GB2168370A - New 2-amino-4-nitro anilines useful as hair dyes - Google Patents

Abstract

2-Amino-4-nitro-6-hydroxyalkyl anilines of formula (I> <IMAGE> wherein: X is an unsubstituted or a mono- or polyhydroxy substituted branched or unbranched alkylene of 2 to 6 carbon atoms; R1 and R2 are the same or different and each is hydrogen. (C1-4)-alkyl, mono- or polyhydroxy-(C1-4)-alkyl, amino-(C1-4) alkyl or mono- or disubstituted amino-(C1-4)-alkyl wherein each substituent is a mono- or polyhydroxy-(C1-4)-alkyl radical or at least one substituent and the nitrogen atom form part of a heterocyclic system; R' is hydrogen or (C1-4)-alkyl; or cosmetically acceptable salts of such compounds are useful in dyeing keratinous fibres, particularly human hair.

Description

SPECIFICATION New 2-amino-4-nitro-anilines The present invention relates to new 2-amino-4-nitro-6-hydroxyalkylanilines, the process for preparation thereof and their use in dying keratinous fibres, and more especially human hair.

It is well known that to perform direct dyeing on hair or endow the latter with complementary glints in the case of oxidation dyeing, nitro derivatives of the benzene series can be used. The use has already been recommended of nitro-ortho-phenylenediamines such as, more especially, 2-amino-4-nitro-6-alkylanilines, both in direct dyeing and in oxidation dyeing.

However, it has been found that, in general, these dyes are insufficiently stable to light and to washing.

The Applicant has hence sought new dyes showing better stability to light and to washing, and has consequently discovered the new compounds of formula (I):

in which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, one of these atoms optionally being able to be substituted with one or more hydroxyl radicals; R, and R2 denote, independently of each other, a hydrogen atom, an alkyl or a mono-or polyhydroxyalkyl radical or an aminoalkyl radical in which the amine group can be mono- or disubstituted with an alkyl or a mono- or polyhydroxyalkyl radical, the nitrogen atom also being able to form part of a heterocyclic system, and the alkyl radical containing 1 to 4 carbon atoms; R' denotes a hydrogen atom or a C, to C4 alkyl radical.

The subject of the present invention is hence the new 2-amino-4-nitro-6-hydroxyalkylanilines of formula (I) given above, as well as the cosmetically acceptable salts thereof.

By way of preferred radicals X, ethylene, propylene, 1,1-dimethylethylene, 1,2-dimethylethylene and 1,1.2-trimethylethylene radicals may be mentioned.

By way of radicals R. and R2 which are more especially preferred according to the invention, hydrogen and methyl, ethyl, n-propyl, p-hydroxyethyl, Py-hydroxypropyl, ss, -dihydroxypropyl, aminoethyl and p- diethylaminoethyl radicals may be mentioned.

Radicals R' which are preferred according to the invention are hydrogen and the methyl radical.

Preferred compounds of formula (I) according to the invention are the following: -2-(2,3-diamino-5-nitrophenyl)ethanol; - 2-[3-amino-2-(p-hydrnxyethyl)amino-5-nitro-phenyl] ethanol; 1-(2,3-diamino-5-nitrophenyl)-2-propanol; -1 -(3-amino-2-methylamino-5-nitrophenyl)-2-propanol, as well as the salts thereof.

The subject of the present invention is also a process for preparing the compounds of formula (I).

The 2-amino-4-nitro-6-hydroxyalkylanilines of formula (I), according to the invention, are prepared by a process which consists in reacting an aqueous ammonia solution or a primary aliphatic amine R1NH2, in which P1 has the meaning given above, with a heterocyclic compound of formula (IV) below, and then performing selective reduction of the 2,4-dinitro-6-hydroxyalkylaniline of formula (III) obtained, to obtain a 2-amino-4-nitro-6-hydroxyalkylaniline of formula (II), which is then optionally subjected to a conventional chemical alkylation, hydroxyalkylation or aminoalkylation process to obtain the final compound of formula (I).

The scheme for the process is as follows:

R', X and R, having the meaning given above.

This process enables excellent yields of the final compound (II) or (I) to be obtained.

The reaction of ammonia or of the primary amine with the heterocyclic compound of formula (IV) is optionally performed under pressure, at a temperature between 20 and 120"C, optionally in the presence of polar protic solvents such as water, alcohols, glycols or glycol ethers, or polar aprotic solvents such as formamide, dimethylformamide, dioxane or tetrahydrofuran.

The selective reduction of the compound of formula (III) is performed either with a hydroalcoholic solution of sodium sulphide in the presence of sulphur at a temperature between 10" and 70"C, or with hydrogen sulphide in the presence of ammonia solution according to 10M. KAMEL, M.l. ALI and M.M.

