AU3248499A - Novel p-aminophenol derivatives and the use thereof - Google Patents

Description

WO 99/31054 1 PCT/EP98/07961 Novel p-aminophenol derivatives and the use thereof This invention relates to new p-aminophenol derivatives, to their use for coloring keratin fibers and to colorants containing these compounds. By virtue of their intensive colors and good fastness properties, so called oxidation colorants play a prominent role in the coloring of keratin 5 fibers, particularly human hair. Oxidation colorants contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates in the presence of oxidizing agents or atmospheric oxygen. 10 Good oxidation dye precursors are expected to satisfy above all the following requirements: they must form the required color tones with sufficient intensity and fastness during the oxidative coupling reaction. In addition, they must be readily absorbed onto the fibers with no significant differences - particularly in the case of human hair - between damaged and 15 freshly regrown hair (levelling behavior). They must be resistant to light, heat and the effect of chemical reducing agents, for example permanent wave lotions. Finally, if they are used to color hair, they should not overly stain the scalp and, above all, should be toxicologically and dermatologically safe. 20 The primary intermediates normally used are primary aromatic amines containing another free or substituted hydroxy or amino group in the para position or the ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6 tetraaminopyrimidine and derivatives thereof. 25 Special representatives are, for example, p-phenylenediamine, p toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2 hyd roxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5- WO 99/31054 2 PCT/EP98/07961 diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6 triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino hydroxy pyrimidine and 1,3-N,N'-bis-(2'-hydroxyethyl)-N,N'-bis-(4'-amino 5 phenyl)-diamino-2-propanol. The secondary intermediates are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable secondary intermediates are 1 naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methyl 10 phenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-amino phenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4 chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-4-hydroxy pyridine, 2-methyl resorcinol, 5-methyl resorcinol and 2-methyl-4-chloro-5 15 aminophenol. In general, natural color tones cannot be obtained with a primary intermediate alone or with a special secondary intermediate/primary intermediate combination. In practice, therefore, combinations of various primary intermediates and secondary intermediates are used so that there 20 is a constant need for new improved dye components. Accordingly, the problem addressed by the present invention was to provide new primary intermediates which would satisfy the requirements oxidation dye precursors are expected to meet to a particular degree. It has now been found that certain, hitherto unknown p-aminophenol 25 derivatives satisfy the requirements primary intermediates are expected to meet to a particularly high degree. Thus, brilliant color tones, more especially in the brown and red range, are obtained using these primary intermediates with most of the known secondary intermediates. In addition, the colors obtained are distinguished by extremely high fastness to light 30 and washing.

