LU84391A1 - NOVEL COMPOUNDS FOR HAIR DYEING, PROCESS FOR THEIR PREPARATION, DYEING COMPOSITION CONTAINING THEM, AND CORRESPONDING HAIR DYEING METHOD - Google Patents

Description

"* ___

Patent application of. September 27, l982 Designation of the Inventor (1) The undersigned Mr. Charles Munchenconseils in patents â ....................

Luxembourg, lia "boulevard Prince-Henri .......................................... ..........................................

acting as depositor - agent of the depositor - (2) L a. ..s oc i é té ... a no ny.m.e .... d ±; te: .. I '.O.REA.L, 1.4 ..,. ru e ..... Ro.y.al e, .... 75 0.08 Bets s (3) of the invention concerning:.,.!. No..uveaux .... comp.Qs. é.s ..... uti .l..i..s.ab les .... pQ ur. la .t £ .ln.tur.e ..... d.es .ch e ve ux ,. l eu r ... p.r..Q, céM ... de ... p.r. separati.Qn,. CQrnpos.i .t.iori. of ... te.i.n.tu.r.e .... the ... containing .......

and hair dyeing process ..... corr.es..pondan.t · !! ^ ....................... .........................

, designates as inventor (s): 1. Surname and first names M.adam.e .... BUG..AU.T .... An.çÎ.r.é.e .. "..... born .... Q.RMA.NLG.EY ....................................... ...............

Address Z. ^ ... Oe des..Abondance ^ 2. Last and first names M.0.nSieur ... G £ .N.EI ... Alain ............. .................................................. .......................................

Address 8.2., ..... bD.u.le.v.ar.d .... EichDt, .... 3.3.36.0 ... J.eu-il.l..y .... .P.la.i.sa.nce, .... Er.a.nc.e ...........

3. Surname and first names ............................................. .................................................. .................................................. ......................

Address ................................................. .................................................. .................................................. ........................................

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

...... Luxembourg, ............................., on ....... 1..8 .... actob.re .............................. 19.82. *.

(signature) A 68026_ (1) Last name, first names, company, address.

(2) Last name, first names and address of the depositor.

2.4629 DESCRIPTION MEMORY filed in support of an INVENTION PATENT application in the Grand Duchy of LUXEMBOURG in the name of L'OREAL SA for: * "New compounds usable for hair dyeing, their preparation process, dye composition containing them and corresponding hair dyeing process ".

NOVEL COMPOUNDS USEFUL FOR HAIR DYEING, THEIR PREPARATION METHOD, DYE COMPOSITION CONTAINING THEM AND CORRESPONDING HAIR DYEING METHOD.

The present invention relates to new compounds (phenoxy-substituted) -1 amino-3-propanol-2, in which the extra-nuclear amine group may or may not be substituted, and to their process of preparation. The invention also relates to hair dye compositions comprising these new compounds and to a dyeing process using said compositions.

The object of the invention is to propose a new class of compounds capable of being used in hair dyes to give powerful dyes, stable to light, and having good resistance to weathering and washing. The invention further aims to propose a new category of compounds having good safety and satisfactory characteristics from the point of view of mutagenesis.

The subject of the present invention is a novel chemical compound of formulas (I) or (IA) (or a corresponding acid salt)

0-CH2-CH0H-CH2-N-Y 0-CH, -CH0H-CH, -f-Y

* A A

AA «« kfA, e 'Λ' S h 30 formulas in which: j jf / - Z represents NO ^ or NH ^; AT.

2 "Y represents two identical or different substituent groups lower or lower hydroxyalkyls having at most 4 carbon atoms, these two groups optionally forming with the nitrogen atom which carries them a 5-morpholi or piperidinic heterocycle, Y 'represents a substituent group k lower alkyl having at most 4 carbon atoms and X represents an anion; - R ^ and 1 * 2 are identical or different and represent a hydrogen atom or m alkyl or hydrosy lower alkyl radical having at most 10 carbon atoms.

; X can advantageously be a halogen, in particular chlorine.

In the case where and represent hydrogen atoms, the compounds of formula (I) can be obtained according to a preparation process which comprises the following steps: a) acting on the known compound of formula (II)

0H

20 LP N ° 2 (n) NHC0CH3 epichlorohydrin to obtain the compound of formula (III) 25 0 l \

O-CHL-CH-CHL

AT

Uf; ° * (III) / / 30 ---- NHC0CH3 * v 3 b) an amine of formula HNY, where Y has the meaning indicated above, is made to act on the compound of formula (III) to obtain the compound of formula (IV) o-ch2-choh-ch2-ny fif 4r N ° 2 a "NHCOCH3 10 c) on the compound of formula (IV), a strong acid is made to act, such as hydrochloric acid, to obtain the compound of formula (V) o-ch2-choh-ch2-ny