KAMEL, TETRAHEDRON 1966, vol. 22, p. 3353, or alternatively by transfer of hydrogen from cyclohexene to the compound (III) in the presence of Pd C, in C,-C4 lower alcohols and at a temperature between 15 C and the boiling point, in a manner similar to that of lan D. Entwistle, Robert A.W. JOHNSTENE and Jeffery POVALL fJ.C.S. PERKIN 1(1975), p. 1300).

The compounds of formula (IV) are obtained by nitration of the compounds of formula (V) below:

in which X and R' have the meanings given above, these compounds being known. The nitration is performed by adding the compound (V) to fuming nitric acid at a temperature between 30 and 35"C according to G. CHATELUS, Ann. Chem. 4, 505-547 (1949), or alternatively be adding the compound (V) to a mixture of concentrated sulphuric and nitric acids, the temperature being maintained in the region of 5"C, according to Charles D. HURD, Rostyslaw DOWBENKO, JACS 80, 4711-14 (1958). The dinitro compound lV) is then isolated by diluting the reaction medium with water.

The compounds of formula (IV) in which X denotes an ethylene, propylene, 1,1-dimethylethylene, 1,2dimethylethylene and 1,1,2-trimethylethylene radical are known.

The alkylation. hydroxyl alkylation or amino alkylation by which the desired compound of formula (I) is obtained from the compound of formula (II) may be effected according to the processes described in French Patents 2 348 911, 2 497 662 and 2 492370 (L'OREAL) or by other well known methods.

The subject of the present invention is also a dyeing composition for keratinous fibres, and more especially for human hair, containing a 2-amino-4-nitro-6-hydroxyalkylaniline of formula (I) above, as well as a process for dyeing keratinous fibres, and more especially human hair, using the said dyeing composition.

The dyeing compositions according to the invention contain, in a solvent medium, at least one compound corresponding to the formula (I), or one of its cosmetically acceptable salts, and can be used for direct dyeing of keratinous fibres or for oxidation dyeing of these fibres, in which case the compounds of formula (I) confer glints which are complementary to the basis coloration obtained by oxidative development of precursors of oxidation dyes.

These compositions contain the compounds according to the invention in proportions of between 0.001 and So by weight and preferably between 0.05 and 2% by weight, relative to the total weight of the composition.

The solvent medium is preferably a cosmetic vehicle generally consisting of water, but organic solvents can also be added into the compositions to solubilise compounds which would not be sufficiently soluble in water. Among these solvents, there may be mentioned lower alkanols such as ethanol and isopropanol, aromatic alcohols such as benzyl alcohol, polyols such as glycerol, glycols or glycol ethers such as 2-butoxyethanol or 2-ethoxyethanol, ethylene glycol and propylene glycol, diethylene glycol monomethyl ether and monoethyl ether and also similar products and mixtures thereof. These solvents are preferablv present in proportions ranging from 1 to 75% by weight, and especially from 5 to 50% by weight relative to the total weight of the composition.

These compositions can contain anionic, cationic, nonionic or amphoteric surfactants, or mixtures thereof. These surfactants are present in the compositions of the invention in proportions of between 0.5 and 55"o by weight. and preferably between 4 and 40% by weight, relative to the total weight of the composition.

The compositions can be thickened, preferably with compounds chosen from sodium alginate, gum arabic. cellulose derivatives such as methylceilulose, hydroxyethylcellulose, hydroxypropylmethylcellu ose and carboxymethylcellulose and various polymers which have the function of a thickener such as, more especially, acrylic acid derivatives. It is possible to use inorganic thickening agents such as benton te. These thickening agents are preferably present in proportions of between 0.5 and 10% by weight, and especially between 0.5 and 2 ó by weight, relative to the total weight of the composition.

The compositions according to the invention can also contain various adjuvants customarily used in dyeing compositions for the hair, and especially penetrants, dispersants, sequestering agents, film-forming agents, buffers and perfumes.

These compositions can take various forms such as liquid, cream or gel form, or any other form suitable for carrying out hair dyeing. They can in addition be packaged in aerosol containers in the presence of a propellant.

The pH of these dyeing compositions can be between 3 and 11.5, and preferably between 5 and 11.5. It is adjusted to the desired value using an alkalinising agent such as ammonia solution, sodium carbonate, potassium carbonate or ammonium carbonate, sodium hydroxide or potassium hydroxide, alkanolamines such as mono-, di- or tri-ethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, or alkylamines such as ethylamine or triethylamine, or using an acidifying agent such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric acid.

When the compositions are intended for use in a process for direct dyeing of hair, they can contain, in addition to the compounds according to the invention, other direct dyes such as azo or anthraquinone dyes, for example 1,4,5,8-tetraaminoanthraquinone, indophenols, indoanilines and nitro dyes of the benzene series other than the compounds of formula (I).

