LU82861A1 - NOVEL NITRO-PARAPHENYLENEDIAMINES, THEIR PREPARATION PROCESS AND THEIR USE IN DYEING KERATINIC FIBERS - Google Patents

Description

* _ 2.4386 ow Patent application i October 16, 1980 Designation of the inventor —-1 - »- 1— (') The undersigned Μ ο n. sir. Charles Mu.nc.he.n.,. patent attorney at I nvpm bourg lia, boulevard Prince-Henri acting as depositor - agent of the depositor - P) the company has η ο nymedi te: L1 OREAL, 14 Rue Royale, 75008 Paris, France (J) de l invention relating to: "New nitro-paraphenylënediami born, their preparation process and their use in fiber dyeing designates as inventor (s): l) Name and first names. Madam ..... Andrée ..... BUG A UT ...... (born ..... ORMANÇEYJ .................................... .............................

Address ......................... l .. = ...... Street ...... des ...... A.bo.nd.an.ces., ...... 92100 Boulogne-Billancourt.

France 2.) Last and first names 11.9..Π..§..1..§.Μ.Μ. ™ .Q..TT.E.BJr.X ...................................... .................................................. ..............................

Address Ruede Ta Source .., 95130 Francon ..... France .....

3. Surname and first names ............................................. .UJJ1.LLLL .............................................. ........................-.-.-..................... .............................................

Address ................................................. ........... U111111L ...................................... .................................................. ....-............................................

He affirms the sincerity of the aforementioned indications and declares to assume full responsibility for them.

....... Luxembour.g ........................................ ..... f the 19 no.vemb.re ...................... 19 ... 80 .., ..

(') Last name, first names, firm, address.

I1 \ Klr "m. nr ^ nnms and nrfres.ce rfii <iénosnnt.

V

i ï.hieb

3733/19 - GD / MB

Public limited company called: L'OREAL

"

New nitro-paraphenylenediamines, their preparation process and their use in dyeing keratin fibers.

Invention of i t ♦ t v 1 l «

New nitro-paraphenylenediamines, their preparation process and their use in dyeing keratin fibers.

The present invention relates to new derivatives of nitro-paraphenylenediamine, to their use in dyeing keratin fibers and in particular to human hair and to their process of preparation.

As is well known, the hair is often given direct coloring or additional reflections in the case of oxidation coloring using nitro derivatives of the benzene series. The use of nitro-paraphenylenediamines, such as more particularly nitro-paraphenylenediamine, has already been recommended, both in direct dyeing and in oxidation dyeing.

The complete harmlessness of nitro-paraphenylenediamine has, however, been questioned in recent years and attempts have therefore been made to replace this colorant in hair dye compositions. Nitro-paraphenylenediamine is often used as a hair dye in the formulation of warm shades such as mahogany, more or less red coppery brown so that for such formulations it is essential to find other direct dyes which make it possible to impart keratin fibers. red shades. The Applicant has discovered new nitro-paraphenylenediamines which can bring red in hair dye formulations.

It also found that the hair dyes 25 thus obtained using this new class of dyes exhibit good stability to light and to washing.

In addition, these dyes have the great advantage of being well preserved in the supports usually used in dyeing oxidation compositions such as in particular in an alkaline medium in the presence of reducing agents, which makes it possible to combine them with the so-called dyes. oxidation to obtain / nuances rich in reflections. / f / - 2

In addition to their remarkable dyeing and preservation qualities, the dyes selected by the applicant have good safety. These compounds present in particular the advantage of being non-mutagenic. As is well known, the non-mutagenic character of dyes is currently appreciated using the Ames test on Salmonella typhimurium. Tests carried out on strains TA 1535, TA 1537, TA 1538, TA 98 and TA 100 with or without Sg mix activated with Arrochlor 1254 have made it possible to establish this fact.

The present invention therefore relates to new nitro-paraphenylenediamines as well as to their process of preparation.

The invention also relates to dye compositions ’containing these nitro paraphenylenes diamines, for kera-tin fibers and in particular for human hair which can be used for direct hair coloring or for coloring by oxidation.

