LU83063A1 - TINCTORIAL COMPOSITION FOR KERATINIC FIBERS BASED ON NITRO-3 ORTHOPHENYLENEDIAMINES, NOVEL NITRO-3 ORTHOPHENYLENEDIAMINES USED AND PROCESSES FOR THEIR PREPARATION - Google Patents

Description

Dye composition for keratin fibers based on 3-nitro orthophenylenediamines, new 3-nitro orthophenylenediamines used and their preparation processes.

As is well known, keratin fibers and in particular human hair are often given direct dyeing or additional reflections in the case of oxidation dyeing using nitro derivatives of the benzene series. The Applicant has discovered that, in order to give the keratin fibers red shades, nitro-orthophenylenediamines could be used, contrary to what could be expected. ' This is particularly surprising when we know that nitro-4-orthophenylenediamine gives rise to yellow coloring.

U It has found that the hair dyes thus obtained using this class of dyes have good light stability.

These dyes also have the advantage of being little or not selective. Selectivity is, as is well known, a significant practical problem in the field of hair dyeing due to the different sensitization of the hair from root to tip. Indeed, the hairdresser is generally in the presence of a hair whose sensitization is practically zero for the freshly pushed root, strong for the previously treated parts having undergone coloring, discoloration or a perm and very strong for the spikes which have undergone several of these treatments and which are exposed daily to the action of light and bad weather.

2q The Applicant has discovered that the new class of 3-nitrophenylenediamines retained makes it possible to obtain substantially similar coloring intensities whether the hair is permed or not.

It also found that the dyes used in accordance with the invention were particularly stable in the oxidation dye carriers and in particular in ammonia medium there in the presence of reducing agents, which makes it possible to combine them with the dyes. so-called oxidation to obtain nuances rich in reflections.

The present invention therefore relates to dye compositions for keratin fibers containing nitro-3 5 orthophenylenediamines.

Another object of the invention consists of the new 3-nitro orthophenylenediamines used in accordance with the invention as well as their methods of preparation.

Other objects of the present invention will become apparent on reading the description and examples which follow.

The dye compositions for keratin fibers in accordance with the invention are essentially characterized in that they contain, in a suitable solvent medium for dyeing keratin fibers, at least one dye corresponding to the formula: NHR0 f o2n - ^ | - NHRi 20 (I)

Z

in which R 1 and R 2 denote, independently of each other, a hydrogen atom, an alkyl group, a mono- or polyhydroxylated alkyl group, an alkyl group substituted by an alkoxy group, an aminoalkyl group, the amino group of which may optionally be mono- or disubstituted by an alkyl group, the radical R2 may also denote a phenyl group, or phenyl substituted by an alkyl, hydroxyl or amino group, Z denotes a hydrogen atom or an alkyl group.

In the above formula, the alkyl radical preferably denotes a radical having from 1 to 4 carbon atoms and the alkoxy group preferably denotes methoxy or ethoxy.

Among the groups which are more particularly preferred, mention may be made, for R2, of a hydrogen atom, a methyl, ethyl, propyl or butyl group, an (i> -hydroxyethyl group, a jl-hyaroxypropyl group, a 1/3 propyl group, a Ν, Ν-diethylamino ethyl group, a p-hydroxyphenyl group, or a / ¾ -methoxyethyl group; for a hydrogen atom, a methyl, ethyl, ß-hydroxyethyl group and for Z a hydrogen atom and a 5 methyl group.

The compounds giving particularly advantageous results in the context of the present invention correspond to formula (I) in which Z necessarily denotes a methyl group. Other compounds giving particularly appreciable results are those for which R 2 is different from hydrogen and denotes in particular methyl or -hydroxy-ethyl. These compounds in particular have good safety.

These compounds can also be used in the form of their cosmetically acceptable salts such as in the form of hydrochloride, sulphate, etc.

The preferred compounds used in accordance with the invention make it possible to obtain copper shades more or less rich in red ranging from 7.5 YR to 10 R according to the Munsell evaluation.

The shade is designated by H in the Munsell notation

20 that a color is defined by the formula HV / C

in which the three parameters respectively designate the shade or "hue" (H), the intensity or "value" (V) and the purity or "chromaticity" (C), the slash being a simple convention.

25 As far as Munsell's notation is concerned, reference may be made to the publication of "Official Digest" April 1964, pages 373 to 377.

Among the compounds used in accordance with the invention, the compounds of formula (II); 30 NHR * 2 0oN - NHR '2 ^ I 1 (XI)

V

35 Z 'in which R *, R'2 and Z' have the meanings indicated above respectively for R ^, R ^ and Z provided that / R'l, R'2 and Z 'cannot simultaneously denote hydrogen ^ ^ 4 when R'2 denotes methyl, R '^ and Z' cannot simultaneously denote hydrogen and when Z 'denotes methyl, at least one of the groups R' ^ and R'2 is different from hydrogen and their salts cosmetically acceptable are new.

The process for the preparation of these compounds which constitutes another object of the invention consists, as regards the compounds of formula (I) for which R1 denotes hydrogen, in effecting a selective reduction of the compounds of formula (III): NHR,

X

o2n-- no2 I (III) 15 z the selective reduction being carried out either using alkaline sulfite according to M. Kamel, M.I. Ali and M.M. Kamel, Tetrahedron 1966, vol. 22, page 3353 or by hydrogen transfer, from cyclohexene to the compound of formula (III) in the presence of palladium on carbon as catalyst according to Ian D. Entwistle, Robert A. W Johnstone and T. Jeffery Povall, JCS Perkin I 1975, page 1300.

The compounds of formula (I) for which R ^ denotes alkyl or substituted alkyl can be obtained by benzene-2 ^ sulfonation or paratoluenesulfonation of the compounds of formula (I) for which R ^ denotes hydrogen. Then reacted on the arylsulfonamides thus obtained a haloalkane of formula XR ^, in which X denotes a halogen atom and R ^ alkyl or substituted alkyl, then after / substitution sulfonamides are hydrolyzed. / 7 / f 5

The reaction scheme can essentially be summarized as follows: nhr2 nhr2 5 0, N Ä NH, O-N HHSO, - / '' \ -K,

-> LU

Z Z

Ro = H or CH

10 3 NHR2 il fi) 1 ~ V "* * 20 NHR, v -Λ- -

AA

25 Ύ

A number of the intermediate compounds of formula (III) used in accordance with the process of the invention are known in themselves. In general, these compounds of formula (III) can be obtained by the action of ammonia or amines of formula R2NH2, in which R2 has the same meaning as that indicated above, on dinitrated, chlorinated or methoxylated compounds by taking advantage of the mobility of the chlorine atom or of the methoxy group.

The compositions in accordance with the invention can be used for the direct dyeing of keratin fibers> or for the oxidation dyeing of these fibers in which case the / f 6 compounds of formula (I) confer reflections complementary to the dyeing of base obtained by oxidative development of oxidation dye precursors. These compositions contain the compounds of formula (I) in proportions of between 0.001 and 5% by weight and preferably between 0.01 and 3% by weight relative to the total weight of the dye composition.

They may contain anionic, cationic, nonionic, amphoteric surfactants or their mixtures. These 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.

The cosmetic vehicle generally consists of water and organic solvents can also be added to the compositions to dissolve compounds which are not sufficiently soluble in water. Among these solvents, mention may be made of lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, ethylene monoethyl ether glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol as well as analogues and their mixtures. 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.