NO

K) NO2 (v) - NH2 20 d) and, optionally, to obtain the compound of formula (I), in which Z represents NH2, a reduction is carried out either by, for example, zinc powder in an alcoholic medium in presence of ammonium chloride, either by catalytic hydrogenation, palladium on carbon being able to act as catalyst, which makes it possible to obtain the compound of formula (VI)

0-CH -CHOH-CH -N-Y

Ai <”>, / 30 n kk '' '' ™ 2 d- 4

In the case where at least one of the radicals or R2 does not represent a hydrogen atom, the compound of formula (VII) is used as starting material

OH

5 --N02 (VII) R2. 10 formula in which and have the meanings previously indicated, and the reactions provided for in steps a) and b) are carried out successively in order to obtain a product of formula (VIII) 15 o-ch2-choh-ch2- ny N ° 2 M _, TL · (VIII)

^ N

20% where Y, and R2 have the meanings indicated above. When it is desired to obtain a compound of formula (i), in which Z represents NH2, the compound of formula (VIII) is subjected to a reduction, as indicated for step d) 25 mentioned above. Alternatively, one can use a preparation process starting from a compound of formula (II), practice steps a), b), c), d), then substitute one of the nuclear amine groups of the compound of formula (VI), for example, by substitution of the corresponding arylsulfonamide ^ / 30 and acid hydrolysis of this substituted arylamide. ^ i · * 5

If it is desired to obtain a compound of formula (IA), the nuclear amine function (s) of the corresponding compound (I) is protected by acetylation, then an agent is made to act. quaternization. Subsequently, by the action of an acid, it is deacetylated and, optionally, the quaternization anion can be changed at the same time.

In the case where Z represents a nitro group, the compounds of formula (I) or (IA) are direct dyes which can be used for dyeing keratin fibers and, in particular, hair. It has been found that these compounds L have good solubility in the solvents generally used in hair dyeing, which makes it possible to use them at a concentration high enough to confer on the keratin fiber a powerful coloring with good leveling. The dye obtained has good light and weather stability. In addition, the use in hair dye of these compounds ------------ --- is characterized by good safety. The invention therefore also relates to a dye composition for hair, characterized in that it comprises, in a cosmetic support, at least one compound of formula (I) or (IA), in which Z represents a nitro group. In a preferred embodiment, the dye composition according to the invention comprises from 0.001% to 4% by weight of at least one compound of formula (I) or (IA), where Z represents a nitro group.

In the case where Z represents a Ni group, the compounds of formula (I) or (IA) are either oxidation bases, if they are para or ortho-diamines, or couplers intended to be used in combination with oxidation bases *, in the case of metadiamines, When 1 & / ν '6 compound of formula (I) or (IA) is an oxidation base, the invention also relates to a dye composition for hair, characterized in that it contains, in a cosmetic support, at least one compound of formula (I) or (IA); in a preferred embodiment, the compound of formula (I) or (IA) is used in a proportion of between 0.001% and 4% by weight relative to the total weight of the composition. In the case where the compound of formula (I) or (IA) is a metaphenylenediamine, the invention also relates to a dye-1 rial composition for hair containing, in a cosmetic support, at least one oxidation base, characterized in that it additionally contains at least one compound of formula (I) or (IA); the compound of formula (I) or (IA) is preferably used in a proportion of between 0.001% and 2.5% by weight relative to the total weight of the composition.

The dye compositions according to the invention may comprise, in addition to the compounds of formula (I) or 20 (IA), oxidation bases consisting of: A - Paraphenylenediamines of general formula (IX) ^ R5

K

25 J> r4 Β'ιγγ r3 U? (IX) /

R'2_fJ

30 * //

nh2 U

7 or the corresponding acid salts, formula in which R * 1 "R'g and Rg are identical or different and represent a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having 1 or 2 carbon atoms, 5 or a halogen atom; in which R ^ and R ,. are the same or different and represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl radical, in which the alkoxy group contains 1 or 2 carbon atoms, carbamyl-alkyl, alkylsulfonamidoalkyl, acetylaminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, aminoalkyl, monoalkylaminoalkyl ^ dialkylamino alkyl, piperidinoalkyl, morpho lino alkyl, alkyl groups in and having from 1 to 4 carbon atoms, or and Rj. form, together with the nitrogen atom to which they are attached, a piperidino or morpholino group, provided that R '^ and R ^ represent a hydrogen atom, when R ^ and R ,. do not represent a hydrogen atom; or again B - The paraaminophenols of general formula (X) "

OH

20 ^ R6 (X) 25 NH2 or the corresponding acid salts, formula in which Rg represents a hydrogen atom, alkyl radical ion com-30 bearing from 1 to 4 carbon atoms or a halogen atom / as, for example, chlorine or bromine. / j // f

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8 C - Heterocyclic bases such as 2,5-diamino pyridine, 3-methyl-7-amino benzomorpholine, 5-amino indole.

