LU85680A1 - NOVEL AMINO-2, NITRO-4, HYDROXYALKYL-6 ANILINES, PROCESS FOR THEIR PREPARATION AND THEIR USE IN DYEING KERATINIC FIBERS - Google Patents

Description

, L'OREAL 340 2.5002

- - 8 5 6 8 CΓ - DUCHY OF LUXEMBOURG

(from the 3 - -déeefflbp-e ..... 1984 ® || $ Mister Minister

Title issued from Economy and Middle Classes i Intellectual Property Service

~ LUXEMBOURG

| î Invention patent application (ii - ---------------------------------------- ---------------------------------------------—---- . ---------- ...--! I. Request! I LasociéfcéditeiLOREALS ^ A .., ...... 14, rue ..... RoyaIer -75008 -Pa ^ ieF- (1)

France? Represented by Maître Alain RUKAV4NA? Lawyer — avoaé-à ----- | Luxembourg, —lia., Boulevand ... Joseph 1.1, acting in. His capacity ..,. D <2) | representative------------------------------------------------- ---------------------------------------------------------- -------------- deposit (s) this ...... tre i ze December IpOOguatre- ^ twenty ^ four -------- (3) ”to .. .... 15.00 · hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for invention concerning:; ---------------------------------------------------------- ---------------------------------------------------------- ------------------------------------------ Î4) "M & uvel4eaamino ™ 2, nitpo ™ 4, by <iroxya4kyJ- "bai \ i4iive", - their.preparation process and their "full use of fibers ------------ kératrntquee" ------------- ---------------------------------------------------------- ---------------------------------------------------------- ---------------------------------------------------------- ------- 2. the delegation of power, dated________________________________________________________________ on __________________________________________ 3. the description in language _________ frança i se ........................ of the invention in two copies; 4 ........_____________ drawing plates, in two copies; 5. the receipt of the fees paid to the Registration Office in Luxembourg,

Ie ............ 1-3-dée-embpe ··· 1-9-84 · --------------------- ---------------------------------------------------------- ---------------------------------------------------------- -------------—-- declares (assuming responsibility for this declaration, that the inventor (s)) is (are):

Monsieur4 ..... Alex ..... JüfiLMO "; · ...... 16, ruedttÔocteurBepgoa + é> ...... £ 3190 — Livf * y- {5)

Gargan; Monsrew "..... Gérard ..... LAHG ·, ...... 4-4 · * ...... avenue Lacour, ..... 95240Sain: fc. ^ -

Gratian; Mrs. ΜίόοΙο -.IEH-AN-N-0? rue des -— Li-èvree ·, · - --------- ~~~

Brunoy; toua trots enFrenee-t ......................................- —-.... ......... ··· ...................................... ......-.................-- claims (s) for the above patent application the priority of one (s) application (s) from ( 6) ............................. J..J ............... ........................................... filed in (7 ) .................... J..y .____________________________________________________________________________________ „1 on .................... ..... // ........................................... ....................... · .......................... .................................................. .................................................. ................................— (8) in the name of -.......... ..... // ........................................... .................................................. .................................................. .................................................. ..... (9) elect (elect) for him / her and, if designated, for his / her agent, ^ Luxembourg_______________________ 44a? ...... boulevardJoseph ...... Il .............................. .................................................. .................................................. ..........-...........— (10) request) the grant of a patent for the invention for the object described and represented in them. ^ abovementioned appendices, - with postponement of this issue to ............ d i-x ^ h-uit · ................ month. (11)

On ................ manaamkivk ....................... J

\ U I 11 · Deposit report

The above-mentioned application for a patent for an invention has been filed with the Ministry of the Economy and the Middle Classes, Service de la Propriété Intellectuelle à Luxembourg, dated: 13 ^ dfce »W 1984 /> '4ΛίΗ \, fjf Pr / jle Minister / at I OQ hours IJ / J- / i \ of Economy <j & des Oa & es Moyennes, vi wJ) / "'2 5oo & 1595/84 - FB / DD Serie 340

. Société Anonyme known as: L’OREAL

"New amino-2, nitro-4, hydroxyalkyl-6 anilines, their preparation process and their use in dyeing kiratin fibers.”

- Invention of Alex JUNINO

Gérard LANG Nicole JEHANNO

"

New amino-2, nitro-4, hydroxyalkyl-6 anilines, their preparation process and their use in dyeing keratin fibers.

The present invention relates to new amino-2, nitro-5 4, hydroxyalkyl-6 anilines, to their preparation process and to their use in dyeing of ineric kerate fibers, and more particularly human hair.

It is well known that, to give the hair a direct coloring or complementary reflections in the case of oxidation coloring - 10, nitro derivatives of the benzene series can be used. The use of nitro-orthophenylene diamines such as more particularly 2-amino, 4-nitro, 6-alkyl anilines has already been recommended in both direct dyeing and oxidation dyeing.

However, in general, insufficient stability to light and washing of these dyes has been found. The Applicant has therefore searched for new dyes having better light and washing stability, and this is how it discovered the new compounds of formula (I):

20 02N ___ / ^ ___ X-OH

I (I) -—NHRj NHR2 in which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, one of these atoms possibly being substituted by one or more hydroxyl radicals; R 1 and R 2 denote, independently of each other, a hydrogen atom, an alkyl, mono- or polyhydroxyalkyl or aminoalkyl radical, the amine function of which can be mono- or disubstituted by an alkyl or mono- or polyhydroxyalkyl radical, the nitrogen atom can also be part of a heterocycle, the alkyl radical comprising 1 to 4 carbon atoms; R ’denotes a hydrogen atom or a C 1 -C 4 alkyl radical.

