CH616840A5 - Dyeing composition for human hair - Google Patents

Abstract

The dyeing composition is an aqueous or aqueous-alcoholic solution containing one or more dyes of formula I' in which the symbols have the meaning given in Claim 1. This composition can, in addition, contain other, direct or oxidation dyes and a cosmetic resin, as well as the usual adjuvants such as wetting, dispersing, swelling agents, and the like, and perfumes. The dyes of formula I' are useful yellow modifiers. They are effective in imparting a uniform depth of dyeing to partially sensitized hair. <IMAGE>

Description

The present invention therefore relates to dye compositions for human hair which contain in solution at least one etheroxide of general formula:

(10

55 in which Z represents a substituted lower alkyl radical chosen from the group carbalkoxyaminoalkyle, alkoxyalkyle, N, N-dialkyl-carbamylalkyle, acylaminoalkyle, ureidoalkyle, mesylaminoalkyle and - (CH2) n — N® - Xe, n being an integer of 1 at 6 and Xe is

| \

60 an anionic residue, in particular a halogen atom where a CH3SO4 radical, and the valences of the nitrogen atom N® which are represented free being saturated by hydrogen atoms and / or non-alkyl or aryl radicals substituted or substituted.

The compositions according to the invention are aqueous or hydroalcoholic solutions which are easily prepared by dissolving in water or in a water / alcohol mixture, of one or more compounds of formula (I '). The alcohols used in these compositions are generally used in the proportion of 20 to 75% by weight

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4

and preferably from 25 to 50%. These alcohols are preferably ethanol or isopropanol.

The concentration of the compounds of formula (I ′) in the dye compositions according to the invention can vary within wide limits due to their good affinity for the hair. This concentration is generally between 0.001 and 5% by weight, and preferably between 0.05 and 5% by weight.

The pH of the compositions according to the invention is generally between 3 and 11.5 and preferably between 3 and 10.5. It is adjusted to the desired value by adding an acid such as phosphoric acid or lactic acid or a base such as triethanol-amine or ammonia.

The compositions according to the invention may contain various adjuvants usually used in cosmetics. For example wetting agents, dispersing agents, blowing agents, penetrating agents, emollients or perfumes. They can also contain solvents such as glycols and glycol esters.

The compositions according to the invention may also contain other direct dyes such as azo or anthraquinone dyes, nitro dyes from the benzene series, indoanilines, indophenols or indamines.

The compositions according to the invention can be used for the purposes of lasting dyeing of the hair: in this case they are applied to the hair for a time varying from 3 to 30 minutes, this application being followed by rinsing and possibly with a washing and drying the hair.

The compositions according to the invention can also be used in the form of hair styling lotions, intended both to impart a light coloring to the hair and to improve the staying power of the styling: in this case they are present in the form of hydroalcoholic solutions containing at least one cosmetic resin and their application is carried out on damp hair previously washed and rinsed which are then coiled and dried.

The cosmetic resins used in the composition of these styling lotions are used in the proportion of 1 to 3% by weight and preferably from 1 to 2% by weight and may in particular be polyvinylpyrrolidone, crotonic acid copolymers - vinyl acetate, vinylpyrrolidone-vinyl acetate or maleic anhydride-butylvinyl ether, maleic anhydride-methyl vinyl ether and its ethyl, isopropyl and butyl esters.

The styling lotions according to the invention generally contain from 20 to 75% by weight and preferably from 25 to 50% by weight of low molecular weight alcohol which is preferably ethanol or isopropanol.

The compositions containing the etheroxides of formula I can also be used in the form of an oxidation dye. Such dye mixtures contain oxidation bases such as paratoluenediamine and paraaminophenol and / or couplers such as metaaminophenol, meta-diaminoanisole and resorcinol.

In the processes using oxidation dyes, the dye composition is prepared at the time of application to the hair by adding an oxidant such as hydrogen peroxide to an ammoniacal solution of one or more "bases" oxidation and / or couplers. Oxygenated water is used in a concentration of 2.4% (8 volumes) to 9% (30 volumes). However, in the case of auto-oxidizable compounds, the application of the composition can take place with or without the addition of hydrogen peroxide. As an oxidant, it is also possible to use peroxides or persalts.

As paraphenylenes diamines serving as oxidation "bases" which can be used in the compositions according to the invention, mention may be made of the paraphenylenes diamines primary, secondary and tertiary, optionally substituted on the benzene ring and preferably those represented by the general formula:

15

nh2

in which rn and r12, which may be identical or different, can mean, hydrogen, a lower straight or branched chain alkyl, moncT- or polyhydroxylated, piperidinoalkyl, carbamylalkyl, dialkylcarbamylalkyl, aminoalkyl, monoalkyl-aminoalkyl, dialkylaminoalkyl, (o-aminosulfonylalkyl) group alkylsulfonamidoalkyle, arylsulfonamidoalkyle, morpholinoalkyle, acylaminoalkyle, sulfoalkyle, groups in which the alkyl radical preferably contains 1 to 4 carbon atoms, Ri j and Ri 2 can also form together a heterocyclic group with five or six members, such as morpholine or piperidine.

ri3, Ri4, Ris, R16 mean independently of one another, a hydrogen or halogen atom, a lower alkyl or lower alkoxy group, preferably comprising 1 to 4 carbon atoms.

Halogen can mean in said fluorine, bromine compounds but preferably chlorine.