The compositions can preferably be thickened with the compounds chosen from sodium alginate, gum arabic, cellulose derivatives such as methylcel-lulose, hydroxyethylcellulose, hydroxypropylmethylcel-lulose, carboxymethylcellulose and polymers. various having the function of thickener such as more particularly derivatives of acrylic acid. It is also possible to use mineral thickening agents such as bentonite. These thickening agents are preferably present in proportions of between 0.5 and 10% by weight and in particular between 0.5 and 3% by weight relative to the / * / total weight of the composition. / ï / f 7

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

These compositions can be in various forms such as liquids, creams, gels or any other form suitable for dyeing the hair. They can also be packaged in aerosol cans 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- or triethanolamine, alkylamines such as ethylamine or triethylamine or using an acidifying agent such as. phosphoric, hydrochloric, tartaric, acetic, lactic or ci-tric acids.

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 for example tetraminoanthraqui -none, nitro dyes of the benzene series different from the compounds of formula (I) and more particularly the following compounds: 2-methyl-6-nitro aniline, 3-nitro-4-amino phenol, 3-nitro-N / i-4-hydroxyethylamino-phenol, 3-nitro-4-amino-6-methyl-phenol, 3-amino-4-nitro phenol, 2-amino-3-nitro phenol, 35 3-nitro, N - / ^ -hydroxyethylamino-6 anisole, / N-ß, ^ - dihydroxypropylamino-3 nitro-4 anisole, r / î 8 "le (N-methylamino-3, nitro-4) phenoxyethanol, (N-methylamino-3, nitro -4) phenyl, ß, Y-dihydroxypropyl-ether, N, N '(- -hydroxyethyl) nitro paraphenylenediamine, 5 nitro-3, N'-methylamino-4, N, N- (di- β-hydroxyethyl) aniline, methyl-2 amino-4 nitro-5 N- ( ?> - hydroxyethylaniline, methyl-2 amino-4 nitro-5 N- (^ -diethylaminoethylaniline, methyl-2 amino-4 nitro-5 N-methylaniline. The concentrations of these direct dyes other than the dyes of formula (I) can be between 0.001 and 5% by weight f relative to the total weight of the composition.

These compositions are applied to the keratin fibers for an exposure time of 5 to 70 minutes, then the fibers are rinsed, optionally washed, rinsed again and dried.

These compositions can also be used in the form of a hair styling lotion intended at the same time to give the hair a light coloring 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 lotions of; styling can be in particular polyvinylpyrrolidone; the copolymers crotonic acid-vinyl acetate, vinylpyrrolidone-vinyl acetate, semi-esters of maleic anhydride-butylvinyl ether and maleic anhydride-methyl vinyl ether copolymers as well as any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of compositions. These cosmetic resins are included in the compositions of the invention in an amount of 1 to 3% by weight and preferably from 1 to 2% by weight based on the total weight of the composition.

When the compositions constitute oxidation dyes, the compounds of formula (I) in accordance with the invention are mainly 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), precursors of 5 dyes by oxidation.

They may contain, for example, para-phenylene diamines such as para-phenylenediamine, para-luylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-dimethyl-3-methoxy-3 para-phenylenediamine, N- (β-methoxyethyl) ) paraphenylenediamine, N, N-di (-hydroxyethyl) 4-amino aniline, N, N- (ethyl, carbamylmethyl) 4-amino aniline, as well as their salts.

They may also contain paraaminophenols, for example: paraaminophenol, N-methyl paraaminophenol, 2-chloro-4 amino phenol, 3-chloro-4 amino phenol, 2-methyl amino 4-phenol, and their salts.

They can also contain heterocyclic derivatives, for example: diamino-2,5 pyridine, N, N-diethylamino-5 amino-2 pyridine, amino-7 benzomorpholine, amino-2 hydro-20 xy-5 pyridine.

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

As couplers, there may be mentioned in particular: meta-diphenols such as resorcin, 2-methyl resorcin, metaaminophenols such as: metaminophenol, 2-methyl-5-amino phenol, 2-methyl-N- ( fi-hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine and their salts, meta-30-nylenediamines such as: (2,4-diamino) phenoxyethanol, 2,4-diamino phenyl -aminoethyl ether, amino -6 benzomor pholine, / / N- (ß-hydroxyethyl) amino-2 amino-47 phenoxy-ethanol, (diamino-2,4) phenyl ^, ^ - di-hydroxypropylether and their salts, metaacylaminophenols, metaurideidophenols, 35 metacarbalcoxyaminophenols such as: 2-methyl acetyl-amino-5-phenol, 2-methyl-5-ureido-phenol, 2-methyl, / 5-carbethoxyamino-phenol.

10

Finally, mention may be made of other couplers which can be used in the compositions of the invention; 1'o (-naphthol, couplers having an active methylene group such as diketonic compounds and pyrazolones and heterocyclic U couplers such as 2,4-diamino pyridine, as well as their salts.

These compositions additionally contain dye precursors by oxidation of reducing agents such as more particularly sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, ascorbic acid and hydroquinone . These reducing agents are present in proportions of between 0.05 and 1.5% 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 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, preferably between 0.015% and 2% by weight. Their pH is preferably between 7 and 11.5 and is adjusted using basifying agents defined above.

We have found that the compounds according to the invention are particularly stable in such compositions.

The process for dyeing keratin fibers, in particular human hair, using revelation! with an oxidant, consists in applying the hair to the | dye position comprising both a dye according to | the invention and the dye precursors by oxidation and! develop the coloring using an oxidizing agent present in the dye composition or else applied to the hair in a second step.

; The oxidizing agent is preferably chosen from water | 35 oxygenated, urea peroxide and persalts. In particular, 20 volumes of hydrogen peroxide solution are used ^^ / y i 11

Once the composition with the oxidizing agent has been applied to the keratin fibers, it is left to stand for 10 -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 presenting a limiting character ^^^ 12 EXAMPLE 1

The following dye composition is prepared:

Amino-2 nitro-3 methyl-5 N-methylaniline ........ 0.9 g

Butoxy-2 ethanol ................................ 10 g 5 Alfol C16 / 18 (50/50) .. .......................... 8 g

Lanette wax ................................. 0.5 g

Cemulsol B ...................................... 1 g

Oleic diethanolamide .......................... 1.5 g

Triethanolamine ................................. 1 g 10 Water ............ .qsp .......................... 100 g

This composition has a pH of 9.

This mixture applied 25 minutes at 28 ° C on bleached hair gives them after rinsing and shampooing a coloring of 2.0 YR 5.5 / 8 according to Munsell.

15 Preparation is carried out in the same way as that indicated above, the compositions mentioned in Table 1 which follows the support being the same as that used in Example 1, the basifying agent being specified as well as the pH. The dyeing conditions such as temperature, rinsing and washing are similar to that indicated in Example 1. An amount of water sufficient for 100 g of composition is always added.

By applying the composition of Example 2 to naturally white hair at 90% previously permed 2 ^ and also proceeding in the same way there is a coloration of 7.5 YR 6/8 according to Munsell identical to that observed on hair naturally white at 90%, dyed under the same conditions.