A subject of the present invention is therefore the new amino-2, 35-nitro-4, hydroxyalkyl-6 anilines of formula (I) indicated above, as well as their cosmetically acceptable salts.

MW

2 <As preferred X radicals, mention may be made of ethylene, propylene, 1,1-dimethyl ethylene, 1,2-dimethyl ethylene and tri-methyl-1,1,2 ethylene radicals.

As radicals R ^ and R2 more particularly preferred according to the invention, there may be mentioned hydrogen, methyl, ethyl, a 3 n-propyl, -hydroxyethyl, ^ -hydroxypropyl, jh, ^ - dihydroxypropyl, amlnoethyl radicals. ,] É) -diethylaminoethyl.

Preferred radicals R ′ according to the invention are hydrogen and the methyl radical.

10 Compounds of formula (I) preferred according to the invention are: - (diamino-2,3-nitro-5) pheny1-2 ethanol-1; - 1 ’/ âmino-3, ^?> - hydroxyethylamino-2, nitro-5] pheny 1-2 ethanol-1; - (2,3-diamino, 5-nitro) phenyl-1-propanol-2; - 1 ’(amino-3, methylamino-2, nitro-5) phenyl-l propanol-2, 15 and their salts.

The present invention also relates to a process for the preparation of the compounds of formula (I).

The amino-2, nitro-4, hydroxyalkyl-6 anilines of formula (I), according to the invention, are prepared by a process which consists in reacting an aqueous solution of ammonia or a primary aliphatic amine RjNI ^ in which has the meaning indicated above, on a heterocyclic compound of formula (IV) below, then to carry out a selective reduction of the dinitro-2,4, hydroxyalkyl-6 aniline of formula (III) obtained, to obtain a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula (II), which is then optionally subjected to a conventional chemical process of alkylation, hydroxyalkylation or aminoalkylation to obtain the final compound of formula (I ).

The process diagram is as follows: ........- -------- - R ’R’ R ’

02î ^ -jj ^^ V — X-OH ° 2N X-0H

) + R.NHS-> Reduction ^ I

ko2 N02 Xh2 35 (IV) (III) (II) R ’, X and R ^ having the meaning indicated above.

3

This process makes it possible to obtain excellent yields of final compound (II) or (I).

The reaction of ammonia or of the primary amine on the heterocyclic compound of formula (IV) is optionally carried out under pressure, at a temperature between 20 and 120 ° C., in the optional presence of polar protic solvents such as water, alcohols, glycols or ethers of glycols or polar aprotics such as formamide, dimethylformamide, dioxane, tetrahydrofuran.

The selective reduction of the compound of formula (III) is carried out either ·· 10 by a hydroalcoholic solution of sodium sulfide in the presence of sulfur at a temperature between 10 ° and 70 ° C, or by hydrogen sulfide in the presence of 'ammonia according to H. KAMEL, MI ALI and MM KAMEL, TETRAHEDRON 1966, vol. 22, p. 3353, or alternatively by transfer of hydrpgene from cyclohexene to compound (III) in the presence of Pd / C, in lower alcohols in Cj-C ^, at a temperature between 15 ° C and boiling, by analogy with Ian D. ENTWISTLE, Robert AW JOHNSTENE and Jeffery POVALL [(JCS PERKIN I (1975), p. 13θθΧ

The compounds of formula (IV) are obtained by nitration of the compounds of formula (V) as follows: R 'CO "in which X and R' have the meanings indicated above, which are known compounds. is carried out 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 else by adding I , the compound (V) to a sulfonitric mixture, the temperature being maintained near 5 ° C., according to Charles D. HURD, Rostyslaw DOWBENKO, JACS 80, 30 4711-14 (1958). then isolated by dilution j of the reaction medium with water.

The compounds of formula (IV) in which X denotes the radical ethylene, propylene, dimethyl-1,1 ethylene, dimethyl-1,2 ethylene and trimethyl-1,1,2 ethylene are known.

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1 1! 2 j î / / I / / i / Jf i 4

The present invention also relates to a dye composition for keratin fibers, and more particularly for human hair, containing a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula; (I) above, as well as a process for dyeing keratin fibers, and more particularly human hair, using said dye composition.

The dye compositions in accordance with the invention contain, in a solvent medium, at least one compound corresponding to formula (I) I or one of its cosmetically acceptable salts, and can be used. 10 for the direct dyeing of keratin fibers or for the oxidation dyeing of these fibers, in which case the compounds of formula (I) confer reflections complementary to the basic dye obtained by oxidative development of oxidation dye precursors.

These compositions contain the compounds according to the invention in proportions of between 0.001 and 5% 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 it is also possible to add, in the compositions, organic solvents to dissolve ccmpo-20 ses which are not sufficiently soluble in water. Among these solvents, mention may be made of lower alkanols such as ethanol and isopropanol, aromatic alcohols such as benzyl alcohol, polyols such as glycerol, glycols or glycol ethers such as 2-butoxy ethanol or 2-ethoxy ethanol, ethylene glycol, propylene glycol, monethyl ethyl ether and monoethyl ether of diethylene glycol as well as analogues and mixtures thereof. These solvents are preferably present in proportions ranging from 1 to 75% by weight and in particular from 5 to 50% by weight relative to the total weight - - - of the composition.