The concentrations of these direct dyes other than the dyes of formula (I) can be between 0.001 and 5 O by weight relative to the total weight of the composition.

These compositions, employed in a direct dyeing process, are applied on the keratinous fibres for an exposure time which varies from 5 to 50 minutes, the fibres are then rinsed, optionally washed with shampoo, rinsed again and dried.

The compositions according to the invention can also be employed in the form of hair setting lotions intended at one and the same time to endow the hair with a light coloration or with glints, and to improve the shape-retention of the set. In this case, they take the form of aqueous, alcoholic or hydroalcoholic solutions containing at least one cosmetic resin, and they are applied on damp hair which has been washed and rinsed beforehand and which is optionally coiled and then dried.

The cosmetic resins which are used in the setting lotions can be, in particular, polyvinylpyrrolidone, crotonic acid vinyl acetate, vinylpyrrolidone/vinyl acetate, maleic anhydride/butyl vinyl ether and maleic anhydride' methyl vinyl ether copolymers, as well as any other cationic, anionic, nonionic or amphoteric polymer customarily used in this type of composition. These cosmetic resins participate in the compositions of the invention in the proportion of 0.5 to 4% by weight, and preferably from 1 to 3% by weight, based on the total weight of the composition.

When the compositions according to the invention constitute oxidation dyes, involving development with an oxidising agent, the compounds of formula (I) according to the invention are mainly used for the ourpose of contributing glints to the final dyeing.

These compositions then contain, in combination with at least one nitro dye of formula (I) and optionaily other direct dyes, oxidation dye precursors.

The compositions can contain, for example, paraphenylenediamines such as: para-phenylenediamine, caratolyenediamine, 2-chloro-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl3-methoxy-para-phenylenediamine, N-(ss-methoxyethyl)-para-phenylenediamine, N,N-bis(p-hydrnxyethyl )- para-phenylenediamine, 4-[N-ethyl-N-(carbamylmethyl)amino]aniline and also the salts thereof.

They can also contain para-aminophenols, for example: para-aminophenol, N-methyl-para-amino Phenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2-methyl-4-aminophenol and the salts thereof.

They can also contain orthoaminophenol.

They can also contain heterocyclic derivatives, for example: 2,5-diaminopyridine and 7-aminobenzomorpholine.

The compositions according to the invention can contain, in combination with the oxidation dye precursors, couplers which are well-known in the state of the art.

By way of couplers, there may be mentioned, in particular: meta-diphenols, meta-aminophenols and the salts thereof, meta-phenylenediamines and the salts thereof, meta-acylaminophenols, meta-ureidophenols and meta-carbalkoxyaminophenols.

As other couplers which can be used in the compositions according to the invention, there may finally be mentioned: v-naphthol, couplers possessing an active methylene group such as diketo compounds and pyrazolones, and heterocyclic couplers derived from pyridine and benzomorpholine.

These compositions contain, in addition to the oxidation dye precursors, reducing agents present in proportions of between 0.05 and 3% by weight relative to the total weight of the composition.

The oxidation dye precursors can be used, in the compositions of the invention, at concentrations of between 0.001 and 5% by weight, and preferably between 0.03 and 2% by weight, based on the total weight of the composition. The couplers can also be present in proportions of between 0.001 and 5% by weight, and preferably between 0.015 and 2% by weight. The pH of these oxidation dyeing compositions is preferably between 7 and 11.5, and is adjusted using alkalinising agents defined above.

The process of dyeing the keratinous fibres, especially human hair, employing development by an oxidising agent, consists in applying on the hair the dyeing composition containing both a dye according to the invention and dye precursors. The development of the coloration can then be accomplished slowly in the presence of the oxygen in the air, but a chemical development system is preferably used, this most equently being chosen from hydrogen peroxide, urea peroxide and persalts. A solution of "20 volumes" hydrogen peroxide is used in particular.

When the composition with the oxidising agent has been applied on the keratinous fibres, it is left in place for 10 to 50 minutes, preferably 15 to 30 minutes, after which the keratinous fibres are rinsed, op optionally washed with shampoo, rinsed again and dried.

The examples which follow are intended to illustrate the invention without being limitative in nature.

Example 1 Preparation of 2-(2,3-diamino-5-nitrophenyl)ethanol

1st stage Preparation of 2-r2-amino-3,5-dinitrophenyl)ethanol 0.17 mole (35.7 g) of 2,3-dihydro-5,7-dinitrobenzofuran, prepared according to Chatelus Ann. chim. (12), 4 505-547 (1949) is suspended in 350 ml of 20% strength ammonia solution and 220 ml of formamide.