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

The nitro-paraphenylenediamines according to the invention correspond to the following formula (I): NHR1> I J "R2 — Λ

25 I

(I) NH2 in which denotes an alkyl radical, an alkyl radical, mono or polyhydroxy, an aminoalkyl radical whose amino group may optionally be mono or disubstituted by an alkyl radical; R2 denotes an alkyl radical, and the cosmetically acceptable salts of these compounds.

In the above formula the alkyl radical preferably denotes a radical having from 1 to 4 carbon atoms.

Among the groups which are more particularly preferred, one can cite for the group R ^ the meanings methyl // · f • '' 3 ethyl, g-hydroxyethyl, ß-hydroxypropyl, ß, γ-di-hydroxy-propyl, Ν, Ν- diethylaminoethyl and for R2 the methyl meaning.

Compounds giving particularly remarkable results correspond to formula (II):

NHR

* 3C ~ f] 10 ^^^ · Ν02 (II) nh2 in which R denotes a methyl radical, a β-hy-droxyethyl radical or else a Ν, Ν-diethÿlamino ethyl radical. In addition to their good dyeing properties mentioned above, these compounds are particularly stable in media usually used in oxidation dyeing and have the advantage of being non-mutagenic according to the Ames test.

Another subject of the invention consists of the process for the preparation of the compounds of formula (I). These compounds can be prepared by direct action of haloalkanes of formula R ^ X in which X denotes halogen and R ^ has the meanings alkyl or substituted alkyl indicated above or an alkyl sulphate such as methyl or ethyl sulphate on 25 alî <yl-2 nitro-5 paraphenylene diamine, for example in an alcoholic medium, at reflux, in the presence of sodium carbonate.

Another process can consist in reacting halo-genoalkanes of formula XR ^ (X and having the same meanings as those indicated above) or t30 alkyl sulfates on 3-alkyl, N-arylsulfonylamino-4 nitro-6 anilines and hydrolyzing the substituted sulfonamides thus obtained.

The alkyl-3, N-arylsulfonylamino-4, nitro-6 anilines used as intermediates are obtained by reacting in pyridine solution between 30 and 60 ° C and in a molar ratio close to or equal to 1, benzenesulfochloride or paratoluenesulfochloride on 2-alkyl-5-nitro para-phenylene diamine. The reaction is selective under these conditions and / only the amine function in meta of the nitro group reacts ./^

T

i J

4 The action of haloalkanes of formula XR ^ or of al-coylsulphates such as methyl or ethyl sulphate can be carried out in an alkaline aqueous medium between 40 and 60 ° C., in dimethylformamide in the presence of alkali hydroxides or alca -5 lino-earthy for example in the presence of lime.

The hydrolysis of the derivatives thus substituted can be carried out by hydrochloric acid between 80 and 100 ° C and preferential-; Lement with concentrated sulfuric acid near 0 ° C.

In the particular case where -CH2CH2QH designates the preferred operating mode consists in reacting the chloro-chloroformate on 2-alkyl-5-nitro-paraphenylenediamine then in hydrolyzing with sodium hydroxide or potassium hydroxide solution the carbamate thus obtained.

The compositions according to the invention are characterized in that they contain, in a cosmetically acceptable solvent medium, at least one compound corresponding to formula (I) and can be used for the direct dyeing of keratin fibers or for the oxidation dyeing of these fibers in which case these compounds of formula (I) give additional reflections to the basic dye obtained by oxidative development of oxidation dyes.

These compositions contain the compounds according to the invention 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 can contain anionic, cationic, nonionic, amphoteric surfactants or their mixtures. These surfactants are present in the compositions of the invention in proportions included. 3q 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 it is also possible to add organic solvents to the compositions to dissolve compounds which are not sufficiently soluble in water. Among these solvents there may be mentioned, lower alkanols such as / ethanol and isopropanol, polyols such as glycerol 5 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 methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers. having the function of thickener such as more particularly derivatives of acrylic acid. It is also possible to use,. 15 read mineral thickening agents such as bentonite.

These thickening agents are preferably present in the 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.