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The following dye composition is prepared:

Amino-2, nitro-3, methyl-5, N-methylaniline ....... 0.5 g

Nitro-3, N'-methylamino-4, N- (?> - aminoethylaniline. 0.1 g 5 (N-methylamino-3, nitro-4) phenoxyethanol .......... 0.28 g

Ethanol at 96 ° ..................................... 5 g

Propylene glycol ................................... 5 g

Diethanolamides of coconut fatty acids ............ 2.2 g

Lauric acid .................................... 0.8 g 10 Monoethyl ether of ethylene glycol .. .............. 2 g

Monoethanolamine .................................. 1.1 g

Water ............... g.s.p ........................... 100 g pH 10.5

This mixture applied 25 minutes at 30 ° C to de-15 dyed white hair gives them, after rinsing and shampooing, a light red copper coloring.

EXAMPLE 11

The following dye composition is prepared:

Amino-2, nitro-3, methyl-5 aniline ................ 0.5 g 20 Nitro-3, N- ^ "- hydroxyethylamino-4 phenol .... ...... 0.15 g Tetraminoanthraguinone ............................ 0.10 g

Butoxy-2 ethanol .................................. 10 g

Cemulsol NP ^ ..................................... 12 g

Cemulsol NP ^ ..................................... 15 g 25 Oxyethylenated oleic alcohol to 2 moles of ethylene oxide ........................................ 1.5 g

Oxyethylene alcohol with 4 moles of ethylene oxide ...................................... 1.5 g

Triethanolamine ................................... 2 g 30 Water .......... ..gsp ............................. 100 g pH 9.

This mixture, applied for 35 minutes at 30 ° C to straw bleached hair, gives it a copper brown color after rinsing and shampooing.

35 EXAMPLE 12 "v

The following dye composition is prepared: // 15

Nitro-3 orthophénylènediamine ..................... 0.3 g

Nitro-3, N'-methylamino-4, N, N-di-ß-hydroxyethyl-aniline ............................ ............... 0.11 g N, N'- -hydroxyethyl 1 nitroparaphenylene diamine ... 0.11 g

96 ° alcohol ...................................... 10 g 5 Carboxymethylcellulose .... ........................ 2 g

Ammonium lauryl sulfate .......................... 5 g

Monoethanolamine .................................. 2 g

Water ........... g.s.p ............................... 100 g pH 10.5.

10 This mixture, applied for 25 minutes at 30 ° to straw-colored bleached hair, gives it a very coppery brown color after rinsing and shampooing.

EXAMPLE 13

The following dye composition is prepared: 15 N-butylamino-2 nitro-3 methyl-5 aniline ........... 0.3 g

Nitro-3, N'-methylamino-4, N, N-di - hydroxyethyl-aniline ............................. ............. .0.05 g

Butoxy-2 ethanol .................................. 10 g

Diethanolamides of coconut fatty acids ........... 2.2 g 20 Lauric acid ....................... 0, 8 g

Monoethyl ether of ethylene glycol ............... 2 g

Monoethanolamine .................................. 1 g

Water ........... gsp .............................. 100 g pH 8.5 25 This mixture applied 30 minutes at 28 ° C on hair bleached in white gives them after rinsing and shampooing a light beige coloring with golden reflections.

EXAMPLE 14

The following dye composition is prepared: 30 N- -diethylaminoethyl-amino-2-nitro-3-methyl-5 aniline ............................. .............. 1 g

Butoxy-2 ethanol .................................. 5 g

Lauric alcohol with 10.5 moles of ethylene oxide ... 5 g

Ammonia at 22 ° B ................................. 1 g / 35 Water ....... ............ qs ...................... 100 g / y PH 9. I dd / 16

This dye composition applied for 25 minutes at 28 ° C on bleached hair gives them, after rinsing and shampooing, a color 6.5 YR 5/10 according to Munsell.

EXAMPLE 15 The following dye composition is prepared:

N- / 3-hydroxypropylamino-2-nitro-3-methyl-5 aniline hydrochloride ................................. .0.5 g

Propylene glycol .................................. 10 g

Carboxymethylcellulose ............................ 10 g ^ q Monoethanol amine ............... ................... 5 g

Water ............. q.s.p ............................. 100 g

This mixture applied 25 minutes at 30 ° C to hair bleached in white gives them after rinsing and shampooing a coloring 4 YR 7/7 according to Munsell.

EXAMPLE 16 1 5

The following dye composition is prepared: N-fi hydrochloride, ^ -dihydroxypropylamino-2 nitro-3 methyl-5 aniline ......................... ......... 1.82 g

Nitro-3, N- ^ -hydroxyethylamino-4 phenol .......... 0.3 g

Nitro-3, N, -methylamino-4, N, N-di- / 3-hydroxyethyl- MV * aniline ......................... .................. 0.5 g

Butoxy-2 ethanol .................................. 10 g

Monoethanolamide of lauric acid ................. 1.5 g

Lauric acid .................................... 1 g 25 Hydroxyethylcellulose ........ ..................... 5 g

Monoethanol amine .................................. 4 g

Water ............ q.s.p .............................. 100 g pH 10.

This mixture, applied for 25 minutes at 30 ° C to naturally white hair at 90%, gives them a light brown, red copper color.

EXAMPLE 17

The following dye composition is prepared: N - ^> - 2-methoxyethylamino-3 nitro-5-methyl aniline. 0.6 g 22 Butoxy-2 ethanol ................... ...............

17

Carbopol 934 ...................................... 2 g "

Monoethanolamine .................................. 2 g

Water ........... g.s.p ............................... 100 g pH 8.8

5 This dye composition applied for 30 minutes at 30 ° C

on bleached hair gives them, after rinsing and shampooing, a 7.5 YR 7/6 color according to Munsell.

EXAMPLE 18

The following dye composition is prepared: 10 N-ß-hydroxypropylamino-2 nitro-3 hydrochloride! 5-methyl aniline .................................. 1 g

Paraphenylenediamine .............................. 0.25 g

Paraaminophenol .................................. .0.065 g Resorcin ........... .............................. 0.2 g 15 Metaaminophenol .............. ..................... 0.08 g Methyl-2, -hydroxyethylamino-5 phenol ......... 0.05 g

Butoxy-2 ethanol .................................. 8 g Càrboxymethylcellulose ......... ................... 2 g

Ammonium lauryl sulfate .......................... 5 g 2o Ammonium acetate .............. .................. 1 g

Propylene glycol ................................... 8 g

Masguol DTPA ...................................... 2 g

Thioglycolic acid ............................. 0.4 g

Ammonia at 22 ° B ................................. 10 g 25 Water ........ ..... qs ............................ 100 g pH 10.6.

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

This mixture applied 30 minutes at 30 ° C to 30 bleached straw blonde hair gives them after rinsing and shampooing a medium brown color with copper highlights.

EXAMPLE 19

The following dye composition is prepared:

Amino-2, nitro-3 methyl-5 aniline ................. 0.8 g 35 Paraphenylene diamine ............... .............. 0.18 g

Paraaminophenol .................................. .0.0E ^^^ / 18 Resorcin ..... .................................... 0.12 g Metaaminophenol ......... .......................... 0.115 g

2,4-diamino dihydrochloride phenoxyethanol ...... 0.03 g

Cemulsol NP ^ ...................................... 12 g 5 Cemulsol NP ^ ... ................................... 15 g

Oleic alcohol with 2 moles of ethylene oxide ....... 1.5 g

Oleic alcohol with 4 moles of ethylene oxide ....... 1.5 g

Propylene glycol .................................. 6 g

Trilon B ................................... 0.12 g

Ammonia at 22 ° B ................................. 11 g

Thioglycolic acid .............................. 0.6 g

Water ......... q.s.p ................................. 100 g pH 10.5.

