LU83315A1 - NOVEL NITRO-PARAPHENYLENEDIAMINES, PROCESS FOR THEIR PREPARATION AND THEIR USE IN DYEING KERATINIC FIBERS - Google Patents

Description

1 t »

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

In its Luxembourg patent application n ° 82861 filed on October 16, 1980 under the title "New nitro-paraphé-nylènediamines, their process of preparation and their use in dyeing keratin fibers; the applicant described the compounds of formula: NHR1 R _ 2 Lil nii2 (I) in which denotes an alkyl radical, a mono or polyhydroxy alkyl radical, an aminoalkyl radical in which the amino group can optionally be mono or disubstituted by an alkyl radical; R2 denotes an alkyl radical, and the salts cosmetically acceptable of these compounds.

The present invention relates to new derivatives of nitro-paraphenylenediamine falling within the general formula (I), to their use in dyeing keratin fibers. nics and in particular human hair and their preparation process. As with the compounds described in the main patent application, the new nitro-paraphenylenediamines can bring red to the hair dye formulations.

It also found that the hair dyes thus obtained using these dyes have good light and washing stability.

: 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 d oxidation to obtain nuances rich in reflections. Ju »2

In addition to their remarkable dyeing and preservation qualities, the dyes selected by the applicant have good safety. These compounds have in particular the advantage of being non-mutagenic or very weakly mutagenic. As is well known, the non-mutagenic nature of the 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 SQ mix y .1 activated with Arrochlor 1254 have established this fact.

The present invention therefore relates to new nitro-paraphenylenediamines and their preparation process.

The invention also relates to dye compositions containing these nitro paraphenylenes diamines for keratin fibers and in particular for human hair which can be used for direct dyeing of the hair or for dyeing by oxidation.

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

The nitro-paraphenylenediamines according to the invention correspond to the following formula (III): NHR 'χ R'2- (III) HH2 in which R' ^ and R'2 have the following respective meanings: ^ 1_ Rl 2 ethyl methyl, - methyl isopropyl methyl ethyl n-propyl methyl /

(l, ^ -dihydroxypropyle methyl M

/ X-aminoethyl methyl / 1 /% 1 f 3

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.

The compositions in accordance with the invention are characterized in that they contain, in a cosmetically acceptable solvent * ', at least one compound corresponding to formula (III) and can be used for the direct coloring of keratin fibers or for the coloring oxidation of these fibers in which case these compounds of formula (III) confer reflections complementary to the basic coloring 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 may contain anionic, cationic, nonionic, amphoteric surfactants or their mixtures. These surfactants are present in the 4 compositions of the invention in proportions of between 0.5 and 55% by weight and preferably between 4 and 40% by weight relative to the total weight of the composition.

The cosmetic vehicle generally consists of water and organic solvents can also be added to the compositions to dissolve compounds which are not sufficiently soluble in water. Among these solvents, mention may be made of lower alkanols such as ethanol and isopropanol, polyols such as glycerol, glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, ethylene glycol monoethyl ether , 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 / /! ί 4 arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and various polymers having the function of thickener 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 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.

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 am-; monium, sodium or potassium hydroxides, alkanolamines such as mono, di- or triethanolamine, alkylamines such as ethylamine or triethylamine or using an acidifying agent such as phos-phoric, 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 compounds according to the invention, other direct dyes such as azo or anthraquinone dyes, such as, for example, tetraaminoanthraquinone , indophenols, indoanilines, indamines, aminoquinones, nitro dyes of the benzene series different from the compounds of formula (III) and more particularly the following compounds: 2-methyl-6-nitro aniline , 3-amino-4-phenol, 3-nitro N - / & - 4-hydroxyethylamino phenol, 3-amino-4-amino 4-methyl-6 phenol, 3-amino-4-phenol, amino- 2 nitro-3 phenol, nitro-3, N - / & - hydroxyethylamino-6 anisole, * 'N- / ¾, / -dihydroxypropylamino-3 nitro-4 anisole, (N-methylamino-3, nitro-4 ) phenoxyethanol, (N-methylamino-3, nitro-4) phenyl, ß, -dihydroxypropyl-ether, N, N '(- / 0-hydroxyethyl) nitro paraphenylenediamine, nitro-3, N'-methyla mino-4, N, N- (di- / 3-hydroxyethyl) aniline, * la (nitro-3, N, ß-hydroxyethylamino-4) phenoxyethanol, la (nitro-3, N-ß-hydroxyethylamino-4) phenyl , ß, ^ - dihydro-, "xypropylether.

