WO1997030968A1

WO1997030968A1 - Novel aminophenol derivatives and their use

Info

Publication number: WO1997030968A1
Application number: PCT/EP1997/000650
Authority: WO
Inventors: David Rose; Bernd Meinigke; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1996-02-22
Filing date: 1997-02-13
Publication date: 1997-08-28
Also published as: AU1724697A; DE19606644A1

Abstract

Aminophenol derivatives of the formula (I) in which R1 is a C¿1-4? alkyl group. a C1-4 alkyl, a C1-4 hydroxyalkyl group, a C1-4 alkoxy group or an alkyl group, R?2¿ is fluorine, chlorine or bromine, R3 is a C¿3-4? dihydroxy alkyl group, a methyl group with 1-3 halogen atoms, especially fluorine atoms, as substituents, a C2-4 alkyl group with a maximum of 1-4 halogen atoms, especially fluorine atoms, as substituents, a -(CH2)x-B group, in which B is a hydroxy group, an NR?5R6¿ group or a CO-NR7R8 group and x is a number from 1 to 4, a -COOR9 group or a -CO-NR10R11 group, where R?5, R6, R7, R8, R10 and R11¿ are mutually independently hydrogen, a C¿1-4? alkyl group, a C1-4 hydroxyalkyl group and R?5 and R6, R7 and R8 and R10 and R11¿ may, together with the nitrogen atom carrying them, also be part of a morpholino, piperidino or pyrrolidino radical and R5 may also be an -SO¿2?CH3 group provided that then R?6¿ is hydrogen and R9 is hydrogen or a C¿1-4? alkyl group and R?4¿ is hydrogen, a C¿1-4? alkyl group or one of the groups listed under R?3¿ said derivatives and their water-soluble salts are eminently suitable as coupling components in oxidation hair colorants. Depending on the selected developer component, they also provide an unusually broad spectrum of brilliant colour gradations.

Description

"New Aminophenol Denvates and Their Use"

The invention relates to new ammophenol derivatives, their use for dyeing keratin fibers and dyes containing these compounds

For dyeing keratin fibers, in particular human hair, the so-called oxidation colorants play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components

Good oxidation dye precursors must first of all meet the following requirements. You have to develop the desired color shades with sufficient intensity and fastness in the oxidative coupling. You also have to have a good ability to draw on the fiber, whereby especially with human hair there may be no noticeable differences between stressed and newly regrown hair (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, for example permanent fluids. Finally, if they are used as hair colorants, they should not stain the scalp too much and, above all, they should be harmless in toxicological and dermatological terms

As the developer components, pπmare aromatic amines are usually used with other free or sub-positions in the para or ortho position. tuieπen hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrirnidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 -Diaminophenyl) -ethanoI, 2- (2,5-diaminophenoxy) -ethanol, l-phenyl-3-carboxyarmdo-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2- Aιninomemyl-4-aminophenol, 2-Hy droxy-4, 5, 6-triarmnopyrimidine, 2,4-DΛydroxy-5,6-diaminopyrimidine and 2,5,6-triammohydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Suitable coupling substances are in particular α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl-3 -methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6 -methyl-3-aminophenol, 2-methyl-resorcinol and 5-methyl-resorcinol.

With regard to other conventional dye components, reference is expressly made to the Cola list, published by the Industrial Association for Personal Care and Detergent, Frankfurt.

With a developer component or a special coupler / developer combination alone, it is generally not possible to obtain a color shade that acts naturally on the hair. Combinations of different developer components and coupler components are therefore usually used in practice. There is therefore a constant need for new, improved dye components. It was therefore the object of the present invention to find new coupler components which meet the requirements for oxidation dye precursors to a particular degree.

It has now been found that certain previously unknown aminophenol derivatives meet the requirements placed on the coupler component to a high degree. Thus, using these coupler components with most known developer components, brilliant red to dark blue shades of color are obtained which are extraordinarily lightfast and washable.

