LU83685A1 - TINCTORIAL COMPOSITION FOR KERATINIC FIBERS BASED ON NITRO-ANILINES, NOVEL NITRO-ANILINES AND THEIR PREPARATION METHOD - Google Patents

Description

t

Dye composition for keratin fibers based on nitroanilines, new nitroanilines and their preparation process.

The present invention relates to dye compositions for keratin fibers and in particular for human hair containing, as direct dye, N-substituted nitroanilines, to new nitroanilines? used in these compositions and in their preparation process.

It is well known that to give the hair direct coloring or additional reflections in the case of oxidation coloring, nitro derivatives of the benzene series can be used.

The Applicant has discovered that it is possible to obtain hair dyes having very good weathering and washing stability and good lightfastness thanks to a particular family of nitroanilines.

These compounds make it possible in particular to provide yellow or red orange in the hair dye formulations.

In addition to their remarkable dye quality, the dyes selected by the applicant have good safety.

These dyes can also be used in dye oxidation compositions in order to obtain colors rich in reflection.

The present invention therefore relates to new dye compositions for keratin fibers, in particular for human hair, based on nitroanilines. The invention also relates to new nitroanilines and their preparation process. The invention also relates to dyeing methods using these compositions.

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

The dye compositions for keratin fibers and in particular for human hair, in accordance with the present invention, are essentially characterized by the fact f / 2 that they contain in a medium suitable for dyeing, at least one dye corresponding to the formula: / Ri

NH-A-N

^ r2 (I) —y

z - I

- R 'in which A denotes an alkylene group, alkylene substituted by one or more OH or alkylene groups interrupted by a heteroome such as oxygen or by a group -NH-; R ^ and R2, which are identical or different, denote hydrogen, alkyl, mono or polyhydroxy alkyl or R ^ and R2 can jointly form a heterocycle chosen from the piperidino or morpholino groups, Y denotes alkoxy or NO2, R denotes hydrogen or lower alkyl, and when Y denotes alkoxy, Z denotes N02 and is found in para of the amine function and when Y denotes NC> 2 (a) Z denotes alkoxy or OH and is found in para of the group N02 or else (b) Z denotes OH and is found in para of the amine function, as well as their cosmetically acceptable salts.

In the above meanings alkylene denotes a group having 2 to 6 carbon atoms and preferably 2 to 4 carbon atoms. The alkyl and alkoxy groups preferably have 1 to 4 carbon atoms.

The compounds entering into the general formula (I) therefore correspond respectively to the following general formulas: f * 3 / Ri

NH- A -N

Γ N

\ _alcoxy R-- | Ύ N02 (IA) “alkoxy (or OH) r — f ~ ii k ^ / ks · ^ 1

Y - NH- A -N

N02 ^ R2 (IB) / Ri

NH- A -N

A.o2XR2 R ^ I 2 OH (IC).

Among the compounds which precede those which are particularly preferred are those for which A denotes ethylene, propylene, hydroxypropylene, R denotes methyl and Y or Z denote methoxy.

Among the compounds of formula (I), a certain number of compounds are known in themselves and have been used as intermediate products, for example in German application 1,945,451 or cited in the technical literature such as more particularly in the article by Foster Ing. JCS 16 ^ 1-4 (1957) or in the article by Foster and Manson in Recueil / 82. (1963) pages 583-6. / jy f 4

The new compounds used in accordance with the invention correspond to the following formula (II): sy ^ —y (ii) R -— |

Z

in which A denotes an alkylene group, alkylene substituted by one or more OH or alkylene groups 7. interrupted by a hetero atom such as oxygen or by a group -NH-, and R2 identical or different denote hydrogen, alkyl, mono or polyhydroxylated alkyl or R1 and R2 may form a heterocycle chosen from piperidino or morpholino rings, R denotes hydrogen or lower alkyl, Y denotes alkoxy or NO2, - when Y is equal to alkoxy, Z is equal to N02 and is in the para position of the amine function, provided that when Y denotes methoxy and A denotes the ethylene group, and R2 do not denote simultaneously hydrogen, - when Y denotes NC> 2: (a) Z denotes alkoxy or OH and is found in para of NO 2 , provided that when Z denotes methoxy and A the ethylene group, R ^ and R2 cannot simultaneously denote hydrogen, methyl or ethyl, and (b) - when Z denotes OH and is found at the para of the Amine Unction, R ^ and R2 have the meanings i mentioned above.

The preferred new compounds are those corresponding to the above formula (II) and in which A denotes an alkylene group, alkylene substituted by one or more OH or alkylene groups interrupted by a heteroatom such as oxygen, R 1 and R 2 identical or different denote hydrogen, alkyl, mono or polyhydroxy alkyl or else R 1 and R 2 may form a heterocycle chosen from the piperidino or / morpholino groups, R denotes hydrogen or lower alkyl, Y denotes alkoxy or N0 ~; / / 1- s * <5 - when Y denotes NO2, A denotes alkylene, Z denotes alkoxy and is found in para of NC> 2, R ^ and R2 are different from hydrogen and alkyl, - when Y denotes NO2 and Z denotes OH and is found in para of NO2, as well as when Z denotes OH and is found in para of the amine position, A, and R2 have the meanings indicated above.

Mention may in particular be made of: - ß - (Ν, Ν-diethyl) amino-ethylamino-3-nitro-4 anisole, - ^ - (Ν, Ν-diethyl) aminopropylamino-3-nitro-4 anisole, - ß- ( Ν, Ν-diethyl) aminoethylamino-2 nitro-5 anisole, - fi> -aminoethylamino-3 nitro-4 phenol, - fi - (N, N-di- [b '-hydroxyethyl) aminoethylamino-2 nitro-5 anisole, '' - Ί - (Ν, Ν-dimethyl) aminopropylamino-2 nitro-5 anisole, - nitro-3 N, N-dimethylaminoethylamino-4 phenol, - nitro-3 N, N-di-fi- hydroxyethylamino 4-ethylamino phenol, - fb - (Ν, Ν-diethyl) aminoethylamino-3 nitro-4 methyl-6 anisole, - nitro-5 N- (3-amino-2 'hydroxy-2' propyl) 2-amino anisole , - Nitro-4 N- (amino-3 'hydroxy-2' propyl) amino-3 anisole, this list not being limiting.

Among the compounds used in accordance with the invention, those which are particularly preferred are the compounds of formula (IB) which exhibit excellent weathering and washing stability and very good light fastness and make it possible to provide yellow shades. Furthermore, the compounds of formula (IC) are also very advantageous insofar as they make it possible to provide red orange shades and that they exhibit very good light fastness as well as very good resistance to bad weather and to shampoos.

These compounds also have the advantage of having very good safety. /

The compounds of formula (IA) are obtained by the action of the / amines of formula / / Ί- on 3-alkoxy-4-methoxy-nitrobenzene or on 3-alkoxy-4-chloro-nitrobenzene. They can also be obtained by condensing a halogen derivative of formula: 6

H2N- A -N

R2 __________ Ri

X- A -N

E2 on benzene or paratoluene sulfonamide obtained by reacting the benzene or paratoluene sulfochloride on * 2-amino-5-nitro-1-alkoxy-benzene followed by acid hydrolysis of the substituted sulfonamide.

P

The compounds of formula (IB) are obtained by the action of the amines of formula:

H2N- A -N

\ r2 on 2-methoxy-4-alkoxy-nitrobenzene or on 2-chloro-4-alkoxy-nitrobenzene.

When and R2 denote alkyl, the compounds of formula (IB) can also be obtained by condensation of the halogenated derivatives

AT

X - A - N

\ R2 S on 2-arylsulfonylamino-4-alkoxy-nitrobenzene, followed by the acid hydrolysis of the substituted sulfonamides previously obtained.

The compounds of formula (IC) can be obtained from / from the halogenated derivatives of general formula: / OH j J / tl NH -A -X (III) in which X denotes a halogen atom such as chlorine or bromine, either by action on the halogenated derivative of formula (III) of an amine 7 ^ Ri

HN

\ r R2 and having the meanings indicated above, either when the aminoalkyl substitution of the aromatic amino function in ortho of the group NC ^ comprises a primary amine (R ^ and R2 denote hydrogen), by action of the phthalimide of potash on the halogenated compound of formula (III) followed by the treatment with hydrazine of the substituted phthalimide thus obtained (Gabriel reaction).