WO 99/31054 3 PCT/EP98/07961 In a first embodiment, therefore, the present invention relates to p aminophenol derivatives corresponding to general formula (1): A C 5 R1 X R2) 10 B D in which - A, B, C and D independently of one another represent an -OH or -NHR group where R is a hydrogen atom or a C 1 4 alkyl group, with the 15 proviso that either A or B and C or D is a hydroxy group, - X stands for oxygen, sulfur, a sulfoxy or a sulfoxyl group and - R 1 and R 2 independently of one another represent hydrogen, fluorine, chlorine, a C14 alkyl or hydroxyalkyl group or a C 2 4 dihydroxyalkyl group, preferably a C 2 dihydroxyalkyl group. 20 These compounds can be produced by known organic synthesis methods. Particulars can be found in the following Synthesis Example. Since all the compounds according to the invention are amino compounds, the known acid addition salts can be prepared from them in the usual way. Accordingly, all statements in this specification-and hence 25 the claimed scope of protection relate both to the p-aminophenol derivatives of formula (1) present in free form and to their water-soluble physiologically compatible salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. 30 Those aminophenol derivatives of formula (1) where X is an oxygen or sulfur atom have proved to be particularly suitable for the purposes of WO 99/31054 4 PCT/EP98/07961 the invention. Oxygen has proved to be a particularly advantageous group x. Those p-aminophenol derivatives corresponding to formula (I) where the groups A, B, C and D which are not OH groups stand for -NH 2 groups 5 are also particularly preferred for the purposes of the invention. In addition, hydrogen has .proved to be a particularly suitable substituent R 1 and R 2 in p-aminophenol derivatives corresponding to formula (1). Finally, those p-aminophenol derivatives corresponding to formula (1) 10 where R 1 and R 2 are the same, A and C are the same and B and D are the same have also proved to be particularly suitable for the purposes of the invention. A compound with particularly outstanding suitability for the purposes of the invention is 4-amino-2-(((5-amino-2-hydroxyphenyl)-methoxy) 15 methyl)-phenol. In a second embodiment, the present invention relates to the use of the above-mentioned p-aminophenol derivatives as primary intermediates in oxidation hair colorants. Finally, in a third embodiment, the -present invention relates to 20 oxidation colorants for coloring keratin fibers containing secondary intermediates and primary intermediates in a water-containing carrier, characterized in that one of the above-mentioned p-aminophenol derivatives is present as the primary intermediate. Keratin fibers in the context of the present invention include pelts, 25 wool, feathers and, more particularly, human hair. Although the oxidation colorants according to the invention are particularly suitable for coloring keratin fibers, there is basically nothing to prevent them from being used in other fields, particularly in color photography. The oxidation colorants according to the invention contain the 30 primary intermediates corresponding to formula (1) and secondary WO 99/31054 5 PCT/EP98/07961 intermediates and, if desired, may contain other primary intermediates and secondary intermediates. According to the invention, preferred other primary intermediates are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 2-(2,5 5 diaminophenyl)-ethanol, N, N-bis-(2-hydroxyethyl)-p-phenylened iamine, 1 phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 4 amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraamino pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triamino pyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-tri 10 aminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol and 4,4' diaminodiphenylamine. 2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5 aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3 N,N'-bis-(2'-hydroxyethyl)-N,N'-(4'-aminophenyl)-diamino-1,3-propan-2-ol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 15 94/08970, such as 4,5-diamino-1-(2'-hydroxyethyl)-pyrazole for example, are also primary intermediates which may advantageously be combined with the primary intermediates according to the invention. Most particularly preferred other primary intermediates are p phenylenediamine, 2,4,5,6-tetraminopyrimidine, 4,5-diamino-1-(2' 20 hydroxyethyl)-pyrazole, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, bis (2-hydroxy-5-aminophenyl)-methane, 2-(2,5-diaminophenyl)-ethanol, 3 methyl-4-aminophenol, 4-hydroxy-2,5,6-triaminopyrimidine, 2-aminomethyl 4-aminophenol and p-toluylenediamine. According to the invention, preferred secondary intermediates are 1 25 naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-amino phenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, 1 -phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3 aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 4-chlororesorcinol, 2 chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 30 2,5-dimethyl resorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2- WO 99/31054 6 PCT/EP98/07961 amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 2-methyl-4 chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3-amino-2 methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis-(2 hydroxyethylamino)-toluene, 3.4-methylenediioxyphenol, 3,4-methylene 5 dioxyaniline, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethyl amino)-anisole and 2,6-dimethyl-3-aminphenol. Particularly preferred secondary intermediates are 1-naphthol, m aminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2 methylaniline, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dimethyl-3 10 aminophenol, 2,4-diaminophenoxy ethanol, 2,7-dihydroxynaphthalene, 6 methyl-1,2,3,4-tetrahydroquinoxaline, 1,7-dihydroxynaphthalene, 2-methyl 4-chloro-5-aminophenol, 3,4-methylenedioxyaniline, 2-methylresorcinol, 4 chlororesorcinol, 3,4-methylenedioxyphenol, 2-amino-3-hydroxypyridine and 2-chloro-6-methyl-3-aminophenol. 15 These other primary and secondary intermediates are normally used in free form. Where they contain amino groups, however, it may be preferable to use them in salt form, particularly in the form of the hydrochlorides and sulfates. The hair colorants according to the invention contain both the 20 primary intermediates and the secondary intermediates in a quantity of preferably 0.005 to 20% by weight and more preferably 0.1 to 5% by weight, based on the oxidation colorant as a whole. The primary intermediates and secondary intermediates are generally used in a substantially equimolar ratio to one another. Although it has proved to be 25 of advantage to use the primary and secondary intermediates in an equimolar ratio, there is no disadvantage in using individual oxidation dye precursors in a certain excess so that primary intermediates and secondary intermediates may be present in a molar ratio of 1:0.5 to 1:3 and, more particularly, 1:1 to 1:2. 30 In one preferred embodiment, the hair colorants according to the WO 99/31054 7 PCT/EP98/07961 invention contain typical substantive dyes in addition to the oxidation dye precursors for further modifying the color tones. Substantive dyes are normally nitrophenylendiamines, nitroaminophenols, azo dyes, anthra quinones or indophenols. Preferred substantive dyes are the compounds 5 known under the International names or trade names of HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 4 -amino-2-nitrodiphenylamine-2' 10 carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2 nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol and 4-N-ethyl 1, 4 -bis-( 2 '-hydroxyethylamino)-2-nitrobenzene hydrochloride. The color ants according to the invention of this embodiment preferably contain the substantive dyes in a quantity of 0.01 to 20% by weight, based on the 15 colorant as a whole. The colorants according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet. 20 Other dye components which may be present in the colorants according to the invention are indoles and indolines and physiologically compatible salts thereof. Preferred examples are 5,6-dihydroxyindole,

