WO2004031164A1 - Hair dyes comprising m-phenylenediamine derivatives as coupling components - Google Patents

Abstract

The invention relates to agents for dyeing keratin fibers, especially human hair, containing at least one m-phenylenediamine derivative of formula (I) or one of the physiologically acceptable salts thereof as a coupling component in a cosmetically acceptable carrier, R1 in formula (I) representing a hydrogen atom, a halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C1 to C4 aminoalkyl group, a C1 to C4 alkoxy-(C1 to C4) alkyl group, or a C1 to C4 dialkylamino-(C1 to C4) alkyl group, R2 and R3 independently representing a hydrogen atom, a C1 to C4 alkyl group, a C2 to C4 monohydroxyalkyl group, a C3 to C4 polyhydroxyalkyl group, a C1 to C4 alkoxy-(C1 to C4) alkyl group, or a C1 to C4 aminoalkyl group, and X representing a saturated, 5-membered, 6-membered, or 7-membered heterocycle which comprises at least one nitrogen atom and an additional optional heteroatom selected among oxygen, sulfur, or nitrogen. Said heterocycle is linked to the aromatic ring system via a nitrogen atom and can optionally carry up to two substituents that are different from hydrogen and are selected among a halogen atom, a C1 to C4 alkyl group, a C1 to C4 monohydroxyalkyl group, a C2 to C4 polyhydroxyalkyl group, a C1 to C4 aminoalkyl group, a C1 to C4 alkoxy-(C1 to C4) alkyl group, or a C1 to C4 dialkylamino-(C1 to C4) alkyl group. The inventive coupling components allow for intensive shiny nuances with very good fastness properties, particularly in combination with p-phenylenediamine derivatives, diaminopyrazole derivatives, and oligo-aminopyrimidine derivatives.

Description

 HAIR COLORING AGENT WITH M-PHENYLENE DIAMINE DERIVATIVES AS A COUPLER COMPONENT

The present invention relates to agents for dyeing keratin fibers which contain special m-phenylenediamine derivatives in which one of the two nitrogen atoms is part of a saturated heterocycle, a process for dyeing hair using these agents, and some of these m-phenylenediamine derivatives themselves and intermediates which arise in the manufacture of these connections.

For dyeing keratin fibers, especially human hair, the so-called oxidation dyes play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and

Intermediates. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.

Primary aromatic amines with a further free or substituted hydroxy or amino group which is in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as developer components ,

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5- Diaminophenyethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2- Hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) - N, N'-bis (4-aminophenyl) diamino-propan-2-ol.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor- cinmonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1, 3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye precursors should primarily fulfill the following prerequisites: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. You must also have a good ability to draw on the fiber, especially in the case of human hair, there must be no noticeable differences between damaged and newly grown hair (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, if they are used as hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view. Furthermore, the coloring achieved should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and is to be reversed.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components which are also problematic in toxicological and dermatological terms.

It was therefore an object of the present invention to develop new coupler components which meet the requirements imposed on oxidation dye precursors, in particular with regard to the toxicological and dermatological properties, and which enable dyeings in a wide color spectrum with good fastness properties.

Surprisingly, it has now been found that m-phenylenediamine derivatives, in which one of the two nitrogen atoms is part of a saturated heterocycle, meet the requirements imposed on coupler components to a high degree. The Allow coupler components according to the invention, in particular in combination with p-phenylenediamine derivatives, diaminopyrazole derivatives and

Oligoaminopyrimidine derivatives, intense brilliant shades with very good fastness properties.

The present invention therefore firstly relates to agents for dyeing keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the formula (I) or one of its physiologically tolerable salts in a cosmetically acceptable carrier as a coupler component

where R ¹ represents a hydrogen atom, a halogen atom, a d to C ₄ alkyl group, a d to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, a Ci to C ₄ aminoalkyl group, a d - to C -alkoxy- (d- to C ₄ ) -alkyl group or ad- to C ₄ -dialkylamino- (Cr to C ₄ ) -alkyl group,

R ² and R ³ are independently a hydrogen atom, a C to C ₄ - alkyl group, a C ₂ - to C ₄ -monohydroxyalkyl group, a C ₃ - to C - polyhydroxyalkyl group, a C to C alkoxy (C to C) alkyl group or a C _r to C ₄ aminoalkyl group and

X stands for a saturated, 5-, 6- or 7-membered heterocycle which has at least one nitrogen atom and optionally another heteroatom selected from oxygen, sulfur or nitrogen, the heterocycle being bonded to the aromatic ring system via a nitrogen atom , and the heterocycle can optionally carry up to two substituents other than hydrogen, which are selected from a halogen atom, a C to C ₄ alkyl group, a d to C ₄ monohydroxyalkyl group, a C ₂ to C ₄ polyhydroxyalkyl group, one Ci to C ₄ aminoalkyl group, ad to C ₄ alkoxy (C to C ₄ ) alkyl group or ad to C ₄ dialkylamino (d to C ₄ ) alkyl group.

Keratinic fibers are to be understood according to the invention to mean furs, wool, feathers and in particular human hair. Although the invention Oxidation dyes are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent them from being used in other areas, particularly in color photography.

Since the m-phenylenediamine derivatives according to the invention are amino compounds, the known acid addition salts can be prepared from them in the usual way. All statements in this document and accordingly the claimed scope of protection therefore relate both to the compounds present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the d- to d-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 d- to C ₄ -alkoxy groups are the methoxy and ethoxy groups. Further preferred examples of a - to C ₄ -monohydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ - polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, CI or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here.

