only one bridging group Y per molecule.

According to the invention, the substituents used in formula (7) are as defined in the foregoing.

Preferred binuclear primary intermediates corresponding to formula (7) are, in particular, N,N'-bis-(.beta.-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diaminopropa- nol, N,N'-bis-(.beta.-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-ethylenediam- ine, N,N'-bis-(4-aminophenyl)-tetramethylene diamine, N,N'-bis-(.beta.-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-tetramethylene diamine, N,N'-bis-(4-methylaminophenyl)-tetramethylene diamine, N,N'-bis-(ethyl)-N,N'-bis-(4'-amino-3'-methylphenyl)-ethylene diamine, 1,8-bis-(2,5-diaminophenoxy)-3,5-dioxaoctane, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane and 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane and physiologically compatible salts thereof.

Most particularly preferred binuclear primary intermediates corresponding to formula (7) are N,N'-bis-(.beta.-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3-diaminopropa- nol, bis-(2-hydroxy-5-aminophenyl)-methane, N,N'-bis-(4-aminophenyl)-1,4-diazacycloheptane and 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane or one of their physiologically compatible salts.

In another preferred embodiment of the invention, a p-aminophenol derivative or a physiologically compatible salt thereof is used as primary intermediate. Particularly preferred p-aminophenol derivatives correspond to formula (8):

##STR00008## in which G.sup.13 stands for a hydrogen atom, a halogen atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a (C.sub.1-4)-alkoxy-(C.sub.1-4)-alkyl radical, a C.sub.1-4 aminoalkyl radical, a hydroxy-(C.sub.1-4)-alkylamino radical, a C.sub.1-4 hydroxyalkyoxy radical, a C.sub.1-4 hydroxyalkyl-(C.sub.1-4)-aminoalkyl radical or a (di-C.sub.1-4-alkylamino)-(C.sub.1-4)-alkyl radical, G.sup.14 stands for a hydrogen atom or a halogen atom, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a (C.sub.1-4)-alkoxy-(C.sub.1-4)-alkyl radical, a C.sub.1-4 aminoalkyl radical or a C.sub.1-4 cyanoalkyl radical, G.sup.15 stands for hydrogen, a C.sub.1-4 alkyl radical, a C.sub.1-4 monohydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a phenyl radical or a benzyl radical and G.sup.16 stands for hydrogen or a halogen atom.

According to the invention, the substituents used in formula (8) are defined as in the foregoing.

Preferred p-aminophenols corresponding to formula (8) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(2-hydroxyethoxy)-phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(.beta.-hydroxyethylaminomethyl)-phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2-((diethylamino)methyl)phenol and physiologically compatible salts thereof.

Most particularly preferred compounds corresponding to formula (8) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2-((diethylamino)methyl)phenol.

The primary intermediate may also be selected from o-aminophenol and its derivatives such as, for example, 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

In addition, the primary intermediate may be selected from heterocyclic primary intermediates such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole/pyrimidine derivatives and physiologially compatible salts thereof.

Preferred pyridine derivatives are, in particular, the compounds described in GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopridine, 2-(4-methoxyphenyl)-amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(.beta.-methoxyethyl)-amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in DE 2359399, JP 02019576 A2 and WO 96/15765, such as 2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyridine.

Preferred pyrazole derivatives are, in particular, the compounds described in DE 3843892, DE 4133957, WO 94/08969, WO 94/08970, EP 740931 and DE 19543988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(.beta.-hydroxyethyl)-pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert.butyl-1-methylpyrazole, 4,5-diamino-1-tert.butyl-3-methylpyrazole, 4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)-pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)-amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4-(.beta.-hydroxyethyl)-amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole-[1,5-a]-pyrimidine corresponding to formula (9) below and tautomeric forms thereof where a tautomeric equilibrium exists:

##STR00009## in which G.sup.17, G.sup.18, G.sup.19 and G.sup.20 independently of one another stand for a hydrogen atom, a C.sub.1-4 alkyl radical, an aryl radical, a C.sub.1-4 hydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a (C.sub.1-4)-alkoxy-(C.sub.1-4)-alkyl radical, a C.sub.1-4 aminoalkyl radical which may optionally be protected by an acetylureide or sulfonyl radical, a (C.sub.1-4)-alkylamino-(C.sub.1-4)-alkyl radical, a di[(C.sub.1-4)-alkyl]-(C.sub.1-4)-aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 links, a C.sub.1-4 hydroxyalkyl or a di-(C.sub.1-4)-[hydroxyalkyl]-(C.sub.1-4)-aminoalkyl radical; the X radicals independently of one another stand for a hydrogen atom, a C.sub.1-4 alkyl radical, an aryl radical, a C.sub.1-4 hydroxyalkyl radical, a C.sub.2-4 polyhydroxyalkyl radical, a C.sub.14 aminoalkyl radical, a (C.sub.1-4)-alkylamino-(C.sub.1-4)-alkyl radical, a di[(C.sub.1-4)-alkyl]-(C.sub.1-4)-aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 links, a C.sub.1-4 hydroxyalkyl or a di-(C.sub.1-4)-[hydroxyalkyl]-(C.sub.1-4)-aminoalkyl radical, an amino radical, a C.sub.1-4 alkyl or a di-(C.sub.1-4 hydroxyalkyl)-amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p+q is not 0, where p+q=2, n has the value 0 and the groups NG.sup.17G.sup.18 and NG.sup.19G.sup.20 occupy the (2,3); (5,6); (6,7); (3,5) or (3,7) positions; where p+q=1, n has the value 1 and the groups NG.sup.17G.sup.18 (or NG.sup.19G.sup.20) and the group OH occupy the (2,3); (5,6); (6,7); (3,5) or (3,7) positions.