As particularly effective compounds in the compositions according to the invention, there may be mentioned, paraphenylenediamine, paratoluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, methyl-2 5-methoxy-paraphenylenediamine, 2,6-dimethyl-5-methoxy-paraphenylenediamine, N, N-dimethylparaphenylenediamine, 3-methyl-4-amino, N- (diethyl) aniline, N, N- (di-ß-hydroxy ethyljparaphenylenediamine, 3-methyl-4-amino-N, N- (di-P-hydroxyethyl) aniline, 3-chloro-amino-4 N, N- (di-ß-hydroxy-ethyl) aniline, 4-amino , N- (ethyl, carbamylmethyl) aniline, 3-methyl-4-amino, N- (ethyl, carbamylmethyl) aniline, 4-amino, N- (ethyl, morpholinoethyl) aniline, 3-methyl- 4 N, N- (ethyl, morpholinoethyl) aniline, amino-4 N, N- (ethyl, acetyl-aminoethyl) aniline, methyl-3 amino-4 N, N- (ethyl, acetylamino-ethyl) aniline, amino-4 N, N- (ethyl, mesylaminoethyl) aniline, methyl-3 amino-4 N, N- (ethyl, mesylaminoethyl) aniline, 4-amino N, N- (ethyl, P-sulfoethyl) aniline, 3-methyl-4-amino, N- (ethyl, P-sulfoethyl) aniline, N - [(amino-4 ') - phenyl] morpholine, N - [(amino-4') - phenyl] piperidine, amino-4 N, N- (ethyl, piperidino-ethyl) aniline, methyl- 3 amino-4 N-methylaniline, chloro-2 amino-4 N, N- (ethyl, sulfonamidomethyl) aniline, chloro-2 amino-4 N- (ethyl) aniline, methyl-2 amino-4 N- ( P-hydroxyethyl) aniline.

These paraphenylenes diamines can be introduced into the dye composition in the form of a free base or in the salified form, for example in the form of mono-, di- or tri-hydrochloride or hydrobromide and sulfate.

Among the other oxidation “bases”, there may be mentioned: paraaminophenol, 2-methyl-4-amino phenol, 3-methyl-4-amino phenol, 2-chloro-4 amino phenol, 3-chloro amino- 4 phenol, 2,6-dimethyl-4-amino phenol, 3,5-dimethyl-4-amino phenol, 2,3-dimethyl-4-amino phenol, 2,5-dimethyl-4-amino phenol, diamino- 2,5 pyridine, dimethylamino-2 amino-5 pyridine, diethylamino-2 amino-5 pyridine, methyl-3 amino-7 pheno-morpholine, amino-5 indole.

The dye compositions which are the subject of the present application may contain, in addition to one or more etheroxides and one or more oxidation bases, couplers. The couplers which can be used in the compositions according to the invention correspond to the general formula:

5

10

15

20

25

30

35

40

45

50

55

60

65

5

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in which Ri7 and Ris, which may be identical or different, can mean hydroxy, - NHR where R can be a hydrogen atom, an acyl, ureido, carbalkoxy, carbamylalkyl, alkyl, dialkyl-carbamylalkyl, hydroxyalkyl group; Ri 7 and Ri 8 can also signify hydrogen, alkoxy and alkyl provided that at least one of the substituents Ri7 and Ri8 denotes OH. R19 and R20 may denote hydrogen, branched or unbranched alkyl, alkoxy, halogen, amino optionally substituted by an alkyl, acylamino, ureido group.

Among the couplers corresponding to the aforementioned general formula, we will more particularly note resorcinol, metaamino-phenol, 2,4-diamino anisole, 2-methyl-5-ureido-phenol, 2,6-dimethylaminophenol, methyl- 2-acetylamino-5 phenol, 2,6-dimethyl acetylamino-5 phenol, 3-amino-4-methoxyphenol.

Other couplers which can be used in the compositions according to the invention are, for example, heterocyclic compounds such as in particular hydroxy-6 phenomorpholine, amino-6 pheno-morpholine, pyridine derivatives, pyrazolones or diketonic compounds , or a-naphthol or hydroquinones.

The diketonic compounds more particularly usable in the compositions according to the invention correspond to the formula:

0

in which R'i and R'2 signify independently of each other alkyl, preferably lower alkyl having 1 to 4 carbon atoms, alkoxy, phenyl,

- NH

c00h

- nh in which Z represents a substituted lower alkyl radical chosen from carbalkoxyaminoalkyl, alkoxyalkyl, N, N-dialkylcarbamyl-alkyl, acylaminoalkyl, ureidoalkyl, mesylaminoalkyl and - (CHî) ,, - N® — Xe where Xe is an anionic residue, in in particular a halogen atom or CH3SO4., the valences of the nitrogen atom N® which are represented free being saturated by hydrogen atoms and / or unsubstituted or substituted alkyl or aryl radicals, and Ri and R2 identical or different, can be a hydrogen atom, a lower alkyl radical or a substituted lower alkyl radical identical or different from Z and the functional groups NO2 and NR1R2 can occupy on the nucleus all the positions relative to OZ.

The compounds of formula (T) are obtained by the action, preferably in DMF, of alkylating agents of formula XZ, in which X represents a halogen atom and Z a substituted alkyl radical as defined above, on the salts alkali of the compounds of formula (II), - in a molar ratio of alkylating agent to said alkaline salt generally between 1 and 11 and preferably l, let 4 -

(ii)

Among the pyrazolones used in the compositions according to the invention, those corresponding to the formula are preferably used:

ch0 c ch

1 2 ii 3

0 = c n

NOT-

&

in which X signifies phenyl substituted or not, by - SO3H and / or halogen. For the term halogen, we mean fluorine, bromine and preferably chlorine.

The concentration of oxidation base is between 0.001 and 5% and preferably between 0.03 and 2% and that of the coupler is between 0.001 and 5% by weight, and preferably between 0.015 and 2%.

The present invention also relates to a process for the preparation of the compounds of general formula:

oz

(I ')

yRl

30 S

in which Y represents the group, Rx and R2 having r2

/ Rl

35 the meanings already given, or a grouping

COCH3

/ Rl

40 and, in the latter case, transformation of the group

COCH3

in an NHRi group, for example by means of hydrochloric acid.

The alkylation reaction can also be performed in HMPT (hexamethylphosphorotriamide). Reaction temperatures are generally in the range of 50 to 120 ° C and preferably between 70 and 100 ° C.

NO2 and Y can occupy all positions on the nucleus with respect to OH.

It is then possible to make new substitutions on the amine function of the compound (I ′) by operating, for example a new condensation of the said compound with the compound XZ.