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

This mixture applied 30 minutes at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a coppery medium brown coloring.

EXAMPLE 20 The following dye composition is prepared: N- (£ -diethylaminoethylamino-2-nitro-3-methyl-5 aniline ......................... .................. 1.5 g

Nitro-3, N'-methylamino-4, N, N-di- £ -hydroxyethyl- aniline ............................ ............... 0.2 g 25 Butoxy-2 ethanol .......................... ........ 10 g

Carboxymethylcellulose ............................ 10 g

Monoethanolamine .................................. 5 g

Water .......... q.s.p ................................ 100 g pH 10.

30 This mixture applied for 30 minutes at 30 ° C to hair bleached in white, gives it, after rinsing and shampooing, an ashy beige coloring.

EXAMPLE 21

The following dye composition is prepared; 35 N- -hydroxyethylamino-2 nitro-3 methyl-5 aniline .................................... .......

119

Butoxy-2 ethanol .................................. 10 g 'Monoethanolamide of lauric acid .... ............. 1.5 g

Lauric acid .......................... 1 g

Hydroxyethylcellulose ............................. 5 g 5 Monoethanolamine ................ .................. 2 g

Water ........... q.s.p ............................... 100 g pH 10.

This mixture applied for 25 minutes at 28 ° C. to hair bleached in white gives them, after rinsing and shampooing 10, a coloring 5 YR 8/6 according to Munsell. ; EXAMPLE 22

The following dye composition is prepared: N- ß-hydroxyethylamino-2-nitro-3 methyl-5 aniline ............................. .............. 1.21 g 15 Paraphenylenediamine .............................. 0.5 g Resorcin ......................................... 0.1 g Metaaminophenol ........... ....................... 0.21 g

Orthoaminophenol .................................. 0.17 g

Carbopol 934 ...................................... 1.5 g 20 Alcohol at 96 °. ,, .................................... 11 g

Butoxy-2 ethanol .................................. 5 g

Trimethyl cetyl ammonium bromide ............... 1 g

Trilon B .......................................... 0.1 g

Ammonia at 22 ° B ................................. 10 g 25 Thioglycolic acid ....... ....................... 0.2 g

Water ............ q.s.p .............................. 100 g pH 10.5.

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

2Q This mixture, applied for 25 minutes at 28 ° C to naturally white hair at 90%, gives them, after rinsing and shampooing, a dark brown color with copper highlights.

EXAMPLE 23

The following dye composition is prepared: 35 Nitro-3 orthophénylènediamine ..................... 0.5 g Methyl-2, nitro-6 aniline ..... ................, .., 0.2 g ^ 20

Paraphenylenediamine .............................. 0.08 g 2-methyl resorcin ........... ..................... 0.045 g Metaaminophenol .......................... ......... 0.06 g

Cemulsol NP ^ ...................................... 21 g 5 Cemulsol NPg.; .. .................................. 24 g

Oleic acid ..................................... 4 g

Butoxy-2 ethanol .................................. 3 g

Ethanol at 96 ° ..................................... 10 g

Masquol DT PA ...................................... 2.5 g 10 Bisulfite solution sodium at 35 ° B ........... 1 g

Ammonia at 2 2 ° B ................................. 10 g

Water ......... q.s.p ................................. 100 g pH 11.

At the time of use, 80 g of hydrogen peroxide are added to 20 volumes.

This mixture applied 25 minutes at 30 ° C on naturally white hair at 90% gives them after rinsing and shampooing a very golden dark blond coloring.

The following examples are intended to illustrate the processes for the preparation of the new compounds used in accordance with the invention. /'AT

21, PREPARATION EXAMPLE 1

Preparation of N-butylamino-2, nitro-3, methyl-5 aniline.

nh-ch2-ch2-ch2-ch3 ° 2N-1 I NH2

V

CH3 10

Cl nh- (ch2) 3-ch3 ° 2N ~ f \ ï ~ N02 ° 2N “ti] -” 02 15 1 ^ · ♦ h2n- <ch2) 3CH3-> CH3 ch3 nh-ch2-ch 2-ch 2- ch 3 20 _ ^ H2N ~ [<|| n02

V

CH3 a) Preparation of dinitro-2,6-methyl-4 N-butylaniline 25 0.05 mol (10.8 g) of dinitro-2,6-methyl-4 is gradually added over 10 minutes with stirring. chlorobenzene in 25 ml of butylamine, cooling the reaction medium if necessary so as not to exceed 50 ° C. When the addition is complete, stirring is continued for 5 minutes and then the reaction medium is poured into 100 ml of ice water. The expected product precipitates, it is drained, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 52 ° C.

Analysis Calculated for Found ^ 11 ^ 15 ^ 3 ^ 4 / / v 35 C% 52.17 52.13 '/ ^

H% 5.93 6.04 W

N% 16.60 16.59 0% 25.30 25.34 22! i b) Preparation of N-butylaroino-2, nitro-3, methyl-5 "aniline.

0.041 mol (10.4 g) of 2,6-dinitro-methyl 4-N-butylaniline is added to 50 ml of ethanol supplemented with 10.8 g of cyclohexene and .2.8 g of Pd / C at 10 %. The reaction medium is brought to reflux for one hour and then it is filtered hot to remove the catalyst. The filtrate is cooled to -15 ° C. The expected product crystallizes. It is wrung, washed with a little iced alcohol and dried under vacuum. It melts at 10 68 ° C.

Analysis Calculated for Found C11H17N3 ° 2 C% 59.19 59.33 H% 7.62 7.75 15 N% 18.83 18.98 0% 14.35 14.44 PREPARATION EXAMPLE 2

Preparation of N-fi-methoxyethylamino-2, nitro-3, methyl-5 aniline 20 nh-ch2-ch2-och3 o „n -

V

25 ch3

Cl NH-CH2-CH2-OCH3 02N -N02_ ^ 02N — X ^ X-NO2 3 ° I HN-CHCHOCH | CH3 CH3 NH-CH2CH20CH3 // ”JZ- ùf -> XX f- H 3 23” a) Preparation of dinitro-2,6-methyl-4 N- / 2> -methoxy etbylaniline.

0.05 mol (10.8 g) of 2,6-dinitro-4-methyl-chlorobenzene is added gradually over 10 minutes with stirring in 25 ml of methoxyethylamine, cooling the medium if necessary. reaction not to exceed 50 ° C. When the addition is complete, stirring is continued for 5 minutes and then the reaction medium is poured into 100 ml of ice water. The expected product precipitates *. It is spun, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 75 ° C.

Analysis Calculated to Found C10H13N3 ° 5 C% 47.06 47.08 H% 5.13 4.99 15 0%. 31.34 31.07. .

N% 16.47 16.50 b) Preparation of N-methoxyethylamino-2, nitro-3, methyl-5 aniline.

0.03 mol (7.65 g) of 2,6-dinitro, 4,2-methyl, 2Q N-y0-methoxyethylaniline is dissolved in 38 ml of absolute alcohol containing 12.3 g of cyclohexene and 3.8 g of Pd / C at 10%. Then the alcoholic solution is brought to reflux for 15 minutes. The hot reaction medium is filtered to remove the catalyst and then, after cooling, 15 ml of alcohol saturated with hydrochloric gas, 2 g of water, are added. The expected product precipitates in the form of hydrochloride. The hydrochloride is drained and washed with a little alcohol, then it is dissolved in water. This ; aqueous solution is made alkaline with ammonia to precipitate the expected product which is drained, washed with water and recrystallized from ethanol, it melts at 71 ° C.