The substituents used in formula (9) are as defined in the foregoing.

If the pyrazole-[1,5-a]-pyrimidine corresponding to formula (9) above contains a hydroxy group in one of the positions 2, 5 or 7 of the ring system, a tautomeric equilibrium exists as illustrated, for example, in the following scheme:

##STR00010##

Among the pyrazole-[1,5-a]-pyrimidines corresponding to formula (9) above, the following may be particularly mentioned: pyrazole-[1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; pyrazole-[1,5-a]-pyrimidine-3,5-diamine; 2,7-dimethylpyrazole-[1,5-a]-pyrimidine-3,5-diamine; 3-aminopyrazole-[1,5-a]-pyrimidin-7-ol; 3-aminopyrazole-[1,5-a]-pyrimidin-5-ol; 2-(3-aminopyrazole-[1,5-a]-pyrimidin-7-ylamino)-ethanol; 2-(7-aminopyrazole-[1,5-a]-pyrimidin-3-ylamino)-ethanol; 2-[(3-aminopyrazole-[1,5-a]-pyrimidin-7-yl)-(2-hydroxyethyl)-amino]-ethan- ol; 2-[(7-aminopyrazole-[1,5-a]-pyrimidin-3-yl)-(2-hydroxyethyl)-amino]-et- hanol; 5,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; 2,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; and physiologically compatible salts thereof and tautomeric forms thereof where a tautomeric equilibrium exists.

The pyrazole-[1,5-a]-pyrimidines corresponding to formula (9) above may be prepared by cyclization from an aminopyrazole or from hydrazine, as described in the literature.

The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorciol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. Particularly suitable secondary intermediates are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethylether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chloreresorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

According to the invention, preferred secondary intermediates are: m-aminophenol and derivatives thereof such as, for example, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2'-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3-(ethylamino)-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and derivatives thereof, m-diaminobenzene and derivatives thereof such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)-benzene, 1,3-bis-(2,4-diaminophenyl)-propane, 2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and 1-amino-3-bis-(2'-hydroxyethyl)-aminobenzene, o-diaminobenzene and derivatives thereof such as, for example, 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene, di- and trihydroxybenzene derivatives such as, for example, resorcinol, resorcinol monomethyl ether, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as, for example, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihdroxynaphthalene, 1,7-dihdroxynaphthalene, 1,8-dihdroxynaphthalene, 2,7-dihdroxynaphthalene and 2,3-dihdroxynaphthalene, morpholine derivatives such as, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as, for example, 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as, for example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1-(2'-hydroxyethyl)-amino-3,4-methylenedioxybenzene.

Particularly preferred secondary intermediates are, for example, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

The oxidation dye precursors or the substantive dyes do not have to be single compounds. On the contrary, other components may be present in small quantities in the hair colorants according to the invention due to the processes used to produce the individual dyes providing these other components do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons.

So far as the dyes suitable for use in the hair colorants and tinting compositions according to the invention are concerned, reference is also expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248 250; substantive dyes) and Chapter 8, pages 264 267; oxidation dye precursors), published as Volume 7 of the Series "Dermatology" (Ed.: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986, and to the "Europaische Inventar der Kosmetik-Rohstoffe" published by the Europaische Gemeinschaft and available on floppy disk from the Bundesverband Deutscher Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel d.V., Mannheim.

The oxidation dye precursors are present in the compositions according to the invention in quantities of preferably 0.01 to 20% by weight and more preferably 0.5 to 5% by weight, based on the composition as a whole.

In a preferred embodiment of the invention, the reactive compounds are stored separately from the benzo[b]furan-3-one and/or benzo[b]thiophen-3-one derivatives and the oxidation dyes so that these components do not react prematurely. Thus, these compounds may be stored in separate aqueous media, such as emulsions for example, which are only combined immediately before application to the fibers.

In addition, one or more of the components may be formulated as one or more aqueous media and the other component(s) may be formulated as powders. In this embodiment, the powder-form components are added to the aqueous medium immediately before use. In a preferred embodiment of the invention, the component containing the compoun