Among the compounds XZ, there may be mentioned, among others, the bromhydrin of glycol, diethylaminoethylchloride, chloracetamide.

The alkaline salts of the compounds (II) can be prepared in a first stage by treating said compounds (II) with an aqueous or hydroalcoholic solution of potassium or sodium hydroxide. However, they can be obtained directly by adding potassium or sodium hydroxide in dimethylformamide, that is to say in the reaction medium in which the condensation of XZ is carried out.

Some examples of preparation will be indicated below by way of illustration. Examples 5 and 6 relate to methods other than that defined in claim 21.

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6

Example 1:

Preparation of (3-nitro 4-amino) phenyl, N, N-diethylcarbamyl-methylether c1ch - co - n - „

2 15

/ C2H5

o - ch2- con ^

Analysis for Ci3Hi9N304:

Calculated: C 55.52 H 6.76 N 14.95%

Found: C 55.41 H 6.71 N 14.91%.

5 Example 3:

Preparation of (3-methylamino-4-nitro) phenyl, $ -methoxy-ethyl ether oh

0.04 mol (6.16 g) of 3-nitro 4-aminophenol is dissolved in 20 cm 3 of hexamethylphosphorotriamide (HMPT) and 5 cm 3 of acetone. To this solution is added 0.06 mole (8.28 g) of potassium carbonate. This mixture, brought to 70 ° C. beforehand, is gradually added with stirring of 0.062 mole (9.34 g) of N, N-diethylchloracetamide. The temperature of the reaction mixture is maintained for 3 hours at 75 ° C. After cooling, the reaction mixture is poured into 80 ml of ice water. The expected product which has precipitated is filtered off and washed with water. After recrystallization from a 5% hydroalcoholic solution and drying under vacuum, the product melts at 145 ° C.

Analysis for C12H17N3O4:

Calculated: C 53.93 H 6.37 N 15.73%

Found: C 53.80 H 6.36 N 15.77%.

Example 2:

Preparation of [3- (N-methylamino) 4-nitro ~ \ phenyl, N, N-diethylcarbamylmethylether

^ C2E5 ClCH, C0Nr2 _V

2 ^ C2H5

AT

h-

o-ch2ch2och3

BrCH2CH2OCH3

nhch-

nhch „

0.03 mol (5 g) of 3- (N-methylamino) 4-nitro-phenol is introduced into 30 ml of hexamethylphosphorotriamide (HMPT). 0.033 mole (4.6 g) of dry potassium carbonate is added. This mixture is heated in a water bath to 80 ° C. and then 0.033 mol (4 g) of 2-methoxy-bromoethane is added. The reaction mixture is kept for 4 h in a boiling water bath and then poured after cooling into 150 ml of ice-cold 0.5N sodium solution. The expected product precipitates in crystallized form. It is wrung, washed with water and recrystallized from acetone. It melts at 94 ° C.

Analysis for C10H14N2O4:

Calculated: C 53.09 H 6.24 N 12.38%

Found: C 53.24 H 6.28 N 12.52%.

30

Example 4:

Preparation of (3-nitro-4-amino) phenyl - $ - methoxyethylether oh och2-ch2 0ch „

BrCH2 CH2 0CH3

n0 „

nhc0ch-

nhcoch-

och2 - ch2 och3

0-CHa-c0n _

2 5 h.s0.96% 2 4

0.04 mol (6.74 g) of 3- (N-methylamino) 4-nitro-phenol is dissolved in 20 cm 3 of hexamethylphosphorotriamide and 5 cm 3 of acetone. To this solution is added 0.06 mole (8.28 g) of potassium carbonate. This mixture previously brought to 70 ° C. is added little by little and with stirring of 0.062 mole (9.34 g) of N, N-diethylchloracetamide. The temperature of the reaction mixture is maintained for 1 hour at 75 ° C. This mixture is then poured into 80 cm 3 of ice water. The expected product precipitates in the form of an oil which crystallizes quickly. The product is drained, washed with water and recrystallized using a 50% hydroalcoholic solution. After drying under vacuum, the product melts at 92 ° C.,

First stage:

Preparation of (3-nitro-4-acetylamino) phenyl, fi-methoxyethyl-

ether

0.7 mole (137.2 g) of 3-nitro 4-acetylaminophenol 60 is introduced into 600 ml of hexamethylphosphorotriamide. 0.77 mole (106.3 g) of anhydrous potassium carbonate is added. The mixture is heated to 60 ° C. and then 0.77 mol (107 g) of: 2-methoxybromoethane is added little by little with stirring.

The reaction mixture is heated for 4 h in a boiling water bath 65 and then poured, after cooling into 2.51 of ice-cold 0.5N sodium solution.

The expected product precipitates. It is drained, washed with water and recrystallized from ethanol. After drying it melts at 80 ° C.

7

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Second step

Preparation of (3-nitro 4-amino) phenyl, P-methoxyethyl ether 0.0157 mol (4 g) of (3-nitro 4-acetylamino) phenyl, P-methoxyethyl ether is dissolved in 10 ml of 96% sulfuric acid. The mixture is brought to 80 ° C. for 3 h, then it is poured into 30 ml of ice water. Neutralized with ammonia at 22 ° B and then the expected product is drained which precipitated in crystallized form. After recrystallization from isopropanol and drying under vacuum, the product melts at 89 ° C.

Analysis for C9H12N2O4:

Calculated: C 50.94 H 5.70 N 13.20%

Found: C 50.81 H 5.59 N 13.34%.

Examples:

Preparation of {3-nitro 4-methylamino) phenyl, P-methoxyethylether ch2och3

o-ch2-ch2och3

so4 (ch3) 2

CHj 0-CHj-C ^ oCH

filtrate using acetic acid. The oily product isolated by decantation is used for the second step.