30

Analysis Calculated to Found C10H15N3 ° 3 C% 53.33 53.46.

H% 6.67 6.70. / 35 N% 18.67 18.55 ///

0% 21.33 21.27 [F

24 EXAMPLE OF PREPARATION 3

Preparation of nitro-2, methyl-4, amino-6 hydroxy-41 diphenylamine.

| N02

H3G ^ - NH ^ ^ —DH

nh2 4 in Cl · OH NO ~ 10 ï I _i 2

ο, N -NO, + \\ _ NH— <7 VS-OH

i 2 i ^ \ = _ / v = y V T ^ 15 fcli3 ^ 2 N02 NO,

- ^ H3C- ^ ^ NH— ^ ^> - OH

nh2 a) Preparation of dinitro-2,6-methyl-4, hydroxy-41 diphenylamine.

0.1 mol (10.9 g) paraaminophenol and 0.05 mol (10.83 g) of 2,6-dinitro-4-methylchlorobenzene in 60 ml of alcohol are heated under reflux for 2 hours. After the reaction medium has cooled, the mixture is filtered and washed with alcohol. dinitro-2,6 methyl-4, hydroxy-4 'insoluble diphenylamine.

After recrystallization from alcohol and drying under vacuum, the product melts at 192 ° C.

b) Preparation of 2-nitro, 4-methyl, 6-amino-4-hydroxy-diphenylamine.

After adding 0.038 mole (11 g) of 2,6-dinitro, 4-methyl, 4-hydroxy-diphenylamine to 200 ml of alcohol supplemented with 20 ml of ammonia at 22 ° B, bubbled with l hydrogen sulfide for 30 minutes in this solution. The reaction medium is then brought to reflux for 2 hours. The alcoholic solution is filtered after cooling and then evaporated to dryness under vacuum. The residue is taken up in 150 ml of 2N hydrochloric solution. It is filtered to remove the insoluble material and then the filtrate is made alkaline with ammonia. The expected product precipitates. It is drained, washed with water, then recrystallized from ethanol, it melts at 163 ° C.

Analysis Calculated for Found C13H13N3 ° 3, C% 60.23 60.03 10 H% 5.02 5.11 N% 16.22 16.25 0% 18.53 18.55 PREPARATION EXAMPLE 4

Preparation of N-ft-hydroxyethylamino-2, nitro-3, 15 methyl-5 aniline. . .

nh-ch2ch2oh o, h —— hh-> 20 ^

Cl HH-CH2CH2OH

25 02n — Xs-no2 - ^ o2n-f ^> - m2 - ^

| h2n-ch2ch2oh K JJ

T

tH3 CH3

30 NH-CHoCH, 0H

î

° 0N -K / l-NH

. I

/ »X / 26« a) Preparation of 2,6-dinitro-methyl-4, N-ft-hydroxy-ethylaniline.

I 0.35 mole (76 g) of 4,6-dinitro-methyl 4-chlorobenzene in 150 ml of ethanolamine is added little by little, with stirring, over 10 minutes, cooling the reaction medium if necessary so as not to exceed 75 ° C. When the addition is complete, stirring is continued for 5 minutes and then the reaction medium is poured into 600 g of ice water. The expected product precipitates. It is drained, washed with water, and then recrystallized from ethanol. After drying under vacuum, it melts at 131 ° C.

Analysis Calculated to Found C9H11N3 ° 5 C% 44.81 44.93 H% 4.56 4.49 15 N%. 17.43 17.32 0% 33.20 33.00 b) Preparation of N-fh-hydroxyethylamino-2, nitro-3, methyl-5 aniline.

After adding 0.4 mole (96.4 g) of 2,6-dinitro-2q methyl-4, N- fi> -hydroxyethylaniline to 1500 ml of absolute alcohol supplemented with 160 ml of ammonia at 22 ° B we make bubble hydrogen sulfide for 30 minutes in this alcoholic solution. The temperature rises to 50 ° C then decreases. The bubbling is then stopped and the reaction medium is brought to reflux for one hour. After concentrating the alcoholic solution to 300 ml, the mineral salts are filtered. The filtrate is then evaporated to dryness. The residue obtained in the form of a red oil is redissolved in 80 ml of ethanol at 96 °. After adding 170 ml of hydrochloric ethanol (730 moles of hydrochloric acid per liter of alcohol) and cooling to 0 ° C. the expected product is drained, which precipitated in the form of the hydrochloride. After washing with alcohol, this hydrochloride is dissolved in 300 ml of water. By neutralizing this solution with ammonia, N-β-hydroxyethylamino-2, nitro-3, methyl-5 aniline is precipitated. This product is drained, washed with water and then recrystallized from alcohol at 96 °. After drying under vacuum, it melts at 96 ° C. / f * 27, Analysis Calculated for Found SH13N3 ° 3 C% 51.18 51.09 H% 6.16 6.21 5 N% .19.91 20.06 0% 22.75 22.75 PREPARATION EXAMPLE 5

Preparation of amino-2, nitro-3, methyl-5 N- /% - hydroxy-? ethyl aniline.

10 nh2

0oN -1 NH-CH-CH-OH

2 I 2 2

T

15 6h3

NH0 NEL

J2 Γ2 02N — i "] - NH Tosyl - N-Tosyl 20 kJJ> ΓΗ ch2ch2oh * ch3 ch3 NH2

25 * JL

0oN - ^ - NH-CHo-CHo0H

2 | 2 2 * CH3 30 a) Preparation of amino- ^, nitro-3, methyl-5 N-ß> -hydroxy “ethyl, N-tosyl aniline.

0.087 mol (28 g) of amino-2, nitro-3, methyl "5, li-tosylaniline are dissolved in 85 ml of DMF previously heated in a boiling water bath. 9.7 g of quicklime 35 are then added. over a period of 30 minutes, 0.174 mole (21.75 g) of glycol hydrobromine is introduced little by little and with stirring, while maintaining the heating in a boiling water bath. After 1 1/2 h / v 28 c> on the hot reaction medium is filtered and then the filtrate is poured into 250 ml of ice water, the expected product precipitates, drained, washed with water and dried under vacuum after recrystallization from acetic acid and drying under vacuum it melts 5 at 20 ° C.

Analysis Calculated for Found

C16H19N3 ° 5S

C% 52.60 52.47 • H% 5.21 5.14 10 N% 11.51 11.41 0% 21.92 21.81 S% 8.77 8.68 b) Preparation of linolino-2, nitro-3, methyl-5 N-ft-hydroxy-ethylaniline.

0.0458 mol (16.7 g) of amino-2, nitro-3, methyl-5, N-fè-hydroxyethyl, N-tosyl aniline are introduced with stirring into 167 ml of concentrated sulfuric acid added 48 ml of water. The mixture is heated for 1 hour in a boiling water bath and then poured over 850 g of crushed ice. The sulfuric solution 20 is neutralized using ammonia. The expected product precipitates. After spinning, washing with water, drying under vacuum and recrystallization from ethanol, it melts at 166 ° C.