The compounds of formula (III) for which A denotes ethylene and X denotes bromine can be easily obtained by the action of hydrobromic acid on N - / ”(2-nitro-2 'hydroxy-4') phenyljoxazolidine-1,3-one -2 itself obtained by the action of sodium hydroxide diluted at room temperature on the N- / T (2-nitro-4 '-hydroxy-4') / 2> -chlorethylphenylcarbamate described in the third step of Example 1 of French patent 2,348,911.

The compositions in accordance with 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 in oxidation dyeing of these fibers, in which case these compounds of formula (I) con-b give reflections complementary to the basic coloring obtained by oxidative development of oxidation dye precursors.

These compositions contain the compounds according to the invention in proportions of between 0.001 and 5% by weight and preferably between 0.01 and 3% by weight relative to the total weight of the dye composition.

They may contain anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof and preferably cationic / and / or nonionic surfactants. These surfactants are presented / v 8 in the compositions of the invention in proportions of between 0.5 and 55% by weight and preferably between 2 and 40% by weight relative to the total weight of the composition.

In these compositions, the vehicle generally consists of water and organic solvents can also be added 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, monoethyl ether. ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol as well as analogous products 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 thickener function such as more particularly acrylic acid derivatives. It is also possible to use mineral thickening agents such as bentonite. These thickening agents are preferably present in the proportions 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 can also contain various adjuvants usually used in dye compositions for hair and in particular penetration agents, sequestering agents, film-forming agents, buffers, perfumes, alkalinizing agents and acidifying agents.

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

The pH of these dye compositions can be between 3 and 11.5. and 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, sodium or potassium hydroxides, alca-nolamines such that mono, di- or triethanolamine, 2-amino-2-methyl-propanol or 2-amino-2-methyl-propan-1,3-diol, alkylamines such as ethylamine, di-ethylamine or triethylamine, or using an aci-ί dification agent such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric 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 dyes, anthraquinone dyes, such as for example the tetraaminoan-thraquinone, aminoquinones, nitro dyes of the benzene series different from the compounds of formula (I) and more particularly the following compounds: 3-nitro-4 amino-6-chloro-6 N - / ^ - aminoethylaniline, nitro-3 N'-methylamino-4 N- / ^ - aminoethylaniline, nitro-3 amino-4 N- / 2> -hydroxyethylaniline, le (nitro-3, N - / ^ - hydroxyethylamino-4) phenoxyethanol, nitro-3, N'-J'à-aminoethylamino-4 N- (di- / 3-hydroxyethyl) - aniline, nitro-3, N - / 'b-hydroxyethylamino-4 chloro-6 aniline, nitro-3 amino-4 methyl -6, N-ß-hydroxyethylaniline, N, N '-di-fb-hydroxyethyl 4-nitro orthophenylenediamine, 2-nitro N- / i-aminoethylaniline, 2-methyl-6 nitro aniline, 3-nitro amino -4 phenol, n itro-3 N - / '2> -hydroxyethylamino-4 phenol, / nitro-3 amino-4-methyl-6 phenol, Π amino-3 nitro-4 phenol, l 10 amino-2 nitro-3 phenol , nitro-3, N - / ^ - hydroxyethylamino-6 anisole, N- ^ -dihydroxypropylamino-3 nitro-4 anisole, (N-methylamino-3, nitro-4) phenoxyethanol, (N-methylamino-3 , nitro-4) phenyl, ß, tf-dihydroxypropyl-ether, N, N'-di (- / 2> -hydroxyethyl) nitro paraphenylenediamine, nitro-3, N'-methylamino-4, N, N- ( di- / 3> -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 during an exposure time. 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 the setting lotions can be in particular polyvinylpyrro-lidone, crotonic acid-vinyl acetate copolymers, vinylpyrrolidone-vinyl acetate, monoesters of maleic anhydride-butyl vinyl ether copolymers, maleic anhydride-methyl vinyl ether as well as any other cationic, anionic, nonionic or amphoteric polymer usually used in this type of composition. These cosmetic resins are included in the compositions of the invention in an amount of 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) according to the invention f, U (11 are essentially used with a view to providing reflections to the final dye.

These compositions then contain, in association with at least one nitrated dye of formula (I), dye precursors by oxidation.

They may contain, for example, paraphenylene diamines such as: paraphenylenediamine, parato-luylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-dimethyl-2,6-methoxy-3 paraphenylenediamine, N- (β-mel-thoxyethyl) paraphenylenediamine , N, N-di (/ i-hydroxyethyl) amino-4 aniline, N, N- (ethyl, carbamylmethyl) amino-4 ani-ΐ line, 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, 2,5-diamino pyridine, 7-amino benzomorpholine.

The compositions according to the invention may contain, in combination with the dye precursors by oxidation of the 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: metaaminophenol, 2-methyl-5-amino phenol, 2-methyl-N- (/ 1-hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine and their salts, metaphenylene diamines such as: (2,4-diamino) phenoxyethanol, (2,4-diamino) phenyl / 1-hydroxypropyl ether , amino-6 benzomorpholine, ÜN- (/ 3-hydroxyethyl) amino-2 amino-4_7 phenoxyetha-nol, (diamino-2,4) phenyl β, 'i * -dihydroxypropylether and their salts, metaacylaminophenols, metauridophenols, metacarbalcoxyaminophenols such as; 2-methyl-5-acetyl-amino phenol, 2-methyl-5-ureido-phenol, 2-methyl-5-carbethoxyamino-phenol.

Finally, mention may be made, as other couplers which can be used in the compositions of the invention, of 0-naphthol, loê /! 12 couplers having an active methylene group such as diketonic compounds, pyrazolones and heterocyclic couplers such as diamino-2f4 pyridine, as well as their salts.

These compositions contain, in addition to dye precursors by oxidation, reducing and / or antioxidant agents such as more particularly sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, ascorbic acid and 1 'hydroquinone. These 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 and preferably between 0.015 and 2% by weight relative to the total weight of the composition. Their pH is preferably between 7 and 11.5 and is adjusted using basifying agents defined above.

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 be developed coloring using an oxidizing agent present in the compound; dye or 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 they are rinsed again and dried. /

The following examples are intended to illustrate the invention without being limiting in nature. j / • · 13 PREPARATION EXAMPLE 1

Preparation of / 2> - ((Ν, Ν-diethyl) amino ethyl-amino-3f-nitro-4-anisole hydrochloride.

och3 och3 Γ ^ Ι -> / C2H5 I h2N-ch2ch2n I / C2h5

1> N> -0CH3 C2H5 1 ^> - ^ H-CH2CH2N

T I C2H5 N02 N02 OCH, _, HC1> - | / C2H5 kx JJ-îîH-CH2CH21SI, HC1 T \ H5 no2

0.25 mol (46 g) of 2,4-dimethoxy-nitrobenzene is added in 140 ml of Ν, Ν-diethylethylenediamine, then the reaction medium is heated for 4 hours at 110 ° C. After cooling, it is poured into 1,500 kg of ice water. The expected product is extracted using ethyl acetate. 50 ml of ethanol saturated with hydrochloric gas are added, with stirring, to the ethyl acetate solution, dried with sodium sulfate and then cooled to 0 ° C. Fo- (Ν, Ν-diethyl) aminoethyl-amino-3, 4-nitro-anisole hydrochloride precipitates. It is drained, washed with ethanol and recrystallized from ethanol. After drying ‘under vacuum, it melts at 157 ° C.

Analysis Calculated for Found C13H22N3 ° 3C1 C% 51.40 51.37 H% 7.25 7.28

N% 13.84 13.91 J

0% 15.81 16.02 /

Cl% 11.70 11.83 / day

II

4ί 14 PREPARATION EXAMPLE 2

Preparation of Y - (Ν, Ν-dimethyl) aminopropyl-amino-3-nitro-4-anisole hydrochloride.