Second step:

5 Preparation of [3-nitro 4- (N-methyl, N-paratoluenesulfonyl-amino)] phenyl, P-methoxyethyl ether

The oil previously obtained is dissolved in 60 ml of IN sodium solution. 10.6 ml of methyl sulphate are added gradually, with stirring and at room temperature, simultaneously with the quantity of 4N sodium solution necessary to maintain the alkaline pH.

The reaction medium is left overnight at room temperature. The expected product precipitated in crystallized form. It is drained, washed with water and recrystallized from ethanol. After drying, it melts at 91 ° C.

Third step:

Preparation of (3-nitro 4-methylamino) phenyl, ß-methoxy-ethyl ether

0.034 mol (13 g) of [3-nitro 4- (N-methyl, N-paratoluenesulfonylamino)] - phenyl, ß-methoxyethyl ether are slowly dissolved at room temperature in 26 ml of 96% sulfuric acid. The reaction medium is kept for 4 h at room temperature and then poured onto 600 g of ice. The expected product is filtered off and precipitated in crystallized form. After washing with water, drying and recrystallization from cyclohexane, it melts at 54 ° C.

Analysis for C10H14N2O4 .:

Calculated: C 53.09 H 6.24 N 12.38%

Found: C 53.07 H 6.32 N 12.43%.

Example 6:

Preparation of (3-nitro-4, $ -hydroxyethylamino) phenyl, fi-methoxyethylether

35 och2-ch2och3

20

clch-

, ch2-c-oci

->

0-ch ”- ch. 0ch „

o-ch2-ch2och3

V ° 4

96%

-ch2ch2c1

nhch,

0-ch

First stage:

Preparation of (3-nitro 4-paratoluenesulfonylamino) phenyl,

P-methoxyethyl ether

0.05 mol (10.61 g) of (3-nitro 4-amino) phenyl, P-methoxyethyl ether (described in Example 4) is dissolved in 20 ml of Pyridine. 0.06 mol (11.4 g) of paratoluenesulfochloride is added little by little with stirring. The temperature rises to 50 ° C. The reaction medium is kept for 4 h at this temperature and then poured into 200 ml of ice-cold 2N hydrochloric solution. The expected product precipitates in the form of a very thick oil. This oil is dissolved in 100 ml of 2N sodium solution, a slight insoluble material is filtered and the sulfonamide is reprecipitated by: acidification of the

NaOH

0CH „

65

- ch20h

First stage :

Preparation of [(2-nitro-4, P-methoxyethylethoxy) phenyl ~ \ -carbamethylcarbamate

0.05 mol (10.61 g) of (3-nitro 4-amino) phenyl, P-methoxyethyl ether (described in Example 4) are introduced into 25 ml of

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dioxane. 0.028 mole (2.8 g) of calcium carbonate is added. The reaction mixture is brought to a boiling water bath and then 0.055 mol (7.9 g) of chloro-chloroformate is added little by little with stirring.

When the addition is complete, heating is maintained in a boiling water bath for 2 h. The reaction mixture is poured into 100 ml of solution, 0.5N hydrochloric ice-cold. The expected product precipitates in the form of an oil which is isolated by decantation and used directly in the second stage of the synthesis.

Second step :

Preparation of (3-nitro 4-fi-hydroxyethylamino) phenyl, P-methoxyethylether

The oil isolated during the first stage of the synthesis is heated, with stirring, for 4 h at reflux, in 50 ml of 4N sodium solution.

After cooling, it is neutralized using a 5N hydrochloric solution and then the expected product is drained, which precipitated in crystallized form. After washing with water, drying and recrystallization from benzene, the product melts at 66 ° C.

Analysis for Ci 1H16N2O5:

Calculated: C 51.56 H 6.29 'N 10.93%

Found: "C 51.37 H 6.19 N 11.06%.

Example 7:

Preparation of (3-nitro 6-amino) phenyl, P-methoxyethylether NHC0CH „NHC0CH„

reading in isopropanol and drying under vacuum, the product melts at 125 ° C.

Analysis for C9H12N2Ö4:

Calculated: C 50.94 H 5.70 N 13.20%

Found: C 50.86 H 5.59 N13.36%.

Example 8:

Preparation of (4-nitro 2-amino) phenyl, P-methoxyethylether OK

0rch2 ch2 och3

^ X-NHCOCHa

(/ X BrCH2CH2OÇH3

HCl 35 1

0CH2-CH20CH3

och2-ch2och3

First stage:

Preparation of (4-nitro 2-acetylamino) phenyl, P-methoxyethyl-30 ether

0.05 mole (11.7 g) of potassium salt of 4-nitro 2-acetylaminophenol is introduced into 40 ml of dimethylformamide (DMF). This mixture is brought to 90 ° C. and then 0.054 mol (7.6 g) of 2-methoxy-bromoethane is added gradually with stirring. The temperature is maintained for 3 h at 90 ° C. The cooled reaction mixture is poured into 200 ml of IN sodium solution. The expected product which is precipitated is filtered off and washed with water. It melts at 104 ° C.

Second step: ■

40 Preparation of (4-nitro-2-amino) phenyl, P-methoxyethyl ether 0.01 mol (2.54 g) of (4-nitro 2-acetylamino) phenyl, P-methoxyethyl ether is introduced into 5 ml of hydrochloric acid at 35%. The hydrochloric solution is heated in a boiling water bath for 30 minutes and then 20 ml of ice water are added. By neutralization with the aid of ammonia, the expected product is precipitated in crystallized form. It is drained, washed with water and recrystallized from ethyl acetate. After drying under vacuum, it melts at 97 ° C.

First stage:

Preparation of (3-nitro 6-acetylamino) phenyl, P-methoxyethyl ether

0.04 mole (7.8 g) of 3-nitro 6-acetylaminophenol is introduced into 40 ml of hexamethylphosphorotriamide. 0.044 mole (6.1 g) of dry potassium carbonate is added. The mixture is heated to around 60 ° C. and then 0.044 mol (6.1 g) of 2-methoxy-bromoethane is added. The reaction mixture is kept for 2 h in a boiling water bath and then poured into 200 ml of ice-cold 0.5N sodium solution. The expected product precipitates. It is drained, washed with water and recrystallized from acetonitrile. After drying it melts at 130 ° C.