N

methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-di hydroxyindole, N-butyl-5,6-dihydroxyindole, 6-hydroxyindole, 6-aminoindole 25 and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6 dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxy indoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. The oxidation dye precursors or the substantive dyes optionally 30 present do not have to be single compounds. On the contrary, other WO 99/31054 8 PCT/EP98/07961 components may be present in small quantities in the hair colorants according to the invention due to the processes used to produce the individual dyes providing these other components do not adversely affect the coloring result or have to be ruled out for other reasons, for example 5 toxicological reasons. So far as the dyes suitable for use in the hair colorants and tinting formulations according to the invention are concerned, reference is also expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264 10 267; oxidation dye precursors), published as Volume 7 of the Series "Dermatology" (Ed.: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basle, 1986, and to the "EuropAische Inventar der Kosmetik Rohstoffe" published by the Europsische Gemeinschaft and available in disk form from the Bundesverband Deutscher Industrie- und 15 Handelsunternehmen fOr Arzneimittel, Reformwaren und K6rperpflegemittel d.V., Mannheim. To produce the colorants according to the invention, the oxidation dye precursors are incorporated in a suitable water-containing carrier. For coloring hair, such carriers are, for example, creams, emulsions, gels or 20 even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair. The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, 25 both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants for the hair colorants according to the 30 invention are any anionic surface-active substances suitable for use on the WO 99/31054 9 PCT/EP98/07961 human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether 5 and amide and hydroxyl groups may also be present in the molecule. The following are examples of suitable anionic surfactants - in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanol ammonium salts containing 2 or 3 carbon atoms in the alkanol group: - linear fatty acids containing 10 to 22 carbon atoms (soaps), 10 - ether carboxylic acids corresponding to the formula

R-O-(CH

2

-CH

2 0)x

CH

2 -COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, - acyl taurides containing 10 to 18 carbon atoms in the acyl group, 15 - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, 20 - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear a-olefin sulfonates containing 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the 25 formula R-O(CH 2

-CH

2 0)x-SO 3 H, in which R is a preferably linear alkyl group containing 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 30 glycol ethers according to DE-A-37 23 354, WO 99/31054 10 PCT/EP98/07961 - sulfonates of unsaturated fatty acids containing 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 in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or 5 propylene oxide with fatty alcohols containing 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 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, more particularly, unsaturated C8- 2 2 10 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. In the context of the invention, zwitterionic surfactants are surface active compounds which contain at least one quaternary ammonium group and at least one -COO( or -SO30 group in the molecule. Particularly 15 suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines 20 containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine. Ampholytic surfactants are surface-active compounds which, in 25 addition to a C 8 18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, 30 N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl WO 99/31054 11 PCT/EP98/07961 aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino propionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine. 5 Nonionic surfactants contain, for example, a polyol group, a poly alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are - products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 10 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group, - C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide onto glycerol, - C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof, 15 - products of the addition of 5 to 60 moles of ethylene oxide onto castor oil and hydrogenated castor oil, - products of the addition of ethylene oxide onto sorbitan fatty acid esters, - products of the addition of ethylene oxide onto fatty acid alkanolamides. Examples of cationic surfactants suitable for use in the hair 20 treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, 25 stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates.