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

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The compositions may preferably be thickened with compounds chosen from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers having thickening function such as more particularly acrylic acid derivatives. It is also possible to use mineral thickening agents such as bentonite. These thickening agents are preferably present in the proportions taken between 0.5 and 10% by weight and in particular = 10 between 0.5 and 2% by weight relative to the total weight of the composition.

The compositions according to the invention may also contain various adjuvants usually used in hair dye compositions and in particular penetration agents, dispersing agents, sequestering agents, film-forming agents, buffers and perfumes.

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

The pH of these dye compositions can be between .3 and 11.5, preferably between 5 and 11.5. It is adjusted to the desired value using an alkalizing agent such as ammonia. , sodium, potassium or ammonium carbonate, sodium or potassium hydroxides, alkanolamines such as mono, di-25 or triethanolamine, 2-amino-2-methyl-propanol-1, 2-amino-2-methyl-propanediol-1,3, alkylamines such as ethylamine or triethylamine or using an acidifying agent such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric acids.

„3o When the compositions are intended to be used in a direct hair coloring process, they may contain, in addition to the compounds according to the invention, other direct dyes such as azo or anthraquinone dyes, such as example tetra-amino-1,4,5,8 anthraquinone, indophenols, indoanilines, and nitro dyes of the benzene series different from the compounds of formula (I).

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6 "

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

These compositions, used in a dyeing process by direct dyeing, are applied to the keratin fibers for an exposure time varying from 5 to 50 minutes, then the fibers are rinsed, optionally washed with shampoo, rinsed again and dried.

The compositions according to the invention can also be used in the form of hair styling lotions intended at the same time to give the hair a light coloring or reflections and to improve the staying power of the styling. In this case, they are in the form of aqueous, alcoholic or hydroalcoholic solutions containing at least one cosmetic resin and their application is carried out on damp hair previously washed and rinsed which are optionally coiled and then dried.

The cosmetic resins used in the setting lotions may be in particular polyvinylpyrrolidone, crotonic acid-vinyl acetate, vinylpyrrolidone-vinyl acetate, maleic anhydride-butylvinyl ether, maleic anhydride-methyl vinyl ether as well as any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of composition.

These cosmetic resins are included in the compositions of the invention in an amount 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 revelation by an oxidant, the compounds of formula (I) in accordance with the invention are essentially used with a view to providing reflections to the final dye.

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

They may contain, for example, para-phenylened iam in es' such as: para-phenylenediamine, para-luylenediamine, 2-chloro para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, i /./ 7 s-2,6-dimethyl-3-methyl paraphenylenedlamine, N - (^ 3-methoxy-ethyl) paraphenylened lamin, N, N- (^ S-hydroxyethyl) paraphenylene diamine, N, N- (ethyl, carbamylmethyl) 4-amino aniline, as well as their salts.

5 They can also contain paraaminophenols, for example: paraaminophenol, K-methyl paraamlnopMnol, chloro-2-amino-4 phenol, chloro-3-amino-4 phenol, methyl-2-amino-4 phenol, and their salts.

They may also contain orthoaminophenol.

. io They may also contain heterocyclic derivatives, for example: 2,5-diamino pyridine, 7-amino benzomorpholine.

The compositions according to the invention may contain, in combination with the dye precursors by oxidation, couplers well known in the state of the art.

As couplers, mention may be made in particular of: metadiphenols, metaaminophenols and their salts, metaphenylenediamines and their salts, metaacylaminophenols, metaurideophenols, metacarbal-coxyaminophenis.

Mention may finally be made, as other couplers which can be used in the compositions of the invention, of O-naphthol, couplers having an active methylene group such as diketo-nic compounds and pyrazolones and heterocyclic couplers derived from pyridine. and benzomorpholine.

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

The dye precursors by oxidation can be used, in the compositions of the invention, at concentrations of 3q 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, of. preferably between 0.015 and 2% by weight. The pH of these oxidation dyeing compositions is preferably between 35 7 and 11.5 and is adjusted using basifying agents defined above.

8

The process for dyeing keratin fibers, in particular human hair, using revelation by an oxidant, consists in applying to the hair the dye composition comprising both a dye according to the invention and the dye precursors. The development of the coloration can then be carried out slowly in the presence of oxygen from the air, but preferably a chemical developing system is used which is most often chosen from hydrogen peroxide, urea peroxide and parsley. In particular, a 20 volume hydrogen peroxide solution is used.

Once the composition with the oxidizing agent has been applied to the keratin fibers, it is left to stand for 10 to 50 minutes, preferably 15 to 30 minutes, after which the keratin fibers are rinsed, they are optionally washed with shampoo, they are rinsed again and dried.