The m-phenylenediamine derivatives of the formula (I) can be prepared using conventional organic methods. As an example, reference is made to the experimental procedures in the context of the exemplary embodiments. In an embodiment preferred according to the invention, the base body of the m-phenylenediamine derivatives of the formula (I) can be synthesized, for example, by reacting 3-fluoronitrobenzene with the corresponding saturated nitrogen-containing heterocycles. According to the invention, the m-phenylenediamine derivatives of the formula (I) can therefore be preferred, the base structure of which can be prepared by reacting 3-fluomitrobenzene with one of the following compounds, which are characterized here with the aid of their chemical abstract number: CA no .: 100158-62-1, CA no .: 1003-28-7, CA no.102308-48-5, CA no.104-89-2, CA no.1064678 -13-9, CA No.:109-05-7, CA No.:109967-01-3, CA No.:110-89-4, CA No.:111- 49-9, CA. -No.:1121-44-4, CA-No.:114143-75-8, CA-No.:116574-75-5, CA-No.:118971-00-9, CA-No.:1193- 12-0, CA No.:121963-72-2, CA No.:123-75-1, CA No.:124602-03-5, CA- No.:133294-31-2, CA- No .: 13748-14-6, CA no .: 138022-00-1, CA no .: 138617-51-3, CA no .: 14066-85-4, CA no .: 144230-52 -4, CA no .: 14446-75-4, CA no .: 1484-80-6, CA no .: 1484-84-0, CA no .: 155106-17-5, CA no .: 15991-59-0, CA no .: 167704-69-0, CA no .: 1722-95-8, CA no .: 174073-64-4, CA no .: 1772-29- 8, CA no .: 180258-82-6, CA no .: 1882-42-4, CA no .: 19168-71-9, CA no .: 198283-99-7, CA no. : 199475-41-7, CA- No.:205180-40-1, CA-No.:205443-01-2, CA-No.:205443-04-5, CA-No.:2088-78-0 , CA- no. ^ 1987-29-1, CA- no .: 222314-27-4, CA- no .: 222314-35-4, CA- no .: 222314-40-1, CA- no .: 22398-09-0, CA no .: 22977-56-6, CA no .: 22990-77-8, CA no .: 2309-21-0, CA no .: 23356-96-9, CA No.:24152-39-4, CA No.:3197-42- 0, CA no .: 3230-23-7, CA no .: 3238- 60-6, CA no .: 32452-45-2, CA no .: 3378-71-0, CA no. : 3433-37-2, CA #: 34375-89-8, CA #: 344329-35-7, CA #: 34446-98-8, CA #: 35794-11-7 , CA no .: 363179-66-2, CA no .: 372963-41-2, CA no .: 383127-24-0, CA no .: 383127-26-2, CA no .: 383128-18-5, CA- no .: 383128-19-6, CA- no .: 383129-05-3, CA- no .: 383129-08-6, CA- no .: 383129-13-3, CA- no .: 383129-28-0, CA- no .: 383129-30-4, CA- no .: 4045-30-1, CA- no .: 4209-65-8, CA- no.452331 -68-9, CA # 458-88-8, CA #: 4606-65-9, CA #: 504-03-0, CA #: 5072-45- 7, CA No.:5119-88-0, CA No.:51503-10-7, CA No.:5347-68-2, CA No.:54288-70-9, CA- No.:555- 92-0, CA No.:57367-18-7, CA No.:57395-89-8, CA No.:57734-57-3, CA- No.:60717-49-9, CA- No .: 60717-51-3, CA No.:6091-44-7, CA No.:622-26-4, CA No.:626-56-2, CA No.:626-58 -4, CA No.:62617-70-3, CA No.:62848-20-8, CA No.:6287-19-0, CA- No.:63126-47-6, CA No. .: 63639-02-1, CA #: 637-49-0, CA #: 64168-10-1, CA #: 6457- 49-4, CA #: 65337-42- 0, CA #: 65944-50-5, CA #: 66928-78-7, CA #: 67318 -88-1, CA #: 68832-13-3, CA #: 69500-64-7, CA #: 70144-18-2, CA #: 70724-66-2, CA - No.:70754-93-7, CA-No.:71172-94-6, CA-No.:7144-05-0, CA-No.:72939-22-1, CA- No.:72939- 23-2, CA No.:72939-24-3, CA No.:73579-06-3, CA No.:76025-62-2, CA- No.:765-38-8, CA- No .: 766-17-6, CA no .: 76946-27-5, CA no .: 78197-27-0, CA no .: 80053- 54-9, CA no .: 80053-55 -0, CA #: 84025-81-0, CA #: 84039-87-2, CA #: 84367-22-6, CA #: 88057-03-8, CA # .: 90203-05-7, CA no .: 90290-05-4, CA no .: 91187-81-4, CA no .: 93621-94-4, CA no .: 10024-89- 2, CA no.10: 3003-01-6, CA no.106-55-8, CA no.108-49-6, CA no.109-07-9, CA no. : 110-85-0, CA No.:110-91-8, CA No.:116143-27-2, CA No.:122894-56-8, CA No.:123-57-9 , CA no .: 128454-20-6, CA no .: 130861-85-7, CA no .: 13961-37-0, CA no .: 141-91-3, CA no .: 142-63-2, CA No.:142-64-3, CA No.:171351-20- 5, CA No.:21655-48-1, CA No. : 25154-38-5, CA no. : 2815-34-1, CA no .: 28631-79-0, CA no .: 393781-72-1, CA no. : 4554-26-1, CA no .: 6091-62-9, CA no. : 6284-84-0, CA No.:6485- 55-8, CA No. : 74879-18-8, CA no .: 75336-85-5, CA no. : 75336-86-6, CA no. : 75336-89-9 and CA no. : 84477-72-5.

Some of the m-phenylenediamine derivatives of the formula (I) are already known from the prior art. However, there is no indication in the literature that these can be used as coupler components in hair dyes. Structurally distantly related m-phenylenediamine derivatives are already known from DE-A1-26 22 451. There, bis-substituted benzenes are described symmetrically with secondary amines, including 1,3-bis (piperidin-1-yl) benzene. However, this application of the prior art gives the person skilled in the art no suggestion whatsoever of using the m-phenylenediamine derivatives now claimed as coupler components. Rather, the synthesis strategy given there does not permit the production of the m-phenylenediamine derivatives now claimed and thus leads away from the subject matter of the present application.

According to the invention, the m-phenylenediamine derivatives of the formula (I) in which R ^{1 represents} a hydrogen atom, a halogen atom, a C to C ₄ alkyl group or a d to C ₄ monohydroxyalkyl group can be preferred. R ¹ particularly preferably represents a hydrogen atom, a chlorine atom, a methyl group or a 2-hydroxyethyl group. M-Phenylenediamine derivatives of the formula (I) in which R ^{1 represents} a hydrogen atom are very particularly preferred.

According to the invention, the m-phenylenediamine derivatives of the formula (I) can furthermore be preferred in which R ² and R ³ independently of one another represent a hydrogen atom, a d- to C -alkyl group or a d- to C ₄ -monohydroxyalkyl group. The substituents R ² and R ³ are particularly preferably independently of one another a hydrogen atom, a methyl group or a 2-hydroxyethyl group. M-Phenylenediamine derivatives of the formula (I) in which

R ² and R ³ each represent a methyl group, one of the radicals R ² or R ^{3 represents} a 2-hydroxyethyl group and the other of the

R ² or R ³ are hydrogen or both R ² and R ^{3 are} each hydrogen. Furthermore, according to the invention, m-phenylenediamine derivatives of the formula (I) may be preferred in which X represents a pyrrolidin-1-yl group, an imidazolidin-1-yl group, a piperidin-1-yl group, a piperazin-1-yl group, a morpholine group 4-yl group, a hexahydroazepin-1-yl group or a hexahydro-1,4-oxazepin-4-yl group. In addition to the abovementioned radicals, their derivatives substituted with an alkyl group, in particular a methyl group, may also be preferred according to the invention. If the heterocycle has a second nitrogen atom, the substituted derivatives in which the substituent is bonded to the second nitrogen atom can be particularly preferred.

Particularly preferred are m-phenylenediamine derivatives of the formula (I) in which X represents a morpholin-4-yl group, a piperidin-1-yl group, a 4-methylpiperazin-1-yl group or a pyrrolidin-1-yl group.

M-Phenylenediamine derivatives of the formula (I) which are particularly preferred according to the invention are selected from the group formed by 3-pyrrolidin-1-ylaniline, 3-piperidin-1-ylaniline, 3-morpholin-4-ylaniline, 3- (4- Methylpiperazin-1-yl) aniline, N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol, 2 - [(3rd -Piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] -ethan-1-ol.

3-Pyrrolidin-1-yl-aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) are very particularly preferred in the context of the present invention ) amino] ethane-1-ol.