Second step :

Preparation of (3-nitro-6-amino) phenyl, P-methoxyethyl ether 0.0157 mol (4 g) of (3-nitro 6-acetylamino) phenyl, P-methoxyethyl ether are introduced into 12 ml of 35% hydrochloric acid . The reaction mixture is heated for 1 hour in a boiling water bath. After cooling, 20 ml of water are added. The expected product is filtered off and precipitated in crystallized form. After washing with water, recrystall-

50

Analysis for C9H12N2O4:

Calculated: C 50.94 H 5.70 N 13.20%

Found: C 50.74 H 5.79 N 13.39%.

Example 9:

Preparation of (3-nitro 6-amino) phenoxyethyl-55 amine hydrochloride

65

9

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NH2 NH2, H2 °

O-CH2-CH2-NH2 HCl _

f / ^ y- O-CH2-CH2-NH2 IX U, HCl

First stage:

Preparation of (3-nitro 6-acetylamino) phenyl, $ -phthalimidoethyl-ether

0.02 mole (3.9 g) of 3-nitro 6-acetylaminophenol is dissolved in 20 ml of hexamethylphosphorotriamide. To this solution is added 0.022 mole (3.04 g) of potassium carbonate and 0.022 mole (5.6 g) of P-bromoethylphthalimide. The reaction mixture is heated in a boiling water bath for 3 h. After cooling, this mixture is poured into 100 cm3 of ice-cold IN sodium solution. The expected product which is precipitated is filtered off. After washing with water, recrystallization from acetic acid and drying under vacuum at 50 ° C. the product melts at 265 ° G.

Analysis for C18H15N3O6:

Calculated: C 58.53 H 4.09 N 11.38%

Found: C 58.38 H 4.08 N 11.54%.

Second step:

Preparation of (3-nitro 6-acetylamino) phenoxyethylamine Heated for 2 h in a boiling water bath 0.057 mol (21 g) of (3-nitro 6-acetylamino) phenyl, P-phthalimidoethyl ether and 5.5 ml of hydrate hydrazine 98% in 250 ml of normal propyl alcohol. After cooling the reaction mixture and adding 150 ml of 0.5N sodium solution, the initial product which has not reacted is recovered by spin drying. The filtrate is acidified using hydrochloric acid in order to remove the phthalhydrazide formed, insoluble in an acid medium, by spinning. By neutralizing the new filtrate with ammonia, the expected product is precipitated, after concentration under vacuum, in the form of hydrochloride.

This hydrochloride is treated with an IN sodium solution. The (3-nitro 6-acetylamino) phenoxyethyl-amine is filtered off and washed with water which, after recrystallization from isopropanol and drying under vacuum at 50 ° C., melts at 132 ° C.

Third step :

Preparation of (3-nitro 6-amino) phenoxyethylamine hydrochloride

Heated for 5 h in a boiling water bath 0.02 mol (4.78 g) of (3-nitro 6-acetylamino) phenoxyethylamine in 15 cm3 of 35% hydrochloric acid. After cooling, 5 cm 3 of water are added and the solution is neutralized with ammonia. The expected hydrochloride is drained. After washing with a dilute hydrochloric solution, recrystallization using a hydroalcoholic solution and drying under vacuum the product melts with decomposition around 260 ° C.

Analysis for C8H12N3O3CI:

Calculated: C 41.12 H 5.18 N 17.98 Cl 15.17%

Found: C 41.14 H 5.14 N 18.14 Cl 15.27%.

Example 10:

Preparation of (3-nitro 6-amino) phenylmesylaminoethyl ether nh ,,

o-ch2-ch2-nhso2ch3

nhcoch.

o-ch2-ch2-nh2

I-

CHgS02Cl nhcoch,

20

HCl

-ch2-ch

, -nh 2 l so2ch3

rjp 0-ch2-ch2-nhs02ch3

35

40

First stage:

Preparation of (3-nitro 6-acetylamino) phenylmesylaminoethyl ether

0.01 mol (2.4 g) of (3-nitro 6-acetylamino) -phenoxyethylamine (2nd step of Example 9) is introduced into 10 ml of pyridine and added little by little, with stirring and at room temperature , 0.02 mole (2.29 g) of mesyl chloride. Stirring is continued for 3 h and then the reaction medium is poured into 60 ml of an ice-cold 2N hydrochloric solution. The expected product precipitates. It is drained, washed with water and recrystallized from ethanol. After drying it melts at 176 ° C.

Second step:

Preparation of (3-nitro 6-amino) phenylmesylaminoethyl ether 0.01 mol (3.17 g) of (3-nitro 6-acetylamino) phenyl-mesylaminoethyl ether is introduced into 10 cm3 of 35% hydrochloric solution. The mixture is heated 25 minutes in a boiling water bath. 50 ml of water are added. On cooling, the mesylated derivative precipitated in crystallized form. After recrystallization from ethanol and drying, it melts at 164 ° C.

Analysis for C9H13N3O5S:

Calculated: C 39.27 H 4.76 N 15.27 Found: C 39.55 H 4.91 N 15.41

S 11.62% S 11.46 11.49%.

Example 11:

Preparation of (3-nitro 6-amino) phenylcarbethoxyaminoethyl-ether nhcoch,

-o-ch2-ch2nh2 ^ cicq2ç2h5 ^

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10

ICOCH ^

o-ch2-ch2 - nh

I

c = 0 1

OC2H5

NH2Nli2, lf? 0

^ H2S04 96%

0-ch2-ch2- nh 10

c = o cn, so9cr j -

no2

0-ch2-ch2 nhso ch

2H5

2 3

NHCOCHo

First stage:

Preparation of (3-nitro 6-acetylaminó) phenylcarbethoxyamino-

ethyl ether

0.02 mole (4.78 g) of (3-nitro 6-acetylamino) -phenoxyethylamine (2nd step of Example 9) is introduced into 15 ml of dioxane. 0.011 mol (1.2 g) of anhydrous sodium carbonate is added. The reaction mixture is heated, with stirring, to a boiling water bath.