OCH ^ OCHo f /> i h2n- (ch2) 3nv Y \ ΑΛ 3 V \ / 3

OCH3 T NH- (CH2) 3-N

N02 N02 CH3 »OCH-

HCl I

^ riAs ch / —NH- (CH0) -, - N, HCl 2 3 χ ch3 no2

0.05 mole (9.15 g) of 2,4-dimethoxy-nitroben-zene is added to 30 ml of Ν, Ν-dimethylpropylenediamine, then the reaction mixture is heated for 4 hours at 110 ° C.

After cooling, it is poured into 300 g of ice water and extracted with ethyl acetate, the oil which has precipitated.

After drying over sodium sulphate, the ethyl acetate phase, cooled to 0 ° C., is added with 10 ml of ethanol saturated with hydrochloric gas.

'Z - (Ν, Ν-dimethyl) aminopropyl amino-3, 4-nitro-anisole hydrochloride precipitates. It is drained, washed with ethanol and recrystallized from ethanol. After drying under vacuum, it melts with decomposition at 204 ° C. nj ft «15

Analysis Calculated for Found C12H20N3 ° 3C1 C% 49.74 49.77 H% 6.91 7.03 N% 14.51 14.36 0% 16.58 16.76

Cl% 12.26 12.45 PREPARATION EXAMPLE 3

Preparation of ß- (N, N ~ diethyl) aminoethyl-amino-2-nitro-5 anisole hydrochloride.

° CH3 .C2H5 ^ -C2H5 h2n ~ (ch2) 2n nh- (ch2) 2-n η-0CH3> C2H5 I ^ C2H5

X V

N02

NH- (CH2) 2-N

C2K5 HCl —OCH-.

* UT, "> N02

0.05 mol (9.15 g) of 3,4-dimethoxy-nitroben-zene is introduced into 30 ml of Ν, Ν-diethylethylenediamine and the solution is heated for 15 hours at 110 ° C. The cooled reaction mixture is then poured into 300 g of ice water. The expected product.

in the form of a free base, precipitates in the form of an oil which is extracted with ethyl acetate. The ethyl acetate / a 16 is removed in vacuo. The residual oil is dissolved in 15 ml of absolute ethanol. After addition of 10 ml of absolute ethanol saturated with hydrochloric gas, a precipitate of ß - (NfN-dietHyl) aminoethylamino-2, 5-nitro-anisole hydrochloride is obtained which, after recrystallization from ethanol at 85 °, and drying under vacuum at 60 ° C bottom with decomposition at 230 ° C.

Analysis Calculated for Found C13H22N3 ° 3C1 C% 51.40 51.41 * H% 7.25 7.21 N% 13.84 13.90 0% 15.81 15.77

Cl% 11.79 11.68 PREPARATION EXAMPLE 4

Preparation of 3-aminoethylamino-3-nitro-4-phenol hydrochloride.

OH

+ h2n-ch2-ch2nh2, h2o -y r

UL

no2

OH OH

LjL ζ \ - "NH-CH0CH? NH0 HCl \> / ^ ~ NH-CH2CH2NH2, HC! N02 no2 ij_% 17

0.432 mol (75 g) of 3-chloro, 4-nitro-phenol are introduced into 282 ml of ethylenediamine and the reaction medium is then heated for 13 hours in a boiling water bath. The cooled solution is then poured into 2.6 liters of ice water supplemented with 1.09 liters of hydrochloric acid (d = 1.18). After cooling to -10 ° C for a few hours the hydrochloride of / X-aminoethylamino-3, 4-nitro phenol crystallizes. It is drained, washed with an ice-cold 2N hydrochloric solution and then with ethanol. After recrystallization from water, the dried product melts with decomposition at a temperature above 260 ° C.

Analysis Calculated for Found C8H-12N3 ° 3C1 C% 41.11 41.22 H% 5.14 5.11 N% 17.99 17.92 0% 20.55 20.44 t

Cl% 15.20 15.38 / * "X * 18 PREPARATION EXAMPLE 5

Preparation of ß- (Ν, Ν-di- / 2> '- hydroxyethyl) hydrochloride amino ethyl 2-amino-5-nitro anisole.

^ 302 - ^^ ^ S02 HN CaO N ^

BrCH2CH2Br H3CO ^> ^ \ CH2CH2Br

I 1 M

V T

N ° 2 N02 f S04H2 NH-CH2CH2Br .-

'CH2CH2OH

—OCH0 HN

I \

CH2CH2OH

no2

CH ~ CHo0H CHoCHo0H

y '2 2 y 2 2

NH-CH_CH0N NH-CH „CH_-N

2 2 2 2 ^

CH2CH2OH CH2CH2OH

OCH3 -OCH3 HCl -> N ° 2 NO2, HCl / ^^ η 19 1st stage: Preparation of N-benzenesulfonyl, N-β-bromo-2-ethylamino-5-nitro anisole.

This compound is obtained by reacting in dimethyl-formamide around 80 ° C, 1,2-dibromo ethane with the calcium salt of N-benzenesulfonylamino-2-nitro-5 anisole according to the process described in French patent 1,491,617 . This product melts at 122 ° C.

2nd stage: Preparation of N-bromoëthylamino-2, nitro-5 anisole.

169 g (0.407 mole) of the substituted benzenesulfonamide obtained according to the preceding step are added little by little, with stirring, in 500 ml of 96% sulfuric acid, while maintaining - the temperature between 15 and 20 ° C. The reaction medium is maintained for 1 hour at this temperature and then poured onto 3 kg of crushed ice. ’The crystallized product which precipitates is drained, washed with water and dried under vacuum at 60 ° C. It melts at 118 ° C.

3rd step: Preparation of hydrochloride / 3- (N, N-di- / ¾’-hydroxy-ethyl) aminoethylamino-2, 5-nitro anisole.

In 110.4 g (1.05 mole) of diethanolamine previously heated to around 100 ° C. is gradually added over 25 minutes and with stirring 41.3 g (0.15 mole) of N- / Î-bromoethyl -2-amino-5-nitro anisole. After 1 hour and a half of heating in the vicinity of 100 ° C., the reaction medium is poured into 400 g of ice-cold normal sodium hydroxide, then the expected product is extracted with ethyl acetate. The ethyl acetate is removed in vacuo.

The residual red oil is dissolved in 120 ml of absolute alcohol. After addition of 50 ml of absolute ethanol saturated with hydrochloric gas, a precipitate of β- (N, N-di- / i'-hydroxyethyl) amino ethylamino-2, 5-nitro-anisole hydrochloride is obtained which, after recrystallization in 1 alcohol at 90 ° and drying under vacuum at 60 ° C on potash bottom with decomposition between 168 and 170 ° C.

Analysis Calculated for Found C13H21N3 ° 5'HC1 C% 46.50 46.74 H% 6.60 6.62 / N% 12.51 12.51 f 0% 23.82 23.65 J /

Cl% 10.56 10.36 / dd 20 PREPARATION EXAMPLE 6

Preparation of Y - (Nf N-dimethyl) aminopropylamino-2, 5-nitro anisole hydrochloride.

0CH3 ^ Η3 ch3 I h2n- (ch2) 3-n ^ nh- (ch2) 3-n —OCh3 ^ CHj CHj

: Y CT

N ° 2 | no2 ^ 3

NH- (CH9) 3-N

\ CH3 HCl v —OCH,

> I

| s ^ CI # Hci N ° 2

0.4 mol (73.2 g) of dimethoxy-3,4-nitroben-v * zene are introduced into 220 ml of Ν, Ν-dimethylpropylenediamine and the solution is heated for 12 hours at 115 ° C. The cooled mixture is then poured into 2 kg 200 of ice water. The expected product in the free base state precipitates in the form of an oil which is extracted with ethyl acetate. The ethyl acetate is removed in vacuo. The residual red oil is dissolved in 100 ml of absolute ethanol. After the addition of 100 ml of absolute ethanol “saturated with hydrochloric gas, a precipitate of Y - (N, N-dimethyl) aminopropylamino-2, 5-nitro anisole hydrochloride is obtained which, after recrystallization from absolute ethanol and drying under vacuum at 80 ° C bottom with decomposition at 181 ° C. /> / "21

Analysis Calculated for Found C12H20N3 ° 3C1 C% 49.74 49.74 H% 6.91 '6/96 N% 14.51 14.52 0% 16.58 16.48

Cl% 12.26 12.30 PREPARATION EXAMPLE 7

Preparation of nitro-3, N, N-dimethylaminoethylamino-4 phenol.