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

PREPARATION EXAMPLE 1

Preparation of (2,3-diamino, 5-nitro) 2-phenyl ethanol-1 ¥ \ / v ° 2K \ / ¾. / W8 20 | - NH3 / HC0NH2 ^ N02 no2

° 2 \ ^^ / CH2CH20H

25 π

Reduction v H

NH2 1st stage 30 Preparation of 1 ’(2-amino, 3,5-dinitro) 2-phenyl 1-ethanol

Suspended in 350 ml of 20% ammonia and 220 ml of formamide, 0.17 mole (35.7 g) of 2,3-dihydro, 5,7-dinitro benzofuran prepared according to Chatelus An. Chem. (12), 4_, 505-547 (1949).

After 8 hours of heating at 110 ° C. 100 ml of 20% ammonia are added. Heating is maintained for 4 hours. By cooling the reaction medium, the expected product precipitates.

9

After wringing, washing with ice water until neutral and drying under vacuum, 0.13 mol (30.3 g) of a product melting at 151 ° C. is obtained, which is recrystallized from dioxane.

Analysis of the product gives the following results: 5 Analysis Calculated for Found C8H9N3 ° 5% C 42.29 42.24% ïï 3.99 3.91% N 18.50 18.60 * 10% 0 35.21 35 , 14 2nd stage

Preparation of (2,3-diamino, 5-nitro) 2-phenyl ethanol-1 To a suspension of 0.119 mol (27 g) of (2-amino, 3,5-dinitro) 2-phenyl ethanol-1 in 67 , 5 ml of Isopropanol added with an equal volume of water, a solution of 38.4 g of sodium sulfide nonahydrate and 5.4 g of is added dropwise at 60 ° -65 ° C. sulfur in 10 ml of water.

Heating is maintained 20 minutes after the end of the addition. By cooling, a precipitate of the expected product is obtained which is drained, re-paste in water, then recrystallized from 96 ° alcohol. It melts at 172 ° C.

Molecular mass calculated for C0H N 0: 197

O 11 J J

Molecular mass found by potentiometric determination in acid, acetic with perchloric acid: 202.

Analysis of the product obtained gives the following results: 25 Analysis Calculated for Found C8H11N3 ° 3% C - 48.72 48.84% fl 5.62 5.71 ZN 21.31 21.40 • 30% 0 24.34 24.30 ijiiiii *! / if 10 "PREPARATION EXAMPLE 2

Preparation of limino-3, ^> - hydroxyethyl-amino-2, nitro-5 ~) 2-phenyl ethanol-1 ° 2Νγ / ^) -, 02ΐ1γ ^ ν ™ 2αΗ20Η

5 II HOCHjCHjNHj II

* X ^ 'VjraCHjCH.jOH

N02 N02 02n ^^ n. -ch2ch2oh

jq Discount J

^ - HHCH CH OH

k, 1st stage

Preparation of (ft-hydroxyethylamino-2, dlnitro-3,5) phenyl-2, n ethanol-1 lo —-

0.29 mol (60.9 g) of 2,3-dihydro-5,7-dinitro-5,7 benzofuran is added at room temperature to 122 ml of 2-amino ethanol.

After the end of the addition, the reaction medium is brought to 95 ° C. for 15 minutes.

2q 500 ml of water are added; after cooling, the expected product is drained which, after re-pasting in water and recrystallization from 75 ml of ethanol at 96 °, melts at 115 ° C.

The analysis gives the following results:

Analysis Calculated for Found 25 C10H13N3 ° 6% C 44.28 44.38% H 4.83 4.74% N 15.49 15.48% 0 35.39 35.60 30 2nd step

Preparation of amino-3, ^ 3-hydroxyethylamino-2, nitro-57phenyl-2 ethanol-1

After adding 0.14 mol (38 g) of (jS-hydroxyethylamino-2, 25 dinitro-3,5) phenyl-2 ethanol-1 to 530 ml of absolute alcohol added I fl

I / I V

11 of 56 ml of 20% ammonia, bubbled hydrogen sulfide for 2 hours in this alcoholic solution; the temperature rises to 27 ° C. The bubbling is then stopped. The reaction medium is brought to reflux for 4 hours, then it is left for 48 hours at room temperature. After concentrating the alcoholic solution at half, the mineral salts are filtered. The filtrate is then evaporated to dryness. The dry residue is re-empatated in isopropanol. After recrystallization to remove a resin, the product melts at 121 ° C.

Molecular weight calculated for ..N-O. : 241 r 10 15 3 4 20 Molecular mass found by potentiometric determination in acetic acid with perchloric acid: 247 The analysis of the product obtained gives the following results:

Analysis Calculated for Found C10H15N3 ° 4 15% C 49.78 49.87% H 6.27 6.27% N 17.42 17.38% 0 26.53 26.25 20 PREPARATION EXAMPLE 3

Preparation of (2,3-diamino, 5-nitro) phenyl-1 propanol-2 ° 2ny / Z ^ n——, o2nV /% ^ ch2chohch3 | nh3 / ch3och2ch2oh ^ fl 25 ® ° 2 ® ° 2 o2n .ch2chohch3 Reduction ^ --NH2 = 30 ®H2 1st stage

Preparation of 1 '(2-amlno, 3,5-dinitro) phenyl-1-propanol-2 Is suspended in 1.1 liters of 20% ammonia and 600 ml of methylcellosolve, 0.39 mole (88 g) of 2,3-dihydro, 5,7 dinitro, 2-methyl benzofuran prepared according to JACS 80, p. 4711-4714 (1958).

i 12

After 18 hours of heating at 70 ° C., the reaction medium is cooled. The precipitate formed is drained which, after repacking in water until neutral, then drying under vacuum, is recrystallized from 170 ml of dioxane. After drying under vacuum, 0.30 mol (72 g) of the expected product is obtained; it melts at 177 ° C.