After 8 hours' heating at 110 C, a further 100 ml of 20% strength ammonia solution are added. Heating is maintained for 4 hours. When the reaction medium is cooled, the expected product precipitates.

After being drained, washed with ice-cold water until neutral and dried under vacuum, 0.13 mole (30.3 g) of a product melting at 151"C is obtained, and this is recrystallized from dioxane. Analysis of the product gives the following results: Analysis Calculated for Found C8H9N3O5 %C 42.29 42.24 %H 3.99 3.91 %N 18.50 18.60 35.21 35.14 2nd stage Preparation of 2-(2,3-diamino-5-nitrophenyl)ethanol To a suspension of 0.119 mole (27 g) of 2-(amino-3,5-dinitrophenyl)ethanoi in 67.5 ml of isopropanol to which an equal volume of water has been added, a solution of 38.4 g of sodium sulphide nonahydrate and 5.4 g of sulphur in 10 ml of water is added dropwise at 60-65"C. Heating is maintained for 20 minutes after the addition is complete. When the mixture is cooled, a precipitate of the expected product is obtained, and this is drained, made into a paste in water and then recrystallized from 96" strength alcohol. It melts at 172"C.

Molecular mass calculated for C8H"N303: 197 Molecular mass found by potentiometric assay in acetic acid using perchloric acid: 202.

Analysis of the product obtained gives the following results: Analysis Calculated for Found C'l',,N2O3 %C 48.72 48.84 %H 5.62 5.71 21.31 21.40 24.34 24.30 Example 2 Preparation of 2-[3-amino-2-fss,-hydroxyethyl)amino-5-nitrophenylyethanol

1st stage Preparation of 2-[2-rss-hydroxyethyl)amino-3,5-dinitrophenyllethanol 0.29 Mole (60.9 g) of 2,3-dihydro-5,7-dinitro-benzofuran is added in small portions at room temperature to 122 ml of 2-amino-ethanol. After the addition is complete, the reaction medium is brought for 15 minutes to 95"C.

500 ml of water are added; after the mixture is cooled, the expected product is drained, and this, after being made into a paste in water and recrystallized from 75 ml of 96" strength ethanol, melts at 115"C.

Analysis gives the following results: Analysis Calculated for Found C10H13N3O6 44.28 44.38 %H 4.83 4.74 %N 15.49 15.48 35.39 35.60 2nd stage Preparation of 2-[3-amino-2-(ss-hydroxyethyl)amino-5-nitrophenyl]ethanol After 0.14 mole (38 g) of 2-[2-(ss-hydroxyethyl)-amino-3,5-dinitrophenyl]ethanol has been added to 530 ml of absolute alcohol to which 56 ml of 20% strength ammonia solution have been added, hydrogen sulphide is bubbled into this alcoholic solution for 2 hours; the temperature rises to 27"C. The bubbling is then stopped. The reaction medium is brought to reflux for 4 hours and then left for 48 hours at room temperature. After concentration of the alcoholic solution to one half, the inorganic salts are filtered off.

The filtrate is then evaporated to dryness. The dry residue is made into a paste in isopropanol. After recrystallization in order to remove a resin, the product melts at 121"C.

Molecular mass calculated for C0H1N3O4: 241 Molecular mass found by potentiometric assay in acetic acid using perchloric acid: 247 Analysis of the product obtained gives the following results: Analysis Calculated for Found C,oHl3N306 %C 49.78 49.87 %H 6.27 6.27 %N 17.42 17.38 %O 26.53 26.25 Example 3 Preparation of 1-(2,3-diamino-5-nitrophenyl)-2-propanol

1st stage Preparation of I-(2-amino-3,5-dinitrophen y/l-2-propanol 0.39 Mole (88 g) of 2,3-dihydro-5,7-dinitro-2-methylbenzofuran, prepared according to J.A.C.S. 80, [p.4711-4714 (1958) is suspended in 1.1 litre of 20% strength ammonia solution and 600 ml of Methyl Cellosolve.

After 18 hours' heating at 70"C, the reaction mixture is cooled. The precipitate formed is drained and, after being made into a paste in water until neutral and then dried under vacuum, is recrystallized from 170 ml of dioxane. After being dried under vacuum, 0.30 mole (72 g) of the expected product is obtained; it melts at 177-t.

Analysis gives the following results: Analysis Calculated for Found C,l'iilliOo 9C 44.81 44.87 %H 4.60 4.62 %N 17.42 17.45 %H 33.17 33.08 2nd stage Preparation of 1-(2,3-diamino-5-nitrophenyl)-2-propanol To a suspension of 0.1 mole (24.1 g) of 1-(2-amino-3,5-dinitrophenyl)-2-propanol in 60 ml of isopropanol to which an equal volume of water has been added, a solution of 33.6 g of sodium sulphide nonahydrate and 4.8 g of sulphur in 9 ml of water is added dropwise at 60"C.