" OH OH

I ->

Na OH ^ | j HBr ^ "° 2 ° iy |

NH-C-O-CH.CH-Cl O

0 ch2— ch2

OH OH

1 ^ CH3 ^ i c "3 f i

I I

I ^ CH3

NH-CH2CH2Br NH-CH2CH2 ~ N

^ ch3 1st step: Preparation of N - / '(2-nitro, 4-hydroxy') phenyl7oxazolidine-1,3 one-2.

0.02 mole (5.2 g) of N-Znitro-2 ', hydroxy-4') is introduced, with stirring, Æ-chlorethyl phenyl7carbamate (obtained according to the operation described in Example 1 of the / patent French 2,348,911 in 17 ml of 2.36N sodium solution at 20 ° C. The addition complete, the reaction medium is kept ^ t 22 30 minutes at 20 ° C. then it is diluted with 20 ml of water and it is neutralized at 0 ° C. using a hydrochloric solution, the expected product precipitates, is wrung, washed with water and recrystallized from ethanol and melts at 170 ° C.

Analysis Calculated for Found C9H8N2 ° 5 C% 48.21 48.36 H% 3.57 3.59 N% 12.50 12.63 0% 35.71 35.59 2nd step: Preparation of nitro-3, fh - 4-bromoethylamino phenol.

0.55 mol (125 g) of N- / T (2-nitro, 4-hydroxy) are added over 10 minutes to 375 ml of 48% hydrochloric acid previously heated to 90 ° C. ) phenyl7oxazolidine-1,3 one-2. The reaction medium is maintained for 30 minutes at 90 ° C. and then filtered while hot. By cooling the filtrate, the expected product precipitates in the form of hydrobromide. The hydrobromide is drained, taken up with stirring with 500 ml of water to release the nitro-3, Jê-bromoethylamino-4 phenol which is drained, washed with water and dried under vacuum. After recrystallization from benzene the product melts at 122 ° C.

Analysis Calculated for Found C8H9N2 ° 3Br C% 36.78 36.95 H% 3.45 3.49 N% 10.73 10.80 0% 18.39 18.24

Br% 30.65 30.54 3rd step: Preparation of nitro-3, N, N-dimethylaminoethyl amino-4 phenol.

0.0766 mol (20 g) of 3-nitro, 4-bromoethylamino-4 phenol in 60 ml of a 40% aqueous dimethylamine solution is heated for 60 minutes to 60 ° C. The reaction medium is poured. in 300 ml of ice water and then neutralized using acid / acetic. The expected product precipitates. We wring it out, wash it% Ί.

* 23 * water and recrystallizes it from ethanol. After drying under vacuum, it melts at 151 ° C.

Analysis Calculated for Found C10H15N3 ° 3 C% 53.33 53.48 H% 6.67 6.77 N% 18.67 18.48 0% 21.33 21.34 PREPARATION EXAMPLE 8

Preparation of nitro-3, (N, N-di- / Î-hydroxyëthy] Jamiiio ethyl-amino4 phenol.

OH ,

I CHoCHo0H

Jv, + H, r2 2 -—> | nch2ch2oh NH-CH2CH2Br

OH

n02 1 ^ ch2ch2oh

NH-CH2CH2-N

^ CH2CH2OH

5.2 g (0.02 mole) of nitro-3, - N- / S-bromoethylamino-4 phenol in 20 ml of diethanolamine are brought to 60 ° C. for 1 hour. The reaction medium is poured into 100 g of ice water and then the solution is neutralized using acetic acid. After a night at 0 ° C., the expected product which is precipitated is filtered off. After washing with a little ice water and drying under vacuum, the product is recrystallized from ethyl acetate. It melts π i 24 ".

. " ί

Analysis Calculated for Found C12H19N3 ° 5 C% 50.52 50.66 H% 6.67 6.74 N% 14.74 14.58 0% 28.07 28.10 PREPARATION EXAMPLE 9

Preparation of β- (Ν, Ν-diethyl) aminoethylamino-3-nitro-4 methyl-6 anisole.

'0CH3 0CH3 h3ç__ HjQ-îJv.

I ciso2c6h4ch3 I -.

_ y-CU3 N02 NO2 0CH3 H3C fîf> »3 -> ^ 2H5. || / N- 'C1CH2CH2N \ x / C2H5

C2H5 T NCH2-CH2-N

N02 C2H5 och3

S ° 4H2 H3C

/ | / C2h5

—NH-CH2CH2-N

^ C2H5 N ° 2 1st stage: Preparation of N-p-toluenesulfonyl 3-amino-4-nitro-6-methyl-anisole.

To a solution of 0.058 mole (10.6 g) of 3-amino-4-nitro. 6-methyl anisole in 60 ml of pyridine, 0.096 mol (18.3 g) of paratoyluene sulfochloride is added gradually, with stirring, between 50 and 55 ° C. After 3 hours of heating between 50 and 55 ° C., the reaction medium is poured into 300 ml of ice water.

The expected product which precipitates is drained, washed with water and recrystallized from dimethylformamide. It melts at 211 ° C.

Analysis Calculated for Found

C15H16N2 ° 5S

C% 53.57 53.80 H% 4.80 4.91 N% 8.33 8.45 0% 23.79 23.84 S% 9.51 9.41 2nd stage: Preparation of £ fcï-p- toluenesulfonyl, N- (/ 3-diethyl-aminoethyl) amino-37 4-nitro-6-methyl-anisole.

0.0353 mole (11.9 g) of N-p-toluenesulfonyl-3-amino-4-methyl-6-anisole in 50 ml of dimethylformamide supplemented with 2.8 g of quicklime is heated with stirring in a boiling water bath. 0.075 mole (10.2 g) of N, N-2-diethylamino-1-chloroethane is gradually added. After 3 hours of heating, the reaction mixture is poured into 200 ml of ice water. The expected product slowly crystallizes. We wring it out, wash it in water. After drying, it is recrystallized from ethanol. It melts at 114 ° C.

Analysis Calculated for Found

C21H29N3 ° 5S

C% 57.92 57.83 H% 6.71 6.72 N% 9.65 9.68 0% 18.37 18.28 S% 7.35 7.29 3rd step: Preparation of / 2> - ( N, N-diethyl) 3-aminoethylamino-4-nitro-6-methyl anisole.

0.021 mole (9.3 g) of substituted paratoluenefulsonamide obtained according to the preceding step, are gradually added, with stirring, to 25 ml of 96% sulfuric acid, while maintaining the temperature between 7 and 10 ° C. When the addition is complete, stirring is maintained for 5 hours at room temperature and then the reaction medium is poured into 200 ml of ice water. / Jh 4 26

While cooling, the reaction medium is made alkaline using an ION sodium solution; the expected product precipitates in the form of an oil which crystallizes quickly. The product is drained, washed with water, dried and recrystallized from hexane. It melts at 70 ° C.

Analysis Calculated for Found C14H23N3 ° 3 C% 59.76 59.64 H% 8.24 8.32 N% 14.94 14.75 0% 17.06 17.21. / · ’.. ξ% 27 EXAMPLE 1

The following dye composition is prepared:--dimethylaminopropylamino-3 hydrochloride, 4-nitro anisole 2 g

Nitro-3, amino-4, chloro-6, N-Æ -aminoethylaniline hydrochloride 0.6 g

Nitro-3, N, -methylamino-4 / N- / i-aminoethylaniline dihydrochloride 07 515 g

Cellosize WP 03 2 g

Cetyl dimethylhydroxyethyl ammonium chloride 2 g

Ammonia at 22 ° B 2.5 g

Water q.s.p. 100 g pH 8.5

This mixture applied 25 minutes at 30 ° C on naturally light brown hair gives them, after rinsing and shampooing, a dark brown color with copper highlights.