The concentrations of these direct dyes other than. ’Dyes of formula (III) may 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 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 styling lotions can be in particular polyvinylpyrro-lidone, crotonic acid-vinyl acetate, / vinylpyrrolidone-vinyl acetate, maleic anhydride-ether / copolymers. f 6 butylvinyligue, 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 at 1 to 3% 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 (III) in accordance with the invention are essentially used with a view to providing reflections to the final dye.

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

They may contain, for example, paraphenylene diamines such as: para-phenylenediamine, para-luylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-dimethyl-3-methoxy-3 para-phenylenediamine, N- (β-methoxyethyl) paraphenylenediamine, N, N-di (/ â-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-2 amino-4 phenol, chloro-3 amino-4 phenol, methyl-2 amino-4 phenol, and their salts.

They can also contain heterocyclic derivatives, for example: 2,5-diamino pyridine, aiTiino-7 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 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 (β -hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine and their salts, metaphenylene diamines such as: (2,4-diamino) phenoxyethanol, /

6-amino benzomorpholine, / N- (β-hydroxyethyl) amino-2 A

i 7 amino-47 phenoxyethanol, (2,4-diamino) phenyl / ¾, Y'-di-hydroxypropyl ether and their salts, metaacylaminophenols, metauridophenols, metacarbalcoxyaminophenols such as: 2-methyl-5-acetylamino phenol, 2-methyl-5 ureido-phenol, 2-methyl-5-carbethoxyamino phenol.

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

These compositions contain, in addition to dye precursors by oxidation, 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 oxidation dyes 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 were particularly stable in such compositions.

The process for dyeing keratin fibers, in particular human hair, using the 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. /// * * ii 8 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, rinsed again and dried.

The examples which follow are intended to illustrate the invention without being limiting in nature. , / *% 9 PREPARATION EXAMPLE 4

Preparation of methyl-2, amino-4, nitro-5 N- /?>, 'Ζ -dihydro-xypropylaniline.

NH-CH9-CHOH-CH „OH

1 H3C _ L 1 ^ γ ^ 02 NH2

0.2 mole (33.4 g) of methyl-2, 4-amino-5-nitro aniline and 0.1 mole (10 g) of lime carbonate suspended in water are heated beforehand in a boiling water bath, with stirring. 100 ml of water. 0.21.6 mole (24 g) of chloro-1 pro-panediol-2,3 is added. The reaction mixture is heated 24 hours in a boiling water bath, adding seven times, every three hours, simultaneously 0.035 mole (3.5 g) of lime carbonate and 0.066 mole (7.3 g) of 1-chloro propanediol- 2.3. The hot reaction mixture is filtered, the filtrate is diluted with 60 ml of water. After cooling for 24 hours at 0 ° C., the expected product is drained, which has crystallized. The product is washed with water and recrystallized three times from ethanol. It melts at 150 ° C.

Analysis Calculated for Found C10H15N3 ° 4 C% 49.79 49.76 HS 6.22 6.21 NS. 17.43 17.55 0% 26.56 26.69 9 PREPARATION EXAMPLE 5. Preparation of methyl-2, amino-4, nitro-5 N- β -amino-ethylaniline.

? nh-ch9ch9nh9 / '-ô / hh2 10

A suspension of 0.05 mol (8.35 g) of methyl-2, amino-4, nitro-5 aniline and 0.035 mol of carbonate of lime (3.5 l is heated beforehand in a boiling water bath, with stirring. g) in 100 ml of water. 0.07 mol (14.35 g) of fb-bromo-ethylaniline hydrobromide dissolved in 20 ml of water is gradually added, with stirring. After two hours of heating in a boiling water bath, the hot reaction medium is filtered. After cooling the filtrate for 24 hours at 0 ° C., the expected product is drained, which has crystallized in the form of hydrobromide. The crude product is washed with acetone and then recrystallized from boiling water. After spinning, washing with acetone and drying under vacuum, methyl-2, amino-4, nitro-5 N - / & -amino-ethylaniline bromhydrate-monohydrate is obtained.