Heating is maintained for 20 minutes after the addition is complete. When the mixture is cooled, the expected product is obtained, and this is drained, made into a paste in water and recrystallized in 96 strength ethanol. It melts at 174"C.

Molecular mass calculated for C0H,3N3O3: 211 Molecular mass found by potentiometric assay in acetic acid using perchloric acid: 216.

Analysis of the product obtained gives the following results: Analysis Calculated for Found CgH13N303 %C 51.17 51.09 6.20 6.19 %N 19.90 20.13 OO 22.73 22.57 Example 4 Preparation of l-(3-amino-2-methylamino-5-nitrophen yl)-2-propanol monohydrochloride

1st stage Preparation of l-(2-methylamino-3,5-dinitrophenyl)-2-propanol 0.056 Mole (12.5 g) of 2,3-dihydro-5,7-dinitro-2-methylbenzofuran is suspended in 100 ml of a 33% strength solution of methylamine in ethanol. After 10 hours' stirring at room temperature in a sealed Erlenmeyer, the reaction mixture is brought for 30 minutes to the refluxing temperature of the alcohol.

After the mixture is cooled, the expected product precipitates. It is drained, washed with alcohol and then recrystallized from 50 ml of 96" strength ethanol. After being dried 0.047 mole (12 g) is obtained of a product which melts at 132"C.

Analysis gives the following results: Analysis Calculated for Found C1,H,,N,O, %C 47.06 47.11 %H 5.13 5.03 %N 16.47 16.52 %O 31.34 31.25 2nd stage Preparation of 1-{3-amino-2-methylamino-5-nitro-phenyl) -2-propanol monohydrochloride After 0.027 mole (6.88 g) of 1-(2-methylamino-3,5-dinitrophenyl)-2-propanol has been added to 100 ml of absolute ethanol to which 10.8 ml of 20% strength ammonia solution have been added, hydrogen sulphide is bubbled into the mixture for 2 h 30 min. After 1 hour, the temperature rises to 35"C and then drops again. After the alcoholic solution is concentrated to one half, the inorganic salts are filtered off.

The filtrate is evaporated to dryness; the dry extract in oily form is taken up with a solution of hydrochloric acid in absolute ethanol. On dilution with ethyl ether, the monohydrochloride of the expected product is obtained, and this is recrystallized from a hydrochloric mixture.

Molecular mass calculated for C10H,6N3O3Cl: 261.

Molecular mass found by potentiometric assay in water using sodium hydroxide: 264.

Analysis of the product obtained gives the following results: Analysis Calculated for Found ClsH,6N303CI %C 45.89 46.00 %H 6.12 6.13 %N 16.06 16.21 %O 18.35 18.38 %CI 13.57 13.64 Example 5 The following dyeing composition is prepared: 2-(2,3-Diamino-5-nitrophenyl)ethanol 0.15 g Propylene glycol lOg CEMULSOL NP 4 12 g CEMULSOL NP 9 15 g Polyglycerolated oleic alcohol (2 moles of glycerol) 1.5 g Polyglycerolated oleic alcohol (4 moles of glycerol) 1.5 g Monoethanolamine in a 20% strength solution in water 1.5 g Water q.s. 100 g pH 10 When applied on hair for 20 minutes at 28"C, this mixture endows it, after shampooing and rinsing, with a coloration: 10 YR 7.518 on hair bleached white:: 5 YR 8;6 on hair which is naturally 90% white, these colours being expressed according to Munsell's notation.

Example 6 The following dyeing composition is prepared: 1-(2,3-Diamino-5-nitrophenyl)-2-propanol 0.51 g 2-Butoxyethanol 10 g TWEEN 80 12 9 Oleic acid 20 g 2-Amino-2-methyl-1 -propanol at 25% strength in water 69 Water q.s. 100g pH 6.4 When applied on hair for 15 minutes at 30"C, this mixture endows it, after shampooing and rinsing, with a coloration: 10 R 69 on hair bleached white 7.5 YR 7'4 on hair which is naturally 90% white, these colours being expressed according to Munsell's notation.

Example 7 The following dyeing composition is prepared: 1 -(2,3-Diamino-5-nitrophenyl)-2-propanol 0.4 g 2-Butoxyethanol 12 9 Carboxymethylcellulose 2g Ammonium lauryl sulphate 5g Triethanolamine in 1% strength solution in water 1.5 9 Water q.s. 100g pH 7.5 When applied on hair for 20 minutes at 30"C, this mixture endows it, after shampooing and rinsing, with a coloration: 6.25 YR 6115 on hair bleached white 1.25 Y 8;13 on hair which is naturally 90% white, these colours being expressed according to Munsell's notation.