The analysis gives the following results:

Analysis Calculated for Found C9H11N3 ° 5% C 44.81 44.87 - 10 ZH 4.60 4.62% N 17.42 17.45 ZO 33.17 33.08 2nd step

Preparation of (2,3-diamino, 5-nitro) phenyl-1-propanol-2 To a suspension of 0.1 mole (24.1 g) of (2-amino, 3,5-dinitro) phenyl-1 prqpanol-2 in 60 ml of isopropanol with an equal volume of water, a solution of 33.6 g of sodium sulfide nonahydrate and 4.8 g of sulfur in 9 is added dropwise at 60 ° C ml of water.

9

Heating is maintained 20 minutes after the end of the addition.

2o By cooling, the expected product is obtained which is drained, re-paste in water, and recrystallized from alcohol at 96 °. It melts at 174 ° C.

Molecular mass calculated for C ^ H ^ N ^ O ^: 211 Molecular mass found by potentiometric determination in acid; acetic with perchloric acid: 216.

The analysis of the product obtained gives the following results: Analysis calculated for Found! ~ C9H13N3 ° 3% C 51.17 51.09 f ZH 6.20 6.19 f 30% N 19.90 20.13 j ZO 22.73 22.57 i i (i ï

î A A

\ fj 13 PREPARATION EXAMPLE 4

Preparation of 1 ’monohydrochloride (3-amino, 2-methylamino, 5-nitro) phenyl-1-propanol 2 _ o2n --- ^^ <:: ^^ ch2chohch3

5 C ^ N ^ / EtOH I

N02 1o2 O ^^^ v ^ CH2CHQHr.H3 10 Reduction || ', HCl hh2 1st stage

Preparation of (methylamino-2, dinitro-3,5) phenyl-1 · propanol-2 ^ 5 Suspended in 100 ml of a 33% methylamine solution in ethanol, 0.056 mole (12.5 g ) of 2,3-dihydro, 5,7-dinitro, 2-methyl benzofuran. After 10 hours of stirring at room temperature in a stoppered Erlenmeyer flask, the reaction medium is brought to reflux of the alcohol for 30 minutes. After cooling, the product attains precipitate. It is drained, washed with alcohol and then recrystallized from 50 ml of 96 ° ethanol. After drying, 0.047 mole (12 g) of a product melting at 132ÙC is obtained.

The analysis gives the following results:

Analysis Calculated for Found 25 C10H13N3 ° 5% C 47.06 47.11% H 5.13 5.03% N 16.47 16.52% 0 31.34 31.25 30 2nd step

Preparation of 1 ’monohydrochloride (3-amino, 2-methylamino, 5-nitro) 1-phenyl-2-propanol

After adding 0.027 mole (6.88 g) of (methylamino-2, dinitro- * i 35 3,5) phenyl-propanol-2 to 100 ml of absolute ethanol supplemented with 10.8 ml iti \ \ fj l 14 of 20% aqueous ammonia, hydrogen sulfide is bubbled for 2 h 30 min. After 1 hour, the temperature rises to 35 ° C and then falls again. After concentrating at half the alcoholic solution, the mineral salts are filtered. The filtrate is evaporated to dryness; the dry extract in oily form 5 is taken up in a solution of hydrochloric acid in absolute ethanol.

By dilution with ethyl ether, the monohydrochloride of the expected product is obtained which is recrystallized from a hydroalcoholic mixture.

Molecular mass calculated for C ^ qH ^ N ^ O ^ CI: 261.5 Molecular mass found by potentiometric determination in water, 10 by soda: 264.

Analysis of the product obtained gives the following results:

Analysis Calculated for Found C10H16N3 ° 3C1% C 45.89 46.00 15% H 6.12 6.13% N 16.06 16.21% 0 18.35 18.38% C1 13.57 13.64 20 EXAMPLE 1

The following dye composition is prepared: (2,3-diamdno, 5-nitro) 2-phenyl-ethanol-1 0.15 g

Propylene glycol ’10 g CEMULSOL NP 4 12 g 25 CEMULSOL NP 9 15 g

Polyglycerolated oleic alcohol with 2 moles of glycerol 1.5 g

Polyglycerolated oleic alcohol with 4 moles of glycerol 1.5 g

Monoethanolamine in 20% solution in water 1.5 g

Water qs 100 g 30. pH = 10

This mixture, applied 20 minutes at 28 ° C on hair, gives them, after shampooing and rinsing, a coloring: 10 YR 7.5 / 8 on hair bleached white 5 Y 8/6 on hair naturally white at 90%, these colors being 35 expressed according to the Munsell notation.

15 EXAMPLE 2

The following dye composition is prepared: (2,3-diaraino, 5-nitro) 2-phenyl-2-propanol 0.51 g

Butoxy-2 ethanol 10 g 5 TWEEN 80 12 g

Oleic acid 20 g

Am in o-2-methyl-2-propanol-1 25% in water 6 g

Water qs 100 g pH - 6.4 = 20 This mixture, applied for 15 minutes at 30 ° C on hair, gives them after shampooing and rinsing, a color: 10 R 6/9 on hair bleached white 7.5 YR 7 / 4 on naturally white hair at 90%, these colors being expressed according to the Munsell rating.