The compositions according to the invention may also contain various adjuvants usually used in hair dye compositions and in particular penetration 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.

s30 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 carbonate, potassium or ammonium carbonate, sodium or potassium hydroxides, alca-35 nolamines such as mono, di- or triethanolamine,, alkylamines such as ethylamine or triethylamine or, using an acidifying agent such as phosyl / 6 acids. phoric, hydrochloric, tartaric, acetic, lactic or citric.

When the compositions are intended to be used in a direct hair dyeing process, they may contain, in addition to compounds according to the invention, other direct dyes such as azo or anthraquinone dyes, such as for example tetraaminoanthra- quinone, nitro dyes from the benzene series different from the compounds of formula (I) and more particularly the following 10 compounds: 2-methyl-6-nitro aniline, 3-amino-4-phenol, 3-nitro-Ng-hydroxyethylamino -4 phenol, nitro-3 amino-4 methyl-6 phenol, 15 amino-3 nitro-4 phenol, amino-2 nitro-3 phenol, nitro-3, Ng -hydroxyethylamino-6 anisole, N-β, γ -dihydroxypropylamino-3. nitro-4 anisole, (N-methylamino-3, nitro-4) phenoxyethanol, 20 (N-methylamino-3, nitro-4) phenyl, β, γ -dihydroxypropyl-ether, N, N '(- g -hydroxyethyl) nitro paraphenylenediamine, nitro-3, N'-methylamino-4, N, N- (di-ß -hydroxyethyl) aniline. 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 are applied to the keratin fibers for an exposure time of 5 to 40 minutes, then the fibers are rinsed, optionally washed, rinsed again, 30 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 wet hair previously washed, rinsed and possibly coiled. then dried.

The cosmetic resins used in the setting lotions can be in particular polyvinylpyrro-5 lidone, the copolymers 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 enter into the compositions of the invention at a rate of 1 to 3% by weight and preferably from 1 t to 2% by weight based on the total weight of the composition.

When the compositions constitute oxidation dyes, the compounds of formula (I) according to the invention are essentially used with a view to providing reflections to the final dye.

These compositions then contain in association with au. minus a nitro dye of formula (I), dye precursors by oxidation.

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

They can also contain paraaminophenols, for example: paraaminophenol, N-methyl paraaminophenol, chloro-2amino-4 phenol, chloro-3 amino-4 phenol, <30 methyl-2 amino-4 phenol, and their salts .

They can also contain heterocyclic derivatives, for example: 2,5-diamino pyridine, 7-amino benzomorpho-line.

The compositions according to the invention may contain in combination with the dye precursors by oxidation of the couplers well known in the art. at! f 8 The following may be mentioned as couplers: meta-diphenols such as resorcin, 2-methyl resorcin, metaaminophenols such as: metaaminophenol, 2-methyl-5-amino phenol, 2-methyl-N- (3-hydroxyethyl) - 5-amino phenol, 5-hydroxy-6 benzomorpholine and their salts, metaphenylene diamines such as: (2,4-diamino) phenoxyethanol, 6-amino benzomorpholine, / / N- (3-hydroxyethyl) amino-2 amino-47 phenoxyethanol, (diamino-2,4) phenyl 3, γ -di-hydroxypropylether and their salts, metaacylaminophenols, jO metauridophenols, metacarbalcoxyaminophenols such as: 2-methyl acetylamino -5 phenol, 2-methyl ureido-5 phenol, 2-methyl-carbethoxyamino-5 phenol.

Finally, other couplers which can be used in the compositions of the invention may be mentioned: Ι'α-naphthol, the 15 couplers having an active methylene group such as diketonic compounds and pyrazolones and heterocyclic couplers such as 2,4-diamino pyridine, and 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 precursors of dyes 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.

The Applicant has found that the compounds according to the invention are particularly stable in such / compositions. , fJ / J r 9

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 and to 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 hydrogen peroxide, urea peroxide and persalts. In particular, a solution of hydrogen peroxide at 20 volumes 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 or rinse again and dry.

The following examples are intended to illustrate the invention. vention without being limiting. to / f 10 PREPARATION EXAMPLE 1

Preparation of methyl-2, amino ~ 4, nitro-5 Ν-β-hydroxyethyl-aniline.