Example 8 The following dyeing composition is prepared: 1 -(3-Amino-2-methylamino-5-nitrnphenyl)- 2-propanol 0.26 g 96" strength alcohol 1.0 g Lauramide 1.5 g Lauric acid 1g CELLOSIZE WP 03 5g Monoethanolamine 2g Water q.s. 100 g pH 9.75 When applied on hair for 20 minutes at 30"C, this mixture endows it, after shampooing and rinsing with a coloration: 5.5 YR 7/10 on hair bleached white 10 YR 7 6 on hair which is naturally 90% white, these colours being expressed according to Munsell's notation.

Example 9 The following dyeing composition is prepared: 2-(2,3-Diamino-5-nitrophenyl)ethanol 0.6 g 2-Methyl-4-am ino-5-nitro-N-(P,y-dihydroxy- propyl)aniline 0.17 g 3-Nitro-4-(ss-aminoethyl)amino-N,N-bis(ss- hydroxyethyl)aniline dihydrochloride 0.12 g COMPERLAN KD 2.2 g Lauric acid 0.8 g 2-Ethoxyethanol 2g Monoethanolamine 1.2 g Water q.s. 100 g pH 9 When applied for 15 minutes at 30"C on hair which has been bleached white, this mixture endows it, after shampooing and rinsing, with a golden chestnut coloration.

Example 10 The following dyeing composition is prepared: 2-[3-Am ino-2-(p-hydroxyethyI )amino-5-nitro- phenyl]ethanol 0.65 g 3-Methylamino-4-nitrophenoxyethanol 0.2 g 3-Nitro-4-(ss-hydroxyethyl)amino-N-methyl- aniline 0.2 g 2-Butoxyethanol 10 g ALFOL Ce2s 8g Lanette Wax E 0.5 g CEMULSOL B 1g Oleic diethanolamide 1.5 g Monoethanolamine, 20% concentration by weight 0.3 g Water q.s. 100 g pH 9.5 When applied for 20 minutes at 30"C on bleached hair, this mixture endows it, after shampooing and rinsing, with a chestnut coloration.

Example 77 The following dyeing composition is prepared: 1-(2,3-Diamino-5-nitrophenyl)-2-propanol 0.1 g 4-Amino3-nitro-N-(-hydrnxyethyl)aniline 0.06 g 4-Methylamino-3-nitro-N,N-bis(ss-hydroxyethyl)- aniline 0.08 g 96- strength alcohol 10 g CARBOPOL 934 2g 5 O strength ammonia solution 4g Water q.s. 100 g pH 5 When applied for 20 minutes at 28"C on light chestnut-coloured hair, this mixture endows it, after shampooing and rinsing, with a golden medium chestnut coloration.

Example 12 The following dyeing composition is prepared: 1-(3-Amino-2-methylamino-5-nitrnphenyl)-2 propanol 0.08 g %([ss-Hydroxylethyl)amino-4-nitrnphenoxyethanol 0.07 g N-(4-methylamino-3-chlorophenyl)-2-methyl-5 ureidobenzoquinoneimine 0.06 g N-{4-[ethyl(carbamylmethylXamino]phenyl}-2- methyl-5-ureidobenzoquinoneimine 0.052 g 96 strength alcohol 10 g ALFOL C- 8g Lanette Wax E 0.5 g CEMULSOL B 1 g Oleic diethanolamide 1.5 g Triethanolamine, 5 i concentration by weight 3 g Water q.s. 100 g pH 8 When applied for 25 minutes at 35-C on bleached hair, this mixture endows it, after shampooing and rinsing, with a golden medium chestnut coloration.

Example 13 The following dyeing mixture is prepared: 2-(2,3-Diamino-5-nitrophenyl)ethanol 0.33 g Resorcinol 0.1 g meta-Aminophenol 0.08 g para-Phenylenediamine 0.08 g para-Aminophenol 0.08 g 3-Acetamido-2,6-dimethylphenol 0.1 g CEMULSOL NP 4 12 g CEMULSOL NP 9 15 g Polygiycerolated oleic alcohol (2 moles of glycol 1.5 g Polyglycerolated oleic alcohol (4 moles of glycerol 1.5 g Propylene glycol 6g TRILON B 0.12 g Ammonia solution, 225 Be 11 g Mercaptosuccinic acid 0.4 g Water q.s. 100 g pH 9.4 At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28C on hair which is naturally 90% white, this mixture endows it, after shampooing and rinsing, with a dark blonde coloration.