0.022 mol (2.39 g) of ethyl chloroformate is gradually added. After 4 h of heating in a water bath, another 0.022 mol of chloroformate and 1.2 g of sodium carbonate are added. Heating is continued for 2 hours and then the reaction mixture, previously cooled, is poured into 60 ml of ice-cold 2N hydrochloric solution.

The expected product is filtered off and precipitated in crystallized form. After washing with water and drying under vacuum, the product is chromatographically pure and melts at 205 ° C.

Second step:

Preparation of (3-nitro 6-amino) phenylcarbethoxyaminoethyl-

-ch2-ch2nhso2-ch3

20

HCl 35 7 °

ether

0.01 mol (3.10 g) of (3-nitro 6-acetylamino) phenyl-carbethoxyaminoethyl ether is dissolved in 10 ml of 96% sulfuric acid. Then the reaction medium is brought to 80 ° C. for 1 hour. After cooling, it is poured into 60 ml of ice water and neutralized using ammonia. The expected product first precipitates in oily form and then it crystallizes. After washing with water, drying and recrystallization from benzene, it melts at 112 ° C.

Analysis for C11H15N3O5:

Calculated: C 49.07 H 5.62 N 15.61%

Found: C 49.15 H 5.68 N 15.40%.

Example 12:

Preparation of (4-nitro 2-amino) phenylmesylaminoethyl ether

0 C

NHC0CH3 BrCH2- CH2-

^ 0 '

"-4

-CH2-CH2-N

NHC0CH

25 First step:

Preparation of (4-nitro 2-acetylamino) phenyl, $ -phthalimidoethyl-ether

0.06 mol (11.75 g) of 4-nitro 2-acetylaminophenol is dissolved in 60 ml of hexamethylphosphorotriamide (HMPT). 12 g of potassium carbonate and 0.066 mol (16.8 g) of p-bromoethylphthalimide are added to this solution. The reaction mixture is heated for 10 h in a boiling water bath and then poured, after cooling into 300 ml of ice-cold IN sodium solution. The expected product which is precipitated is filtered off. After washing with water and drying under vacuum, it melts at 224 ° C.

Second step:

Preparation of (4-nitro 2-acetylamino) phenoxyethylamine 40 Heated for 2 h in a boiling water bath 0.018 mole (6.64 g) of (4-nitro 2-acetylamino) phenyl, p-phthalimidoethyl ether and 1.8 ml of hydrazine hydrate 98% in 50 ml of normal propyl alcohol. The reaction medium is cooled to 0 ° C. The expected product is filtered off and precipitated in crystallized form. It is washed several times 45 times with a 0.5N sodium solution and then with water. After recrystallization from alcohol the product melts at 158 ° C.

Analysis for C10H13N3O4 .:

Calculated: C 50.20 H 5.48 N 17.57%

50 Found: C 50.12 H 5.64 N 17.34%.

Third step

Preparation of (4-nitro 2-acetylamino) phenylmesylamino-ethyl ether

0.22 mol (52.62 g) of (4-nitro 2-acetylamino) -phenoxyethylamine is introduced into 210 ml of pyridine. 0.33 mol (26 ml) of methanesulfochloride is added little by little, with stirring and without exceeding 65 ° C., to this suspension. Stirring is continued for 3 h at room temperature and then the pyridine solution is poured into 1250 ml of ice-cold 2N hydrochloric solution. The expected product precipitates in crystallized form. It is wrung out, washed with skin. After drying it melts at 194 ° C,

Step four

Preparation of (4-nitro 2-amino) phenylmesylaminoethyl ether 0.117 mole (3.7 g) of (4-nitro 2-acetylamino) phenyl-mesylaminoethyl ether is introduced into 110 ml of 35% hydrochloric acid. The reaction mixture is heated in a boiling water bath for

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2 hrs. After cooling, 400 ml of ice water are added and then ammonia at 22 ° B is added until pH = 6. The expected product precipitates in crystallized form. It is drained, washed with water and recrystallized using isopropanol. After drying it melts at 106 ° C. s

Analysis for C9H13N3O5S:

Calculated: C 39.27 H 4.76 N 15.27 S 11.62%

Found: C 39.40 H 4.94 N 15.30 S 11.71 11.77%.

Example 13:

Preparation of (3-nitro 4-amino) phenoxyethylamine OH

BrCH2CH2Br,

.N0 „I I

0-CH2-CH2-Br nhcoch.

o-ch2-ch2- n nh2nh2, h2o nhcoch q-ch2-ch2-nh2

HCl 357.

20

o-ch2-ch2-nh2

First stage:

Preparation of (3-nitro 4-acetylamino) phenyl, fi-bromoethyl ether 1 mole (196 g) of (3-nitro 4-acetylamino) -phenol is introduced into 750 ml of hexamethylphosphorotriamide (HMPT) and

375 ml of acetone. 1.5 moles (207 g) of potassium carbonate are added. The mixture is brought to a boiling water bath and then 5 moles (445 ml) of dibromoethane are added, with stirring. After 2 hours of heating in a boiling water bath, 50 g of potassium carbonate and 222 ml of dibromoethane are added. These same additions are repeated after 4 h and 6 h of heating. After 12 h of heating, the reaction medium is poured into 9 kg of ice water. The expected product first precipitates in oily form and then it crystallizes. It is wrung, washed with water and then recrystallized from a 50% hydroalcoholic mixture. After drying under vacuum, it melts at 116 ° C.

Analysis for CioHuN204Br:

Calculated: C 39.60 H 3.63 N9.24 Br 26.40%

Found: C 39.65 H 4.00 N 9.24 Br 26.65%.