In addition to the m-phenylenediamine derivatives of the formula (I), the colorants according to the invention can also contain at least one developer component.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and the like are usually used as developer components Derivatives used. It may be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

G ¹ represents a hydrogen atom, a d- to C ₄ alkyl, a d- to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (d-C) alkoxy (C ₄ to C ) alkyl radical, a 4'-aminophenyl radical or ad- to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, ad to C ₄ alkyl, ad to C monohydroxyalkyl, C ₂ to C polyhydroxyalkyl, (d to C) alkoxy (d to C ₄ ) alkyl radical or ad- to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, ad- to C -alkyl radical, a Ci- to C ₄ -monohydroxyalkyl radical, a C ₂ - to C -polyhydroxyalkyl radical, one d- to C -hydroxyalkoxy, a C to C - acetylaminoalkoxy, a C _r to C ₄ - mesylaminoalkoxy or a d to C ₄ - carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a d- to C ₄ -alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the Ci to C alkyl radicals 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 radicals. C to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Farther As preferred examples of a C to C -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ polyhydroxyalkyl group containing 1, 2- dihydroxyethyl is. Examples of halogen atoms according to the invention are F, CI or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, monoalkylamino groups d- to C, D to C ₄ dialkylamino, d- to C - trialkylammonium, C ₄ to C -Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 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- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 - methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2 -Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acet ylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

According to the invention, p-phenylenediamine derivatives of the formula (E1) which are particularly preferred are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

It can also be preferred according to the invention to use, as developer component, compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups. Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical, which is optionally substituted by a d- to C -alkyl radical, by a d- to C -hydroxyalkyl radical and / or by a bridging Y or the optional part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as, for example, a linear or branched alkylene chain or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or Nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 -C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a d- to C -alkyl radical, a C to C -monohydroxyalkyl radical, a C ₂ - to C -polyhydroxyalkyl radical, a d- to C ₄ -aminoalkyl radical or a direct one Connection to bridge Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to bridge Y or a d- to C ₄ -alkyl radical, with the provisos that the compounds of the formula ( E2) contain only one bridge Y per molecule and - the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom. According to the invention, the substituents used in formula (E2) are defined analogously to the above statements.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) propan-2-ol , N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p -phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7, 10- tetraoxadecane and their physiologically tolerable salts.

Very particularly preferred dual-core developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, 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 acceptable salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C to C ₄ alkyl radical, a d to C ₄ monohydroxyalkyl radical, a C ₂ to d polyhydroxyalkyl radical, a (d to C) alkoxy- (d- to C ₄ ) -alkyl radical, ad- to C -aminoalkyl radical, a hydroxy- (C to C ₄ ) -alkylamino radical, a C _r to C -hydroxyalkoxy radical, a C to C ₄ - Hydroxyalkyl- (d-to C ₄ ) -aminoalkyl or a (di-C to C ₄ -alkylamino) - (C to C ₄ ) -alkyl, and

G ¹⁴ represents a hydrogen or halogen atom, a C to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a (C to C ₄ ) alkoxy (d to C) ₄ ) -alkyl radical, a C to C ₄ -aminoalkyl radical or ad- to C-cyanoalkyl radical,

G ¹⁵ represents hydrogen, ad to C ₄ alkyl, ad to C ₄ monohydroxyalkyl, C ₂ to C ₄ polyhydroxyalkyl, phenyl or benzyl, and

G ¹⁶ represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (ß-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino- 2- (diethylaminomethyl) -phenol.

Furthermore, the developer component can be selected from o-aminophenol and its derivatives, such as, for example, 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable salts. Preferred pyridine derivatives are, in particular, the compounds described in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine , 2,3-diamino-6-methoxy-pyridine, 2- (ß-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2 359 399, Japanese laid-open patent publication JP 02019576 A2 or in laid-open publication WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 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- triaminopyrimidine.

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP 740 931 and DE 195 43 988, such as 4.5 -Diamino-1-methylpyrazole, 4,5- diamino-1- (ß-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- (β-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- (ß-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- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] -pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:

in which: G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, ad- to C ₄ -alkyl residue, an aryl residue, ad- to C -hydroxyalkyl residue, a C ₂ - to C -polyhydroxyalkyl residue a ( C to C ₄ ) -alkoxy- (d- to C) -alkyl radical, a C to C ₄ -aminoalkyl radical which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C ₄ ) - Alkylamino (C to C) alkyl, a di - [(d to C ₄ ) alkyl] - (C to C ₄ ) aminoalkyl, the dialkyl radicals optionally being a carbon cycle or a heterocycle with 5 or 6 chain links form a d- to d-hydroxyalkyl or a di- (d- to C) - [hydroxyalkyl] - (d- to C ₄ ) -aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, ad- to C ₄ alkyl, an aryl residue, a d- to d-hydroxyalkyl residue, a C ₂ to C ₄ polyhydroxyalkyl residue, a d to C aminoalkyl residue, a (C to C ₄ ) alkylamino (C to C ₄ ) alkyl radical, a di - [(d- to C ₄ ) alkyl] - (d- to C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a d- to C -hydroxyalkyl or a Di- (d- to C ₄ -hydroxyalkyl) -aminoalkyl, an amino, ad- to C ₄ -alkyl or di- (C to C-hydroxyalkyl) -amino, 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 equal to 0 if p + q is 2, n is 0 and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

According to the invention, the substituents used in formula (E4) are defined analogously to the above statements.

If the pyrazole [1,5-a] pyrimidine of the formula (E4) above contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme: H

NG ¹⁷ G ¹⁸ NG ¹⁷ G ^1Y

OH o

Among the pyrazole [1, 5-a] pyrimidines of the above formula (E4), one can mention in particular:

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] ethanol;

2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

5,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazole- [1,5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

The pyrazole [1, 5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine.

In a further preferred embodiment, the colorants according to the invention contain at least one further coupler component.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components. Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1, 7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-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-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 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 -Dichlor-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives 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-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene, pyridine derivatives such as 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 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine and 6-amino-benzomo holin, Quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 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 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.

Coupler components which are particularly preferred according to the invention are 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-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

The following have been found to be particularly suitable according to the invention

Couplers / developer combinations proved:

3-pyrrolidin-1-yl-aniline / p-toluenediamine,

3-pyrrolidin-1-yl-aniline / 2,4,5,6-tetraaminopyrimidine,

2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol / p-toluenediamine,

2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol / 1- (2-hydroxyethyl) -4,5-diaminopyrazole,

2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol / p-toluenediamine,

2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol / 1- (2-hydroxyethyl) -2,5-diaminobenzene,

2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol / 4-hydroxy-2,5,6-triaminopyrimidine,

2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol / 1- (2-hydroxyethyl) -4,5-diaminopyrazole and

2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol / 2,4,5,6-tetraaminopyrimidine.

In a further embodiment of the present invention, the colorants can contain at least one precursor of a nature-analog dye. Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. exhibit. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Derivatives of 5,6-dihydroxyindoline of the formula (IIIa) are particularly suitable as precursors of naturally analogous hair dyes,

in the independent

'

R ¹ represents hydrogen, a dC ₄ -alkyl group or a CC -hydroxy-alkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a dd-alkyl group,

- R ⁴ stands for hydrogen, a dC ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CrC ₄ alkyl group, and

- R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially the 5 6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (IIb) are also outstandingly suitable as precursors of natural hair dyes,

(Ilb) R ¹ in the independently

R ¹ represents hydrogen, a CrC -alkyl group or a dC -hydroxyalkyl- group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a dd-alkyl group,

R ⁴ stands for hydrogen, a dC -alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CrC -alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 are to be emphasized -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides, are used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one To use amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; very particularly preferred α-amino acids are arginine, omithin, lysine, serine and histidine, in particular arginine.