Analysis Calculated for Found C9H14N4 ° 2 'HBr' H2 ° C% 34.95 35.00 H% 5.50 5.51: N% 18.12 17.98 0% 15.53 15.52

Br% 25.89 25.82

The hydrobromide thus obtained is dissolved in water. After alkalinization using a 2N sodium solution, the methyl-2, amino-4, nitro-5, N- / 3 -aminoethylaniline is drained. After washing with water, drying and recrystallization from ethyl acetate, the product melts at 115 ° C. / / i Μ 11 PREPARATION EXAMPLE 6

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

NH Tosyl CH2-CH2-CH3 N ^ h3c — H3C_Tosyl

I BrCH2CH2CH3 v Y

NK 2 'NH2

nh-ch2ch2ch3 h3c —YY

^ γ / ~ "° 2 ™ 2 1st step

Preparation of methyl-3, N, N- (propyl, tosyl) amino-4 / nitro-6 aniline.

0.164 mole (52.5 g) of methyl-3, N-tosyl-amino-4, nitro-6 aniline obtained according to the first step of Example 2 of the parent application is dissolved in 210 ml of dimethylformamide. 0.090 mole (5.04 g) of quicklime is added. The mixture is brought to the vicinity of 60 ° C. and then 0.18 mol (16.4 ml) of propyl bromide is added little by little with stirring. After 2 hours at 65 ° C., 0.019 mol (1.08 g) of quicklime and 0.036 mol (3.28 ml) of propyl bromide are added simultaneously with stirring. Heating is continued for another 2 hours. The hot reaction medium is filtered and then the filtrate is diluted with 2 liters of ice water. The expected product precipitates. It is wrung, washed twice with a normal sodium solution, then with water. After recrystallization from acetic acid and drying under vacuum, it melts at 170 ° C. / · / /

Analysis Calculated for Found 12

. T

C17H21N3 ° 4S

C% 56f 20 56.03 H% 5.78 5.75 N% 11.57 11.58 0% 17.63 17.68 S% 8.82 8.82 2nd stage

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

0.129 mol (47 g) of the substituted paratoluenesulfonamide obtained according to the first step is gradually introduced, with stirring, into 235 ml of concentrated sulfuric acid at 0 ° C.

When the dissolution is complete, the reaction mixture is kept near 0 ° C. for 6 hours and then poured onto 2.3 kg of crushed ice. The expected product precipitates in the form of sulfate. The sulfate is wrung, washed with a little cold water. It is then suspended in 50 ml of water, then poured with stirring, this suspension in 50 ml of pyri-dine. Stirring is continued for 30 minutes and then 500 ml of water are added. The methyl-2, amino-4, nitro-5, N-propyl-aniline is drained which, after washing with water, drying and recrystallization from toluene, melts at 115 ° C.

Analysis Calculated for Found C10H15N3 ° 2 C% 57.42 57.28 H% 7.18 7.18 N% 20.09 '20, 12 0% 15.31 15.33 / "ï ï 13 PREPARATION EXAMPLE 7

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

NH Tosyl. C2H5

I N

H3C _ \ Tosyl il (^ 5 ^ 4 H3C- N ° 2 k | J ^ o

Nile 2 nh2 nhc2h5 H-C _

Q

xy ^ No2 NH2 1st stage

Preparation of methyl-3, N, N- (ethyl, tosyl) amino-4, nitro-6 aniline.

0.04 mole (12.84 g) of 3-methyl-N-tosyl-amino-4, 6-nitro-aniline obtained according to the first step of example of preparation 2 of the parent application is dissolved in 50 ml of dimethylformamide. 0.024 mole (1.34 g) of quicklime is added. The mixture is brought to the vicinity of 50 ° C. and then 0.048 mol (6.47 ml) of ethyl sulphate is gradually introduced, with stirring. The reaction medium is kept at 50 ° C for 6 hours and then filtered hot. 500 g of ice water are added to the cooled filtrate. The expected product precipitates in crystallized form. It is wrung, washed twice with a normal sodium solution and then with water. After recrystallization from acetic acid and drying under vacuum / /

Analysis Calculated for Found 14

C16HlA ° 4S

C% 55.01 55.05 H% 5.44 5.43 N% 12.03 12.10 0% 18.34 18.44 / S% 9.17 9.22 Step 2 »Preparation of 2-methyl , 4-amino, 5-nitro N-ethylaniline.