A first subject of the present invention are therefore aminophenol derivatives of the general formula (I)

in R ¹ stands for

a C 1 -hydroxyalkyl group,

- A C _M alkoxy group or

- an allyl group,

R ² stands for fluorine, chlorine or bromine, R ³ stands for

a C ₃ ^ -dihydroxyalkyl group,

a methyl group which carries 1 to 3 halogen atoms, in particular fluorine atoms, as substituents, - A C ₂ ^ alkyl group with a maximum of 1 - 4 halogen atoms, especially fluorine atoms, as substituents

- a group - (CH ₂ ) _X -B, m the B stands for

- a hydroxy group,

- a group NR ⁵ R ⁶ or

a group CO-NR ⁷ R ⁸ and x for a number from 1 to 4,

- a group -COOR ⁹ or

- A group -CO-NR ¹⁰ R ^π , where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ independently of one another represent hydrogen, a C 1 -C 4 -alkyl group, a C _M -hydroxyalkyl group and R ⁵ and R ⁶ , R ⁷ and R ⁸ and R ¹⁰ and R ¹ ', together with the nitrogen atom carrying them, can also be part of a morpholino, piperidino or pyrrolidino radical and R ⁵ also for a group -S0 ₂ -CH ₃ can be provided that then R ⁶ stands for hydrogen, and R ⁹ stands for hydrogen or a C _H alkyl group, and R ⁴ stands for hydrogen, a C _M alkyl group or one of the groups mentioned under R ³ , and their water-soluble salts

These compounds are prepared starting from the m-6-substituted 2-halo-3-aminophenols. For details, reference is made to the synthesis examples detailed in the example section.

Since all of the substances according to the invention are amino compounds, the known acid addition salts can be prepared from them in a conventional manner. All statements in this section and accordingly the claimed scope therefore relate both to the ammophenol derivatives according to the formula which are in free form (I) as well as their water-soluble, physiologically acceptable salts. Examples of such salts are the hydrochloride, the hydrobromide, the sulfate, the phosphate, the acetate, the propionate, the citrate and the lactate. The aminophenol derivatives according to formula (I) in which R ^{2 represents} chlorine have proven to be particularly suitable according to the invention.

Also preferred according to the invention are those compounds of the formula (I) in which R ^{1 represents} a C 1.3 alkyl group or an allyl group. Compounds with R ¹ equal to methyl have proven to be very particularly suitable.

Halogenated C _M alkyl groups, in particular with a terminal trifluoromethyl group, are particularly suitable as substituents R ³ .

The substances in which the 3-amino group has only one long-chain substituent, and R ⁴ is therefore hydrogen, have also proven to be particularly suitable.

Suitable substances are particularly outstanding in the sense of the overall invention

2-chloro-6-memyl-3-N-ß-hydroxyemylaminophenol,

2-chloro-6-methyl-3-N-carbemoxyaminophenol,

- 2-chloro-6-methyl-3-ureidophenol, - 4 - (^ - (N \ N'-diemyl-carbamyl) -memylaπüno] -2-hydroxy-3-chlorotoluene,

- 3- (2-Ammoemylanιino) -2-chloro-6-methylphenol,

- 2-CWor-6-memyl-3-mesylanmιoemyl-aminophenol and

- 2-chloro-6-memyl-3-N (2-trifluoroethyl) aminophenol.

Within this group, in turn, 2-chloro-6-methyl-3-N-ß-hydroxyethylaminophenol has particularly good properties. A second subject of the present invention is the use of the abovementioned aminophenol derivatives as a coupler component in oxidation hair colorants.

Finally, a third object of the present invention are oxidation colorants for dyeing keratin fibers containing coupler components and developer components in a water-containing carrier, which contains one of the aforementioned aminophenol derivatives as a coupler component.

Keratin fibers are to be understood here as furs, wool, feathers and in particular human hair. Although the oxidation colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas, particularly in color photography.