The reaction scheme is as follows: 5 NH * _X î H3C - "- ^ | + Cl CH2-CH2-0-C -Cl —- ^ N02 10 NH2

O

. NH - C -O - CH2 - CH2C1 NH-CH2CH2OH

15 H3C ___H3C

% ^ - N02 NH2 nh2 2 0 1st stage

Preparation of N - /, ~ (2-methyl, 4-amino-5-nitro-5) phenylj ß-chloroethyl carbamate

0.6 mol (100 g) of methyl-2, amino-4, 5-nitro-aniline and 0.36 mol (50 g) of potassium carbonate "25 are added to 500 ml of dioxane supplemented with 145 ml of water . The mixture is brought to 90 ° C. with stirring and then 0.6 moles (86 g) of chlorethylchloroformate are added gradually over 10 minutes. When the addition is complete, heating is continued for 10 minutes at 90 ° C., the reaction medium is cooled to 15 ° C. and then the expected product is filtered. After washing with a little dioxane, then with water and alcohol the product is recrystallized with dioxane and then dried under vacuum. It melts at 192 ° C. / / f 11 *

Analysis Calculated to Found C10H12N3 ° 4C1 C% 43.87 43.85 * 5 H% 4.39. 4.43 N% 15.35 15.25 0% 23.40 23.60

Cl% 12.98 12.78 read 2nd stage

Preparation of methyl-2, amino-4, nitro-5 N-ß-hydroxy ’ethylaniline.

In 2625 ml of hydroalcoholic solution (30% 1 ^ 0, 70% ethanol) containing 9.32 moles (522 g) of potassium hydroxide is introduced 15 at 55 ° C, with stirring, in 15 minutes, 1.86 mole (510 g ) of N- / methyl-2, amino-4, nitro-5) phenyl? 3-chloroethyl carbamate The temperature rises to 72 ° C. When the addition is complete, a liter of water is added to the reaction medium while maintaining the temperature between 70 and 75 ° C. The hot reaction medium is filtered to remove a slight insoluble material. 5 liters of ice water are added to the filtrate and then neutralized with acetic acid. The expected product precipitates. It is wrung, washed with water, recrystallized from alcohol. After drying under vacuum, it melts at 141 ° C.

2 b _

Analysis Calculated for Found G9H13N3 ° 3 C% 51.18 51.13 30 H% 6.16 6.18 N% 19.91 19.86 0% 22.75 22.64

Preparation example 2 y

35 Preparation of 2-methyl-4-amino-5-nitro Ν-β-diethyl- / 7 aminoethylaniline. / M

f 12

The reaction scheme is as follows: NH2 NH tosyl i z2 “5 5 H3C H3C __C1CH2CH2N; hci

La,,> La -> 'C2Hs

N02 pyndme j N02 CaO

paratoluene i0 NH ^ sulfochloride NH2 ^ isosyl ^ C2H5 H2S04 C2H5

N / __ ^ NH-CH2CH2-N

15 d C2H5 H3C-A XC2h5 B3C ^ \

XX U

. NO N02 20 nh2 nh2 1st stage

Preparation of methyl-3, N-tosylamino - 4, nitro-6 25 aniline.

0.149 mol (25 g) of 2-methyl, 5-nitro-5-phenylene diamine is dissolved in 75 ml of pyridine. 0.161 mole (30.5 g) of paratoluene sulfochloride is added little by little, at 40 ° C. to this pyridine solution, with stirring, and the reaction medium is then maintained at 40 ° C. for 3 hours. The pyridine solution is then poured into 600 g of ice water.

By addition of hydrochloric acid the expected product precipitates. It is wrung, washed with water and then recrystallized from acetic acid. After drying under vacuum, it melts at / 35 174 ° C.

* 13

Analysis Calculated to Found C14H15N3 ° 4S

C% 52.34 52.47 b H% 4.67 4.70 N% 13.08 12.96 0% 19.94 20.05 S% 9.97 9.79 - 9.93 __ 10 2nd stage

Preparation of methyl-3, Ν, Ν-diethylaminoethyl, tosyl amino-4, nitro-6 aniline.