Analysis Calculated for Found C9H13 ° 3N3 25 C% 51.18 50.93 H% 6.16 6.20 N% 19.91 19.85 / 0% 22.75 22.68 // f 29 “EXAMPLE PB PREPARATION 6

Preparation of amino-2, nitro-3, methyl-5, N-methylaniline OT2 jNH2

5 ° 2N-- NH2- ^ ° 2N- | - NH

v V ^ 'ch3 CH3 10 NH2 nh2 O, N A- N-Tosyl — J O, N —- NHCH, 2. I | 2 I 3 V '' 3 v 15 CH3 CH3 a) Preparation of amino-2, nitro-3, methyl-5, N-tosyl-aniline.

0.15 mol (25.05 g) of amino-2, nitro-3 and 5-methyl aniline are dissolved in 75 ml of pyridine and then little by little, with stirring, between 40 and 45 ° C., 0.165 mole (31.4 g) of paratoluenesulfochloride. When the addition is complete, stirring is continued for 1 hour at 45 ° C., then the reaction medium is poured into 450 ml of ice water and neutralizes the pyridine using hydrochloric acid. The expected product which is precipitated is filtered off, washed with water and then recrystallized using acetic acid. After drying under vacuum, it melts at 184 ° C.

Analysis Calculated for Found

C14H15N3 ° 4S

C% 52.34 52.33 30 H% 4.67 4.69 N% 13.08 12.89 0% 19.94 19.86 S% 9.97 10.12 b) Preparation of amino-2 , 3-nitro, 5-methyl, N-methyl, N-tosyl aniline.

0.246 mole (79 g) of amino-2, nitro-3, methyl-5 N-tosylaniline is dissolved in 260 ml of normal sodium solution at 40 ° C. X

30

0.286 mol (30 ml) of methyl sulphate is gradually added over 3 hours, maintaining the temperature in the vicinity of 40 ° C. Towards the end of the addition of methyl sulfate, the pH of the alkaline reaction medium is maintained by simultaneously adding 20 ml of normal sodium solution. After cooling to around 10 ° C., the expected product which is precipitated is filtered off. It is washed with a normal sodium solution and then with water and it is recrystallized using acetic acid.

. After drying under vacuum, it melts at 208 ° C.

10 Analysis Calculated for Found

C15H17N3 ° 4S

C% 53.73 53.81 H% 5.07 5.11 N% 12.54 12.39 15 0% .19.10 19.01 S% 9.55 9.41 c) Preparation of the amino- 2, 3-nitro, 5-methyl N-methyl aniline.

In 354 ml of concentrated sulfuric acid added with 60 ml of water and previously heated to 90 ° C., 0.1785 mole (59.8 g) of amino is added little by little, with stirring over 1 hour 15 minutes. -2, nitro-3, N-methyl, N-tosyl aniline. Heating is continued for another 15 minutes and then the reaction medium is poured into 1.5 kg of ice water. The expected product precipitates in the form of sulfate. We wring it out, wash it with a little ice water. The sulfate is suspended in water and by addition of ammonia with stirring, the amino-2, nitro-3, methyl-5, N-methylaniline are released which after spinning, washing with water and drying under vacuum bottom at 113 ° C. j · 30 Analysis Calculated for Found! C8H11N3 ° 2 C% 53.04 53.12 H% 6.08 6.13 N% 23.20 23.14 / 35 0% 17.68 17.54 7 7 r 31 PREPARATION EXAMPLE 7

Preparation of amino-2, nitro-3, N-methylaniline NH2 NH2 5 - OT2 -)> ° 2N-f ^ S | - nhso2 - <^> - CH3 NH. NH.

10 I 2 2 ^ o2n —- n-so2. ^ Y-CH3 ° 2n "Y ^ j- nhch3 l ^ JJ |, H '-'> 15 a) Preparation of amino-2, nitro-3, N -tosylaniline

0.1 mol (15.3 g) of 3-orthophenylene diamine nitro is dissolved in 50 ml of pyridine and then gradually added, with stirring, between 40 and 45 ° C. 0.11 mol (21 g) of paratoluenesul -chloride. When the addition is complete, stirring is continued for 20 minutes and then the reaction medium is poured into 250 ml of ice water. The expected product precipitates. It is wrung, washed with water and recrystallized using acetic acid. It melts at 195 ° C.

b) Preparation of amino-2, nitro-3, N-methyl N-tosylaniline 0.093 mol (28.5 g) of amino-2, nitro-3, N-tosylaniline are dissolved in 112 ml of sodium solution normal at 30 ° C.

0.122 mol (15.45 g) of methyl sulphate is added little by little, with stirring, over 1 hour 30 minutes. The temperature is maintained between 35 and 40 ° C. Towards the end of the addition of the methyl sulphate, 3 ml of ION sodium solution are gradually added simultaneously in order to maintain the alkaline pH.

The reaction medium is cooled and then the expected product which is precipitated is filtered off. It is washed with a normal sodium solution and then with water and alcohol. After recrystallization in acetic acid and drying under vacuum, it melts at / ΐ83 ° ο.

»32 m c) Preparation of amino-2, nitro-3, N-methylaniline

In 230 ml of concentrated sulfuric acid added with 23 ml of water and previously heated to 90 ° Cf 0.0716 mole (23 g) of 5-no-2 friend is gradually added over 10 minutes, with stirring , 3-nitro, N-methyl, N-tosylaniline. When the addition is complete, the reaction medium is kept for 5 minutes at 90 ° C. and then poured onto crushed ice. The acidic aqueous solution obtained is made alkaline with ammonia to precipitate the expected product. It is drained, washed with water and recrystallized from 40 ml of alcohol. After drying under vacuum, it melts at 93 ° C.

Analysis Calculated to Found c7h9n3o2 C% 50.30 50.51 15 H%. 5.39 5.31 N% 25.15 25.04 0% 19.16 19.02 PREPARATION EXAMPLE 8

Preparation of N- / 2> -hydroxypropylamino-2 hydrochloride 3-nitro, 5-methyl aniline nh-ch2choh-ch3 o2n—- NH2 25, HCl

Ih3 0CH3 NH-CH2-CHOH-CH3 30 02N-- N ° 2 _ ^ 02N-- N02 t NHo-CHo-CH0H-CH- |

2 2 3 KJ

CH3 'ch3 35 NH-CH2-CHOH-CH3 o2n-- nh2 f / _, HCl / -ff V / 33 * a) Preparation of 2,6-dinitro-methyl-4 N- | ^ -hydroxy propyl aniline

0.05 mole (10.6 g) of 2,6-dinitro-4-anisole is gradually introduced, with stirring, into 30 ml of amino-1 propa-5 nol-2. The reaction medium is brought to 60 ° C. for 30 minutes and then poured into 120 g of ice water. The expected product precipitates. It is wrung, washed with water and then recrystallized using a hydroalcoholic mixture. After drying under vacuum. * it melts at 80 ° C.

10 Analysis Calculated for Found C10H13N3 ° 5 C% 47.06 47.05 H% 5.13 5.10 0% 31.34 31.44 15 N% 16.47 16.36 b) Preparation of N- ß hydrochloride > -hydroxypropylamino 2-nitro-3, methyl-5 aniline.

0.02 mole (5.10 g) of 2,6-dinitro-methyl 4 N- (!? - hydroxypropyl aniline) is dissolved in 40 ml of absolute alcohol containing 0.1 mole (8.6 g) of cyclohexene. 2.5 g of Pd / C at 10% are added, then the alcoholic solution is brought to reflux for 10 minutes. After cooling, the reaction medium is filtered to remove the catalyst. About 20 ml of alcohol are removed in vacuo then 7 ml of ethanol saturated with 25 hydrochloric gas are added, after cooling to -10 ° C. the expected product crystallizes out, is wrung, washed with a little alcohol and then recrystallized using absolute alcohol After drying under vacuum, the expected hydrochloride melts with decomposition between 145 and 150 ° C.