WO 99/31054 12 PCT/EP98/07961 Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2 7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethi cone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified 5 silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil@-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80). Alkyl amidoamines, particularly fatty acid amidoamines, such as the 10 stearyl amidopropyl dimethyl amine obtainable as Tego AmidoS 18, are distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed 15 under the trade name of Stepantex@ and the products marketed under the trade name of Dehyquart@, such as Dehyquart AU-46, are also readily biodegradable. One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat@100 20 (INCI name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are 25 obtained. The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog 30 distribution are mixtures of homologs which are obtained in the reaction of WO 99/31054 13 PCT/EP98/07961 fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, 5 hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be of advantage. Other active substances, auxiliaries and additives are, for example, - nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate 10 copolymers and polysiloxanes, - cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quater 15 nized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, - zwitterionic and amphoteric polymers such as, for example, acrylamido propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2 20 hydroxypropyl methacrylate copolymers, - anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic 25 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, for example methyl cellulose, hydroxyalkyl cellulose and 30 carboxymethyl cellulose, starch fractions and derivatives, such as WO 99/31054 14 PCT/EP98/07961 amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structurants, such as glucose and maleic acid, 5 - hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils, - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, 10 - perfume oils, dimethyl isosorbide and cyclodextrins, - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - antidandruff agents, such as piroctone olamine and zinc omadine, - other substances for adjusting the pH value, 15 - active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, - cholesterol, - UV filters, 20 - consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, - fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, - fatty acid alkanolamides, 25 - complexing agents, such as EDTA, NTA and phosphonic acids, - swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, - opacifiers, such as latex, 30 - pearlizers, such as ethylene glycol mono- and distearate, WO 99/31054 15 PCT/EP98/07961 - propellents, such as propane/butane mixtures,

N

2 0, dimethyl ether, C02 and air and - antioxidants. To produce the colorants according to the invention, the constituents 5 of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole. In principle, the color can be oxidatively developed with atmospheric 10 oxygen. However, a chemical oxidizing agent is preferably used, particularly when human hair is to be not only colored, but also lightened. Particularly suitable oxidizing agents are persulfates, chlorites and, in particular, hydrogen peroxide or addition products thereof with urea, melamine or sodium borate. Oxidation may also be carried out with 15 enzymes. In this case, the enzymes may be used to transfer atmospheric oxygen to the primary intermediate or to enhance the effect of an oxidizing agent present in small quantities. One example of an enzymatic process is the procedure whereby the effect of small quantities (for example 1% and less, based on the formulation as a whole) of hydrogen peroxide is 20 enhanced by peroxidases. The preparation of the oxidizing agent is preferably mixed with the preparation of the oxidation dye precursors immediately before coloring of the hair. The ready-to-use hair coloring preparation formed should preferably have a pH value in the range from 6 to 10. In a particularly 25 preferred embodiment, the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 400C. After a contact time of about 5 to 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant 30 content, for example a coloring shampoo, has been used.

WO 99/31054 16 PCT/EP98/07961 The following Examples are intended to illustrate the invention. Examples 5 1. Synthesis Example Synthesis of 4-amino-2-(((5-amino-2-hydroxyphenyl)-methoxy)-methyl) phenol Diazonium solution (solution A): 10.35 g (0.115 mole) of sodium nitrite in 125 ml of water were added 10 at a temperature of +50C to a solution consisting of 26 g (0.15 mole) of sulfanilic acid and 75 ml (0.15 mole) of 2N sodium hydroxide. 131 ml (0.38 mole) of 10% hydrochloric acid were added dropwise while cooling (+50C) over a period of 30 minutes. Solution A was added dropwise to an ice-cooled solution consisting 15 of 17.25 g (0.075 mole) of bis-(2-hydroxybenzyl)-ether in 120 ml (0.3 mole) of 10% sodium hydroxide. After the addition, the whole was stirred for 1.5 hours at 200C. 69 g (0.4 mole) of sodium dithionite were then added over a period of 2 minutes. After 20 minutes at 75 0 C, the product was filtered off under 20 suction and washed with water. The product was obtained in the form of colorless crystals with a melting point of 1750C (decomp.). 2. Coloring A cream base with the following composition was first prepared [all 25 quantities are in g, unless otherwise indicated]: tallow fatty alcohol 17.0 Lorol@techn.

1 4.0 Texapon@N 282 40.0 30 Dehyton@K 3 25.0 WO 99/31054 17 PCT/EP98/07961 Eumulgin@B 24 1.5 distilled water 12.5

C

12

-

18 fatty alcohol (HENKEL) 5 2 Sodium lauryl ether sulfate (ca. 28% active substance; INCI name: Sodium Laureth Sulfate) (HENKEL) 3 Fatty acid amide derivative with a betaine structure corresponding to the following formula: R-CONH(CH 2

)

3

N*(CH

3

)

2

CH

2 COO- (ca. 30% active substance; INCI name Cocoamidopropyl Betaine) (HENKEL) 10 4 Cetyl stearyl alcohol containing ca. 20 moles EO (INCI name: Ceteareth-20) (HENKEL) The following hair coloring cream emulsion was then prepared on the basis of this cream: 15 cream base 50.0 primary intermediate 7.5 mmoles* secondary intermediate 7.5 mmoles* Na 2

SO

3 (inhibitor) 1.0 20 (NH 4

)

2

SO

4 1.0 conc. ammonia solution to pH 10 water to 100 * unless otherwise indicated 25 The ingredients were mixed in the order listed. Substantive dyes were optionally added with corresponding reductions in the water content. After addition of the oxidation dye precursors and the inhibitor, the emulsion was first adjusted to pH 10 with concentrated ammonia solution 30 and was then made up with water to 100 g.