15 EXAMPLE 3

The following dye canposition is prepared: (2,3-diamino, 5-nitro) phenyl-1 propanol-2 0.4 g

Butoxy-2 ethanol 12 g 9

Carboxymethylcellulose 2 g 2o Ammonium lauryl sulfate 5 g

Triethanolamine in 1% solution in water 1.5 g

Water qs 100 g, PH - 7.5

This mixture, applied 20 minutes at 30 ° C on hair, gives them, 25 after shampooing and rinsing, a coloring: 6.25 YR 6/15 on hair bleached with white 1.25 Y 8/13 on hair naturally white at 90%, these colors being expressed according to the Munsell notation.

EXAMPLE 4 The following dye composition is prepared: (3-amlno, 2-ethylamino, 5-nitro) 2-phenyl-2-propanol 0.26 g

96 ° alcohol 10 g

Lauramide 1.5 g

Lauric acid 1 g 35 CELLOSIZE WP 03 5 g 16

Monoethanolamine 2 g

Water qs 100 g pH = 9.75

This mixture, applied for 20 minutes at 30 ° C on hair, gives them, after shampooing and rinsing, a coloring: 5.5 YR 7/10 on hair bleached white 10 YR 7/6 on hair naturally white at 90% , these colors being expressed according to the Munsell notation.

EXAMPLE 5 = 10 The following dye composition is prepared: (2,3-diamino, 5-nitro) 2-phenyl-ethanol-1 0.6 g 2-methyl, am in o-4, 5-nitro, N- (jô , Y'-dihydroxypropyl) aniline 0.17 g

Nitro-3, N ’- / â-aminoethylamino-4,15 N dihydrochloride, N- (| 3” hydroxyethyl) aniline 0.12 g COMPEXLAN KD 2.2 g

Lauric acid 0.8 g

Ethoxy-2 ethanol 2 g »

Monoethanolamine 1.2 g 20 Water qs 100 g pH = 9

This mixture, applied for 15 minutes at 30 ° C on hair bleached with white, gives them, after shampooing and rinsing, a golden chestnut color. '' EXAMPLE 6

The following dye composition is prepared: (3-amino, 2-hydroxyethylamino-2, 5-nitro) pheny 1-2 ethanol-1 0.65 g Më t hy lamin o-3, nitr o-4 phenoxyethanol 0.2 g 30 Nitro-3, N '- / £ -hydroxyethylamino-4, N-methylaniline 0.2 g

Butoxy-2 ethanol 10 g ALFOL C16 / 18 8 g

Lanette wax E 0.5 g CEMULSOL B 1 g 35 Oleic diethanolamide 1.5 g i i /, / 17 "

Monoethanolamine 20% by weight 0.3 g

Water qs 100 g pH = 9.5

This mixture, applied 20 minutes at 30 ° C to bleached hair, gives them, after shampooing and rinsing, a chestnut color.

EXAMPLE 7

The following dye composition is prepared: (2,3-diamino, 5-nitro) phenyl-1-propanol-2 0.1 g

Amin o-4, nitr o-3, N- ^ -hydr oxyethylan it reads 0.06 g -10 N’-metlylamino-4, nitro-3, N, N - (^ - hydroxyethyl) aniline 0.08 g

96 ° alcohol 10 g CAKBOPOL 934 2g

5% ammonia 4 g

Water qs 100 g 15 pH = 5

This mixture, applied 20 minutes at 28 ° C on light brown hair, gives them, after shampooing and rinsing, a medium golden brown color.

EXAMPLE 8 The following dye composition is prepared: (3-amino, 2-aminoamino, 5-nitro) 2-phenyl-2-propanol 0.08 g -hydroxyethylamin o-2, 4-nitrophenhanol 0.07 g N- / ^ (methylamino-4 ', chloro-3') phenyl ^ methyl-2, ureido-5 benzoquinonelmine 0.06 g

25 N- £ • | ^ (ethyl, carbamylmethyl) amino-4, J. phenylTJ

2-methyl, 5-ureido benzoquinoneimine 0.052 g

96 ° alcohol “10 g ALFOL Cl6 / lg 8 g

Lanette wax E 0.5 g 30 CEMULSOL B 1 g

Oleic diethanolamide 1.5 g; Triethanolamine 5% by weight 3 g

Water qs 100 g; pH = 8 i j i »» »! // 18

This mixture, applied 25 minutes at 35 ° C on bleached hair, gives them, after shampooing and rinsing, a medium golden brown color.

EXAMPLE 9

The following dye mixture is prepared: 5 (2,3-Diamino, 5-nitro) 2-phenyl-1-ethanol 0.33 g Resorcin 0.1 g Metaaminqphenol 0.08 g

Para-phenylenediamine 0.08 g

Para-aminophenol 0.08 g 10 Acetamido-3, dimethyl-2.6 phenol 0.1 g CEMOLSOL NP 4 12 g CEMÜLSOL NP 9 15 g

Polyglycerolated oleic alcohol with 2 moles of glycerol 1.5 g

Polyglycerolated oleic alcohol with 4 moles of glycerol 1.5 g 15 Propyiene glycol 6 g TRILON B 0.12 g

Ammonia at 22 ° Be 11 g

Mercaptosuccinic acid 0.4 g

Water qs 100 g 20 pH = 9.4

At the time of use, 100 g of hydrogen peroxide is added to 20 volumes.