30 Analysis Calculated for Found C10H15N3 ° 3 / HC1 C% 45.89 45.96 H% 6.12 6.14 35 N% 16.06 16.19 0% 18.36 18.43

Cl% 13.58 13.76 34 PREPARATION EXAMPLE 9

Preparation of N- β> hydrochloride, jf-dihydroxypropylamino-2, nitro-3 / methyl-5 aniline.

NH-CHo-CH0H-CH o0H

I 2 2 5 02N-- NH2, HCl fcH3 10

0CH3 NH-CH2CHOH-CH2OH

0oN --N0_ 0oN - N0o 2 I 2 2 | 2

U. DD -> u DD

NH2CH2CHOHCH2OH X / · - K ^ 3

NH-CH2CHOH-CH2OH

o, n —- nh0 20 Δ I Δ ^, HCl CH 3 a) Preparation of dinitro-2,6-methyl-4 N- t> t Y-dihydroxy 25 propylaniline.

0.05 mol (10.6 g) of 2,6-dinitro-4-methyl anisole is dissolved in 50 ml of absolute alcohol. To this solution is gradually added, with stirring, 0.1 mole (9.1 g) of amino-l propane-diol-2,3. The solution is refluxed for 3 hours 30 minutes. The alcohol is removed under vacuum and 40 ml of ice water are added to the residual red oil. The expected product crystallizes. It is wrung out and washed with water. After recrystallization using a hydroalcoholic mixture and drying under vacuum, it melts at 118 ° C. / 35 35 * Analysis Calculated for Found c10h13n3 ° 6 C% 44.28 44.33 H% 4.80 4.80 5 N% 15.50 15.72 0% 35.42 35.80 b) Preparation of hydrochloride N- (S, Y-dihydroxypropyl amino-2, nitro-3, methyl-5 aniline

0.03 mol (8.13 g) of 2,6-dinitro-methyl-4 10 N-H >> Y-dihydroxypropylaniline is dissolved in 60 ml of absolute alcohol containing 12.3 g of cyclohexene. 4 g of 10% Pd / C are added. The alcoholic solution is brought to reflux for 10 minutes. After cooling, the reaction medium is filtered to remove the catalyst. About 30 ml of alcohol are removed in vacuo and then 8 ml of ethanol saturated with hydrochloric gas are added. After · -cooling to -10 ° C the expected product precipitates. The hydrochloride is drained, washed with a little ethyl ether and dried under vacuum. After two recrystallizations from absolute alcohol, the expected product melts with decomposition between 130-134 ° C.

Analysis Calculated for Found C10H15N3 ° 4 'HC1 C% 43.24 43.18 H% 5.77 5.82 25 N% 15.14 15.30 0% 23.06 23.10 /

Cl% 12.79 12.88 / d / 30 / - 36 PREPARATION EXAMPLE 10

Preparation of N-methylamino-2, nitro-3, methyl-5 aniline.

nhch3 '5 ^ ~~ f |) - H “2

X

10

Cl NHCH3 nhch3 ° 2N —N02 _-N “iTil- * 1! -NH2

^ I l \ U - *. I

15 1 ^ NH2CB3 St 'ch3 ch3' ch3 a) Preparation of 2,6-dinitro-methyl-4, N-methylaniline 40 ml of a 33% solution of methylamine in ethanol are added little by little , with stirring, 0.05 mole (18 g) of 2,6-dinitro-4 methyl-chlorobenzene. The temperature rises to 50 ° C. and the expected derivative precipitates immediately. When the addition is complete, stirring is continued for 5 minutes, then the 2,6-dinitro-2,6-methyl, N-methylaniline is filtered off and washed with water, which, after recrystallization from alcohol and drying under vacuum at 132 ° C. .

Analysis Calculated to Found 25 C8H9N3 ° 4 C% 45.50 45.40! . _ H% 4.27 4.38 N% 19.91 19.94 0% 30.33 30.26 30 b) Preparation of N-methylamino-2, nitro-3, 5-methyl aniline.

0.0407 mole (8.6 g) of 2,6-dinitro-4,4-methyl-N-methylaniline is dissolved in 45 ml of alcohol containing 0.203 mole (16.7 g) of cyclohexene. 4.3 g of 10% Pd / C are added. The mixture is brought to reflux for 20 minutes and then the boiling reaction medium is filtered to remove the catalyst. By cooling the filtrate, the expected product crystallizes. It is wrung ^ ', / 37, washed with a little alcohol and recrystallized from ethanol. After drying under vacuum, it melts at 131 ° C.

Analysis Calculated for Found C8H11N3 ° 2 5 C% 53.04 53.07 H% 6.08 6.06 m 23.20 23.26 0% 17.68 17.57 PREPARATION EXAMPLE 11 10 Preparation of N-fo -diethylaminoethyl-2-amino, 3-nitro, 5-methyl aniline.

^ 2H5 NH-ch9-ch „-n A. C2H5 15 o2n. —Η — nh2

V

CH3 20 Cl C2H5

I NH-CH2CH2-N

° 2N —rTl ~ N02 _> / 2H5 I ^ C2H5 H_N-CH_-ClÎi-N 00 »γχΝ-N00 \ 2 2 2 V 2 j 2

V c * t J

25 CH g N / CH 3 / ° 2Η5 __ ^ nh-ch2-ch2-n

30 cyclohexene I

Pd / C 10% 0 „N - NHo 2 .2 / X ^ 3/35 38. a) Preparation of 2,6-dinitro-methyl-4, N, N-diethyl-amino ethylaniline.

0.05 mole (10.8 g) of 2,6-dinitro-4-methyloblorobenzene in 25 ml 5 of Ν, Ν-diethylaminoethylamine is added little by little, with stirring over 10 minutes, while cooling the reaction medium so as not to not exceed 50 ° C. When the addition is complete, stirring is continued for 5 minutes and then the reaction medium is poured into 150 ml of ice water. The expected product precipitates. It is drained, washed with water and recrystallized from ethanol. After drying under vacuum, it melts at 72 ° C.

Analysis Calculated to Found C13H20N4 ° 4 C% 52.70 52.59 H% 6.76 6.79 15 N%. 18.92 '18.99 0% 21.62 21.50 a) Preparation of N- / 3-diethylaminoethyl amino-2, nitro-3, methyl-5 aniline.

0.03 mole (8.52 g) of 2,6-dinitro-methyl 4,20 Ν, Ν-diethylaminoethylaniline is dissolved in 42 ml of ethanol containing 0.15 mole (12.3 g) of cyclohexene and 4, 3 g of 10% Pd / C. The reaction mixture is brought to reflux for 30 minutes and then filtered while boiling to remove the catalyst. After cooling, 30 ml of hydrochloric ethanol (containing 7 moles of hydrochloric gas per liter) are added to the filtrate.

The expected product precipitates in the form of the hydrochloride. The hydrochloride is drained, washed with a little acetone and then * dissolved in 30 ml of water. By neutralization of this aqueous solution with ammonia, the N- / 3-diethylaminoethylamino-2, nitro-3, methyl-5 aniline is precipitated. This product is drained, washed with water and then recrystallized from 95 ° alcohol. After drying under vacuum, it melts at 45 ° C.