0.02 mole (6.42 g) of methyl-3, N-tosyl-amino-4, nitro-6 aniline and 0.03 mole (1.68 g) of lime are introduced into 5 24 ml of dimethylformamide . The mixture is brought to 80 ° C. and then 0.022 mol (3.8 g) of diethylaminoethyl chloride is gradually introduced, with stirring. The temperature is maintained for 1 hour 15 at 80 ° C., then the reaction medium is poured into 100 ml of ice water. The expected product precipitates. It is wrung there, washed with water and then recrystallized from dio-xanne. After drying under vacuum at 50 ° C it melts at 181 ° C.

Analysis Calculated to Found C20H28N4 ° 4S

25___ C% 57.14 57.21 H% 6.67 6.65 N% 13.33 13.28 0% 15.24 15.34 D0 S% 7.62 7.50 - 7.67 3rd stage

Preparation of methyl-2, amino-4, nitro-5, N-3-diethylaminoethylaniline. ^ 3Ü 0.0426 mol / (17.9 g) of the substituted paratoluene sulfonamide, obtained ty / 14 in the preceding step, is gradually introduced, with stirring, into 90 ml of sulfuric acid at 0 ° C. When the dissolution is complete, the reaction medium is kept for 3 hours at 0 ° C. and then poured onto 700 g of crushed ice. Neutralize with ammonia. The expected product which is precipitated is filtered off. After washing with water, drying and recrystallization from ethyl acetate, it melts at 78 ° C.

Analysis Calculated for Found C13H22N4 ° 2 read C% 58.65 58.50 H% 8.27 8.29 N% 21.05 21.15 0% 12.03 12.15 15 PREPARATION EXAMPLE 3

Preparation of methyl-2, amino-4, nitro-5 N-methyl-aniline.

NH Tosyl (CH-j) 2S04 - CH3

20 I

H C-- :—) H C J. N Tosyl ΧΛ Xjl N0o ^ / ^ N0o 25 1 d 1 NH2 NH2 30 NHCH3

H2S ° 4 H3C

'Ô ^ ./ J 5 // NH2 (j ’' * 15 1st stage

Preparation of methyl-3, Ν, Ν-methyl, tosylamino-4, nitro-6 aniline.

0.05 mol (16.05 g) of 3-methyl-N-tosyl-5 to mino-4, 6-nitro-aniline obtained according to the first step of Preparation Example 2 is dissolved in 110 ml of sodium hydroxide 0.5 N at 40 ° C. To this sodium solution is added dropwise, with stirring 0.055 mole (6.93 g) of dimethyl sulfate, while. now the alkaline pH. After 2 hours at 40 ° C., the reaction medium is cooled and the expected product is filtered off. We wash it. with a cold 0.5 N sodium solution and then with water. After two recrystallizations from acetic acid and drying under vacuum, it melts at 160 ° C.

’2nd step 1 b Preparation of methyl-2, amino-4, nitro-5, N-methyl-aniline.

0.239 mol (8 g) of the substituted paratoluenesulfonamide obtained according to the first step are gradually introduced, with stirring 0.239, into 40 ml of concentrated sulfuric acid at 0 ° C. 20 Dissolution is slow. When the dissolution is complete, the reaction medium is kept for 2 hours at 0 ° C. and then poured onto 400 g of crushed ice. The expected product precipitates in the form of sulfate. The sulfate is drained and then it is dissolved in water. The methyl-2-amino-4, 5-nitro-5 N-methylaniline is precipitated by addition of ammonia. The product is drained, washed with water, dried under vacuum. After recrystallization from benzene it melts at 136 ° C.

Analysis Calculated for Found '3 u C8H11N3 ° 2 C% 53.04 52.91-53.06 H% 6.08 6.18-6.14 N% 23.20 23.09-23.33, 35 0% 17.68 17.75 / 16 EXAMPLE 1

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N-ß -diethylaminoethyl- aniline ........................ ................... 0.25 gb Propylene glycol ......... 5 g '

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

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

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

Water q.s.p ......................... 100 g 10 PH 9r5

This mixture applied 25 minutes at 30 ° C on hair bleached in white gives them after rinsing and shampooing a light red coloration.