Example 14 The following dyeing mixture is prepared: 1 -(2,3-Diamino-5-nitrophenyl)-2-propanol 0.65 g para-Phenylenediamine 0.21 g Resorcinol 0.16 g 2,4-Diaminophenoxyethanol(dihydrochloride) 0.075 g 3-(ss-Hydroxyethyl)amino-6-methylphenol 0.15 g CELLOSIZE WP 03 2g Ammonium lauryl sulphate 5g 2-Butoxyethanol 15 g 96" strength alcohol 5g Ammonia solution, 22" Bé 10 g Ammonium thiolactate 0.8 g Water q.s. 100 g pH 10.4 At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28"C on bleached hair, this mixture endows it, after shampooing and rinsing, with a light chestnut coloration.

Example 15 The following dyeing mixture is prepared: 1 -(3-Amino-2-methylamino-5-nitrophenyl)-2 propanol monohydrochloride 0.12 g para-Aminophenol 0.06 g 4-Methylaminophenol hemisulphate 0.09 g 2-Methoxy-5-aminophenol 0.150 g 7-Hydroxybenzomorpholine 0.05 g 4-[Ethyl(carbamylmethyl)amino]aniline 0.1 g CEMULSOL NP 4 21 g CEMULSOL NP 9 24 g Oleic acid 4g 2-Butoxyethanol 3g 96" strength ethanol 10 g MASQUOL DTPA 2.5 g Thioglycolic acid 0.6 g Ammonia solution, 22" B:aae 10 g Water q.s. 100 g pH 10 At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28"C on bleached hair, the mixture endows it, after shampooing and rinsing, with an ashen sandy coloration.

Example 16 The following dyeing mixture is prepared: 2-[3-Amino-2-(ss-hydroxyethyl )amino-5-nitro phenyliethanol 0.26 g 4-[Bis(ss-hydroxyethyl)aminolaniline dihydrochloride 0.19 g Resorcinol 0.07 g 4-Amino-2-chlorophenol hydrochloride 0.07 g 3-Carbamylmethylamino-6-methylphenol 0.1 g ALFOL C 16118 8g Lanette Wax E 0.5 g CEMULSOL B 1 g Oleic diethanolamide 1.5 g MASQUOL DTPA 2.5 g Mercaptosuccinic acid 0.5 g Ammonia solution, 22" Bé 11 g Water q.s. 100 g pH 10.4 At the time of use, 80 g of "20 volumes" hydrogen peroxide are added.

When applied for 25 minutes at 30"C on hair which has been bleached to a reddish colour, the mixture endows it, after shampooing and rinsing, with a golden light brown coloration.

The various trade names used in the above examples are clarified in greater detail below: CARBOPOL 934 :acrylic acid polymer of MW 2 to 3 million, sold by Goodrich Chemical Company.

CEMULSOL NP4 :nonylphenol treated with 4 moles of ethylene oxide, sold by Rhone-Poulenc CEMULSOL NP9 :nonylphenol treated with 9 moles of ethylene oxide, sold by Rhône-Poulenc ALFOL Cl61s :cetyl/stearyl alcohol, sold by Condéa (50,50) Lanette Wax E :partially sulphated cetyllstearyl alcohol, sold by Henkel.

CEMULSOL B ethoxylated castor oil, sold by Rhone-Poulenc TWEEN 80 :polyoxyethylated sorbitol mono-oleate.

LAURAMIDE :lauric acid monoethanolamide, sold by Witco.

COMPERLAN KD :Coconut fatty acid diethanolamide, sold by Henkel.

CELLOSIZE WP 03 :hydroxyethylcellulose, sold by Union Carbide.

MASQUOL DTPA :diethylenetriaminepentaacetic acid pentasodium salt, sold by PROTEX.

TRILON B : Ethylenediaminetetraacetic acid.

Claims (29)

1. A 2-amino-4-nitro-6-hydroxyalkyl aniline of formula (I):

wherein: X is an unsubstituted or a mono- or polyhydroxy substituted branched or unbranched alkylene of 2 to 6 carbon atoms; R1 and R2 are the same or different and each is a hydrogen, (C14) alkyl, mono- or polyhydroxy (C,,4) alkyl, amino (C1 4) alkyl or mono- or disubstituted amino (C14) alkyl wherein each substituent is a monoor polyhydroxy (C, 4) alkyl radical or at least one substituent and the nitrogen atom form part of a heterocyclic system; R' is hydrogen or (cut4) alkyl; or a cosmetically acceptable salt of such a compound.

2. A compound according to claim 1, wherein X is ethylene, propylene, 1,1-dimethylethylene, 1,2-dimethylethylene or 1,1,2-trimethylethylene, R' is hydrogen or methyl, and R1 and R2 are the same or different and each is hydrogen or methyl, ethyl, n-propyl, (3-hydroxyethyl, n-hydroxypropyl, ss,- dihydroxypropyl, aminoethyl or ss-diethylaminoethyl.