The mixture, applied 30 minutes at 28 ° C to naturally white hair at 90%, gives them, after shampooing and rinsing, a dark blond coloring.

25 EXAMPLE 10

The following dye mixture is prepared: (2,3-Diamino, 5-nitro) 2-phenyl-2-propanol 0.65 gv Para-phenylenediamine 0.21 g Resorcin 0.16 g 30 2,4-Diamino phenoxyethanol (dihydrochloride) 0.075 g ^ -hydroxyethylamino-3, methyl-6 phenol 0.15 g CELLOSIZE WP 03 2g

Ammonium lauryl sulfate 5 g

Butoxy-2 ethanol 15 g i - 19

96 ° alcohol 5 g

Ammonia at 22 ° Be 10 g

Ammonium thiolactate 0.8 g

Water qs 100 g .5 pH = 10.4

At the time of use, 100 g of hydrogen peroxide is added to 20 volumes.

The mixture, applied 30 minutes at 28 ° C to bleached hair, gives them, after shampooing and rinsing, a light brown coloring.

EXAMPLE 11 The following dye mixture is prepared:

Mono-hydrochloride (3-amino, 2-methylamino, 5-nitro) 1-phenyl-2-propanol 0.12 g

Para-aminophenol 0.06 g 4-methylamino-phenol hemi-sulfate 0.09 g 15 2 -oxy-5-amino phenol 0.105 g

Hydroxy-7 benzomorpholine 0.05 g N, N- (ethylcarbamylmethyl) amino-4 aniline 0.1 g CEMULSOL NP 4 21 g CEMULSOL NP 9 24 g 20 Oleic acid 4 g 'Butoxy-2 ethanol 3 g

Ethanol at 96 ° 10 g MASQUOL DIPA 2.5 g

Thioglycolic acid. 0.6 g 25 Ammonia at 22 ° Bë 10 g

Water - qs 100 g pH = 10 „At the time of use, 100 g of hydrogen peroxide at 20 volumes are added.

The mixture, applied for 30 minutes at 28 ° C. to bleached hair, gives them, after shampooing and rinsing, an ashy sand coloring.

EXAMPLE 12

The following dye mixture is prepared: (Amin o-3, | â-hy dr oxyë thy lam in o-2, nitr o-5) phêny 1-2 ethanol-1 0.26 g 35 N, N-bis dihydrochloride (j & -hydroxyethyl 1) 4-amino aniline 0.19 gii 1 * | | , /! η l, 20 Resorcin 0.07 g

Amino-4 hydrochloride, 2-chloro-phenol 0.07 g

Carbamylmethylamino-3, methyl-6 phenol 0.1 g ALFOL C 16/18 8 g 5 LANETTE E wax 0.5 g CEMULSOL B 1 g

Oleic diethanolamide 1.5 g MASQXIOL DTPA 2.5 g

Mercaptosuccinic acid 0.5 g 10 Ammonia at 22 ° Bë 11 g

Water qs 100 g pH = 10.4

At the time of use, 80 g of hydrogen peroxide are added to 20 volumes. The mixture, applied 25 minutes at 30 ° C to bleached hair 15 with roax> gives them, after shampooing and rinsing, a coloring, light golden brown.

»T i \» ri i r i - i 7 j 'i t 4 i i

J

.1

-I

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The different trade names used in the above examples are explained in more detail below:

CARBOPOL 934: Polymer of PM acrylic acid

2 to 3 million sold by Goodrich 5 Chemical Company.

CMULSOL NP ^: Nonylphenol containing 4 moles of ethylene oxide sold by Rhône Poulenc.

CEMULSOL ΝΡ ^: Nonylphenol with 9 moles of ethylene oxide sold by Rhône Poulenc.

v. 10 ALFOL C16 / 18 (50/50): Cetylstearyl alcohol sold by the

Condéa company.

Lanette E wax: Partially sulfated cetylstearyl alcohol sold by Henkel.

15 CEMULSOL B: Ethoxylated castor oil sold by

Rhône Poulenc.

TWEEN 80 s Polyoxyethylenated sorbitol monooletate.

LAURAMIDE: Monoethanolamide of lauric acid sold by Witco.

20 COMPEKLAN KD: Diethanolamide of coconut fatty acid sold by Henkel.

CELLOSIZE WP 03: Hydroxyethylcellulose sold by Union

Carbide.

MASQUOL DTPA: Pentasodium salt of diethylene 25 triamine pentacetic acid sold by PROTEX.

TRILON B: Ethylene diamine tetracetic acid.