0.0715 mol (25 g) of the substituted paratoluenesulfonamide obtained according to the first step are gradually introduced, with stirring, into 125 ml of sulfuric acid at 0 ° C. When the dissolution is complete, the reaction medium is kept for 6 hours at 0 ° C. and then poured onto 1.250 kg of crushed ice. The expected product precipitates in the form of sulfate. The sulfate is wrung, = .; then wash it with a little cold water. It is then suspended in 50 ml of water and this suspension is poured, with stirring, into 50 ml of pyridine. After 15 minutes of agitation; tion, 500 ml of water are added. The methyl-2, amino-4, nitro-5 N-ethylaniline is drained which, after washing with water, recrystallization from a 50/50 dimethyl sulfoxide / water mixture and drying under vacuum at 125 ° C.

Analysis Calculated for Found C9H13N3 ° 2 C% 55.38 55.23 H% 6.66 6.66 N% 21.54 21.45 0% 16.41 16.65 / / ts "t 15 PREPARATION EXAMPLE 8

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

H, C NH0 CH-, NH SO ~ _ /? v \ _CH-, i ï i3 1 \ = s 3 HCw> \ ~ \ - £ Οοα HC - // \

He I 3 2, 'ML

H3C 'y — N02? H3c N02 nh2 nh2 \ 3 Γ \ s04 (ch3) 2 Y-A \ CH ^ I CH- m2 H0C NHCHo 1 λ

HC _ A

SO, H- H ^ C j 4 ^ y J \ \ y \ o2 H «2 1st stage

Preparation of 11isopropyl-3, N-tosylamino-4, nitro-6 aniline.

r 0.0947 mol (18.5 g) of 2-isopropyl, 4-amino, 5-nitro aniline (mp 68 ° C.) is dissolved in 47 ml of pyridine. Little is added: little by little, with stirring, 0.1 mol (19 g) of paratoluenesulfochloride so as not to exceed 50 ° C. When the addition is complete, the reaction medium is maintained for 30 minutes at 50 ° C. and then poured onto 350 g of crushed ice. The expected product precipitates in the form of yellow crystals. It is drained, washed with water, dried and recrystallized from ethanol. After drying / V under vacuum, it melts at 178 ° C. f ff k> -î

Analysis Calculated for Found16

C16H19N3 ° 4S

C% 55.01 54.93 H% 5.48 5.53 N% 12.03 12.01 0% 9.16 9.15 S% 18.32 18.34 2nd stage

Preparation of isopropyl-3, N, N- (methyl, tosyl) amino-4, nitro-6 aniline.

0.061 mol (21 g) of isopropyl-3, N-tosyl-amino-4, nitro-6 aniline are dissolved in 60 ml of dimethylformamide. 0.072 mole (4 g) of lime is added. 0.072 mol (9.1 g) of methyl sulphate is added little by little with stirring to the reaction mixture, the temperature being maintained between 40-45 ° C. When the addition is complete, the mixture is left for one hour at 45 ° C., then filtered and poured into 350 ml of ice water.

The expected product precipitates in the form of yellow crystals. It is drained, washed with water, recrystallized from ethanol. After drying it melts at 154 ° C.

Analysis Calculated for Found

C17H21N3 ° 4S

C% 56.19 56.23 H% 5.83 5.79 N% 11.57 11.60 0% 17.61 17.70 S% 8, SI 8.78 3rd stage

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

0.052 mol (18.9 g) of the substituted paratoluenesulfonamide obtained in accordance with the ^: 2nd step are introduced slowly with stirring. When the dissolution is complete, the reaction medium is left for 2 hours at 20 ° C., then poured onto 600 g of crushed ice. The expected product precipitates in the form of / sulfate. It is wrung out, then it is introduced into 100 ml of water at / 7 f V * ** 17 40 ° C. Then basified, with stirring, using 20% ammonia. Isopropyl-2-amino-4, nitro-5 N-methyl-aniline is drained. The product is washed with water, dried, recrystallized from cyclohexane.

After drying it melts at 105 ° C.