In addition to the m-phenylenediamine derivatives of the formula (I) according to the invention, in another preferred embodiment of the present invention, the colorants according to the invention can contain one or more direct dyes for shading. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 2 - (2'-Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carbo Acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agents according to the invention can contain a cationic direct dye. Are particularly preferred

(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

(c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, at that point explicit reference is made to claims 6 to 11.

Preferred cationic direct dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

CI ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic direct dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the production process for the individual dyes, may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

Another possibility for dyeing keratin-containing fibers is offered by the use of colorants which, in addition to the m-phenylenediamine derivatives of the formula (I) according to the invention, contain reactive carbonyl compounds, i.e. Compounds containing at least one reactive carbonyl group and / or CH-acidic compounds. The abovementioned compounds are generally not themselves dyes and are therefore not suitable for dyeing keratin fibers on their own. In combination, they form dyes in a non-oxidative process. This process, also called oxo dyeing, is described, for example, in the publications WO-A1 -99/18916, WO-A1 -00/38638, WO-A1-01 / 34106 and WO-A 1-01 / 47483.

Reactive carbonyl compounds according to the invention have at least one carbonyl group as the reactive group, which reacts to form a covalent bond. Furthermore, according to the invention, such compounds are also reactive Carbonyl compound can be used in which the reactive carbonyl group is derivatized in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the coupler components according to the invention and / or the CH-acidic compounds is always present. These derivatives are preferably addition compounds of a) amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound and c) of water to form hydrates.

The reactive carbonyl compound is preferably selected from compounds of the formula (01)

in which

AR stands for benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1,2,3-triazine, 1,3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, benzimidazole, 1, 3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphenylamine, stilbene, where the N-heteroaromatics can also be quaternized,

R ¹ represents a hydrogen atom, a dC ₆ -alkyl, C ₂ -C ₆ -acyl, C ₂ -C ₄ -alkenyl, CC _t -perfluoroalkyl, an optionally substituted aryl or heteroaryl group,

• R ^2, R ³ and R ⁴ independently represent a hydrogen atom, a halogen atom, a dC ₆ alkyl, -C ₆ alkoxy, -C ₆ aminoalkyl, Cι-C ₆ - hydroxyalkyl group, a Cι-C ₆ -Alkoxy-CrC ₆ -alkyloxy group, a C ₂ -C ₆ -acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo-, sulfato, sulfonamide, sulfonamido, C ₂ -C ₆ -alkenyl- , an aryl, an aryl -CC ₆ alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, a Amino or ammonio or a 1-imidazole (in) io group, the last three groups with one or more Ci-Ce-alkyl, d-Ce-carboxyalkyl, C ₁ -C ₆ - hydroxyalkyl, C ₂ - C ₆ -alkenyl, Ci-Ce-alkoxy-Ci-Ce-alkyl-, with optionally substituted benzyl groups, with sulfo (CC ₄ ) alkyl or heterocycle (CrC ₄ ) alkyl groups, where also two of the radicals from R ² , R ³ , R ⁴ and -ZYR ¹ together with the rest of the molecule can form a fused, optionally substituted 5-, 6- or 7-ring, which can also carry a fused-on aromatic ring, the system AR depending on the size of the ring, can carry further substituents which independently of one another can stand for the same groups as R ² , R ³ and R ⁴ ,

• Z stands for a direct bond, a carbonyl, a carboxy (CrC) alkylene, an optionally substituted C ₂ -C ₆ alkenylene, C ₄ -C ₆ alkadienylene, furylene, thienylene, arylene -, vinylene arylene, vinylene furylene, vinyl thienylene group, where Z together with the -YR ¹ group can also form an optionally substituted 5-, 6- or 7-ring,

Y represents a group which is selected from carbonyl, a group according to formula (02) and a group according to formula (03),

in which

R ^s stands for a hydrogen atom, a hydroxyl group, a CrC alkoxy group, a C ₆ alkyl group, a CrC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a CrC ₆ alkoxy CrC ₆ alkyl group,

• R ⁶ and R ⁷ independently of one another represent a CrC ₆ alkyl group, an aryl group or together with the structural element OCO of the formula (01) form a 5- or 6-membered ring.

The reactive carbonyl compound is particularly preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone Hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5- Trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone-diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3, 5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromoacetophenone, 4-hydroxy-3-nitroacetophenone carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4- Trihydroxybenzophenon, 2-hydroxy-1-acetonaphthon, 1-hydroxy-2-acetonaphthon, chromon, chromon-2-carboxylic acid, flavon, 3-hydroxyflavon, 3,5,7-trihydroxyflavon, 4 ', 5,7-trihydroxyflavon , 5,6,7-trihydroxyflavon, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzald ehyd, 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-3-methyl-benzaldehyde, 4-hydroxy-2,3-dimethyl-benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4- Hydroxy-3,5-dimethoxy-benzaldehyde, 4-hydroxy-3,5-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, 2,5-dihydroxybenzaldehyde, 2, 6- dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 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-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-

Morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2- Methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 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-hydroxy-1-naphthaldehyde, 4-dimethylamino 1-naphthaldehyde, 4-dimethylamino cinnamaldehyde, 2-

Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino-benzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-lmidazole ) - benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1 H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1 H, 5H- benzo [ij] quinolizine-9-carboxaldehyde, N-

Ethyl carbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribase aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1 -Acetylindol-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1- Methyl 2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, Furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromon-3-aldehyde, 3- (5'-nitro-2'-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2 -aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone , 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone, benzylidene acetone, 4-hydroxybenzylidene acetone, 2-hydroxybenzylidene acetone, 4-methoxybenzylidene acetone n, 4-hydroxy-3-methoxybenzylidene acetone, 4-dimethylaminobenzylidene acetone, 3,4-methylenedioxybenzylidene acetone, 4-pyrrolidinobenzylidene acetone, 4-piperidinobenzylidene acetone, 4-morpholinobenzylidene acetone, 4-diethylaminobenzylidene acetone, 3-pentamidine 3- (4'-Hydroxybenzylidene) -2,4-pentanedione, 3- (4'-Dimethylami- nobenzylidene) -2,4-pentanedione, 2-benzylidene cyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2 - (4'-Dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1, 3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) - 1, 3- cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidene cyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-diena l, 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, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5 -dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- ( 4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3, 5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-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-nitrob enzaldehyde, 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, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 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, 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 -, 4-Acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylchi nolinium, 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-allylquinoline, 6-formyl-1-allylquinolinium, 7-formyl-1-allylquinolinium and 8-formyl-1-allylquinolinium, 5-acetyl-1-methylquinolinium, 6- Acetyl-1-methylquinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1- ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5- Acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7-acetyl-1-allylquinolinium and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridini around-, 4- (2'-Formylvinyl) -1-methylpyridinium-, 1,3-dimethyl-2- (4'-formylphenyl) -benzimidazolium-, 1,3-dimethyl-2- (4'-formylphenyl) -imidazolium -, 2- (4'-formylphenyl) -3-methylbenzothiazolium-, 2- (4'-acetylphenyl) -3-methylbenzothiazolium-, 2- (4'-formylphenyl) -3-methylbenzoxazolium-, 2- (5'-Formyl-2'-furyl) -3-methylbenzothiazolium-, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium-, 2- (5'-formyl-2'-thienyl ) -3-methylbenzothiazolium-, 2- (3'-formylphenyl) -3-methylbenzothiazolium-, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium-, 5-chloro-2- (4'-formylphenyl ) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium benzenesulfonate, -p-toluenesulfonate, -methanesulfonate, -perchlorate, -sulfate, -chloride, -bromide, -iodide, - tetrachlorozincate, methyl sulfate, 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-M ethylquinisatin, and any mixtures of the above compounds.