Second step:

Preparation of (3-nitro 4-acetylamino) phenyl, ß-phthalimido-ethyl ether

0.01 mol (3.03 g) of (3-nitro 4-acetyamino) phenyl, P-bromoethyl ether and 0.012 mol (2.22 g) of potassium phthalimide are introduced into 15 ml of dimethylformiamide. This mixture is brought under stirring 2 V2 h in a boiling water bath. After cooling, the reaction medium is poured into 100 ml of ice water. The expected product precipitates in crystalline form, it is wrung, washed with water and recrystallized twice from acetic acid. After drying under vacuum, it melts at 193 ° C.

Analysis for C18H15N3O6:

Calculated: C 58.53 H 4.06 N 11.38%

Found: C 58.75 H 4.30 N 11.43%.

Third step :

Preparation of (3-nitro 4-acetylamino) phenoxyethylamine 0.25 mol (92.25 g) of (3-nitro 4-acetylamino) phenyl, P-phthalimidoethyl ether is added to 720 ml of normal propyl alcohol. The propanolic solution is brought to reflux and then 0.5 mol (24.2 ml) of hydrazine hydrate is added gradually with stirring. When the addition is complete, the reflux is maintained for 40 min. After cooling, 120 ml of 35% hydrochloric acid are added. The mixture is maintained for 30 min at -10 ° C. The expected product precipitates in the form of the hydrochloride in admixture with phthalhydrazide hydrochloride.

This mixture of hydrochlorides is dissolved in an ice-cold IN sodium solution. The sodium solution is extracted with chloro-45 form. The chloroform phase is washed with a little water, dried over sodium sulfate and evaporated in vacuo. The oily residue constituted by the expected product is added with a little petroleum ether. It crystallizes. It is filtered, recrystallized from cyclo-hexane and dried under vacuum. It melts at 99 ° C.

50 Analysis for C10H13N3O4:

Calculated: C 50.21 H 5.44 N 17.57%

Found: C 50.23 H 5.37 N 17.65%.

55 Fourth step:

Preparation of (3-nitro 4-amino) phenoxyethylamine 0.1 mol (23.9 g) of (3-nitro 4-acetylamino) -phenoxyethylamine is introduced into 75 ml of 35% hydrochloric acid and 20 ml of acetic acid. After 1 hour of heating in a boiling water bath 60 with stirring, the reaction medium is cooled and the expected product is drained crystallized in the form of dihydrochloride. It is wrung out and then dissolved in 150 ml of ice water. A 4N sodium solution is added until a pH equal to 2 is obtained in order to obtain the expected product which precipitates in the form of red “orange 5 monohydrochloride which melts with decomposition at 247 ° C. (monohydrochloride used in Example 15).

By treatment of this monohydrochloride with an IN sodium solution at 60 ° C., (3-nitro 4-amino) phenoxyethylamine is obtained.

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12

After spinning, washing with water, drying under vacuum and recrystallization from benzene the product melts at 110 ° C.

Analysis for C8H11N3O3:

Calculated: C 48.73 H 5.58 N 21.32%

Found: C 48.86. H 5.61 N 21.58%.

Example 14:

Preparation of (3-nitro 4-amino) phenyl, $ -acetylaminoethylether

0-ch -ch0-nh-c-oco h-

.22 „5

nhcoch.

o-ch2-ch2-nh2

o-ch, -ch.-nh-co-ch ^ I Ci 5

(CH3C0) a0 ^

h2s ° 4

öch2-ch, -nh-c-0cohc 2 | f 2 5

no.

0.05 mol (10 g) of (3-nitro 4-amino) phenoxy-ethylamine (see example 13) is dissolved in 100 ml of dioxane at 50 ° C. To this solution is added little by little, with stirring, 0.052 mole (5.35 g) of acetic anhydride. When the addition is complete, the temperature is obtained at 50 ° C. for a few minutes, the reaction medium is cooled and then 50 ml of petroleum ether are added thereto. The expected product precipitates in crystallized form. It is drained and recrystallized from ethyl acetate. It melts at 133 ° C.

Analysis for C10H13N3O4:

Calculated: C 50.21 H 5.44 N 17.57%

Found: C 50.05 H 5.43 N 17.79%.

Example 15:

Preparation of (3-nitro 4-amino) phenyl, fi-ureidoethyl ether

0-CH2-CH2 NH2 HCl o-ch2-ch2-nh-c = o nh „

K-N = C = 0,

no2

0.01 mol (2.33 g) of (3-nitro 4-amino) phenoxyethylamine hydrochloride is dissolved in 25 ml of water. To this solution is added at 40 ° C, 0.012 mol (1 g) of potassium isocyanate dissolved in 5 ml of water. The reaction medium is maintained for 10 min at 40 ° C. and then filtered. By cooling the filtrate to 0 ° C the expected product precipitates in crystallized form. It is drained and then recrystallized from a 50% hydroacetic solution. After drying under vacuum, it melts at 223 ° C.

Analysis for C9H12N4O4:

Calculated: C 45.00 H 5.00 N 23.33%

Found: C 44.92 H 5.11 N 23.11%.

Example 16:

Preparation of (3-nitro 4-amino) phenylcarbethoxyaminoethyl-

First stage :

20. F ■

Preparation of (3-nitro 4-acetylamino) phenylcarbethoxyamino-ethyl ether

0.0126 mol (3 g) of (3-nitro 4-acetylamino) -phenoxyethylamine (3rd step of Example 13) is introduced into 25 ml of dioxane. 0.007 mole (0.7 g) of calcium carbonate is added and then gradually, with stirring 0.0138 mole (1.35 ml) of ethyl chloroformate. Stirring is continued for 1 hour at 35 ° C. The reaction medium is filtered and then poured into 150 ml of ice-cold 2N hydrochloric solution. The expected product is filtered off and precipitated in crystalline form, and washed with water. After drying it melts at 140 ° C.