The oxidation colorants according to the invention can contain one or more developer components and, if desired, further coupler components in addition to the coupler components according to the invention. With regard to the further developer and coupler components, reference is made to the substances listed at the beginning of the description, which are preferred further dye components. Particularly preferred developer components are 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triarnmopyrimidine, l- (β-hydroxyemyl) -2,5-diaminobenzene, p-phenylenediamine, p-toluenediamine, p- Aminophenol, 3-methyl-p-aminophenol and 2-anήnomethyl-p-aminophenol. These further developer and coupler components are usually used in free form. For substances with amino groups, however, it may be preferred to use them in salt form, in particular in the form of the hydrochlorides and sulfates. The hair colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the entire oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1: 0.5 to 1: 2.

In a preferred embodiment, the hair dye compositions according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes, e.g. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as e.g. those under the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Picramic Acid and Rodol 9 R known compounds, in an amount of 0.01 to 20% by weight, based on the entire oxidation hair dye . 4-Amino-2-nifro-diphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, Rodol 9 R and HC Red BN are particularly preferred direct dyes according to the invention.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. On the contrary, due to the production processes for the individual dyes, the hair colorants according to the invention can also contain further components in subordinate amounts, insofar as these are not adversely affect the coloring result or must be excluded for other reasons, e.g. toxicological.

To produce the colorants according to the invention, the oxidation dye precursors are incorporated into a suitable water-containing carrier. For the purpose of hair coloring, such carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. Shampoos, aerosols or other preparations that are suitable for use on the hair.

Furthermore, the colorants according to the invention can contain all active ingredients, additives and auxiliaries known in 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 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, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as 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 R-0- (CH ₂ -CH ₂ 0) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 carbon atoms in the acyl group, acyl taurides with 10 to 18 carbon atoms in the acyl group, acyl isethionates with 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon 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 alkanesulfonates 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 Atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH ₂ -CH ₂ 0) _χ -

OSO H, in which R is a preferably linear alkyl group with 10 to 18 carbon 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 addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto 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 C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO - or -S0 ₃ group in the molecule. Particularly suitable secondary surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammomum glycinate, N-acyl-ammopropyl-N, N-dimethylammonium glycinate, for example the cocoacylammopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoIine each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoemylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C -

Acylsarcosine.

Nonionic surfactants contain z as a hydrophilic group. 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

Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the

Alkyl group,

Cι ₂ . ₂₂ fatty acid monoesters and diesters of addition products from 1 to 30

Mole of ethylene oxide to glycerol,

C alkyl mono- and oligoglycosides and their ethoxylieπe analogs,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as trimethylammonium chlorides, diaucyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammomum chloride, disteatyldmethylammonium chloride, lauryldimemylammonium chloride, lauryldimethylbenzylammomum chloride and

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) will), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Gold¬ schmidt; diquaternary polydimethylsiloxanes, Quaternium-80). Alkylaimdoamines, in particular fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ^® S 18, are characterized not only by a good conditioning effect but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-"esterquats" named, such as those sold under the trademark Stepantex ^® and methyl dialkyl hydroxyalkyldialkoyloxyalkyl- ammoniummetho sulfate.

An example of a suitable cationic surfactant quaternary Zucker¬ derivative is the commercially available product Glucquat ^® 100 is, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural 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 adducts of ethylene and / or propylene oxide with fatty alcohols or derivatives of these adducts, 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 homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyπolidone / vinyl acrylate copolymers, polyvinylpyπolidone and vinylpyπolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallyl polymers, dimethyldiallyl -Dimethyldiallylammonium chloride copolymers, dimethylammoemytaethacrylate-vinylpyπolidone copolymers quaternized with diethyl sulfate,

Vinylpyrrolidone-lnήdazolmiuminethochlorid copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylic amidopropyl trimethylammonium chloride / acrylate copolymers and octylacrylamide / - methyl methacrylate / tert-butylammoethylmetal, for example polyacrylate polymers, such as acrylate polymers such as acrylate copolymers - acrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyπolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-teπ.Butylacrylamide teφolymers

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 as. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils, protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, dyes for coloring the preparations, anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyπolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

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

Complexing agents such as EDTA, NTA and phosphonic acids, swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate, blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, CO and air and antioxidants. The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