EXAMPLE 2 j5 The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N-g-hydroxyethyl-aniline .................... 0 , 3 g

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

Alfol C16 / C18 ..................................... 8g 2 (j Lanette wax .. .................... 0.5 g

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

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

Triethanolamine ................................... 1 g

Water ................. q.s.p ......................... 100 g 25 PH 9 *

This mixture applied 30 minutes at 30 ° C to hair bleached in white gives them, after rinsing and shampooing a light red coloring.

EXAMPLE 3 The following dye composition is prepared: 2-methyl, 4-amino, 5-nitro, N-g-hydroxyethyl-aniline .................... ... 0.25 g

Amino-2, nitro-3 phenol ........................... 0.21 g

Nitro-3, N- g-hydroxyethylamino-6-anisole .......... 0.08 g 3b Tetraaminoanthraquinone ..........'.......... ....... 0.055 g η

Butoxy-2 ethanol .................................. 6 g '17

Propylene glycol ................................... 4 g

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

Monoethanolamine .................................. 6 g

Water ................... gsp ...................... 100 g 5 pH 10.5 .

This mixture applied 20 minutes at 30 ° C to 90% white hair gives them, after rinsing and shampooing a light coppery brown coloring.

. EXAMPLE 4 The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- ß-hydroxyethyl- aniline ..................... ...................... 0.3 g

Amino-2, nitro-3 phenol ........................... 0.4 g Tetraaminoanthraquinone .......... ................. 0.2 g 15 Butoxy-2 ethanol ........................ .......... 6 g

Lauric acid monoethanolamide ................. 1.5 g

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

Hydroxyethylcellulose ............................. 5 g

Monoethanolamine .............................; .... 2 g 20 Water ........... ......... qs ..................... 100 g pH 10.

This mixture applied for 30 minutes at 28 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a medium brown color with red copper-2b reflections.

EXAMPLE 5

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- ß-diethylamino-ethylaniline ........................ .............. 0.39 g * 30 Nitro-3, amino-4, methyl-6 phenol ................. 0 , 2 g

Nitro-3, N'-methylamino-4, N, N- (di- ß-hydroxyethyl) - aniline .......................... ................. 0.4 g

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

Carbopol 934 ...................................... 2 g 3 5 Ammonia at 22 ° B. ................................ 5 g,

Water ................ q.s.p .......................... 100 g a /

pK 10. f W

18

This mixture applied 25 minutes at 28 ° C to bleached hair gives them, after rinsing and shampooing, a very red brown coloring.

EXAMPLE 6 The following dye composition is prepared: 2-methyl, 4-amino, 5-nitro, N-g-hydroxyethyl-aniline ..................... ...................... 0.2 g

Nitro-3, N- g-hydroxyethylamino-4-phenol .......... 0.15 g (N-methylamino-3, nitro-4) phenyl, 3, Y-dihydroxypropyl ether .. ..................................... 1 g Tetraaminoanthraquinone .......... * ................ 0.25 g

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

Propylene glycol ............... * .................. 3 g 'Cemulsol NP4 ......... .............................. 12 g lbCemulsol NPg ................ ...................... 15 g

Oxyethylene alcohol oxyethylenated with 2 moles of ethylene oxide ...................................... ........ 1.5 g

Oxyethylenated alcohol with 4 moles of ethylene oxide ...................................... ........ 1.5 g 20 Water ................ qs .................... ..... 100 g pH 7.2.

This mixture applied for 30 minutes at 28 ° C to 95% white permed hair gives it a dark blond color after rinsing and shampooing.

25 EXAMPLE 7

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- g-hydroxyethyl-aniline ........................ ................... 0.155 g

Nitro-3, 4-amino phenol ........................... 0.5 g 3qN, N '(- 8-hydroxyethyl) nitro para-phenylenediamine. 0.05 g Nitro-3, N'-methylamino-4, Ν, Ν-fdi ß -hydroxyethyljh aniline ........................ .................... 0.2 g

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

Coconut fatty acid diethanolamides ........... 2.2 g 35 Lauric acid .......................... .......... 0.8 g

Ethylene glycol monoethyl ether ........... 2 g.