EXAMPLE 2

The following dye composition is prepared: N- ^ -dimethylaminopropylamino-2 hydrochloride, 5-nitro anisole O, 6 g

Nitro-3, N- / 1-hydroxyethylamino-4 phenol 0.25 g

Nitro-3, amino-4, N- / J-hydroxyethylaniline 0.26 g • N- / 4-hydroxyethylamino-2, (N, N-di-fi -hydr oxy-ethylamino-4) anilino-5 benzoquinone-1 , 4 0.3 g

Butoxy-2 ethanol 10 g

Cemulsol NP4 12 g

Cemulsol NP9 15 g

Oxyethylene alcohol oxyethylenated with 2 moles of ethylene oxide 1.5 g

Oxyethylenated oleic alcohol with 4 moles of ethylene oxide 1.5 g

20% triethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 8.7.

This mixture applied 30 minutes at 30 ° C to J hair that is naturally white at 90% gives them, after rinsing and J shampoo, a light red color. f U

‘28% EXAMPLE 3

The following composition is prepared:

N- / 3 -aminoetliylamino-3 hydrochloride 4-nitro anisole 0.4 g (Nitro-3, -hydroxyethylamino-4) phenoxyethanol 0.5 g

Nitro-3, N'-methylamino-4, N— fî> —aminoethyl aniline dihydrochloride 0.63 g

Butoxy-2 ethanol 6 g

Lauramide 1.5 g; Lauric acid 1 g

Hydroxyethylcellulose 5 g

Monoethanolamine 2 g

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

This mixture applied 20 minutes at 25 ° C to hair bleached in white gives them, after rinsing and shampooing, a red coppery brown coloring.

EXAMPLE 4

The following dye composition is prepared: N- / 3 -aminoethylamino-3 hydrochloride, 4-nitro anisole 0.40 g (Nitro-3, [b-hydroxyethylamino-4) phenyl, / ¾-hydroxy-propyl ether 0.935 g

Nitro-3, Ν'-ß-aminoethylamino-4 N-di- / 3-hydroxyethylaniline dihydrochloride 0.605 g

Nitro-3, N- fi, -hydroxyethylamino-4, chloro-6 aniline 0.525 g

Butoxy-2 ethanol 10 g

Aifoi C16 / 18 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic diethanolamide 1/5 g

Aqueous solution of triethanolamine at 20% by weight 1 g,

Water q.s.p. 100 g, / pH 7 l 29

This mixture applied 30 minutes at 28oC to naturally white hair at 90% gives them / after rinsing and shampooing a copper-red brown shade.

EXAMPLE 5

The following dye composition is prepared; Jß -diethylaminoethylamino-3 hydrochloride, 4-nitro anisole 0.26 g Tetraaminoanthraquinone 0.3 g

Nitro-3, amino-4, methyl-6 N - ^ - hydroxyethyl-, aniline 0.15 g

Propylene glycol 10 g

Carbopol 934 2g

Ammonia at 22 ° B 4g

Water q.s.p. ’100 g pH 5.8

This mixture applied 30 minutes at 28 ° C on hair bleached in white gives them after rinsing and shampooing a golden blonde coloring.

EXAMPLE 6

The following dye composition is prepared: N- / a> -aminoethylamino-3 hydrochloride, 4-nitro anisole 0.8 g / ltf-methyl-amino-3, 47-nitro-phenoxyethanol 0.11 g

Nitro-3, amino-4, N-ß-hydroxyethylaniline 0.51 g Tetraaminoanthraquinone 0.1 g

Butoxy-2 ethanol 10 g

Cellosize WP 03 2g

Cetyldimethylhydroxyethylammonium chloride 2 g

20% triethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 7.2

This mixture applied for 25 minutes at 28 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a medium brown color with golden reflections. / EXAMPLE 7 /

The following dye composition is prepared: / lr • 30

N- / 2 ”-aminoethylamino-3 hydrochloride, 4-nitro-anisole 1.2 g N, N'-di- / 2> -hydroxyethyl nitro-4 orthophenylene diamine. 0.8 g

Nitro-3, N, -methylamino-4, N- / 2> -aminoethyl aniline dihydrochloride 0.5 g

Ethanol at 96 ° 10 g

Alfol C16 / 18 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic diethanolamide 1.5 g

20% triethanolamine aqueous solution 2 g

Water q.s.p. 100 g pH 9.5

This solution applied for 20 minutes at 28 ° C on hair bleached with straw yellow gives them, after rinsing and shampooing, a coppery brown coloring.

EXAMPLE 8

The following dye composition is prepared: Fô- (Ν, Ν-diethylaminoethyl) amino-2, 5-nitro anisole hydrochloride 1.1 g

Nitro-3, amino-4, chloro-6 N-ß -aminoethylaniline hydrochloride 0.5 g Tetraaminoanthraquinone 0.5 g, 96 ° ethanol 10 g

Lauramide 1.5 g

Lauric acid 1 g

Hydroxyethylcellulose 5 g

Monoethanolamine 2 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, after rinsing and shampooing, a light brown coloring with copper reflections. / EXAMPLE 9 /

The following dye composition is prepared: //% 31 • f

^ -Dimethylaminopropylamino-3 hydrochloride, 4-nitro anisole 0.05 g

Nitro-3 amino-4, methyl-6 phenol 0.055 g

Nitro-3, N'-methylamino-4, N, N-di- / i-hydroxy-ethylaniline 0.1 g

Butoxy-2 ethanol 6 g

Lauramide 1.5 g

Lauric acid 1 g

Hydroxyethylcellulose 5 g; Monoethanolamine 2 g

Water q.s.p. 100 g pH 10

This mixture applied for 30 minutes at 28 ° C on bleached hair gives them, after rinsing and shampooing, a golden blonde coloring.

EXAMPLE 10

The following dye composition is prepared: Ν- ^ δ-aminoethylamino-3 hydrochloride, 4-nitro phenol 0.4 g

Nitro-3, N '- / ^ - aminoethylamino-4 N, N-di- / i-hydroxyethylaniline dihydrochloride 0.2 g

Nitro-3, N- ^ -hydroxyethylamino-4 phenol 0.09 g

Propylene glycol 10 g

Carboxymethylcellulose 2 g, Ammonium lauryl sulfate 5 g

1.2% triethanolamine aqueous solution 1.2 g

Water q.s.p. 100 g pH 6.5

This mixture applied 25 minutes at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a clear copper coloring.

EXAMPLE 11

The following dye composition is prepared: 3-nitro hydrochloride, N- / i-aminoethylamino-6 anisole 0.25 g /

Nitro-3, N'-methylamino-4, N-β- j aminoethylaniline dihydrochloride 0.23 9/1 //%. * 32

Nitro-3, amino-4, methyl-6 N- / 3-hydroxyethyl-aniline 0.15 g

Alfoi C16 / 18 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic ethanolamide 1 # 5 g

20% triethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 7.3

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

EXAMPLE 12

The following dye composition is prepared: Nitro-3 hydrochloride, N - /?> - (di- / 2'-hydroxyethyl) aminoethyl 6-amino anisole 0.16 g

Nitro-3, N'-methylamino-4, N-di- / i-hydroxyethyl-aniline 0.2 g

Nitro-3, N - ^ - 4-hydroxyethyl amino phenol 0.1 g

Ethanol at 96 ° 10 g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid O, 8 g

Ethylene glycol ethyl monoether 2 g

Monoethanolamine 1 g

Water q.s.p. 100 g pH 7.6

This mixture applied for 25 minutes at 28 ° C on hair bleached in white gives them, after rinsing and shampooing, a copper-red chestnut color.

EXAMPLE 13

The following dye composition is prepared: N- / 3-aminoethylamino-3 hydrochloride, 4-nitro anisole 0.7 g

Nitro-3, amino-4, methyl-6 N - ^ - hydroxyethyl-aniline 0.233 g /

Nitro-3, amino-4, N- / i-hydroxyethylaniline 0.97 g / d / 33

Nitro-2r hydrochloride N- ^ i-aminoethylaniline '0.5 g

Cemulsol NP4 12 g

Cemulsol NP9 15 g j

Oxyethylenated oleic alcohol with 2 moles of ethylene oxide 1/5 g

Oxyethylene oxyethylenated with 4 moles of ethylene oxide 1/5 g

20% triethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 7.5

This mixture applied 25 minutes at 30 ° C to hair bleached with straw yellow, gives them after rinsing and shampooing an intense red color.