The CH-acidic compounds are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3 , 3-tetramethyl-3H-indolium methanesulfonate, 1, 3,3-trimethyl-2-methylene indoline

(Fischer's base), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 2,3-dimethyl-naphtho [1, 2-d] thiazolium-p-toluenesulfonate, 3-ethyl-2 -methyl-naphtho [1, 2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1, 4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobar-bituric acid, 1.3 -Dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-

Diethylbarbituric acid, oxindole, 3-indoxy acetate, 2-coumaranone, 5-hydroxy-2-coumaranone, 6-hydroxy-2-coumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1,2-dione, indan-1,3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylene indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3- dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl- 2-methylquinolinium iodide, 1, 2,3-

Trimethylquinoxalinium iodide, 3-ethyl-2-methyl-benzoxazolium-p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2- methylquinolinium p-toluenesulfonate, 1, 2,3-trimethylquinoxalinium p-toluenesulfonate, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1,2-dihydro- 1, 3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1,3, diethyl-4,6-dimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro- 1, 3 dipropyl-4,6-dimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3,4- trimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4-methyl 2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2- oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4,6-dimethyl-2- thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2- thioxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-thioxo- pyrimidinium chloride, 1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-thioxo-pyrimidinium-c chloride, 1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-dipropyl-4-methyl-2-thioxopyrimidinium chloride and 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium hydrogen sulfate.

With regard to the dyes which can be used in the hair dyeing and toning agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials." ", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim.

The colorants according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic Group such as B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, methyl alpha-sulfofatty acid esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated Cs-d _∑ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Non-ionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, Cirdr fatty acid mono - and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 mol of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R O- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹ consists essentially of C ₈ and C ₀ alkyl groups, essentially C ₁₂ and C ₄ alkyl groups, essentially C ₈ to C 6 alkyl groups or essentially C ₁₂ - Until Cι ₆ alkyl groups. Any mono- or oligosaccharides can be used as the sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(_) - or -SOa ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are understood to mean those surface-active compounds which contain in addition to a C ₈ -C ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C ₁ -C ₈ -acyl sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quatemium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, a N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound from this group of substances which is particularly suitable according to the invention is that commercially available stearamidopropyldimethylamine under the name Tegoamid ^® S 18.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if, for example, hydrotaicites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred. Furthermore, the colorants according to the invention can contain other active ingredients, auxiliaries and

Additives, such as for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyl diallyl ammonium chloride copolymers, with diethyl sulfate quaternized Dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl-methacrylate / methyl-methacrylate / lat Copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate-crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, active substances which improve the fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,

- Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate Defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol,

Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizing agents for hydrogen peroxide and other oxidizing agents, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants, contain

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant ones known to those skilled in the art Manuals, e.g. B. Kh. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a d-C alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. According to the invention, however, the oxidation coloring agent can also be applied to the hair together with a catalyst which oxidizes the dye precursors, e.g. activated by atmospheric oxygen. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner. Suitable enzymes are, for example, peroxidases, which can significantly intensify the expression of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific for this, for example

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerin oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or its salts,

Choline oxidase and choline,

Amino acid oxidase and amino acids.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 45 minutes, the hair dye is rinsed off from the hair to be colored. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

Particularly in the case of hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the skin is rinsed and, if necessary, re-shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors is supposed to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.

A second subject of the present application is the use of the m-phenylediamine derivatives according to the invention for dyeing keratin fibers.

A third object of the present invention is a process for dyeing keratin fibers, in which a hair dye according to the invention is applied to the fibers and rinsed off again after an exposure time.

A fourth object of the present invention are m-phenylenediamine derivatives selected from the group formed by N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol, 2 - [(3-piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol.

A fifth object of the present invention are the first intermediates in the synthesis of the m-phenylenediamines according to the invention, selected from the group formed by (2-chloroethoxy) -N- (3-morpholin-4-ylphenyl) carboxamide, (2- Chloroethoxy) -N- (3-piperidin-1-ylphenyl) carboxamide and (2-chloroethoxy) -N- (3-pyrrolidin-1-ylphenyl) carboxamide.

A sixth object of the present application are the second intermediates in the synthesis of the m-phenylenediamine derivatives according to the invention, selected from the group formed by 3- (3-morpholin-4-ylphenyl) -1, 3-oxazolidin-2-one, 3 - (3-Piperidin-1-ylphenyl) -1, 3-oxazolidin-2-one and 3- (3-pyrrolidin-1-ylphenyl) -1, 3-oxazolidin-2-one. Ausführunαsbeispiele

1 syntheses

1.1 3-Pyrrolidin-1 -ylaniline

1.1.1 3-pyrrolidin-1-nitrobenzene

23.5 g of 3-fluoronitrobenzene and 66.8 g of pyrrolidine were dissolved in 250 ml of dimethyl sulfoxide and stirred at 100 ° C. for 60 hours. After cooling, it was poured into 2 l of water. The precipitated product was filtered off and dried in vacuo. Yield: 31 g (95%)

Melting point: 85 - 87 ° C

1.1.2 3-Pyrrolidin-1 -ylaniline

30.8 g of 3-pyrrolidin-1-nitrobenzene were dissolved in 450 ml of ethanol and 50 ml of water and mixed with 0.3 g of Pd / C (5%). The mixture was then hydrogenated in an autoclave at 50 ° C. and 50 bar for 12 h. After cooling, the mixture was filtered and concentrated on a Rotavapor. The brown oil obtained was distilled in a Kugelrohr (boiling point: 132-155 ° C. at 0.08-0.1 mbar). A clear, brown liquid was obtained. Yield: 16.8 g (65%)

1.2 3-Piperidin-1 -ylaniline

1.2.1 3-Piperidin-1 -ylnitrobenzol

14.1 g of 3-fluomitrobenzene and 46.8 g of piperidine were dissolved in 150 ml of dimethyl sulfoxide and stirred at 100 ° C. for 60 hours. After cooling, it was poured into 1 liter of water. The mixture was extracted several times with tert-butyl methyl ether, and the combined organic phases were dried with sodium sulfate. The solvent was then removed on a Rotavapor. The desired product was obtained as a light brown liquid. Yield: 20.9 g (100%)

1.2.2 3-Piperidin-1 -ylaniline

20.0 g of 3-piperidin-1-nitrobenzene were dissolved in 270 ml of ethanol and 30 ml of water and 0.2 g of Pd / C (5%) was added. The mixture was then hydrogenated in an autoclave at 80 ° C. and 100 bar for 12 h. After cooling, the mixture was filtered and concentrated on a Rotavapor. Yield: 11.4 g (68%)

1.3 3-morpholin-4-ylaniline

1.3.1 3-Morpholin-4-ylnitrobenzene

14.1 g of 3-fluomitrobenzene and 48.0 g of morpholine were dissolved in 150 ml of dimethyl sulfoxide and stirred at 100 ° C. for 60 hours. After cooling, it was poured into 1 liter of water. The precipitated product was filtered off and dried in vacuo. Yield: 18.8 g (90%)