3. A compound according to claim 1 or claim 2, selected from: 2-(2,3-diamino-5-nitrophenyl)ethanol, 2-[3-amino-2-(t3-hydroxyethyl)amino-5-nitrophenyliethanol, 1-(2,3-diamino-5-nitrophenyl)-2-propanol and 1-(3-amino-2-methylamino-5-nitrophenyl)-2-propanol, and the salts of these compounds.

4. A compound according to claim 1 and substantially as hereinbefore described with reference to any one of Examples 1 to 4.

5. A process for preparing a 2-amino-4-nitro-6-hydroxyalkylaniline of formula (I) as defined in claim 1, comprising reacting an aqueous solution of a compound of formula R1NH2 wherein R1 is as defined in claim 1, with a heterocyclic compound of formula (IV):

wherein R' and X are each as defined in claim 1, at a temperature from 20 to 120 C, to form a 2,4-dinitro6-hydroxyalkylaniline of formula (III)::

wherein R', X and R, are each as defined in claim 1, and selectively reducing the compound of formula (III) using (a) sodium sulphide in the presence of sulpur in a hydroalcoholic solution, or (b) hydrogen sulphide in the presence of ammonia solution, or (c) cyclohexene in the presence of palladium on carbon and in alcoholic solution, to form a compound of formula (I) wherein R2 is hydrogen and, where necessary, alkylating, hydroxyalkylating or aminoalkylating the compound of formula (I) so formed to form a compound of formula (I) wherein R2 is other than hydrogen.

6. A process according to claim 5, wherein the reaction of the compound of formula (IV) and the compound of formula R.NH2 is conduted under pressure.

7. A process according to claim 5 or claim 6, wherein the reaction of the compound of formula (IV) and the compound of formula R,NH2 is conducted in the presence of a polar protic solvent or a polar aprotic solvent.

8. A process according to claim 5 and substantially as hereinbefore described with reference to any one of Examples 1 to 4.

9. A composition for dyeing keratinous fibres, comprising at least one compound as defined in any one of claims 1 to 4 or as produced according to any one of claims 5 to 8 in a solvent medium.

10. A composition according to claim 9, containing from 0.001 to 5% by weight, of at least one compound of formula (I) relative to the total weight of the composition.

11. A composition according to claim 10, containing from 0.05 to 2% by weight of at least one compound of formula (I), relative to the total weight of the composition.

12. A composition according to any one of claims 9 to 11, having a pH of from 3 to 11.5.

13. A composition according to claim 12, having a pH of from 5 to 11.5.

14. A composition according to any one of claims 9 to 13, wherein the solvent medium comprises one or more lower alkanol, aromatic alcohol, polyol, glycol or glycol ether, or water or mixture thereof.

15. A composition according to any one of claims 9 to 14, further comprising one or more cosmetic adjuvant selected from anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof, thickeners, dispersants, penetrants, sequestering agents, film-forming agents, buffers, perfumes and alkalinising and acidifying agents.

16. A composition according to any one of claims 9 to 15, formulated as a direct dye for human hair, comprising at least one compound of formula (I) and at least one other direct dye selected from azo dyes, anthraquinone dyes, indophenols, indoanilines and nitro derivatives of the benzene series.

17. A composition according to any one of claims 9 to 15, formulated as a hair setting lotion and comprising an aqueous, alcoholic or hydroalcoholic solution containing at least one cosmetic resin.

18. A composition according to any one of claims 9 to 15, formulated as an oxidation dye and comprising at least one oxidation dye precursor.

19. A composition according to claim 18 having a pH of from 7 to 11.5, and further comprising a reducing agent.

20. A composition according to claim 9, and substantially as hereinbefore described with reference to any one of Examples 5 to 16.

21. A process for dyeing keratinous fibres comprising applying a composition as defined in any one of claims 9 to 16 to the fibres, leaving the composition on the fibres for 5 to 50 minutes, then rinsing and drying the fibres.

22. A process according to claim 21 wherein after rinsing, the fibres are washed with shampoo and rinsed again then dried.

23. A process for dyeing keratinous fibres comprising applying a composition as defined in claim 17, to fibres which have previously been washed and rinsed, then drying the fibres.

24. A process according to claim 23 wherein before drying the fibres are coiled.

25. A process for dyeing keratinous fibres, comprising applying a composition as defined in claim 18 or claim 19, to the fibres, leaving the composition on the fibres for 10 to 50 minutes, then rinsing and drying the fibres.

26. A process according to claim 25, wherein an oxidising agent is added to the composition applied to the fibres.

27. A process according to claim 25 or claim 26, wherein, after rinsing the fibres are washed with shampoo, rinsed again and then dried.

28. A process according to any one of claims 21 to 27, wherein the keratinous fibres are human hairs.

29. A process according to claim 21 and substantially as hereinbefore described with reference to any one of Examples 5 to 16.