WO 99/31054 18 PCT/EP98/07961 The color was oxidatively developed with 3% hydrogen peroxide solution as the oxidizing solution. To this end, 50 g of hydrogen peroxide solution (3%) were added to and mixed with 100 g of the emulsion. The coloring cream was applied to approximately 5 cm long tresses 5 of standardized, 90% grey but not specially pretreated human hair and left thereon for 30 minutes at 32 0 C. On completion of the coloring process, the hair was rinsed, washed with a normal shampoo and dried. The following primary and secondary intermediates and substantive dyes were used for coloring: 10 Primary intermediates e 4-amino-2-(((5-amino-2-hydroxyphenyl)-methoxy)-methyl)-pheno (El) * 2,4,5,6-tetraaminopyrimidine (E2) * 4,5-diamino-1-(2-hydroxyethyl)-pyrazole (E3) 15 * p-phenylenediamine * N,N-bis-(2-hydroxyethyl)-p-phenylenediamine (E5) e 4-hydroxy-2,5,6-triaminopyrimidine (E6) e p-toluylenediamine * 2-(2,5-diaminophenyl)-ethanol (E8) 20 e 2-aminomethyl-4-aminophenol (E9) * 4-amino-3-methylphenol * bis-(2-hydroxy-5-aminophenyl)-methane (El 1) Secondary intermediates 25 e 1-naphthol (K1) e 2-methyl-5-aminophenol (K2) * 2-chloro-6-methyl-3-aminophenol (K3) " 2-amino-3-hydroxypyridine (K4) WO 99/31054 19 PCT/EP98/07961 * 2,6-dimethyl-3-aminophenol (K5) * m-aminophenol (K6) * 2,7-dihydroxynaphthalene (K7) * 4-chlororesorcinol (K8) 5 * 2 -methyl-4-chloro-5-aminophenol (K9) e 6-methyl-1, 2

,

3 ,4-tetrahydroquinoxaline (K10) * 2-methyl resorcinol (K1 1) * 3 -amino- 2 -methylamino-6-methoxypyridine (K12) * 2 ,4-diaminophenoxyethanol (K13) 10 a 3-methylsulfonylamino-2-methyl aniline (K14) * 1,7-dihydroxynaphthalene (K15) * 3 ,4-methylenedioxyphenol (K16) e 3 ,4-methylenedioxyaniline (K17) e m-phenylenediamine (K18) 15 Substantive dyes * 6-nitro-1, 2

,

3

,

4 -tetrahydroquinoxaline (D1) e 2 -nitro- 4 -aminodiphenylamine-2'-carboxylic acid (D2) * 2 -amino-6-chloro-4-nitrophenol (D3) 20 e 2-nitro-1-amino- 4 -bis-(2-hydroxyethyl)-aminobenzene (D4) * 2-nitro-1 -( 2 -hydroxyethyl)-amino-4-methylbenzene (D5) e 2

-(

2 '-hydroxyethylamino)-4,6-dinitrobenzene (D6) S1-(2'-hydroxyethyl)-amino-2-nitro-4-bis-(2-hydroxyethyl)-aminobenzene (D7) 25 * 1-(2-hydroxyethyl)-amino-2-nitro-4-aminobenzene (D8) * 4 -(2-nitrophenyl)-aminophenol (D9) WO 99/31054 20 PCT/EP98/07961 The following colors were obtained: Primary Secondary Substantive dye Hair color intermediate intermediate El K1

-

Grey-red El K2 Grey-orange El K3

-

Brown-red El K4 - Light orange El K5 - Grey-red El K6

.