Melting point: 109-110 ° C

1.3.2 3-morpholin-4-ylaniline (6)

18.5 g of 3-morpholin-4-ylnitrobenzene were dissolved in 270 ml of ethanol and 30 ml of water and 0.2 g of Pd / C (5%) was added. This was followed by an autoclave at 50 ° C for 12 h and hydrogenated 30 bar. After cooling, the mixture was filtered and concentrated on a Rotavapor. The light brown crystals obtained were dried in vacuo. Yield: 12.6 g (80%)

Melting point: 117-118 ° C

1.4 3- (4-methylpiperazin-1-yl) aniline

1.4.1 3- (4-Methylpiperazin-1-yl) nitrobenzene

14.1 g of 3-fluomitrobenzene and 48.0 g of N-methylpiperazine were dissolved in 150 ml of dimethyl sulfoxide and stirred at 100 ° C. for 60 hours. After cooling, it was poured into 1 liter of water and extracted several times with tert-butyl methyl ether. The mixture was then evaporated to dryness on the Rotavapor. The precipitated waxy product was dried in vacuo.

Yield: 19.5 g (88%)

Melting point: 40 - 48 ° C

1.4.2 3- (4-Methylpiperazin-1-yl) aniline

19.2 g of 3- (4-methylpiperazin-1-yl) nitrobenzene were dissolved in 270 ml of ethanol and 30 ml of water and 0.2 g of Pd / C (5%) was added. The mixture was then hydrogenated in an autoclave at 50 ° C. and 30 bar for 12 h. After cooling, the mixture was filtered and concentrated on a Rotavapor. The product was obtained as a highly viscous oil.

Yield: 12.6 g (83%) 1.5 N, N-dimethyl-3-, pyrrolidin-1-yl) aniline

^CH

6.5 ml of sulfuric acid (25%) and 7.5 ml of aqueous formaldehyde solution (37%) were dissolved in 50 ml of tetrahydrofuran at room temperature and introduced. A suspension of 5.5 g of sodium borohydride and 4.1 g of 3-pyrrolidin-1-ylaniline (see point 1.1) in tetrahydrofuran was then added in portions (approx. 1 h). The temperature of the reaction mixture was checked so that it did not exceed 35 ° C. After adding half the amount of suspension, a further 6.5 ml of sulfuric acid (25%) were added. After the addition had ended, the mixture was stirred at room temperature for 1 h, diluted with 200 ml of water and adjusted to pH 10-11 with 50% KOH. The resulting organic phase was separated and the aqueous phase extracted twice with tert-butyl methyl ether. The combined organic phases were washed twice with a saturated aqueous NaCl solution and dried over sodium sulfate. The mixture was then concentrated in vacuo. The black, viscous liquid obtained was then distilled in a bulb tube (123-143 ° C. at 0.06-0.08 mbar).

Yield: 1.5 g (32%)

1.6 2-f (3-morpholin-4-ylphenyl) amino.ethan-1-ol

1.6.1 (2-chloroethoxy) -N- (3-morpholin-4-ylphenyl) carboxamide

50 g of 3-morpholin-4-ylanilin (for preparation, see section 1.3) and 50.6 g of calcium carbonate were placed in 800 ml of dioxane and heated to 90 ° C. 44.5 g of 2-chloroethylchloroformate were then added dropwise over the course of 15 minutes, and the mixture was added under thin layer chromatography (TLC) control stirred for a further 4 h. After cooling, the salts were filtered off and the filtrate was poured into 1 liter of ice water. The mixture of filtrate and ice water was extracted several times with ethyl acetate, the combined organic phases were dried over sodium sulfate and evaporated to dryness on a Rotavapor. The residue was dried in vacuo overnight. Yield: 45 g (56%)

Melting point: 116-119 ° C

1.6.2 3- (3-Morpholin-4-ylphenyl) -1, 3-oxazolidin-2-one

200 ml of 20% NaOH were placed in a three-necked flask and heated to 45.degree. Then 44.0 g (2-chloroethoxy) -N- (3-morpholin-4-ylphenyl) carboxamide were added in portions. A heterogeneous system formed under slight exotherm. After adding 400 ml of dioxane, a clear solution was obtained which was stirred at room temperature overnight. It was then poured onto ice water and neutralized with half-concentrated HCI. The precipitated product was washed thoroughly and dried in vacuo overnight. Yield: 33.4 g (90%)

Melting point: 166-168 ° C

1.6.3 2 - [(3-Morpholin-4-ylphenyl) aminoethan-1-ol

33 g of 3- (3-morpholin-4-ylphenyl) -1, 3-oxazolidin-2-one were refluxed in 500 ml of 20% ethanolic KOH for 3 h. The mixture was then added to 1.5 IH ₂ O, neutralized with half-concentrated HCl and extracted several times with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was distilled in a Kugelrohr (0.08 bar, 200-230 ° C). Yield: 17.9 g (62%)

1.7 2-r.3-piperidin-1-ylphenyl) aminolethan-1-ol

1.7.1 (2-chloroethoxy) -N- (3-piperidin-1-ylphenyl) carboxamide

65 g of 3-piperidin-1-ylanilin (for preparation, see section 1.2) and 66.5 g of calcium carbonate were placed in 1 l of dioxane and heated to 90.degree. 59.3 g of 2-chloroethyl chloroformate were added dropwise within 15 min and the mixture was stirred for a further 4 h under TLC control. After cooling, the salts were filtered off and the filtrate was poured into 1 liter of ice water. The mixture of filtrate and ice water was extracted several times with ethyl acetate, the organic phase was dried over sodium sulfate and evaporated to dryness on a Rotavapor. The residue was dried in vacuo overnight to give a black oil. Yield: 16.5 g (16%)

1.7.2 3- (3-Piperidin-1-ylphenyl) -1, 3-oxazolidin-2-one

80 ml of 20% NaOH were placed in a three-necked flask and heated to 45.degree. 16.0 g of (2-chloroethoxy) -N- (3-piperidin-1-ylphenyl) carboxamide were then added in portions. A heterogeneous system formed under slight exotherm. After adding 400 ml of dioxane, a clear solution was obtained which was stirred at room temperature overnight. It was then poured onto ice water and neutralized with half-concentrated HCI. The aqueous phase was extracted several times with ethyl acetate. The combined organic phases were evaporated to dryness in vacuo to give a dark oil. Yield: 6.0 g (43%)

1.7.3 2 - [(3-piperidin-1-ylphenyl) amino] ethan-1-ol

6 g of 3- (3-piperidin-1-ylphenyl) -1, 3-oxazolidin-2-one were refluxed in 200 ml of 20% ethanolic KOH for 3 h. The mixture was then added to 1.0 IH ₂ O, neutralized with half-concentrated HCl and extracted several times with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was distilled in a Kugelrohr (0.08 mbar, 160-204 ° C). Yield: 2.0 g (37%) 1.8 2-f (3-pyrrolidin-1-ylphenyl) amino1ethan-1-ol