The dye compositions according to the invention 5 can contain, in addition to the compounds of formula (I) or (IA), the following products, taken individually or in combination: 1) when the composition contains at least one oxidation base, at least a coupler taken from the group formed by resorcin, pyrocatechol, 2-methyl resorin, 2-ethyl resorcin, metaaminophenol, 2-methyl-5-amino phenol, 2-methyl N - (( 6-hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpholine, 2,6-dimethyl acetyl-3-amino phenol, 2-methyl-5-carbethoxyamino-phenol, 2-methoxy-5-carbethoxyamino-phenol, methyl- 2 ureido-5 15 phenol, 2,4-diamino phenoxyethanol, 2,4-diamino ani-sole, 2,6-dimethyl metaphenylenediamine, (2-amino-4-methylamino) phenoxyethanol, (diamino -2,4) phenyl, $ -me-thoxyethylether, (2,4-diamino) phenyl, C> -mesylaminoethyl ether, N-carbamylmethylamino-2 amino-4 anisole, amino-3 20-methoxy-4 phenol, oC-naphthol, diamino-2,6 pyridine, diamîno-3,5 dimethoxy-2,6pyridine, 1-phenyl-3-methyl-pyrazoLone-5, 3e (2-amino-N -J * -hydroxyethylamino-4) pheny 1 JB-hydrosypropyl-ether; 2) orthophenylenediamines and orthoamino-phenols optionally comprising substituents on the nucleus or on the amine functions or alternatively ortho-diphenol, these products, by complex oxidation mechanisms, which can lead to new colored compounds, either by cyclization on themselves, or by action on paraphenylenediamines; 3) dye precursors of the benzene-30 series comprising on the nucleus at least three substituents chosen from the group formed by hydra ^^ 9 methoxy or amino groups such as 2,6-diamino hydrochloride hydrochloride, trichlorhydrate diamino-2,6 N, N-bis- (ethyl) amino-4 phenol, diamino-2,4 phenol dihydrochloride, 1,2,4,4-trihydroxy benzene, 2,3,5-trihydroxy toluene orthe 4-methoxy-2-amino N - (^ - hydroxyethyl) aniline; 4) dye precursors of the naphthalene series such as 2-hydroxy naphthoquinone-1,4 and hydroxy-5 naphthoquinone-1,4; 5) leucodérives d1 indoanilines, indophéiols or indanines 10 such as dihydroxy-4,4 'amino-2-methyl-5 diphenylamine, dihydroxy-4,4' N - (^ - hydroxyethyl) amino-2 methyl -5-chloro-2 'diphenylamine, diamino-2,4' hydroxy-4 methyl-5 diphenylamine, dihydroxy-2,4 N - (^ - methoxyethyl) amino-4 'diphenylamine, dihydroxy-2,4 methyl- 5 N - (^ - methoxyethyl) 15-amino 4 'diphenylamine; 6) direct dyes chosen from the class of ni-very coloraats from the benzene series such as 2-amino-3-nitro phenol, 1-amino-2-nitro N-ß hydroxyéÜiylamino-4-meth.yl-5 benzene , N, N-bis- (£ -hy-droxyethyl) amino-1 nitro-3 N'-methylamino-4 benzene, N, N- 20 (methyl, ^ -hydroxyethyl) amino-1 nitro-3 N ' - (p -hydroxyethyl) amino-4 benzene, N, N- (methyl, ß -hydroxyethyl) amino-1 nitro-3 N'-methylamino-4 benzene, nitro-3 N- (J * -hydroxyé-thyl ) amino-4 anisole, nitro-3 N- (£ -hydrcs? yethyl) amino-4 phenol, (nitro-3 amino-4) phenoxyethanol, (nitro-3 N-25 methylamino-4) phenoxyethanol, N-methylamino-3 nitro-4 phenoxyethanol, (nitro-3 N-ß> -amino-ethylamino-4) phenoxyethanol, N- (p -hydroxyethyl) amino-2 nitro-5 anisole; 7) various conventional adjuvants such as water, penetration agents, foaming agents, thickening agents, antioxidant agents, alkalizing or acidifying agents, perfumes, agents / sequestrants, products film-forming agents and processing agentsEb ^% 10

The pH of the dye compositions according to the invention is between 5 and 11.5. Among the alkalinizing agents which can be used, there may be mentioned ammonia, alkylamines such as ethylamine or triethylamine, alkanolamines such as mono, di or triethanolamine, alkylalkanolamines such as methyl diethanolamine, sodium or potassium hydroxides, sodium, potassium or ammonium carbonates. Among the acidifying agents which can be used, there may be mentioned lactic acid, acetic acid, tartaric acid and phosphoric acid.

It is also possible to add to the composition according to the invention water-soluble, anionic, cationic, nonionic, amphoteric surfactants or their mixture. Among the surfactants which are particularly usable, mention may be made of alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfates, ether sulfates and sulfonates of fatty alcohols, quaternary ammonium salts such as trimethylketyl ammo- bromide. 20 nium, cetylpyridinium bromide, diethanolamides of fatty acids, or polyoxyethylenated or polyglycerolated acids, alcohols or alkylphenols. Preferably, the surfactants are present in the composition according to the invention in a proportion of between 0.5 and 55% by weight and, advantageously, between 4 and 40% by weight relative to the total weight of the composition .