Mono ethanol amine .................................. 1.05 g /

Water ............ qs ............................. 100 g // pH 8, 8. lÿ '19

This mixture applied 20 minutes at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing an intense red copper coloring.

EXAMPLE 8 The following dye composition is prepared; Methyl- ^ 2, · amino-4, nitro-5, N- 3 -hydroxyethyl- aniline ............................. ............... 0.22 g Resorcin .............................. ......; ..... 0.055 g Metaaminophenol ................................... 0.15 g 10 Paraphenylenediamine ...............'................ 0.05 g

Paraaminophenol .................................... 0.2 'g Methyl-2, N- 3 - hydroxyethylamino-5-phenol .......... 0.05 g Cémulsol NP ^ ................ ... 12 g Cémulsol ΝΡ ^ .... ................................... 15 g 15 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 20 Thioglycolic acid ............ 0.6 g

Water ............... qs ........................... 100 g pH 10.5 .

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

25 This mixture, applied for 30 minutes at 30 ° C on hair bleached with straw yellow, gives them, after rinsing and shampooing, a medium coppery brown coloring.

EXAMPLE 9

The following dye composition is prepared:. 30 Methyl-2, amino-4, nitro-5, N-methylaniline ....... 0.2 g

ButoXy-2 ethanol .................................. 10 g

Carboxymethylcellulose ............................ 2 g

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

Ammonia at 22 ° B ................................. 0.5 g 3b Water ...... .......... qs ......................... 100 g 1 pH 9.5. ft * 20

This mixture applied 25 minutes at 30 ° C to hair bleached in white, gives them after rinsing and shampooing a slightly purple red coloring.

EXAMPLE 10 The following dye composition is prepared: 2-methyl, 4-amino, 5-nitro N-methylaniline ...-..... 0.5 g, 2-methyl resorcin ........ ........................ 0.15 g Metaaminophenol ..................... .............. 0.05 g

Paraaminophenol ......................... 0.4 g lu Paraphenylenediamine .................. 0.08 g Methyl-2, N- g-hydroxyethylamino-5 phenol ......... 0.15 g

Cemulsol MP ^ ...................................... 21 g

Cemulsol NP ^ ...................................... 24 g 'Oleic acid .... ................................. 4 g 15 Butoxy-2 ethanol .......... ........................ 3 g

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

Masquol DTPA ...................................... 2.5 g

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

Ammonia at 22 ° B ................................. 10 g 2q Water ........ ...... qs ........................... 100 g pH 10.3.

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 2b at 90% gives them, after rinsing and shampooing, a light brown, copper-red coloring.

If a dye composition is applied under the same conditions, to hair of the same batch, which differs from the previous one only by the absence of methyl-2, amino-4, nitro-5,. 3g N-methylaniline gives a fairly dull beige shade.

EXAMPLE 11

The following dye composition is prepared: NP-methoxyethylamino-4 aminobenzene dihydrochloride ................................. ..... 1 g 35 Paraaminophenol ................................... 0.3 g.

Resorcin ......................................... 0.25 g. / 7 "21 Metaaminophenol ................................... 0.15 g Methyl-2 amino-4 nitro-5, N-ß-hydroxyethyl-aniline ....................................... .... 0.4 g

Glycerolated oleic alcohol with 2 moles of glycerol .... 5 g 5 Glycerolated oleic alcohol with 4 moles of glycerol .... 5 g

Oleic acid ..................................... 5 g

Oleic difchanolamine ............................ 5 g

Oleic diethanolamide ............................ 12 g

Ethyl alcohol .................................. 10 g 10 Ethyl glycol ......... ............................. 12 g

Ethylene diamino tetracetic acid ............... 0.2 g

Ammonia at 22 ° Be ................................ 10.2 g

Sodium bisulphite at 35 ° Be ....................... 1.3 g

Hydroqûinone ...................................... 0.15 g 15 phenyl-1 methyl-3 pyrazolorie-5 .................... 0.15 g

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

This liquid dye composition is diluted at the time of use with an equal amount of hydrogen peroxide at 20 volumes.