"

Claims (16)

1. Amino-2, nitro-4, hydroxyalkyl-6 aniline of general formula (I): x “oh \\ (I) 5 k. —— ΝΗΙ4 ’^ * 2 in which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, one of these atoms possibly being substituted by one or more hydroxyl radicals; R ^ and R £ denote, independently of one another, a hydrogen atom, an alkyl, mono- or polyhydroxyalkyl or amlnoalkyl radical, the amine function of which may be optionally substituted by an alkyl or mono- or polyhydroxyalkyl radical, nitrogen atom may also be part of a heterocycle, the alkyl radicals having 1 to 4 carbon atoms; R ′ denotes a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; and the cosmetically acceptable salts of this compound. 2. Compound according to Claim 1, characterized in that X 20 is an ethylene, propylene, 1,1-dimethyl ethylene, 1,2-dimethyl ethylene or trimethyl-1,1,2 ethylene radical, R 'is an atom of hydrogen or a methyl radical, R ^ and R2 independently of one another denote a hydrogen atom, a methyl, ethyl, n-propyl, -hydroxyethyl, '^ -hydroxypropyle, £>, -dihydroxypropyle radical , aminoethyl or β-diethylaminoethyl. 3. Compound according to Claim 1 -or 2, characterized in that it is chosen from the group comprising: (2,3-diamino, 5-nitro) 2-phenyl-ethanol-1, 1 '[j & mlno-3 , p-hydroxyethylamino-2, nitro-J0 phenyl-2 ethanol-1, le (diamino-2,3, nitro-5) phenyl-l propanol-2 and 1 '(amino-3, methylamino-2, nitro- 5) 1-phenyl-2-propanol, as well as the salts of these compounds. 4. Process for the preparation of a amino-2, nitro-4, hydroxyalkyl-6 aniline of formula (I) according to claim 1, characterized by the / V //. / 23 reacting an aqueous ammonia solution or a primary amine of formula RjNH2 in which has the same meaning as in claim 1, on a heterocyclic compound of formula (IV): .5 ¥ - / \ - x \ TXJ (IV) k2 in which R 'and X have the meanings indicated in claim 1, at a temperature between 20 and 120 ° C, optionally under pressure and optionally in the presence of polar protic solvents or polar aprotic solvents, to obtain a 2,4-dinitro-6, hydroxyalkyl-6 aniline of formula (III): R '15 ° 21 ^^^ ν_.χ-0Η | (III) —nhr1 T ° 2 in which R ', X and have the meanings indicated above, then a selective reduction of the compound of formula (III) is carried out, either with sodium sulfide in the presence of sulfur in a hydroalcoholic solution, either by hydrogen sulphide in the presence of ammonia, or by hydrogen transfer from cyclohexene to compound (III) in the presence of Pd / C, in an alcoholic solution, to obtain the compound of formula (II): R '° 2NVX ^ VX “' 0H | <η> \ îj ^ NHR1 NH2 and finally, optionally, alkylation, hydroxyalkylation or aminoalkylation of the compound of formula (II) is carried out to obtain the compound of formula (I). ♦ 24 5. Dye composition for keratin fibers, and in particular for human hair, characterized in that it contains, in a solvent medium, at least one compound as defined in any one of claims 1 to 3. 6. Composition according to claim 5, characterized in that it contains 0.001 to 5% by weight, and preferably 0.05 to 2% by weight, relative to the total weight of the composition, of at least one compound of formula (I) according to any one of claims 1 to 3. 7. Composition according to claim 5 or 6, characterized in that the _ 20 has a pïï between 3 and 11.5, and preferably between 5 and 11.5. 8. Composition according to any one of claims 5 to 7, characterized in that the solvents are chosen from water, ”lower alkanols, aromatic alcohols, polyols, glycols or glycol ethers and mixtures thereof . 9. Composition according to any one of claims 5 to 8, characterized in that it also contains cosmetic adjuvants chosen from anionic, cationic, nonionic, amphoteric surfactants or their mixtures, thickeners, 2o dispersing agents, penetration agents, sequestrants, film-forming agents, buffers, perfumes, alkalinizing or acidifying agents. 10. Composition according to any one of claims 5 to 9, intended to be used for the direct dyeing of human hair, characterized in that it contains, in addition, other direct dyes chosen from dyes azo ' ics, anthraquinone dyes, Indophenols, indoanilines and nitro derivatives of the benzene series other than those of formula (I). 11. Composition according to any one of claims 5 to 9, 30 intended for use as a styling lotion, characterized in that it is in the form of an aqueous, alcoholic or hydroalcoholic solution, containing at least a cosmetic resin. 12. Composition according to any one of claims 5 to 7, intended to be used for oxidation dyeing, characterized in that it additionally contains at least one dye precursor by oxidation. 25 13. Composition according to claim 12, characterized in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing agent, 14. Process for dyeing keratin fibers, and in particular for human hair, characterized in that a composition as defined in any one of claims 5 to 10 is applied to the fibers, it is left to stand for 5 to 50 minutes, rinse, optionally wash with shampoo, rinse again and dry. 15. Process for dyeing keratin fibers, and in particular for human hair, characterized in that a composition as defined in claim 11 is applied to the washed and rinsed fibers, optionally wound and dried. 16. A process for dyeing keratin fibers, in particular human hair, characterized in that a composition as defined in claims 12 and 13 is applied to the fibers, optionally added with an oxidizing agent, leave on for 10 to 50 minutes, rinse, optionally wash with shampoo, rinse again and dry. , Drawings: plates —pages of which ........ A ...... cover page ........... description pages ..... H claim pages Abbreviated description Luxembourg, ie \ 3 DEC. ÎS84 Le m <yidiüaire Me ÂlaiflfRukavina f) ftiÆW /) *