It is also possible to add to the composition according to the invention organic solvents among which mention may advantageously be made, for example, of ethanol, isopropanol, glycerin, glycols and their ethers such as / butoxy. -2 ethanol, ethylene glycol, propylene glycola / f

V

11 monoethyl ether and monomethyl ether of diethylene glycol and similar solvents. The solvents may advantageously be present in the composition in a proportion ranging from 1 to 40% by weight and, preferably, between 5 and 30% by weight relative to the total weight of the composition.

The thickening products which can be added to the composition according to the invention can advantageously be taken from the group formed by sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, the sodium salt of carboxymethylcellulose and polymers of acrylic acid; mineral thickeners such as bentonite can also be used. Preferably, the thickening agents are present in a proportion of between 0.5 and 5% by weight relative to the total weight of the composition and, advantageously, between 0.5 and 3% by weight.

The antioxidants which can be added to the composition according to the invention can advantageously be taken from the group formed by sodium sulfite, thioglycolic acid, mercaptosuccinic acid, sodium bisulfite, asoartacic acid and hydroquinone. These antioxidants can be present in the composition in my proportion between 0.05 and 1.5% by weight relative to the total weight of the composition.

The dye composition according to the invention, when it contains at least the oxidation base, contains, at the time of use, oxidizing agents such as hydrogen peroxide, urea peroxide or persalts such than ammonium /? / persulfate. / jf / f 12 (\

The dye composition according to the invention may be in the form of a liquid, cream, gel, aerosol or in any other form suitable for dyeing keratin fibers.

5 The present invention also relates to a new hair dyeing process, characterized in that the dye composition defined above is allowed to act on the hair for an exposure time> varying between 10 and 45 min, that it is rinsed, which optionally is washed and rinsed again and the hair is dried.

In the case where the dye composition used contains at least the oxidation base, the abovementioned process comprises the initial phase in which the sufficient composition of oxidizing agents is mixed with the said composition, at the time of use.

To better understand the object of the invention, we will now describe, by way of purely illustrative and nonlimiting examples, several embodiments. f; -λ /

V

13

Example 1:

Preparation of the hydrochloride, monohydrate of | ^ (2,4-diamino) phenoxyj -1 dimethylamino-3-propanol-2 5 / CH3

0-CH, -CH-CH, O-CH.-CHOH-CH.-N

X 2 "V 2 A 2 2

/ X V y / X rjlJ

j NHCOCH. f] - NH0 3

Uf m (CH3) 2 ,, | D

1st stage '10 no2 N02 CH.

/ 3

OCH. -CHOH-CH. -NOT

5 1 2 2 v.

/ \ CH.

H2 Pd / C -HCl (pNH2 3 2nd stage * ^ 3HC19 ^ 0

V

NH2: Preparation of | j (amino-2l nitro-40phenos ^ j-1 dimethylamino-3 propanol-2

0.085 mol (21.5 g) of [[(acetylamino-2-nitro-4) phenoxyj-1 epoxypropane-2,3 (compound described in Luxembourg patent application No. 83,900 filed on January 26, 1982) are introduced into 100 ml of 40% aqueous dimethylamine solution and the reaction mixture is stirred for 30 min at room temperature. After dilution by the addition of / 30 225 ml of ice water then neutralization using acidfïy

V

14 acetic acid, evaporated to dryness under vacuum. The dry residue is taken up in 150 ml of ethyl acetate. The insoluble ethyl acetate, after washing with acetone, consists of 28.5 g of dj (2-acetylamino-4-nitro) phenoxy] J-1 dimethylamino-3 5 --—-— propanol-2. This acetylated derivative is brought to reflux for two hours in 220 ml of ethanol saturated with hydrochloric gas. After cooling the reaction medium, the expected product is drained in the form of the hydrochloride. After dissolving this hydrochloride in water and alkali-10 nization of the aqueous solution using a sodium solution, the J ^ (2-amino-4-nitro) phenoxyJ-1 dimethyl-amino is precipitated -3 propanol-2 in crystallized form.

The product is drained, washed with water and dried under vacuum. It melts at 123 ° C.

15 The elementary analysis gives the following results:

Analysis (%) Calculated for cu 0 ^ Found C 51.76 51.65 20 H 6.67 6.72 N 16.47 16.40 0 25.10 25.02

Second floor: Preparation of the hydrochloride, monohydrate of dj (diamino-2 ', 4!) Phenoxyjj-l dimethylamino-3 propanol-2

Is subjected to a catalytic hydrogenation at 80 ° C, under a pressure of 40 bars of hydrogen, 0.12 mol (30.6 g) of | ~ (2-amino-nitro-40phenoxyj-1 dimethylamino-3 propanol- 2 dissolved in 92 ml of absolute alcohol and in the presence of 4.5 g of 10% palladium on carbon, the catalyst is removed by filtration while receiving the alcoholic filtrate / ^ / /

V

15 out of 143 ml of ice-cold ethanol saturated with hydrochloric gas.