Topaz yellow E1+E3a K1+K3a

-

Old pink El+E2a K2+K7a

-

Flat violet E1+E6a K8+K9a

-

Grey-red E1+E7a K1+1a

-

Champagne E1 +E4a K2- Black E1+E5a K5+K1 3a .. Black-blu-e E1+E8a K12+K14a - Blue-grey E1+E9a K15+K16a 0.1% by weight Dl Brown-orange E1+E10a K17 0.3% by weight D2 Flat red E1+EI1a K18 0.1% by weight D3 Hair brown El K3 0.1% by weight D4 + 0.1% Copper by weight D5 El K3 0.1% by weight D6 + 0.1% Tomato red by weight D7 El K9 0.1% by weight D8 + 0.1% Lacquer red by weight D9 a 0.375 mmole

Claims (13)

1. p-Aminophenol derivatives corresponding to general formula (1): A C 5 R 1 X R(2 10 B D in which - A, B, C and D independently of one another represent an -OH or -NHR group where R is a hydrogen atom or a C- alkyl group, with the 15 proviso that either A or B and C or D is a hydroxy group, - X stands for oxygen, sulfur, a sulfoxy or a sulfoxyl 'group and - R 1 and R 2 independently of one another represent hydrogen, fluorine, chlorine, a C 1 .4 alkyl or hydroxyalkyl group or a C 2 .4 dihydroxyalkyl group, preferably a C 2 dihydroxyalkyl group, 20 and physiologically compatible salts of these compounds.

2. p-Aminophenol derivatives as claimed in claim 1, characterized in that X stands for an oxygen or sulfur atom, more particularly an oxygen atom.

3. p-Aminophenol derivatives as claimed in claim 1 or 2, characterized 25 in that the groups A, B, C and D which are not -OH groups are -NH 2 groups.

4. p-Aminophenol derivatives as claimed in any of claims 1 to 3, characterized in that R 1 and R 2 represent hydrogen.

5. p-Aminophenol derivatives as claimed in any of claims 1 to 4, 30 characterized in that the groups R 1 and R 2 are the same, WO 99/31054 22 PCT/EP98/07961 A and C are the same and B and D are the same.

6. 4-Amino-2-(((5-amino-2-hydroxyphenyl)-methoxy)-methyl)-phenol.

7. The use of the p-aminophenol derivatives claimed in any of claims 1 5 to 6 and physiologically compatible salts thereof as primary intermediates in oxidation colorants.

8. An oxidation colorant for coloring keratin fibers containing secondary intermediates and primary intermediates in a water-containing carrier, characterized in that it contains at least one p-aminophenol derivative 10 according to any of claims 1 to 6 as a primary intermediate.

9. An oxidation colorant as claimed in claim 8, characterized in that it contains at least one secondary intermediate selected from the group consisting of 1-naphthol, m-aminophenol, 5-amiro-2-methylphenol, 3 methylsulfonylamino-2-methylaniline, 3-amino-2-methylamino-6-methoxy 15 pyridine, 2,6-dimethyl-3-aminophenol, 2,4-diaminophenoxy ethanol, 2,7 dihydroxynaphthalene, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 1,7 dihydroxynaphthalene, 2-methyl-4-chloro-5-aminophenol, 3,4-methylene dioxyaniline, 2-methylresorcinol, 4-chlororesorcinol, 3,4-methylenedioxy phenol, 2-amino-3-hydroxypyridine and 2-chloro-6-methyl-3-aminophenol. 20

10. An oxidation colorant as claimed in claim 8 or 9, characterized in that it contains at least one other primary intermediate in addition to the p aminophenol derivatives claimed in any of claims 1 to 6.

11. An oxidation colorant as claimed in claim 10, characterized in that the other primary intermediate is selected from 2,4,5,6-tetraaminopyrimi 25 dine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1-(2-hydroxyethyl) pyrazole, p-toluylenediamine, 2-aminomethyl-4-aminophenol, N,N-bis-(2 hyd roxyethyl)-p-phenylenediamine, p-phenylenediamine, 2-(2,5-diamino phenyl)-ethanol, 3-methyl-p-aminophenol and bis-(2-hydroxy-5-amino phenyl)-methane. 30

12. An oxidation colorant as claimed in any of claims 8 to 11, WO 99/31054 23 PCT/EP98/07961 characterized in that the primary intermediates are used in a quantity of 0.005 to 20% by weight and preferably in a quantity of 0.1 to 5% by weight while the secondary intermediates are used in a quantity of 0.005 to 20% by weight and preferably in a quantity of 0.1 to 5% by weight, based on the 5 oxidation colorant as a whole.

13. An oxidation colorant as claimed in any of claims 8 to 11, characterized in that it contains at least one substantive dye.