1.8.1 (2-chloroethoxy) -N- (3-pyrrolidin-1-ylphenyl) carboxamide

60 g of 3-pyrrolidin-1-aniline (for preparation see point 1.1) and 66.5 g of calcium carbonate were placed in 1 l of dioxane and heated to 90 ° C. 59.3 g of 2-chloroethyl chloroformate were added dropwise within 15 min and the mixture was stirred for a further 4 h under TLC control. After cooling, the salts were filtered off and the filtrate was poured into 1 liter of ice water. The mixture of filtrate and ice water was washed several times with ethyl acetate, the combined organic phases were dried over sodium sulfate and evaporated to dryness on a Rotavapor. The residue was dried in vacuo overnight. Yield: 71 g (72%)

Melting point: 87 - 90 ° C

1.8.2 3- (3-Pyrrolidin-1-ylphenyl) -1, 3-oxazolidin-2-one

340 ml of 20% NaOH were placed in a three-necked flask and heated to 45.degree. 70 g of (2-chloroethoxy) -N- (3-pyrrolidin-1-ylphenyl) carboxamide were then added in portions. A heterogeneous system formed under slight exotherm. After adding 400 ml of dioxane, a clear solution was obtained, which was stirred further at room temperature overnight. It was then poured onto ice water and neutralized with half-concentrated HCI. The precipitated product was washed thoroughly and dried in vacuo overnight. Yield: 58.8 g (97%)

Melting point: 138-142 ° C 1.8.3 2 - [(3-Pyrrolidin-1-ylphenyl) amino] ethan-1-ol

58 g of 3- (3-pyrrolidin-1-ylphenyl) -1, 3-oxazolidin-2-one were refluxed in 500 ml of 20% ethanolic KOH for 3 h. The mixture was then added to 1.5 IH ₂ O, neutralized with half-concentrated HCl and extracted several times with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was distilled in a bulb tube (0.08 mbar, 205-225 ° C). Yield: 38.3 g (62%)

Melting point: 36-38 ° C (74%)

2 coloring bunas

2.1 Carrying out the experiment

For the production of the coloring cream, 50 g of a cream base were weighed into a 250 ml beaker and melted at 80 ° C. The cream base used had the following composition:

Hydrenol ^® D ¹ 17.0% by weight

Lorol ^® tech. ² 4.0% by weight

Texapon ^® NSO ³ 40.0% by weight

Dehyton ^® K ⁴ 25.0% by weight

Eumulgin ^® B2 ⁵ 1.5% by weight

Water 12.5% by weight

¹ C ₁₆ -ββ-fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² Ci ₂ -ι ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ lauryl ether sulfate, sodium salt (approx. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis)

⁴ N, N-Dimethyl-N- (C ₈ -ι ₈ -kokosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

In each case 1/400 mol of the developer or coupler component was suspended separately in distilled water or dissolved under heating. Then ammonia (<1 ml; 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were worked into the hot cream one after the other. The mixture was then made up to 97 g with distilled water and the pH was adjusted to 9.5 with ammonia. After filling up to 100 g with distilled water, the mixture was stirred cold (<30 ° C.), a homogeneous cream being formed. Unless otherwise noted, 25 g of coloring cream were mixed with 25 g of the following oxidizing agent preparation for the colorations.

Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal ^® SL ⁶ 1.50% by weight

Texapon ^® N28 ⁷ 2.00% by weight

Acrysol ^® 22 ⁸ 0.60% by weight

Hydrogen peroxide, 50% 12.0% or 2% by weight

Sodium hydroxide solution, 45% 0.80% by weight

Water ad 100

⁶ 1-hydroxyethane-1,1-diphosphonic acid (approx. 58 - 61% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

⁷ Lauryl ether sulfate sodium salt (at least 26.5% active substance content; INCI name: Sodium Laureth Sulfate) (Cognis)

⁸ acrylic polymer (approx. 29.5 - 30.5% solids in water; INCI name: Acrylates / Steareth-20 methacrylate copolyme)

A strand of hair (80% gray; 330 mg to 370 mg in weight) was added to each of the mixtures thus obtained. The mixtures and the strands of hair were then each placed on a watch glass and the strands of hair were well embedded in the coloring creams. After 30 minutes (± 1 minute) Reaction time at room temperature were removed and the strands of hair so washed many times, until the color was removed with an excess of an aqueous solution Texapon ^® EVR. ⁹ The strands of hair were air-dried and their shade determined and noted under the daylight lamp (color testing device HE240A) (Taschenlexikon der Farben, A. Komerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag; Zurich, Göttingen).

⁹ Lauryl ether sulfate sodium salt with special additives (approx. 34 to 37% active substance content; INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis)

The results obtained in the coloration tests are shown in the tables below. 2.2 Ausfärbunαen with 3-pyrrolidin-1 -ylaniline

(colored with 6% by weight hydrogen peroxide solution)

2.3 Colorings with 3-piperidin-1 -ylaniline

(colored with 1% by weight hydrogen peroxide solution)

2.4 Colorings with 3-morpholin-4-ylanilin

(colored with 6% by weight hydrogen peroxide solution)

2.5 Colorings with 3- (4-methylpiperazin-1-yl) aniline (colored with 6% by weight hydrogen peroxide solution)

2.6 Colorings with N, N-dimethyl-3- (pyrrolidin-1-yl) aniline (colored with 6% by weight hydrogen peroxide solution)

2.7 Colorings with 2- (3-morpholin-4-ylphenyl) aminolethan-1-ol (colored with 6% by weight hydrogen peroxide solution)

2.8 Colorings with 2 -. (3-piperidin-1-ylphenyl) aminolethan-1-ol (colored with 6% by weight hydrogen peroxide solution)

2.9 Colorings with 2-f (3-pyrrolidin-1-ylphenyl) aminolethan-1-ol (colored with 6% by weight hydrogen peroxide solution)

Anwendunasrezepturen

3.1 Recipe 1

3.2 Recipe 2

3.3 Recipe 3

3.4 Recipe 4

3.5 Recipe 5

3.6 Recipe 6

3.7 Recipe 7

3.8 Recipe 8

3.9 Recipe 9

3.10 Recipe 10

.11 Oxidizer preparation

The following raw materials were used in the application formulations: 0 Cetylstearyl alcohol with approx. 12-EO units (INCI name: Ceteareth-12) (Cognis) 1 quaternized hydroxyethyl cellulose (INCI name: Polyquaternium-10) (Amerchol) ₂ dimethylaminoethyl methacrylate-vinylpyrrolidone Copolymer, quaternized with diethyl sulfate (approx. 19% solids in water; INCI name: Polyquatemium-11) (ISP) ₃ quaternized cellulose derivative (INCI name: Polyquatemium-4) (National Starch)

4 - [(2-Hydroxyethyl) amino] -3-nitrophenol (INCI name: 3-nitro-p-hydroxyethylaminophenol) 5 (INCI name: CI 45100) 6 lauryl myristyl ether sulfate sodium salt (approx. 68% to 73% active substance content ^' ; INCI name: Sodium Myreth Sulfate) (Cognis) 7 Cι ₂ -Ci ₆ fatty alcohol-1,4-glucoside unpreserved, boron-free approx. 50-53%

Active substance) (Cognis Corporation (Emery)) 8 Lauryl alcohol-4.5-EO-Acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 carboxylate) (Chem-Y) 9 2-Octyldodecyl alcohol (INCI- Name: octyldodecanol) (Cognis) 0 approx. 20% by weight active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen) Guar hydroxypropyltrimethylammonium chloride (at least 93% solids; INCI name: guar hydroxypropyltrimonium chloride) (Cognis CorporationCosmedia)