The expected product precipitates in the form of hydrochloride. This trihydrochloride is drained and recrystallized from a hydroalcoholic hydrochloric solution. After drying under vacuum, it melts with decomposition between 205 and 206 ° C.

The elementary analysis gives the following results:

Analysis Calculated for Cni H-0 N „0o, 3HC1, ËLO Found j il iy 5 î, z 10 C 37.44 37.31 H 6.81 6.87 N 11.91 11.79 0 13.62 13, 89

Cl 30.21 30.07 15

Example 2:

Preparation of dihydrochloride, hydrochloride of | jiydroxy-2 (diamino-2 ', 4') phenoxy-J] propyltri- / methylammonium / y “-V ξ 25 \ 30 \ 16

CH

O-CH -CH0H-CHo-N / tt3

JL 2 2 N 0-CH9-CH0H-CHo-N

nh CH3 JL 2 2 \ 5 H2Pd / C CH3. Acetic anhydride ^ ^ V kk

NO0 I

2 NHCOCH3 10 ^ CH,

0-CH2-CH0H-CH -N - CH

nhcoch ch 15 ICH3 ^, H20

V

NHC0CH3 20 @ / CH3 n 0-CH9-CH0H-CHo-N Cl® 1 2 2 l \ / X pu CH, f y- nh CH 3 HCl v in 2

25> \ Jj /, 2HC1. 0.5H20 I

Y '# NH2 Uf s 17

First stage: Preparation of [(diacetylamino- ^ AOphé-noxyjj-l dimethylamino-3 propanol-2.

According to the conditions described in the second step of Example 1, a catalytic 5-hydrogenation in the presence of 0.1 mol palladium on carbon (25.5 g) of [(amino-2 'nitro-40phenoxyj- 1-dimethylamino-propanol-2 in alcoholic solution The catalyst is removed by filtration, the solvent 1 is removed in vacuo, and the oily residue is taken up in 200 ml of ethyl acetate which is gradually added to little 17 ml of acetic anhydride The expected diacetylated derivative precipitates in crystallized form, is drained, washed with acetone and dried under vacuum.

It melts at 118-120 ° C.

Second stage: Preparation of iodide, hydroxy-2 monohydrate, (2-diacetylamino *, 4 ') phenoxy-3 ^ j propyltri-methylammonium.

0.03 mol (9.3 g) of the diacetylated derivative obtained during the first step is dissolved in 30 ml of acetone supplemented with 3 ml of water. The solution is brought to 50 ° C. and then 0.06 mol (3.75 ml) of methyl iodide is added, with stirring. The reaction medium is maintained for 30 min at 50 ° C. The expected quaternary derivative precipitates. It is wrung, washed with acetone and dried. It melts, with decomposition between 159 and 160 ° C. λ / - \ ~ f * v 18 Elementary analysis gives the following results:

Analysis _. -> _ TT _ „_„ λ Found (%) Calculate for C16 H26 ° 4 N3 1 '“Z0 5 C 40.94 40.87 H 5.97 6.02 N 8.95 8.87 0 17 , 06 17.21 1 27.08 27.02 10

Three ± èrae ^ eta. ^ E: Preparation of the dihydrochloride, semi-hydrochloride of jjhydroxy-2 (diamino-2 ', 4') phenoxy-3j p ropy ltriméthy lammonium.

0.0137 15 mol (6.2 g) of the quaternary salt obtained in the second step are heated for three hours at reflux in 30 ml of ethanol saturated with hydrochloric gas. The expected product precipitates. It is spun, washed with absolute alcohol and dried under vacuum. It melts with decomposition between 258 and 260 ° C.

20 The elementary analysis gives the following results:

Calculated for C12H24 N3 02 Cl3, y2H20 | T — é C 40.28 40.51 25 H 6.99 6.72 N 11.75 11.77 0 11.19 11.21 29.80 29.95 / 30 ( Î Λ

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19

Example 3;

The following dye composition is prepared: - Compound of Example 1 ...................., 0.836 g - Paraphenylenediamine ........... ............ 0.256 g 5 - Nonylphenol containing 4 moles of ethylene oxide sold by the company "RHONE POULENC" under the name "CEMULSOL NP4" ........... 21 g - Nonylphenol containing 9 moles of ethylene oxide sold by the company "RHONE POULENC" under the name "CEMULSOL NP9" ............ "24 g - Oleic acid .. ............................ 4 g - Butoxy-2 ethanol ............... ............ 3 g - Ethanol (at 96 °) ..................... 10 g - Pentasodium salt from diethylene 15 triamine pentaacetic acid sold under the name "MASQUOL DTPA" ................ 2.5 g - Thioglycolic acid .............. ......... 0.6 g - Ammonia (at 22 ° Be) ............. 10 g - Water ... qs ........ .......................... 100 g 20 The pH of the composition is equal to 10.2.