EXAMPLE * 14

The following dye composition is prepared:

Paraphenylene diamine 0.15 g Resorcorcin 0.08 g Metaaminophenol 0.04 g

Orthoaminophenol 0.030 g

(2,4-diamino) phenoxyethanol dihydrochloride 0.042 g

Nitro-3, amino-4, methyl-6 N - /)? - hydroxyethyl “aniline 0.11 g

N - ^ - aminoethylamino-3, nitro-4 'anisole hydrochloride 0.6 g

Carbopol 934 1/5 g

Ethanol at 96 ° 11 g

Butoxy-2 ethanol 5 g

Trimethylketylammonium bromide 1 g

Trilon B 0.1 g

Thioglycolic acid 0.2 g

Ammonia at 22 ° B 10 g

Water q.s.p. 100 g pH 10

At the time of use, 100 g of hydrogen peroxide are added to 20 volumes. This mixture applied 30 minutes at 28 ° C to naturally white hair at 90% gives them, after rinsing and / shampooing, a dark brown color with golden reflections.Γ J f 34 EXAMPLE 15

The following dye composition is prepared:

Nitro3, N, N-dimethylaminoethylamino-4 phenol 0.7 g

Aifoi C16 / 18 8 g

Lanette wax E 0.5 g

Cemulsol B 1 g

Oleic diethanolamide 1.5 g

20% monoethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 9.

This dye solution applied for 25 minutes at 28 ° C on hair bleached in white gives them, after rinsing and shampooing, a tangerine coloring.

EXAMPLE 16

The following dye composition is prepared:

Nitro-3, NfN-dimethylaminoethylamino-4 phenol 0.7 g

Nitro-3 dihydrochloride, N '- / î> -aminoethylamino-4 N, N-di - ^ - hydroxyethylaniline 0.605 g

N- / to-aminoethylamino-3 hydrochloride, 4-nitro anisole 0.4 g

Ethanol at 96 ° 5g Alfol C16 / 18 8g

Lanette wax E 0.5g 'Cemulsol B 1g

Oleic diethanolamide 1.5 g

20% monoethanolamine aqueous solution 1 g

Water q.s.p. 100 g pH 8.3.

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

The examples which follow are intended to illustrate other compositions in accordance with the invention. In each case, the nuances noted according to Munsell on bleached or naturally white hair at 90% are mentioned, after application of the compositions to the hair under the conditions illustrated / 1 above. fh * 35 EXAMPLE 17

N- / èr-aminoethylamino-3-nitro-4 anisole hydrochloride 0.1 g

Butoxy-2 ethanol. 10g

Nonylphenol with 4 moles of ethylene oxide 12 g

Nonylphenol to 9 moles of ethylene oxide 15 g

Oxyethylenic oleic alcohol with 2 moles of ethylene oxide 1.5 g

Oxyethylenic oleic alcohol with 4 moles of ethylene oxide. 1.5 g

20% monoethanolamine aqueous solution 1 g

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

*

On bleached hair: 5.5 Y 8/6.

On 90% naturally white hair: 5.5 Y 6/4. EXAMPLE 18

N- / 1-aminoethylamino-3-nitro-4 phenol hydrochloride 0.2g

Butoxy-2 ethanol 10 g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid 0.8 g

Ethylene glycol ethyl monoether 2 g

Monoethanolamine 1 g

Water q.s.p. 100 g pH 6.8.

On bleached hair: 6.5 Y 8.5 / 8.

On 90% naturally white hair: 6.5 Y 6.5 / 6. EXAMPLE 19

Ss-äiéthy1aminoéthy1 amino-3 nitro-4 anisole hydrochloride 1 g

Ethanol at 96 ° 10 g

Alfol C16 / lg 8 g

Lanette wax E 0.5g

Cemulsol B 1 g

Oleic diethanolamide 1.5 g

20% monoethanolamine aqueous solution 0.5 g /

Water q.s.p. 100 g / 1 /

pH 7.7. not a word

36

On bleached hair: 7 Y 8/9.

On 90% naturally white hair: 7 Y 6.5 / 6.

EXAMPLE 20

^ -Dimethylaminopropyl-3-amino-4-nitro-anisole hydrochloride 0.4 g

Butoxy-2 ethanol 10 g

Hydroxyethylcellulose 2 g

Cetyldimethylhydroxyithylammonium chloride 2 g

20% triethanolamine aqueous solution 1 g

Water q.s.p. - 100 g pH 8

On bleached hair: 7 Y 8/10.

On 90% naturally white hair: 7 Y 7/6.

EXAMPLE 21

Nitro-3 N- / ¾-aminoethylamino-6 anisole hydrochloride 0.55 g

Butoxy-2 ethanol 10 g

Carboxymethylcellulose 2 g

Ammonium lauryl sulfate 5 g

20% monoethanolamine aqueous solution 2 g

Water q.s.p. 100 g pH 9.5.

On bleached hair: 7 Y 8/13.

On 90% naturally white hair: 7 Y 6.5 / 8.

4 EXAMPLE 22

Nitro-3 N-ß -aminoethylamino-6 anisole hydrochloride 0.05 g

Butoxy-2 ethanol 6 g

Lauramide 1.5 g

Lauric acid 1 g

Hydroxyethylcellulose 5 g

Monoethanolamine 2 g

Water q.s.p. 100 g pH 10.4.

On bleached hair: 7 Y 8/6. /

On 90% naturally white hair: 7 Y 7/4 ^ / f 37 EXAMPLE 23

N, N-2-diethylaminoethyl-5-nitro-anisole hydrochloride 0.705 g

Butoxy-2 ethanol. 10g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid 0.8g

Ethyl ethylene glycol 2g monoether

Monoethanolamine 1 g

Water q.s.p. 100 g pH 6.6.

On bleached hair: 7.5 Y 8/10.

On naturally white hair at .90%: 7.5 Y 6/6.

EXAMPLE 24

^ -N hydrochloride, N-dimethylaminopropylamino-2, 5-nitro anisole 1 g

Ethanol at 96 ° 10 g

Cemulsol NP4 12 g

Cemulsol NP 9 15 g

Oxyethylated oleic alcohol with 2 moles of ethylene oxide 1.5 g

Oxyethylated oleic alcohol with 4 moles of ethylene oxide 1.5 g

20% triethanolamine aqueous solution 2 g

Water q.s.p. 100 g pH 8.

On bleached hair: 7.5 Y 8.5 / 14.

On 90% naturally white hair; 7.5 Y 6/8.

EXAMPLE 25

Fi- (N, N-di- / V-hydroxyethyl) aminoethylamino-2 nitro-5 anisole hydrochloride 2 g

Butoxy-2 ethanol 10 g

Hydroxyethylcelluluse 2 g

Cetyldimethylhydroxyethylammonium chloride 2 g

20% monoethanolamine aqueous solution 2.5 g /

Water q.s.p. 100 g / ξ 38

On bleached hair: 7.5 Y 8/13.

On naturally white hair at 90%: 7.5 Y 6/8.

EXAMPLE 26

The following dye composition is prepared: N- / 3-aminoethylamino-3 hydrochloride, 4-nitro anisole 0.258 g

N, N-diethylaminoethylamino-3, nitro-4 anisole hydrochloride 0f 305 g 2-methyl resorcin 0.20 g Metaaminophenol 0.08 g

Diamino-2,4-phenyl dihydrochloride, ß-hydroxypropyl ether 0.09 g

Paraphenylenediamine 0.105 g

Oxylated nonylphenol with 4 moles of ethylene oxide 12 g

Nonylphenol oxyethylenated to 9 moles of ethylene oxide 12 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

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

This mixture applied 25 minutes at 30 ° C to naturally white hair at 90% gives them, after rinsing and shampooing a gray-blue coloring with metallic reflections.