Analysis Calculated for Found C10H15N3 ° 2 C% 57.40 57.36 H% 7.23 7.24 N% 20.08 20.06 0% 15.29 15.42 PREPARATION EXAMPLE 9

Preparation of ethyl-2, amino-4, nitro-5 N-methylaniline.

nh2 Nh-so2- ^ 3-ch3 JL 'N—' H5C2 — H5C2 | ^ iN ||

| I

NH2 nh2 ^ ch3

H

I X sor <Cy> -CH3 (° Η3) 2 N / A Βή _ ^ \

--7 I

NH2 NHCH3

K2S04 -, H5C2 — J

(jf NH, »18 1st stage

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

0.087 mol (15.8 g) of ethyl-2, amino-4, 5-nitro aniline (mp = 138 ° C.) is dissolved in 45 ml of pyridine. 0.092 mol (17.5 g) of paratoluene sulfochloride are added little by little with stirring so as not to exceed 50 ° C. When the addition is complete, the reaction medium is maintained for 30 minutes near 50 ° C. and then poured onto 350 g of crushed ice. The expected product precipitates in crystallized form. After spinning, washing with water, drying and recrystallization from alcohol, it melts at 182 ° C.

Calculated Analysis to Find

C15H17N3 ° 4S

C% 53.73 53.76 H% 5.11 5.13 NS 12.53 12.55 =: 0% 19.0.9 18.95 SS 9.54 9.51 2nd step * Preparation of ethyl-3 , Ν, Ν-methyl, tosyl amino-4, nitro-6 aniline.

'0.061 mol (20.1 g) of ethyl-3, N-tosylamino-4, nitro-6 aniline are dissolved in 60 ml of dimethylformamide. 0.072 mole of lime (4 g) is added. The reaction mixture is brought to around 40 ° C. and then added little by little, with stirring. 0.072 mole (9.1 g) of methyl sulfate. When the addition is complete, the reaction medium is maintained for 1 hour at 45 ° C. It is filtered and then the filtrate is poured onto 350 g of crushed ice. The expected product precipitates in crystalline form. It is wrung, washed with water, and recrystallized from alcohol. After drying it melts at 167 ° C.

Analysis Calculated for Found

C16B19K3 ° 4S

Ci 55.01 54.95 H% 5.48 5.56 / 7 / N% 12.03 11.84 / 1 / OS 18.32 18.26 Jf

S% 9.16 9.22 A

i 19 3rd step

Preparation of ethyl-2, amino-4 / nitro-5 N-methylani-line.

0.0466 mol (16.3 g) of the substituted paratoluenesulfonamide obtained according to the second step are gradually introduced, with stirring, into 55 ml of 96% sulfuric acid while maintaining the temperature between 15 and 20 ° C. When the dissolution is complete, the reaction medium is kept for 2 hours at room temperature and then poured onto 500 g of crushed ice. The expected product precipitates in the form of sulfate. It is drained and then taken up in 200 ml of water at 40 ° C and basified with stirring with 20% ammonia. The ethyl-2, amino-4, nitro-5 N-methylaniline is drained in the form of red crystals. After washing with water, drying and recrystallization from benzene, the product melts at 123 ° C.

Analysis Calculated for Found C9H13N3 ° 2 C% 55.37 55.38 H% 6.71 6.70 / ”N% 21.53 21.60 a / 0% 16.39 16.43 / d / yy * *“% 20 EXAMPLE 12

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- ß,) / - dihydroxypropyl- aniline ..................... ...................... 0.5 g

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

Monoethanolamide of lauric acid ................. 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 30 ° C to hair bleached in white gives them, after rinsing and shampooing a red coloring 1.25 R 4/8 according to the Munsell evaluation.

EXAMPLE 13

The following dye composition is prepared: hydrobromide, 2-methyl monohydrate, 4-amino, 5-nitro N- / â -aminoethylaniline ...................... ...... 0.81 g

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

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

Lauric acid .................................... 0.8 g

Ethyl ethylene glycol monoether .......... 2 g

20% monoethanolamine solution ................ 3 g

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

This mixture applied 30 minutes at 28 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a red coloration 3.75 R 3.5 / 5 according to Munsell's evaluation.

EXAMPLE 14

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N-propylaniline ....... 0.22 g

Nitro-3-hydrochloride, N, ^ - aminoethylamino-4, N'N'- di - $ - hydroxyethylaniline ......................... 0 , 16 g

Nitro-3, 4-amino phenol ........................... 0.4 g

Ethoxy-2 ethanol .................................. 10 g / / * 1 21 t

Monoethanolamide of lauric acid ................. 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 28 ° C on 90% natural white hair gives them, after rinsing and shampooing, a red color.