At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

This mixture, applied for 25 min at 28 ° C. to naturally white hair at 90%, gives them, after rinsing and shampooing, a midnight blue coloring.

Example 4:

The following dye composition is prepared; - Compound of Example 2 ..................... 0.35 g - Paraphenylenediamine ................ ....... 0.108 g / 30 - Nonylphenol oxyethylenated with 4 moles of oxide /) / ethylene sold under the name /// * 20

V

"REMCOPAL 334" by the company "GERLAND" .... 21 g - Nonylphenol oxyethylenated with 9 moles of ethylene oxide sold under the name "REMCOPAL 349" by the company "GERLAND" .. 24 g 5 - Oleic acid ., ......................., 4 g - Butoxy-2 ethanol ......... 3 g - Ethanol (at 96 ° ) ........................... 10 g - Pentasodium salt of diethylene-triamine-pentaacetic acid sold under the name "MASQUOL DTP" A ".............. 2.5 g

Sodium bisulphite (at 35 ° Be) ............ 1 g - Ammonia (at 22 ° Be) ........ 10 g - Water ... qs ... ............................. 100 g

The pH of the composition is equal to 10.

At the time of use, 100 g of generated oxy water are added to 20 volumes.

This mixture, applied for 20 min at 30 ° C. to naturally white hair at 90 ° C., gives them, after rinsing and shampooing, a blue-gray coloration.

20 Example 5:

The following dye composition is prepared; - Compound of Example 1 ................... 0.35 g - Paraaminophenol .................. ........ 0.109 g - Polymer of acrylic acid having a molecular weight of 2 to 3 million sold under the name "CARBOPOL 934" by the company "GOODRICH CHEMICAL CO" ....... 3 g - Ethanol (at 96 °) .......................... 11 g - Butoxy-2 ethanol ....... ...... 5 g 30 - Trimethylketyl ammonium bromide ....... 2 g / "en 21.

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- Ethylene-diamine-tetraacetic acid sold under the name "TRILON B" ...... 0.2 g - Ammonia (at 22 ° Bé) ............. 10 g - Bisulfite sodium (at 35 ° Be) .............. 1 g 5 - Water .. .qsp .......... 100 g

The pH of the composition is equal to 9.8.

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

This mixture, applied for 25 min at 28 ° C to 10 bleached white hair, gives them, after rinsing and shampooing, a pink shade with golden reflections.

Example 6:

The following dye composition is prepared; - Compound of Example 1 ..................... 0.13 g 15 - Paraphenylenediamine ............... ........ 0.08 g - Paraaminophenol ............................ 0.16 g - Resorcin .. ................................ 0.13 g - Metaaminophenol ............ ................ 0.09 g - Methyl-2 N - ^ - 5-hydroxyethylamino phenol .... 0.1 g 20 - N-methylamino-3 nitro-4 phenoxyethanol ..... 0.03 g - Oleic alcohol oxyethylenated with 2 moles of ethylene oxide ......................... 4, 5 g - Oxyethylenated oleic alcohol with 4 moles of ethylene oxide ......................... 4.5 g 25 - Oxyethylenated oleic amine at 12 moles of ethylene oxide sold under the name "ETHOMEEN T0 ^ 2" by the company * "ABMOUR HESS" ......................... ..... 4.5 g - Diethanolamines of coconut fatty acids. ,,. 9 g 30 - Propylene glycol ............................ 4 g - Butoxy-2 ethanol .. ,, ...... ...,., ........... 8 g / »22 - EtilälXOl (à 96 ^ o« «.. .......... ....... ...... 6 § - Pentasodium salt of diethylene-triamine-pentaacetic acid sold under the name "MASQUOL DXPA" .................... 2 g 5 - Hydroquinone ............................... 0.15 g - Sodium bisulfite solution (at 35 ° Be) ,. 1.3 g - Ammonia (at 22 ° Be) ....................... 10 g - Water ... qs ..... .................... 100 g

The pH of the composition is equal to 10.

10 At the time of use, 120 g of generated oxy water are added to 20 volumes.

This mixture, applied for 25 min at 28 ° C to naturally white hair at 90%, gives them, after rinsing and shampooing, a hazelnut color.