EXAMPLE 27

The following dye composition is prepared i Nitro-3, N, N-di- / 3> -hydroxyethylaminoethyl amino-4 phenol 0.41 g

N, N-dimethylaminoethylamino-3, / nitro-4 anisole monohydrochloride 1.34 g /? / T

V

39

Di nitro-3 hydrochloride, N '- / ¾-aminoethylamino-4, N, N-di- / î> -hydroxyethylaniline 0.26 g

Nitro-3, amino-4, methyl-6, N- / 3-hydroxyethyl-aniline 0.1 g

Cellosize WP03 2 g

Cetyldimethyl hydroxyethyl ammonium chloride 2 g 5% ammonia solution 5g

Water q.s.p. 100 g pH 8

This mixture applied for 15 minutes at 30 ° C to hair, which is naturally white at 90%, gives it, after rinsing and shampooing, a medium coppery brown coloring.

EXAMPLE 28

The following dye composition is prepared: fi- (Ν, Ν-diethyl) aminoethylamino-3, nitro-4 methyl-6 anisole 0.15 g (ni.tro-3, N-ß -hydroxyethylamino-4) phenyl, / î -hydroxy-propylëther 0.10 g

Nitro-3-dihydrochloride, N '- ^ - aminoethyl amino-4 Ν, Ν-di-f ^ -hydroxyethylaniline 0.135 g

Butoxy-2 ethanol 10 g

Diethanolamides of coconut fatty acids 2.2 g

Lauric acid 0.8 g

Monoethyl ether of 11 ethylene glycol 2 g i Monoethanolamine 1 g

Water q.s.p. 100 g pH 7

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

EXAMPLE 29

The following dye composition is prepared: fi- (Ν, Ν-diethyl) aminoethylamino-3, nitro-4, methyl-6 anisole 0.805 g.

Butoxy-2 ethanol 10 g / aifoi c16 / 18 8 9 // 40

Lanette wax E 0.5g '

Cemulsol B 1 g

Oleic diethanolamide 1/5 g

5% ammonia 0.35 g

Water q.s.p. 100 g pH 8.5.

This mixture applied 20 minutes at 25 ° C to bleached hair gives them, after rinsing and shampooing, a very intense yellow coloring.

The examples of references which follow are intended to illustrate the preparation of nitrous dyes used in the compositions in accordance with the invention in combination with the dyes of formula (I). / 1 /% 41 • »REFERENCE EXAMPLE 1

Preparation of (nitro-3, N-ft-hydroxyethylamino-4) phenyl fi-hydroxypropyl ether.

oh o-ch2-choh-ch3 J. cich2choh-ch3 X \ || ->. | Ι ^^ Ι1-_Ν02 ^ γ> - "02

NH-CH2CH2OH NH-CH2CH2OH

A solution of 0.2 mole (39/6 g) of nitro-3 / N - ^ - hydroxy-ethyl-amino-4-phenol in 104 ml of sodium solution 2.3 N (0/24 mole) is previously heated in the vicinity at 100 ° C and then 0.24 mol (22.7 g) of chloro-1, propanol-2 is added to it. After maintaining the reaction medium in a boiling water bath for 2 hours, 12 ml of ION sodium solution and 0.12 mol (11.34 g) of 1-chloro-propanol-2 are added. Heating is further maintained in a boiling water bath for 2 hours. After cooling to 0 ° C the medium is alkalized to pH 9 using a sodium solution.

The expected product crystallizes, it is wrung, washed with a normal sodium solution and then with water. After drying under vacuum at 60 ° C, it melts at 118 ° C. After recrystallization from ethanol and recrystallization from ethyl acetate, it melts at 122 ° C.

Analysis Calculated for Found C11H16N2 ° 5 C% 51.56 51.73 H% 6.29 6.24 N% 10.93 10.82 d 0% 31.22 31.15 / 42 REFERENCE EXAMPLE 2

Preparation of (nitro-3, ^ 7-aminoethylamino-4) phenoxyethanol OH. OCH2-CH2OH

I -> | k ^ y> “N02 --7

Cl Cl

0-CH2CH20H

NH 'NH-CH2CH2NH2 1st step: Preparation of (nitro-3, chloro-4) phenoxyethanol.

2.5 moles (434 g) of chloro-4, nitro-3, phenol are dissolved in 1300 ml of dimethylformamide previously heated to 70 ° C. To this solution are added 3 moles of potassium hydroxide powder (210 g of 80% potassium hydroxide) then, while maintaining the temperature at 70 ° C., 3 mol (534 g) of hydrobromine are introduced over 30 minutes, with stirring. glycol. When the addition is complete, the reaction medium is maintained for 1 hour at 70 ° C. We add. then 1 mole of powdered potassium hydroxide (70 g of 80% potassium hydroxide) and 1 mole of glycol hydrobromine (178 g). After 1 hour of heating, 1 mole of potassium hydroxide and 1 mole of glycol hydrobromine are again added. Heating is continued for another 1 hour then the cooled reaction medium is poured into 7.5 liters of ice water. The expected product precipitates. It is wrung, carefully washed with a 3N sodium solution and then with water. After drying under vacuum, it melts at 96 ° C.

2nd stage: Preparation of (nitro-3, / i-aminoethylamino-4) phenoxyethanol. /

0.4 mol (87 g) of / (nitro-3, chloro-4) phenoxyethanol in 225 ml of ethylenedia / Y is heated at reflux for 1 hour.

//% 43 mine. The cooled reaction medium is poured into 500 g of ice water. The solution is made alkaline to pH 10 using an ION sodium solution. The expected product crystallizes. It is drained, washed with cold water, dried under vacuum at 50 ° C. It melts at llOeC. After recrystallization from ethanol it melts at 112 ° C. Analysis Calculated for Found C10H15N3 ° 4 C% 49.78 49.86 H% 6.27 6.32 N% 17.42 17.35 0% 26.53 26.41 REFERENCE EXAMPLE 3

Preparation of 2,4-phenylphenyl dihydrochloride, A-hydroxypropyl ether. * OK o-ch2-choh-ch3 —HHCOCH CICH-CHOHCH, NHCOCH, 3 --2I 3

V V

N02 N02

0-CH2-CH0H-CH3 Alcohol, Zn, C1NH4 I

^ NHCOCH 3 L Γ ->, HCl nh2 0-CH-CHOH-CH _ 1 2 3 U Γ 2HC1 / NH2 fj j * '' 44 * 1st stage: Preparation of 1 '/ acetylamino-2, nitro-47 phenyl, / ¾-hydroxypropy1ether.

0.5 mol (117 g) of potassium salt of 4-nitro, 2-acetylamino-phenol in 300 ml of dimethylformamide is brought to a boiling water bath, with stirring. 0.5 mol (47.25 g) of 1-chloro-propanol-2 is added to the mixture. While maintaining the heating, 0.5 mole (47.25 g) of 1-chloro-propanol-2 and 0.25 mole (34.5 g) of carbonate are added every 2 hours, four times, each time. potassium. After 10 hours of heating, the reaction medium is poured into 1500 ml of ice water. The expected product which is precipitated is filtered off. It is washed with a 0.5 N sodium solution and then with water. After drying under vacuum at 60 ° C, it melts at 123 ° C.

Analysis Calculated for Found C11H14N2 ° 5 C% 51.96 52.18 H% 5.55 5.60 N% 11.02 11.22 0% 31.47 31.44 2nd stage: 2-acetylamino hydrochloride, amino-47 phenyl / i-hydroxypropyl ether.

To 70 ml of hydroethanolic solution (60 ml C2H50H / 10 ml H ^ O) 1.5 g of ammonium chloride and 37.5 g of zinc powder are added and this mixture is stirred beforehand. reflux. 0.048 mole (12.2 g) of / acet is then added. ylamino-2, nitro-47phenyl, / ¾-hydroxypropylether by adjusting the addition so as to maintain the reflux without heating. When the addition is complete, reflux is maintained for 10 minutes, filter boiling on 5 ml of ethanol supplemented with 5.1 ml of 36% hydrochloric acid cooled to -20 ° C. The expected product precipitates in the form of monohydrochloride. It is drained, washed with a little ice-cold ethanol and dried under vacuum at 50 ° C. It melts with / decomposes between 220 and 225 ° C. fl / j r t * 45

Analysis Calculated for Found C11H16N2 ° 3'HC1 C% 50.67 50.82 H% 6.57 6.61 N% 10.74 10.82 0% 18.41 18.59

Cl% 13.60 13.58 3rd step: Preparation of dihydrochloride ./diamino-2,47 phenyl, / ¾-hydroxypropylether.