20 The gel obtained is applied for 30 minutes to light brown hair.

After rinsing, shampooing and drying, the hair is colored in an iridescent mahogany blonde shade.

The coloring result obtained is substantially identical, whether operating with a fresh liquid dye composition or one which has been stored for a long time after manufacture. / y.

• 22 *

NOT

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 Goodrich Chemical Company.

5 CEMULSOL NP ^: Nonylphenol containing 4 moles of ethylene oxide sold by Rhône Poulenc. CEMULSOL NPç: 'Nonylphenol with 9 moles of ethylene oxide sold by Rhône Poulenc. ALFOL CjL6 / 18E Cetylstearyl alcohol sold by lu (50/50): the Condéa Company.

* Lanette Wax E: Partially sulfated cetylstearyl alcohol sold by Henkel.

CEMULSOL B: Ethoxylated castor oil sold by Rhône Poulenc.

15 MASQUOL: Sodium salt of diethylene triamine pentacetic acid ^^ y *

Claims (14)

1. Nitroparaphenylenediamine derivative characterized in that it corresponds to formula (I); NHR1 2. S ^ / ^ NO2 (II) NH2 in which R denotes a methyl group, a g-hydroxyethyl group, a β-hydroxypropyl group, a β-γ, di-hydroxypropyl group, an N, N-diethylamino-ethyl group . 2. Compound according to claim 1, characterized in that the alkyl group denotes a group having 1 to 4 carbon atoms. 3. Compound according to claim 1, characterized in that it corresponds to the formula: NHR h3c - 4. Dye composition for keratin fibers, characterized in that it contains in a solvent medium at least one compound as defined in any one of claims 1 to 3. 5. Composition according to Claim 4, intended for the dyeing of human hair, characterized in that it? / "24 <A contains in a cosmetically acceptable medium at least one compound of formula (I) or (II) in proportions of 0.001 to 5% by weight. 5 I R2-% ^^ Ν02 6. Dye composition according to claim 4 or 5, b characterized in that the solvents are chosen from water, lower alkanols, polyols, glycols or glycol ethers or their mixtures. 7. Composition according to claim 4 or 5, characterized in that it additionally contains cosmetic adjuvants chosen from surfactants, thickeners, penetration agents, sequestrants, film-forming agents, buffers, perfumes, basifying or acidifying agents. 8. Composition according to claim 4 or 5, intended to be used for the direct coloring of the hair, characterized in that it contains, in addition to other direct dyes chosen, from azo, anthraquinino dyes, the nitrous derivatives of the benzene series other than those of formula (I). 2o 9. Composition according to claim 4 or 5, intended for use as a styling lotion, characterized in that it is in the form of an aqueous, alcoholic / Rydroalcoholic solution, containing at least one cosmetic resin. 10. Composition according to claim 4 or 5, intended to be used for oxidation dyeing, characterized in that it also contains at least dye precursors. oxidation. NH2 (I) in which R ^ denotes an alkyl group, a mono- or polyhydroxylated alkyl group, an aminoalkyl group in which the amino group can optionally be 'mono or disubstituted by an alkyl group, R2 denotes a lb-alkyl group or the salts cosmetically acceptable of these compounds. 11. Composition according to claim 10, characterized »jq in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing agent. i 12. Process for dyeing keratin fibers, characterized in that a composition as defined in any one of claims 3 to 8 is applied to the fibers, it is left to stand for 5 to 40 minutes, * rinse, wash if necessary, rinse again and dry. / / v 25 4 i 13. A process for dyeing keratin fibers, characterized in 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, wash evenly with shampoo, rinse again and dry. Drawings: ...... pages pages of which ....... To ........ ρ ·? Ηο guard .Al ......: · .; : · -Ja c ^ ccri pilon _______ 3 _____- 1 i ‘jïioi ..... X. .. X-X description Luxenibci r: ·. s fc 80 "