15 Example 7:

The following dye composition is prepared: - Compound of Example 1 ..................... 0.25 g - Paraphenylenediamine ......... .............. 0.4 g - Paraaminophenol ............................ 0, 6 g 20 - 2-methyl resorcin ......................... 0.4 g - 2-methyl-N - $ - 5-hydroxyethylaraino phenol. ... 0.25 g - Amino-2 nitro-3 phenol, .................... 0.2 g - Nonylphenol oxyethylenated with 4 moles of oxide d ethylene sold under the name "REMCOPAL 334" by the company "GERLAND" .... 21 g - Nonylphenol oxyethylenated to 9 moles of ethylene oxide sold under the name "REMCOPAL 349" by the company "GERLAND". .... 24 g - Oleic acid ................... 4 g 30 - Butoxy-2 ethanol, ............. ........ 3 g / - Ethanol (at 96 °) .................. 10 gy J.

f 23 "- Pentasodium salt of diethylene-triamine-p acid in taac etic sold under the name" MASQUOL DTP A "................. 2.5 g - Solution sodium bisulfite (at 35eBé) ... 1 g 5 - Ammonia (at 22eBé) ........................ 10 g - Water .. .qsp ................................... 100 g

The pH of the composition is equal to 10.1.

At the time of use, 120 g of hydrogen peroxide are added to 20 volumes.

10 This mixture, applied for 15 min at 30 ° C on hair bleached with straw yellow, gives them, after rinsing and shampooing, my copper-brown coloring. Example 8:

The following dye composition is prepared: 15 - Compound of Example 1 ...................... 0.075 g - Paraphenylenediamine ......... ............ 0.20 g - N, N-di-hydrochloride - $ - hydroxyethyl- paraphenylenediamine .................... .... 0.09 g - N-methyl paraaminophenol sulfate ......... 0.115 g 20 - 2-methyl resorcin .................. ........ 0.3 g - Metaaminophenol ............................. 0.085 g - Amino-1 nitro -2 N - ^ - 4-hydroxyethylamino-5-methyl benzene ............................ '0.18 g - (Nitro- 3 N- ^ aminoethylamino-4) phenoxyethanol ..................................... 0 , 15 g - Cetylstearyl alcohol sold under the name "ALFOL C16 / 18E" by the company "CONDEA" ............................ ........ 8 g - Sodium cetylstearyl sulfate sold under the name "CIKE DE LANETTE E" by the company "HENKEL" .................. .......... 0.5 g "24 - Castor oil ethoxylated sold under the name" CEMULSOL B "by the company" RHONE POULENC "... ___ ___........____........ 1 g - Oleic diethanolamide ............., ........ 1.5 g 5 - Pentasodium salt of diethylene-triamine-pentaacetic acid sold under the name "MASQUOL DTPA"., ............... 2.5 g - Mercaptosuccinic acid ...... .............. 0.3 g ** Ammonia (at 22 ° Be) 11 g 10 - Water .. .qsp .............. ..................... 100 g

The pH of the composition is equal to 9.3.

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

This mixture, applied for 25 min at 25 ° C. to 15 naturally white hair at 90 ° 7 ", gives them, after rinsing and shampooing, a dark brown coloring with copper reflections.

Example 9:

The following dye composition is prepared; 20 - Compound of Example 2 ...................... 0.1 g - Paratoluylenediamine dihydrochloride ...... 0.085 g - Paraaminophenol .. ........................... 0.155 g - Resorcin ................... ................ 0.08 g - Metaaminophenol ............................ 0.09 g 25 - Methyl-2 N - ^ - hydroxyethylamino-S phenol .., .. 0.1 g - Polymer of acrylic acid having a molecular weight of 2 to 3 million sold under the name "CARBOPOL 934 "by the company" GOODRICH CHEMICAL CO "........... 1.5 g 30" Ethanol (at 96 °) .................. ........... 11 g - Butoxy-2 ethanol ............................ 5 g «/ î * $ 25 h - Trimethylketylammonium bromide ...... e, ».... 1 g - Ethylene-diamine-tetraacetic acid sold under the name" TRILON B "........... .... 0.1 g - Ammonia (at 22 ° Be) .......................... 10 g 5 - Thioglycolic acid .. ........................ 0.2 g - Water .. .qsp ................ ........... 100 g

The pH of the composition is equal to 9.9.

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

10 This mixture, applied for 25 min at 28 ° G to naturally white hair at 90%, gives them, after rinsing and shampooing, a hazelnut color ^^ /

Claims (22)