EXAMPLE 15

The following dye composition is prepared: Methyl-2, amino-4, nitro-5., N-propylaniline ....... 0.36 g

Ethoxy-2 ethanol .................................. 20 g

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

20% monoethanolamine solution ................ 10 g

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

pH B

This mixture applied for 25 minutes at 30 ° C. to hair bleached in white gives them, after rinsing and shampooing, a salmon pink coloration, EXAMPLE 16

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N, fi-aminoethylamine ........................ ...................... 0.02 g

Tetraaminoanthraquinone ........................... 0.05 g Methyl-2, amino-4, 5-nitro phenol ...... ........... 0.05 g

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

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

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

Monoëthanolamine .......................'........... 2 g

Water .......... q.s.p ................................ 100 g pH 7; This mixture applied 25 minutes at 30 ° C to hair bleached in white gives them after rinsing and shampooing a golden sand coloring. / k *? 22 EXAMPLE 17

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- / 5, V-dihydroxypropyl-aniline ..................... ...................... 0.05 g (N-methylamino-3, nitro-4) phenyl, ß, -dihydroxy- propy 1 ether ... .................................... 0.05 g * N- / 3-hydroxyethylamino-2 ( 01- / ¾ -hydroxyethylamino-4 anilino) -5 benzoquinone-1,4 ....................... 0.11 g

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

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

4% aqueous ammonia solution ................. 0.5 g

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

This mixture applied 20 minutes at 30 ° C to hair * bleached in white gives them, after rinsing and shampooing a golden blond coloring.

EXAMPLE 18

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- / ¾-hydroxyethylanine ....................... ....................... 0.125 g

Nitro-4, N, N '- / â-hydroxyethylorthophenylene diamine ................................... ........ 0.165 g Tetraaminoanthraquinone ........................... 0.26 g

Diethanolamides of coconut fatty acids ........... 2.2 g> Lauric acid ......................... ........... 0.8 g

Ethylene monoether of ethylene glycol ........... 2 g

Monoethanol amine .................................. 1 g

Water ......... q.s.p ................................. 100 g pH 7

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

By replacing the above nitrated dyes with the following dyes: 2-methyl, 4-amino, 5-nitro N - / $ -hydroxyethyl- y aniline ................. .......................... 0.08 g ή / (f * Λ "" 23 Methyl-2, amino-4, nitro-5 N-fà, ^ - dihydroxypro-pylaniline .......................-................. 0.1g

Under the same conditions, a mahogany blond coloring is obtained.

EXAMPLE '19

The following dye composition is prepared: "2-methyl, 4-amino, 5-nitro, N- / 3-aminoethylanine ..................... ......................... 0.01 g '/ nitro-3, N- / 3-hydroxyethylamino-47phenoxyethanol ..... ...................................... 0.25 g

Nitro-3, N-methylamino-4, N ', N'-di- / 3-hydroxyethyl- aniline .......................... ................. 0.2 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 * Solution of 10% lactic acid ................... 0.5 g

Water .......... qs .p ................................ 100 g pH 6 , 5

This mixture applied 20 minutes at 28 ° C to hair bleached in white gives them, after rinsing and shampooing a pink champagne coloring.

EXAMPLE 20

The following dye composition is prepared: Methyl-2, amino-r4, nitro-5, N-β-hydroxyethylanine ........................ ...................... 0.11 g / nitro-3, N- / â-hydroxyethylamino-4 / phenyl, β, '^ - di- hydroxypropylether ................................ 0.15 g

Nitro-3, N-methylamino-4, N *, Ν'-dihydroxyethyl- aniline ........ 0.15 g Methyl-2, nitro-6 aniline ........... .............. 0.18 g

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

Alfol C16 / 18 ....................................., 8 g / V

'/ * * i 24

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

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

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

10% lactic acid solution ................... 0.5 g

Water ............. q.s.p ............................. 100 g pH 7

This mixture applied 35 minutes at 28 ° C on hair bleached with straw yellow gives them after rinsing and shampooing a coppery brown color.

EXAMPLE 21

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N- / ¾, Ù-dihydroxypropyl- aniline ..................... ...................... 0.2% N, / 3-hydroxyethylamino-2, 5-nitro phenol .......... 0 , 15 g Resorcin ......................................... 0.2g Metaaminophenol. ................................... 0.15 g

Paraphenylenediamine .............................. 0.15 g

Paraamino phenol .................................. 0.15 g

Remcopal 334 ...................................... 21 g 'Remcopal 349 ..... ................................. 24 g

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

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

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

Mas what DT PA ...................................... 2.5 g

Sodium bisulfite solution at 35 ° B ............ 1 g

Ammonia at 22 ° B ................................. 10 g

Water ........... q.s.p ............................... 100 g pH 10.6

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

This mixture applied 20 minutes at 28 ° C to naturally white hair at 90% gives them, after rinsing and shampooing, a dark golden blonde coloring.