In principle, the oxidative development of the coloring can take place 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. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used to transfer atmospheric oxygen to the developer component or to enhance the effect of small amounts of oxidizing agents present. An example of an enzymatic process is the procedure to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, such as a coloring shampoo, has been used. The following examples are intended to explain the subject of the invention in more detail

B e i s p i e l e

1. Synthesis examples

1.1. Synthesis of 2-chloro-6-methyl-3-N-ß-hydroxyethylaminophenol (Kl)

1st stage: β-chloroethyl- (2'-chloro-3'-hydroxy-4'-methylphenyl) carbamate 7.9 g (0.05 mol) of 2-chloro-6-methyl-3-aminophenol were dissolved in 25 ml of dioxane. After adding 2.75 g (0.028 mol) of calcium carbonate, the mixture was heated to 90.degree. Then 7.9 g (0.055 mol) of 2-chloroethyl formate were added dropwise with stirring. After the addition of the 2-chloroethyl formate had ended, the mixture was stirred at 90 ° C. for 1 hour. After cooling, the mixture was filtered off with suction to remove the mineral salts and ice water was added to the filtrate. The product which precipitated was filtered off with suction and dried in vacuo at about 50.degree. The product had a melting point of 84-87 ° C.

2nd stage: N- (2 '-chloro-3'-hydroxy-4'-methylpheny 1) - 1, 3-oxazolidin-2-one

9.6 g (0.036 mol) of the product from stage 2 were introduced into 22 ml of 4.3N sodium hydroxide solution at 45 ° C. After 20 minutes at this temperature, the mixture was neutralized with dilute hydrochloric acid. The product which precipitated was dried under vacuum at 70 ° C. in vacuo; it had a melting point of 124 ° C.

3rd stage: 2-chloro-6-memyl-3-N-β-hydroxyethylaminophenol 6.8 g (0.03 mol) of the product from stage 2 were introduced at 70 ° C. in 20 ml of 5N NaOH solution. After 30 minutes at this temperature, the mixture was cooled to 0 ° C. and neutralized with concentrated acetic acid. The product was dried under vacuum at 60 ° C in a vacuum; it had a melting point of 104 ° C. 1.2. 2-chloro-6-methyl-3-N-carbethoxyaminophenol fK2)

15.8 g (0.1 mol) of 2-chloro-6-methyl-3-aminophenol and 5.5 g (0.06 mol) of calcium carbonate were suspended in 75 ml of dioxane. 12 g (0.11 mol) of chloroformic acid ethyl ether were then added dropwise at the boiling point. After 30 minutes, the hot reaction mixture was filtered. Then the cooled filtrate was mixed with ice water and the precipitated product was suctioned off; it had a melting point of 70.5 ° C.

1.3. Synthesis of 2-chloro-6-methyl-3-ureidophenol (K3)

19.4 g (0.1 mol) of 2-chloro-6-memyl-3-aminophenol hydrochloride were dissolved in 100 ml of water. 8.1 g (0.1 mol) of potassium cyanate, dissolved in 25 ml of water, were then added dropwise to this solution. After stirring for an hour, the precipitated product was filtered off with suction. The product was stirred for 15 minutes with 150 ml of hydrochloric acid and suction filtered again. After drying at 60 ° C in vacuum, the product had a melting point of 216-220 ° C.

1.4. Synthesis of 4- [N- (N \ Nϊdiethyl-carbamyl) -memylaminol-2-hvdroxy-3-chlorooluene (K4)

15.2 g (0.096 mol) of 2-chloro-6-methyl-3-aminophenol were dissolved under reflux in 80 ml of ethanol water (1: 1). 5 g of calcium carbonate were then added to this solution and a solution of 15 g (0.1 mol) of N- (2-chloroacetyl) diethylamine in 80 ml of water was added dropwise under reflux. After one hour it was filtered hot; the filter residue was recrystallized from ethanol. The product had a melting point of 129 ° C. 1.5. Synthesis of 3- (2-Ammoethylamino) -2-chloro-6-methylphenol (K5)

A mixture consisting of 100 ml of water, 27 g (0.26 mol) of calcium carbonate and 78.8 g (0.5 mol) of 2-Cωor-6-memyl-3-aminophenol was heated to 95 ° C. 112 g (0.54 mol) of bromoethylamine hydrobromide, dissolved in 60 ml of water, were added dropwise with stirring. After the addition had ended, heating was continued for a further 20 minutes. The reaction mixture was then filtered hot. The product precipitated as a hydrobromide after cooling; it had a melting point of 229-232 ° C.