1. New chemical compound of formulas O-ŒL-CHOH-CH-NY 0-CHo-CH0H-CHo-N ^ Y 5 (xz Ä (0 OR "r, X® (IA) vr2 10 or corresponding acid salt , formulas in which: - Z represents NO2 or NH ^; - Y represents two identical or different substituent groups lower alkyl or lower hydroxyalkyls having at most 4 carbon atoms, these two groups optionally forming with the nitrogen atom which carries it a morpholinic or piperidinic heterocycle, Y ′ represents a substituent group lower alkyl having at most 4 carbon atoms and X represents vin anion; - and R ^ are identical or different and represent a hydrogen atom, or a radical lower alkyl or hydroxyalkyl having at most ------ 4 carbon atoms. 2. Dye composition for hair, characterized in that it comprises, in a cosmetic support, at least one compound of formula (I) or (IA). 25 3 - Composition according to claim 2, characterized in that the compound of formula (i) or (IA) is present in the composition at a concentration between 0.001 and 4% by weight relative to the total weight of the composition. 30 4 - Composition according to claim 3, in which there is present at least wine compound of formula (I) or / (IA) for which Z represents an NH0 group in positioj / Oi / a -V · 27 meta relative to NR ^ ïC, * characterized in that the said compound of formula (I) or (IA) is present in the composition at a concentration of between 0.001 and 2.5% by weight relative to the total weight of the composition. 5. Composition according to one of claims 2 to 4, characterized in that it contains, in addition to the compounds of formula (i) or (IA), at least me oxidation base taken from paraphenylenediamines, paraamino- phenols or heterocyclic bases. : 10 6 - Composition according to one of claims 3 or 5, characterized in that it contains at least one coupler taken from the group formed by resorcin, pyrocatechol, 2-methyl resorcin, 2-ethyl resorcin, metaaminophenol, 2-methyl-5-amino phenol, 2-methyl 7. Composition according to one of claims 2 to 6, characterized in that in addition to the compounds of formula (I) or (IA), it contains orthophenylenedia-mines and orthoaminophenols, optionally substituted 3q on the nucleus or on amine functions, or ortho-diphenol ", / 8. Composition according to one of claims fj / "{* 28 ν 'to 7, characterized in that it contains dye precursors of the benzene series comprising, on the nucleus, at least three substituents chosen from the group formed by hydroxy, methoxy or amino groups. 9. Composition according to one of claims 2 to 8, characterized in that it contains dye precursors of the naphthalene series. 10. Composition according to one of claims 2 to 9, characterized in that it comprises leuco-derivatives of indoaniline, indophenol or indamine, 11. Composition according to one of claims 2 to 10, characterized in that it contains, in addition to the compounds of formula (I) or (IA), nitro dyes from the benzene series. 15 12 - Composition according to one of claims 2 to 11, characterized in that its pH is between 5 and 11.5. 13. Composition according to one of claims 2 to 12, characterized in that it comprises at least 20 adjuvant taken from the group formed by penetration agents, foaming agents, thickening agents, antioxidant agents, alkalizing or acidifying agents, perfumes, sequestering agents, film-forming products and treatment agents. 25 14 - Composition according to one of claims 2 to 13, characterized in that it comprises from 0.5 to 55% by weight relative to the total weight of the composition of at least one surfactant. 15. Composition according to one of claims 2 to 30 14, characterized in that it contains from 1 to 40% λ by weight relative to the total weight of the composition of // J 29 f V Λ minus one solvent selected from the group consisting of ethanol, isopropanol, glycerin, glycols and their ethers such as butoxy-2 ethanol, ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol. 15 N- (φ-hydroxyethyl) 5-amino phenol, 6-hydroxy benzomorpho-line, 2,6-dimethyl-3-acetylamino phenol, 2-methyl-5-carbethoxyamino-phenol, 2-methoxy-5-carbethoxyamino phenol , 2-methyl-5 ureido-phenol, 2,4-diamino pheo-noxyethanol, 2,4-diamino anisole, 2,6-dimethyl metaphenylenediamine, 1 '(2-amino-4-methylaminoamino) phenoxy - "Ethanol, (2,4-diamino) phenyl Ç'-methoxyethyl ether, (2,4-diamino) phenyl Çi-mesylaminoethyl ether, N-carbamyl-methylamino-2 amino-4 anisole, 3-amino methoxy -4 phenol, ot-naphthol, diamino-2,6 pyridine, diamino-3,5 dimeto-xy 2,6 pyridine, phenyl-1 methyl-3 pyrazolone-5. 16. Composition according to Claim 13, characterized in that the thickening agents are present at a concentration of between 0.5 and 5% by weight relative to the total weight of the composition. 10 17 - Composition according to claim 13, charac terized in that the antioxidants are present at a concentration between 0.05 and 1.5% by weight relative to the total weight of the composition. 18. Composition according to one of claims 2 to 15 17, characterized in that it is in the form of liquid, cream, gel or aerosol. 19. A method of dyeing hair, characterized in that a composition according to one of claims 2 to 18 is made to act on the hair for a time 20 from P ° varying between 10 and 45 tons, that the it is rinsed, which is optionally washed and rinsed again, and the hair is dried. 20. The method of claim 19, wherein the dye composition used contains at least one oxidation base, characterized in that at the time of use, a sufficient amount of agent is added to the dye composition used. oxidant. 21. Process for the preparation of a quaternary compound of formula (IA), characterized in that the corresponding tertiary compound is acetylated; that a quaternization agent is then made to act; and finally we deacetylated by the action of an acid, 22. The method of claim 21, characterized in that methyl iodide is used as the quaternizing agent. Drawings: - pages pages of which ....... A - cover page ...... Z5 ...... description pages ........ 5 ~ - claims pages .. ...... A ....... descriptive abbreviation Luxembourg, le tï ScPJ982 Le m ^ nàataire: / Λ / Charles München