Analysis Calculated for Found C13H22N4 ° 2 35 C% 58.65 58.75 H% 8.27 8.29 /! N% 21.05 21.03 A / | 0% 12.03 11.92 ij / 39 PREPARATION EXAMPLE 12

Preparation of N - & - hydroxyethylamino-2, nitro-3 aniline.

NH-CH0-CH0OH

ί, 5 ° 2N ~ fi] —NIi2

Cl NH-CHoCHo0H

»I I

° 2 N —- N02_> ° 2 tLY ^ 7) -N02 --->

JJ H2N-CH2CH2OH M

15 nh-ch2ch2oh O -NH, 20 a) Preparation of dinitro 2,6-N - hydroxyethylaniline

0.05 mol (10.125 g) of 2,6-dinitro-chlorobenzene in 25 ml of ethanolamine is gradually added with stirring, while cooling the reaction medium so that the temperature does not exceed 50 ° C. The reaction medium is poured into 100 ml of ice water. The expected product precipitates. It is wrung, washed with water, recrystallized from ethanol. After drying under vacuum, it melts at 100 ° C.

2o Analysis Calculated for Found C8H9N3 ° 5 C% 42.29 42.36 H%. 3.96 4.05 N% 18.50 18.44 / 35 0% 35.24 35.30 /// 40 b) Preparation of N-ß-hydroxyethylamino-2, nitro-3 aniline.

After adding 0.04 mole (9.1 g) of dinitro-2,6, Ν-β-hydroxyethylaniline to 160 ml of absolute ethanol added 5 of 16 ml of ammonia at 22 ° B is bubbled with hydrogen sulfide for 30 minutes in this alcoholic solution. The bubbling is stopped then the reaction medium is brought to reflux for 2 hours. The boiling alcoholic solution is filtered to remove the mineral salts and then the filtrate is evaporated to dryness. The red residue obtained is redissolved hot in alcohol. By cooling the expected product crystallizes. It is wrung, washed with a little cold alcohol and dried under vacuum. It melts at 78 ° C.

Analysis Calculated for Found 15 · C8H11N3 ° 3 C% 48.73 48.88 H% 5.58 5.61 N% 21.32 21.46 / 0% 24.37 24.49 s / 20 / «/ \ / i 41, The various trade names used in the preceding examples are explained in more detail below: CARBOPOL 934: Polymer of acrylic acid of PM 2 to 3 million sold by 5 Goodrich Chemical Company.

CEMÜLSOL NP ^ î Nonylphenol with 4 moles of ethylene oxide sold by Rhône Poulenc.

CEMÜLSOL NPg: Nonylphenol with 9 moles of ethylene oxide sold by Rhône Poulenc.

10 ALFOL C1 / r / 1Q Cetylstearyl alcohol sold by 16 18 (50/50): the Condëa Company.

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

CEMÜLSOL B î Ethoxylated castor oil sold 15. by Rhône Poulenc.

MASQÜOL DTPA: Sodium salt of diethylene triamine pentacetic acid.

TRILON B î Sodium salt of ethylenediaminetetraacetic acid. / /

Claims (15)

42 1. Dye composition for keratin fibers, characterized in that it contains at least one dye corresponding to formula (I); c NHR ~ JL 02N -11-- NHR1 I (I) V 10 z in which R1 and R2 denote independently of one another a hydrogen atom, an alkyl group, a mono- or polyhydroxylated alkyl group, a alkyl group substituted by an alkoxy group, an aminoalkyl group in which the amino group can optionally be mono- or disubstituted by an alkyl group, the radical R2 can also denote a phenyl group, or phenyl substituted by an alkyl, hydroxyl or amino group , Z denotes a hydrogen atom or an alkyl group or their cosmetically acceptable salts. 2. Dye composition for keratin fibers according to claim 1, characterized in that it contains at least one dye of formula (I) in which Z denotes hydrogen or methyl, R2 denotes hydrogen, methyl, ethyl, propyl, butyl, en -hydroxyethyl, ß-hydroxypropyl, [h, ^ -dihydroxypropyl, p> -methoxyethyl, N, N-diethylamino-ethyl, p-hydroxyphenyl, R ^ denotes hydrogen, methyl, ethyl or -hydroxyethyl. 3. Composition according to claim 1, characterized by - 3q the fact that the dye corresponds to formula (I) in which Z denotes methyl or in which R2 is other than hydrogen. 4. Dye composition according to any one of claims 1 to 3, intended for dyeing human hair, characterized in that it contains in a cosmetically acceptable medium at least one compound of formula (I) in proportions from 0.001 to 5% by weight f (f. 43% y ' 5. Dye composition according to any one of claims 1 to 4, characterized in that it contains a solvent chosen from water, lower alkanols, polyols, glycols or glycol ethers or their mixtures. . 6. Composition according to any one of claims 1 to 3, characterized in that it contains, in addition to cosmetic adjuvants chosen from surfactants, thickeners, penetration agents, sequencers, film-forming agents, buffers, perfumes, basifying or acidifying agents. 7. Composition according to any one of claims 1 to 6, characterized in that it has a pH between 3 and 11.5 and preferably between 5 and 11.5. 8. Composition according to any one of claims 1 to 4, intended to be used for direct dyeing of the hair, characterized in that it contains, in addition to other direct dyes chosen from azo, anthraquinone dyes, the nitres derivatives of the benzene series other than those of formula (I). 9. Composition according to any one of claims 1 to 4, intended to be used as styling lotion, characterized in that it is in the form of an aqueous, alcoholic or hydroalcoholic solution, containing at least 25 a cosmetic resin. 10. Composition according to any one of claims 1 to 4, intended to be used for oxidation dyeing, characterized in that it additionally contains at least dye precursors by oxidation. 30 11 · Composition according to claim 10, characterized in that it has a pH between 7 and 11.5 and that it additionally contains a reducing agent. 12. Process for dyeing keratin fibers, characterized in that a composition as defined in any one of claims 1 to 11 is applied to the fibers, it is left to stand for 5 to 70 minutes, / rinsed, optionally washed, rinsed again and dried ^ / 7/44. * / 13. Process for coloring keratin fibers, characterized by the fact that a composition as defined in claim 9 is applied to the washed and rinsed fibers, which is optionally rolled up and dried. 14. Process for dyeing keratin fibers, ca characterized by the fact that a composition as defined in claims 10 or 11 is applied to the fibers, optionally added with an oxidizing agent which is left to stand for 10 to 50 minutes, rinse, optionally wash with shampoo, rinse again and dry. 15. Nitro-orthophenylenediamine derivatives, characterized in that they correspond to the formula: NHR'2 15. J. 00N - ('s' η- NHR' 1 V 20 in which R '^, R'2 and z' have the meanings indicated in claim 1 or 2, respectively for R ^, R2 and Z under provided that R'R'2 and Z 'cannot simultaneously denote hydrogen, and when R'2 denotes methyl, R' ^ and Z 'rte can both denote simultaneously hydrogen and when Z' denotes methyl at least one of groups R '^ or R'2 is different from hydrogen and their cosmetically acceptable salts Drawings: - p / rrs'iGS ... parts including - J -........ pc? e à * ....... - r; ^ rcrip- "on 3 ..." L * v --2: ....... d'-tcriptif LuXSfnhr:: rr. i ^