1.6. Synthesis of 2-CMor-6-methyl-3-mesylammoethyl-aminophenol (K6)

1st stage: 2-CWor-6-memyl-3- (N-mesyl-n-ß-mesylamino-ethylamino) -mesyloxy-benzene

45 g (0.16 mol) of 3- (2-Ammoethylanιmo) -2-chloro-6-methylphenol hydrobromide (product from synthesis 1.5) were dissolved in 120 ml of pyridine and gradually at 15-20 ° C with stirring with 48 ml (0.60 mol) of methanosulfonic acid chloride were added. Then the reaction mixture was kept at 20 ° C for 2 hours and then poured into 400 ml of 2.5N hydrochloric acid. The precipitated product was suctioned off and immediately processed according to the 2nd stage.

2nd stage: 2-chloro-6-methyl-3- (N-mesyl-N-ß-mesylammo-ethylamino) phenol

55 g (0.13 mol) of the substance from stage 1 were heated in 120 ml of 4N NaOH solution for 3 hours on the boiling water bath. After cooling, neutralized with acetic acid. The precipitated product was suctioned off and immediately processed according to the 3rd stage. 3rd stage: 2-chloro-6-methyl-3-mesylanιmoethylaminophenol 31 g (0.087 mol) of the substance from stage 2 were heated to 90 ° C. in 30 ml of concentrated hydrochloric acid for 16 hours. After cooling, 30 ml of water were added, neutralized with ammonia and the product was filtered off with suction; After drying, the light brown product had a melting point of 126 ° C.

2. Discolorations

First, a cream base of the following composition was produced [unless otherwise stated, all data are in g]:

Taig fat alcohol 17.0 Lorol ® techn. ^* 4.0

Texapon ^® N 28 40.0

Dehyton ^® K ³ 25.0

4

Eumulgin ^® B 2 1.5 distilled water 12.5

1

C ₁₂ _i8 fatty alcohol (HENKEL)

Natriiutüauryl ether sulfate (approx. 28% active substance; CTFA name: Sodium Laureth Sulfate) (HENKEL)

Fatty acid amide derivative with betaine structure of the formula R-CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO ^" (approx. 30% active substance; CTFA name Cocoamidopropyl Betaine) (HENKEL)

Cetylstearyl alcohol with approx. 20 mol EO (CTFA name: Ceteareth-20) (HENKEL)

The following hair dye cream emulsion was then produced on the basis of this cream: Cream base 50.0

Developer component 7.5 mmol

Coupler component 7.5 mmol

Na ₂ S0 ₃ (inhibitor) 1.0

(NH ₄ ) ₂ S0 ₄ 1.0 conc. Ammonia solution ad pH 10 water ad 100

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the solution was then made up to 100 g with water.

The oxidative development of the color was carried out using a 3% hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.

The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 32 ° C for 30 minutes. After the dyeing process had ended, the hair was rinsed, washed with a customary shampoo and then dried.

The following coupler and developer components were used for the colorations:

- Coupler components

2-chloro-6-methyl-3 -N-ß-hydroxyemylaminophenol (Kl), 2-chloro-6-memyl-3-N-carbethoxyaminophenol (K2), 2-chloro-6-methyl-3-ureidophenol (K3) , 4- [N- (N ', N' -diemyl-carbamyl) -memylamino] -2-hydroxy-3-chlorotoluene (K4), 3- (2-aminoethylamino) -2-chloro-6-methylphenol (K5) and 2-CWor-6-methyl-3-mesylaminoethyl aminophenol (K6).