EXAMPLE 22

The following dye composition is prepared: /

Ethyl-2, amino-4, nitro-5 N-methylaniline ......... 0.45 g / J

i I ^ 25

Butoxy-2 ethanol .........................'......... 9 g

Coconut fatty acid diethanolamides ............ 2.2 g

Lauric acid .... '................................ 0.8 g

Ethylene monoether of ethylene glycol ........... 2 g

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

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

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

EXAMPLE 23

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N-ethylaniline ........ 0.33 g

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

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

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

4% ammonia solution ......................... 0.2 g

Water ......... qs ................................ 100 g fold 7 * This mixture applied 30 minutes at 30 ° C on hair bleached with white gives them, after rinsing and shampooing a light red coloration.

EXAMPLE 24

The following dye composition is prepared: Methyl-2, amino-4, nitro-5, N-ß, ^ -dihydroxypropyl- aniline ...................... ..................... 0.2 g (3-nitro, N- / 3-hydroxyethylamino-4) phenoxyethanol ........ ....................................... 0.4 g Tetraaminoanthraquinone ...... ..................... 0.3 g

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

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

20% monoethanolamine aqueous solution ........ 0.1 g

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

This mixture applied 20 minutes at 28 ° C to hair. discolored with straw yellow gives them, after rinsing and shampooing / coloring, a red copper brown coloring. // »* * 26 EXAMPLE 25

The following dye composition is prepared: Isopropyl-2, amino-4, nitro-5, N-methylaniline .... 1 g Methyl-2, nitro-6 aniline .............. ........... 0.1 g

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

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

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

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

4% ammonia solution ......................... 1 g

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

This mixture applied 25 minutes at 28 ° C to hair bleached in white gives them after rinsing and shampooing a light red copper coloring.

/ Î 27

Preparation of (nitro-3, N / P> -hydroxyethyl-amino-4) phenyl, A,) (- dihydroxypropylether used in examples 17 and 20)

OH 0- CH CH OH- CH OH

I ClCHoCH0H-CH o0H I

rl ~? he

Xy ^ \ N02 N02

NH-CH2-CH20H NH-CH2CH2OH

0.2 mole (39.6 g) of 3, N, β-hydroxyethyl-amino-4-phenol is dissolved in 125 ml of 2N sodium solution. To this solution, previously heated to around 90 ° C., 0.25 mole (27.5 g) of 1-chloro-2,3-propanediol is added. Heating is continued for another 2 hours. After the reaction medium has cooled, the latter is extracted using ethyl acetate. After evaporation to dryness of the solvent, 29 g of expected product are obtained, in the form of orange crystals.

After recrystallization from isopropanol and drying under vacuum, the product melts at 102 ° C. f Analysis Calculated for Found C11H16N2 ° 6 C% 48.52 48.53 H% 5.92 5.88 N% 10.29 10.29 0% 35.26 35.15 / /. * * »28

Preparation of (nitro-3, N, ß-hydroxyethylamino-4) phenoxy-ethanol used in Examples 19 and 24.

O-CH -CH OH O-CH.CH.OH

I M M I 2 * £ »° ^ 1 ClC-0-CH-CHoCl ^ 1 I il -i-i-7 [il ^ K02 ^ γ ^ ° 2 NH2 NH-C-0-CH2CH2Cl

O

0-CH2CH20H

NaOH |

NH-CH2CH2OH

1st step

Preparation of / T (nitro-2, β-hydroxyethoxy-4) phenyljcarba-mate of / 3> -chlorethyl.

The raw material used is (3-amino-4-amino) phenoxyethanol described in Example 1 of French patent 2,290,186.

4 moles (792 g) of (3-nitro, 4-amino) phenoxyethanol are dissolved in 1600 ml of dioxane. 2.4 moles (240 g) of lime carbonate are added. The temperature is raised to around 90 ° C and then gradually introduced, with stirring, 4.8 moles (686 g) of β-chloroethyl chloroformate. When the addition is complete, the heating is maintained for 30 minutes at 90 ° C. The hot reaction medium is filtered. The cooled filtrate is diluted with petroleum ether to precipitate the expected product after recrystallization using dioxane and drying under vacuum / vacuum at 119 ° C. / 7 f »*% 29 2nd stage

Preparation of nitro-3, N- / 3-hydroxyethylamino-4) phenoxy-ethanol.