0.109 mol (28.4 g) of acetylamino-2-amino-47phenyl monohydrochloride / ¾-hydroxypropyl ether is dissolved in reflux in 80 ml of ethanol saturated with hydrochloric gas and added with 25 ml of 36% hydrochloric acid. . The reaction mixture is heated for 1 1/2 hours at reflux. By cooling the expected product precipitates in the form of dihydrochloride. The product is drained, washed with a little absolute alcohol and dried under vacuum at 50 ° C. It melts with decomposition between 215 and 220eC.

Analysis Calculated for Found C9H14N2 ° 2 '2HC1 C% 42.36 42.27 H% 6.32 6.33 N% 10.98 10.96

0% 12.54 12.55 J

Cl% 27.79 27.62 "46

The trade names used in the examples denote the following products:

Cemulsol NP4 Nonylphenol with 4 moles of ethylene oxide sold by the company Rhône Poulenc.

Cemulsol NP9 Nonylphenol with 9 moles of ethylene oxide sold by the Rhône Poulenc Company.

Cellosize WP03 Hydroxyethylcellulose sold by the

Union Carbide Company.

Lauramide Monoethanolamide of laurigue acid sold by the company Witco.

Alfol Cetylstearyl alcohol sold by lu lo - 'the Condéa Company.

Lanette E wax Partially sulfated cetylstearyl alcohol sold by the Henkel Company.

Cemulsol B Ethoxylated castor oil sold by the Rhône Poulenc Company.

Carbopol 934 Polymer of acrylic acid of molecular weight 2 to 3 million. sold by Goodrich Chem. J Company. / 1 / f *

Claims (19)

4 47 1. Dye composition for keratin fibers and in particular for human hair, characterized in that it contains in an appropriate medium. And in an amount sufficient for the dyeing of keratin fibers at least one dye corresponding to the formula; R1 NH- A -N ^^ R2 'xN-ï 7 ^ ... R (I) in which A denotes an alkylene group, alkylene substituted by one or more OH groups or alkylene group interrupted by a heteroatom such as oxygen or by a group -NH-; R ^ and R2, which are identical or different, denote hydrogen, alkyl, mono or polyhydroxy alkyl or and R2 can jointly form a heterocycle chosen from the piperidino or morpholino groups, Y denotes alkoxy or NO2, R denotes hydrogen or lower alkyl, and when Y denotes alkoxy , Z denotes N02 and is found in para of the amine function and when Y denotes NC> 2 (a) Z denotes alkoxy or OH and is found in para of the N02 group or else (b) Z denotes OH and is found in para of the amine function, as well as their H cosmetically acceptable salts. 2. Composition according to Claim 1, characterized in that the dye corresponds to the formula: A NH- A - N '\ R R2 —alkoxy * T t \ no2 (IA) t / 1 - l 4 48 in which R ^, R ^ / R and A have the same meanings as those given in claim 1. 3. · Composition according to claim 1, characterized in that the dye corresponds to the formula: alkoxy (or OH) Λ R- | R, NH- A -N „___ T ^" * 2 NO (IB) f wherein R ^, R2, R and A have the same meanings as those given in claim 1. 4. Composition according to claim 1, characterized in that the dye corresponds to the formula: yRi NH- A -N ^ R2 N0o * ^ r OH (IC) in which R, R ^, R2 and A have the same meanings as those indicated in claim 1. 5. Composition according to any one of claims * r 1 to 4, characterized in that it contains in a cosmetically acceptable medium at least one compound of formula (I) in proportions of 0.001 to 5% by weight. 6. Dye composition according to claims 1 to 5, characterized in that the solvents are chosen from water, lower alkanols, polyols, glycols or glycol ethers or their mixtures. 7. Composition according to Claims 1 to 5, characterized in that it additionally contains at least one cosmetic adjuvant chosen from surfactants, thickening agents, penetrating agents, seguestants, film-forming agents. , tampons, perfumes, basifying or acidifying agents. 8. Composition according to Claims 1 to 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 dyes, anthraquino-dyes, aminoguinones, derivatives nitrates of the benzene series other than those of formula (I). 9. Composition according to claims 1 to 5., 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 one resin, P cosmetic. 10. Composition according to claim 8 or 9, characterized in that it has a pH between 3 and 11.5 and preferably 5 to 11.5. 11. Composition according to any one of claims 1 to 5, intended to be used for oxidation dyeing, characterized in that it additionally contains at least dye precursors by oxidation. 12. Composition according to claim 11, characterized in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing and / or antioxidant agent. 13. A process for dyeing keratin fibers, characterized in that a composition as defined in any one of claims 1 to 8 or 10 is applied to the fibers, it is left to stand for 5 to 70 minutes, it is rinsed , optionally washed, rinsed again and dried. 14. Process for dyeing keratin fibers, characterized in that a composition as defined in claim 9 or 10 is applied to the washed and rinsed fibers, which is optionally rolled up and dried. 15. A process for dyeing keratin fibers, characterized by the fact that a / composition as defined in claims 11 or / y is applied to the fibers. „—_ -.....—- w“ 50 • “leave on for 10 to 50 minutes, rinse, which can be washed with shampoo, rinse again and dry. 16. Nitroaniline characterized in that it corresponds to the formula m- a -N .. "* 2 R— Z in which A denotes an alkylene group, alkylene substituted by one or more OH or alkylene groups interrupted by a heteroatom such as oxygen or by a group -NH-, R ^ and identical or different denote hydrogen, alkyl, mono or polyhydroxylated alkyl or R ^ and R2 can form a heterocycle chosen from piperino-dino or morpholino rings, R denotes hydrogen or alkyl lower, Y denotes alkoxy or N02, - when Y is equal to alkoxy, Z is equal to N02 and is in the para position of the amine function, provided that when Y denotes methoxy and A denotes the ethylene group, R 1 and R 2 do not simultaneously denote hydrogen, - when Y denotes NC> 2: (a) Z denotes alkoxy or OH and is in para of N02, provided that when Z denotes methoxy and A denotes the ethylene group, R ^ and R2 cannot denote simultaneously hydrogen, methyl or ethyl, and (b ) - when Z denotes OH and is found in para of the amine function, R ^ and R2 have the meanings indicated above. 17. Process for preparing the compounds according to claim 16, in which Y denotes OCH 4, Z denotes NO 2 and is / is in the para position of the amine function and characterized ''. J ----------- ----- ~ i% 51 ♦ w ^ R1 H2N- A R2 on 3-alkoxy-4-niethoxy-nitrobenzene or on 3-alkoxy-4-chloro-nitrobenzene or that one proceeds to the condensation of a halogenated derivative of formula R1 X - A -N R2 where X denotes a halogen on benzene or paratoluene Sulfonamide, followed by acid hydrolysis. 18. A process for preparing the compounds according to claim 16, in which Y denotes NO ?, Z denotes alkoxy or OH and is found in para de'N02, characterized in that an amine of formula ^ Ri is reacted H, N- A -N "" "R2 on 2-methoxy-4-alkoxy-nitrobenzene or on 2-chloro-4-alkoxy-nitrobenzene, or else when R 1 and R 2 denote alkyl, a derivative is condensed halogenated with the formula R- / 1 X - A - N r2 on the 2-arylsulfonylamino-4-alkoxy-nitrobenzene and that an acid hydrolysis of the substituted sulfonamides previously obtained is then carried out. 19. Process for the preparation of the compounds of claim 16, in which Z denotes OH and is found in para of the amine function, characterized in that one starts with halogen derivatives of formula (III) OH Λ / (III) | U NH- A -XW 52 "t" * in which X denotes halogen and which is reacted on this compound either: R ^ (1) an amine of formula HN R2 ° u (2) when R ^ and R £ denotes hydrogen, potassium phthalimide followed by a hydrazine treatment of the substituted phthalimide. to 'Drawings: plates; S ... Z ...... passs dent ....... À ........ cover page Ij, t ....... p? ~? S of description. ........ 4 ...... esnes of claims ........ abidgê descriptif Luxembourg, le -B ÛCOÏ81 Le raiQ spire 1 Charles München