- Developer components p-toluenediamine (El) 2,4,5,6-tetamammopyrimidine (E2) 3-methyl-4-aminophenol (E3) N, N-bis (2-hydroxyethyl) -p-phenylenediamine (E4) 2- (2-hydroxyemyl) -p-phenylenediamine (E5) 2- (2,5-diaminophenoxy) ethanol (E6) p-aminophenol (E7)

The following colors were found:

Coupler developer shade of colored hair Kl El dark purple

Kl E3 violet brown

Kl E5 violet brown

Kl E7 earthbeeπot

K2 El dark blue

K2 E2 honey yellow

K2 E3 brown orange

K2 E4 dark blue

K2 E5 dark blue

K2 E6 dark purple

K3 El dark blue

K3 E2 red blonde K3 E4 dark blue

K3 E5 black-blue

K3 E6 titian red

K4 El dark purple

K4 E5 dark purple

K4 E7 red-brown

K5 El umbra

K5 E2 dark brown

K5 E7 red gold

K6 El oxide red

K6 E3 venetian red

K6 E4 dark purple

K6 E5 dark purple

K6 E6 dark purple

K6 E7 dark purple

The colorations with colorants, which contained the coupler Kl in combination with the developers El and E5, were particularly outstanding.

Claims

Patent claims

1. Aminophenol derivatives of the general formula (I), OH

in the R ^! stands for

a C _M alkyl group,

a C _M hydroxyalkyl group,

- A C _M alkoxy group or

- an allyl group,

R ² stands for fluorine, chlorine or bromine, R ³ stands for

a C ₃ ^ -dihydroxyalkyl group,

a methyl group which carries 1 to 3 halogen atoms, in particular fluorine atoms, as substituents,

a C 1-4 alkyl group with a maximum of 1 to 4 halogen atoms, in particular fluorine atoms, as substituents,

- a group - (CH ₂ ) _X -B, in which B stands for

- a hydroxy group,

- a group NR R ⁶ or

a group CO-NR ⁷ R ⁸ and x for a number from 1 to 4,

- a group -COOR ⁹ or

a group -CO-NR ^{, 0} R ^π , where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ independently represent hydrogen, a C _M alkyl group, a C _M hydroxyalkyl group and R ⁵ and f _* i R inii

R, R and R, and R and R, together with the nitrogen atom carrying them, can also be part of a morpholino, piperidino or pyπolidino radical and R ^{3 can} also represent a group —SO ₂ —CH ₃ with the proviso that then R ⁶ stands for hydrogen, and R ⁹ stands for hydrogen or a C _M - alkyl group, and R ⁴ stands for hydrogen, a Cι_4-alkyl group or one of the groups mentioned under R ³ and their water-soluble salts.

2. aminophenol derivative according to claim 1, characterized in that R ^{2 is} chlorine.

3. aminophenol derivative according to claim 1 or 2, characterized in that R ^{1 represents} a C 1-4 alkyl group or an allyl group.

4. aminophenol derivative according to claim 3, characterized in that R ^{1 represents} a methyl group.

5. aminophenol derivative according to any one of claims 1 to 4, characterized gekenn¬ characterized in that R ^{4 is} hydrogen.

6. Use of the aminophenol derivatives and their water-soluble salts according to one of claims 1 to 5 as a coupler component in oxidation hair colorants.

7. oxidation dye for dyeing keratin fibers containing Kuppler¬ components and developer components in a water-containing carrier, characterized in that it contains an aminophenol derivative as a coupler component according to any one of claims 1 to 5.

8. Oxidation coloring agent according to claim 7, characterized in that developer components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, and coupler components in an amount of 0.005 to 20% by weight, preferably 0 , 1 to 5% by weight, based in each case on the entire oxidation colorant, are contained.

9. oxidation dye according to claim 7 or 8, characterized in that at least one developer component selected from 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 1 - (ß-hydroxyethyl) - 2,5-diaminobenzene, p-phenylenediamine, p-toluenediamine, p-aminophenol, 3-methyl-p-aminophenol and 2-anήnomethyl-p-aminophenol, is contained.

10. Oxidation dye according to one of claims 7 to 9, characterized gekenn¬ characterized in that it also contains at least one substantive dye.