0.1 mol (30.45 g) of / '(2-nitro, / ¾-hydroxy-ethoxy-4) phenyl ^ β-chloroethyl carbamate is introduced into 62 ml of water. 10 ml / of ION sodium solution are gradually added over a few minutes with stirring. The temperature rises to around 60 ° C. The temperature of the reaction medium is then raised to 70 ° C. and then 22 ml of ION sodium solution are added with stirring. Stirring is continued for 15 minutes at 70 ° C. After cooling, the expected product is drained which, after washing with water, drying and recrystallization from methanol melts at 82 ° C.

Analysis Calculated for Found C10H14 ° 5N2 CS 49.58 49.72 rH% 5.33 5.82 NS 11.57 11.62 /

0% 33.03 33.00 rJ

X

30

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.

CEMULSOL NP ^: Nonylphenol with 4 moles of oxide. ethylene sold by Rhône Poulenc.

CEMULSOL NPg: Nonylphenol with 9 moles of ethylene oxide sold by Rhône Poulenc. ALFOL C ^ / ^ gE Cetylstearyl alcohol sold by (50/50): the Condéa Company.

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

CEMULSOL B ': Ethoxylated castor oil sold by

Rhône Poulenc.

MASQUOL: Sodium salt of diethyl-, lene-triamine pentacetic acid.

: /

Claims (12)

1. Nitroparaphenylenediamine derivative according to claim 1 of Luxembourg patent application No. 82 861, characterized in that it corresponds to formula (III): NHR '1 ,, - A ^ γ ^ ο2 nh2 (III ) in which R '^ and R'2 denote: ^ _ R, 2 ethyl methyl methyl isopropyl methyl ethyl; n-propyl methyl fi, i -dihydroxypropyl methyl fi-aminoethyl methyl. 2. Dye composition for keratin fibers, * characterized in that it contains in a solvent medium at least one compound as defined in claim 1. 3. Composition according to claim 2, intended for the. dye for human hair, characterized in that it contains in a cosmetically acceptable medium at least one compound of formula (III) in proportions of 0.001 to 5% by weight. 4. Dye composition according to claim 2 or 3, characterized in that the solvents are chosen from water, lower alkanols, polyols, glycols or glycol ethers or their mixtures. "> 5. Composition according to claim 2 or 3, characterized in that it contains in addition cosmetic adjuvants chosen from surfactants, thickeners, penetration agents, sequestering agents, film-forming agents, / buffers, perfumes, alkalizing agents or a.cxà \ .- / y reliant s. /// jd è 32 6. Composition according to claim 2 or 3, intended to be used for direct dyeing of the hair, characterized in that it contains, in addition to other direct dyes chosen from azo, anthraquinino dyes, indophenols, indoanilines, indamines, aminoquinones, nitro derivatives of the benzene series other than those of formula (III). 7. Composition according to claim 2 or 3, intended for use as a styling lotion, characterized in that it is in the form of an aqueous alcoholic or hydroalcoholic solution containing at least one cosmetic resin. 8. Composition according to claim 2 or 3, intended to be used for oxidation dyeing, characterized in that it additionally contains at least dye precursors by oxidation. * 9. Composition according to Claim 8, characterized in that it has a pH of between 7 and 11.5 and that it additionally contains a reducing agent. ^. 10. Process for coloring keratin fibers, ca- | characterized by the fact that a composition as defined in any one of claims 2 to 6 is applied to the fibers, it is left to stand for 5 to 40 minutes, rinsed, optionally washed, rinsed again and dried . 11. Process for dyeing keratin fibers, characterized in that a composition as defined in claim 7 is applied to the washed and rinsed fibers, which is optionally rolled up and dried. 12. Process for dyeing keratin fibers, characterized in that a composition as defined in claims 8 or 9 is applied to the fibers, optionally added with an oxidizing agent which is left to stand for 10 to 50 minutes, rinse, wash with shampoo, rinse again and dry. Desîsîrs: ....... Z ........: - / - .35 .......- '; ........ to ........ "r'- '·' ··? 3Q ....., -. /: ': or. ........ .. "- dvandicatior., ..... j uwSom $ f / jAt