Poly [N- (3- (dimethylammonium) propyl] -N '- [3-ethyleneoxyethylene dimethylammonium) propyl] urea di-chloride (approx. 64% solids in water; INCI name: Polyquaternium-2) ( Rhodia)

4 [(3-hydroxypropyl) amino] -3-nitrophenol

4-Hexyl-5 (6) -carboxy-2-cyclohexen-1-octanoic acid potassium salt (approx. 41% active substance in water) (Westvaco Chemicals)

Dimethyldiallylammonium chloride acrylamide copolymer (approx.8.1-9.1% active substance in water; INCI name: Polyquaternium-7) (Ondeo-Nalco)

Vinylimidazolium methochloride-vinylpyrrolidone copolymer (30:70) (38-42% solids in water; INCI name: Polyquatemium-16) (BASF)

Dimethyldiallylammonium chloride Acrylic acid copolymer (approx. 35 active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)

Vinyl pyrrolidone, methacrylamidopropyl trimethyl ammonium chloride copolymer (19-21% active substance in water; INCI name: Polyquaternium-28) (ISP)

2,7-naphthalenedisulfonic acid, 5-amino-4-hydroxy-3- (phenylazo) -, disodium salt

Oleic acid (INCI name: Oleic Acid) (Cognis Deutschland GmbH (Caldic))

Ci ₂ -ι fatty alcohol with approx. 2-EO units (INCI name: Laureth-2) (Cognis Deutschland GmbH)

Lauryl alcohol with approx.4.5-EO units -acetic acid-sodium salt (approx. 80-84% active substance in water; INCI name: Sodium Laureth-5 carboxylate) (Kao)

N, N-Dimethyl-N (C8-18-cocosacylamidopropyl) amine-N-oxide (approx. 35%

Active substance in water; INCI name: Cocamidopropylamine Oxide) (Goldschmidt)

Poly (dimethyldiallylammonium chloride) (approx. 40% solids; INCI name: Polyquatemium-6) (Ondeo-Nalco)

Silk protein (approx. 99% protein; INCI name: Silk, Serica (Linne)) (Ikeda Bussan Kaisha)

Hydrolyzate from Merino virgin wool, obtained enzymatically (21-23% solids; INCI name: Aqua (Water), Hydrolyzed Keratin, Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben) (Cognis Deutschland GmbH (Grünau)) approx. 40% active substance (INCI - Name: Sodium Silicate) (HENKEL) non-ionic silicone emulsion (INCI name: Dimethicone, approx. 10% active substance) (Dow Corning)

Acid-containing, cross-linked acrylic copolymer (INCI name: Acrylates Copolymer, approx. 28% active substance) (Rohm & Haas) 3.12 discoloration

The dye product preparations 1 to 10 were mixed immediately before use in a 1: 1 ratio with a 6% hydrogen peroxide preparation (see point 3.11). The resulting application preparation was on natural white strands

(Kerling) applied and left there for 30 minutes at 32 ° C. Then the

Reams of hair rinsed thoroughly with water and washed with a commercially available shampoo.

Claims

claims

1. Agent for dyeing keratin fibers, in particular human hair, containing at least one m-phenylenediamine derivative of the formula (I) or one of its physiologically tolerable salts in a cosmetically acceptable carrier as a coupler component

where R ¹ represents a hydrogen atom, a halogen atom, a C to C alkyl group, a d to C ₄ monohydroxyalkyl group, a C ₂ to C polyhydroxyalkyl group, a d to C ₄ aminoalkyl group, a d to C -Alkoxy- (d- to C ₄ ) -alkyl group or ad- to C -dialkylamino- (d- to C) -alkyl group, R ² and R ³ independently of one another represent a hydrogen atom, a C to C- _t -alkyl group , a C ₂ to C monohydroxyalkyl group, a C ₃ to C ₄ polyhydroxyalkyl group, a d to C ₄ alkoxy (d to C ₄ ) alkyl group or a d to C ₄ aminoalkyl group and

X represents a saturated, 5-, 6- or 7-membered heterocycle which has at least one nitrogen atom and optionally a further heteroatom selected from oxygen, sulfur or nitrogen, the heterocycle being bonded to the aromatic ring system via a nitrogen atom, and the heterocycle can optionally carry up to two substituents other than hydrogen, which are selected from a halogen atom, a d to C alkyl group, a Cr to C ₄ monohydroxyalkyl group, a C ₂ to C polyhydroxyalkyl group, a d to C-aminoalkyl group, ad- to C-alkoxy- (d- to C ₄ ) -alkyl group or ad- to C ₄ -dialkylamino- (Cr to C) - alkyl group.

2. Composition according to claim 1, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ¹ represents Hydrogen atom, a chlorine atom, a methyl group or a 2-hydroxyethyl group.

3. Composition according to one of claims 1 or 2, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ² and R ³ independently of one another represent a hydrogen atom, a methyl group or a 2-hydroxyethyl group.

4. Composition according to claim 3, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which R ² and R ³ each represent a methyl group.

5. Composition according to claim 3, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which one of the radicals R ² or R ^{3 is} a 2-hydroxyethyl group and the other of the radicals R ² or R ^{3 is} a Hydrogen atom.

6. Composition according to claim 3, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which both radicals R ² and R ³ each represent a hydrogen atom.

7. Composition according to one of claims 1 to 6, characterized in that it contains an m-phenylenediamine derivative of the formula (I) in which X is a morpholin-4-yl group, a piperidin-1-yl group, a 4-methylpiperazine 1-yl group or a pyrrolidin-1-yl group.

8. Composition according to claim 1, characterized in that the m-phenylenediamine derivative of the formula (I) is selected from 3-pyrrolidin-1-ylaniline, 3-piperidin-1-ylaniline, 3-morpholin-4-ylaniline, 3- (4th -Methylpiperazin-1-yl) aniline, N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol, 2- [ (3-piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol.

9. Composition according to one of claims 1 to 8, characterized in that it contains at least one developer component.

10. Agent according to one of claims 1 to 9, characterized in that it contains at least one further coupler component.

11. Agent according to one of claims 1 to 10, characterized in that it further contains at least one substantive dye.

12. Composition according to claim 11, characterized in that the substantive dye is cationic.

13. A process for dyeing keratin fibers, in which an agent according to one of claims 1 to 12 is applied to the fibers and rinsed off again after an exposure time.

14. m-phenylenediamine derivatives selected from the group formed by N, N-dimethyl-3- (pyrrolidin-1-yl) aniline, 2 - [(3-morpholin-4-ylphenyl) amino] ethan-1-ol , 2- [(3-piperidin-1-ylphenyl) amino] ethan-1-ol and 2 - [(3-pyrrolidin-1-ylphenyl) amino] ethan-1-ol.

15. Synthesis intermediates selected from the group consisting of (2-chloroethoxy) -N- (3-morpholin-4-ylphenyl) carboxamide, (2-chloroethoxy) -N- (3-piperidin-1-ylphenyl) carboxamide and (2-chloroethoxy) -N- (3-pyrrolidin-1-ylphenyl) carboxamide.

16. Synthesis intermediates selected from the group consisting of 3- (3-morpholin-4-ylphenyl) -1, 3-oxazolidin-2-one, 3- (3-piperidin-1-ylphenyl) -1, 3 - oxazolidin-2-one and 3- (3-pyrrolidin-1-ylphenyl) -1,3-oxazolidin-2-one.