Second step:

Preparation of (3-nitro 4-amino) phenylcarbethoxyaminoethyl ether

0.00306 mol (0.95 g) of (3-nitro 4-acetylamino) -phenyl, carbethoxyaminoethyl ether, is gradually introduced, with stirring, into 5 ml of concentrated sulfuric acid. When the dissolution is complete, the sulfuric solution is kept for 45 min at 75 ° C. and then poured over 50 g of crushed ice. Ammonia is added until pH = 5. The expected product precipitates in the form of an oil which crystallizes quickly. It is drained, washed with water and recrystallized from a benzene / cyclohexane mixture. After drying under vacuum, it melts at

read.

Analysis for C11H15N3O5:

Calculated: C 49.07 H 5.57 N 15.61%

Found: C 49.24 H 5.56 N 15.78%.

Example 17:

50 Preparation of (3-nitro 4-amino) phenylmesylaminoethylether o-ch2-ch2 nh2

0-ch2-ch2-nhs02ch3

cvs ° 2 cs f.

nhcoch ether.

o-ch2-ch2 nh2

60

NHCOCH3

0-ch2-ch2-nhs02ch3

cicooc2 h5

naoh nhcoch.

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First stage:

Preparation of (3-nitro 4-acetylamino) phenylmesylamino-ethyl ether

0.017 mole (4 g) of (3-nitro 4-acetylamino) phenoxy-ethylamine prepared in step 3 of Example 13 is introduced into 20 ml of pyridine. To this suspension is added little by little, with stirring, and at room temperature 0.019 mol (1.47 ml) of methanesulfo-chloride. The reaction medium is maintained for 1 hour at room temperature. The pyridine solution is then poured into 50 ml of ice water. The expected product precipitates in crystallized form. It is wrung, washed with water and dried under vacuum. It melts at 140 ° C.

Second step:

Preparation of (3-nitro 4-amino) phenylmesylaminoethyl ether 0.01 mol (3.17 g) of (3-nitro 4-acetylamino) -phenyl mesylaminoethyl ether is dissolved in 15 ml of 2N sodium solution. The sodium solution is kept for 40 min in a boiling water bath. After cooling, 30 ml of ice water are added and then a 10N hydrochloric solution is added until pH = 7. The expected product precipitates in crystallized form. It is wrung, washed with water and dried under vacuum. After recrystallization from acetic acid and drying under vacuum, the product melts at 137 ° C.

Analysis for C9H13N3O5S:

Calculated: C 39.27 H 4.72 N 15.27 S 11.63%

Found: C 39.30 H 4.80 N 15.46 S 11.50%.

Example 18:

Preparation of methyldiethyl- (3-nitro 4-amino) phenoxyethyl-ammonium o-ch2-ch24

no,

nh,

0.003 mole (0.76 g) of (3-nitro 4-amino) phenyl, P-N, N-diethylaminoethyl ether (Example 16 of the main patent application) is dissolved in 12 ml of benzene. 0.0032 mol (0.2 ml) of methyl iodide is added. The reaction medium is left overnight at room temperature. The expected quaternary derivative is drained and washed with a little benzene. It melts with decomposition at 170 ° C.

Analysis for C13H22N3O3I:

Calculated: 132.15%

Found: 131.98%.

Examples of dye compositions containing the compounds of formula (I) are given below by way of illustration and without limitation.

Examples of semi-permanent dye and styling lotion. Example A

The following dye composition is prepared:

dye from Example 2 0.25 g butylglycol 10 g water q.s.p 100 - g ammonia at 22 ° B q.s.p ...... i ......... pH = 9

This composition applied to bleached hair for 15 min at 25 ° C. gives them, after rinsing and shampooing, a daffodil coloring.

Example B

The following dye composition is prepared:

dye of example 17 0.65 g monopropylene glycol 25 g monomethyl ester of diethylene glycol 7 g ammonia at 22 ° B q.s.p pH = 10

This composition applied to bleached hair for 20 min at 35 ° C gives them, after rinsing and shampooing, a golden honey coloring.

Example C

The following dye composition is prepared:

dye from Example 15 0.1 g butylglycol 10 g triethanolamine q.s.p. pH = 6.5

water q.s.p 100 g

This dye composition applied to bleached hair 20 min at 30 ° C gives them, after rinsing and shampooing, a clear apricot coloring.

Example D

The following dye composition is prepared:

dye from Example 16 0.23 g

• ethylglycol 20 g butylglycol 8 g ammonia at 22 ° B q.s.p pH = 9

water q.s.p 100 g

This dye composition applied for 20 min at 25 ° C to bleached hair, gives them, after rinsing and shampooing, a topaz color.

Example E

The following dye composition is prepared:

dye from Example 9 1 g sodium lauryl sulfate at 19% starting oxyethylene alcohol 20 g

Trilon B 0.2 g ammonia at 22 ° B 10 g water q.s.p 100 g final pH = 10.5.

This dye composition applied for 10 min at 20 ° C to bleached hair gives them a gorse coloring.

Example F

The following dye composition is prepared:

dye from Example 1 '. 0.2 g alcohol, lauric to 10.5 mole of ethylene oxide 10 g ammonia at 22 ° B q.s.p pH = 8

water q.s.p 100 g

This dye composition applied for 20 min at room temperature to bleached hair gives them, after rinsing and shampooing, a golden sand coloring.

Example G -

The following dye composition is prepared:

dye from Example 13 0.18 g C12-C14 ammonium alkyl sulfate

70% C12 and 30% Cu 15 g lauric alcohol at 10.5 moles of ethylene oxide 5 g ammonia at 22 ° B 10 g water q.s.p. 100 g final pH = 10.

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This dye composition applied for 15 min at 25 ° C on bleached hair gives them, after rinsing and shampooing, a buttercup coloring.

Example H

The following dye composition is prepared:

dye from Example 13 4 g C12-C14 ammonium alkyl sulfate

70% of C12 and 30% of Ci * 15 g lauric alcohol with 10.5 moles of ethylene oxide ...... 5 g ammonia at 22 ° B 10 g water q.s.p 100 g final pH = 10.

This dye composition applied for 15 min at 20 ° C to naturally white hair at 95% gives them a flamboyant orange coloring.

Example I

The following dye composition is prepared:

dye from Example 4 0.55 g

ethyl glycol 25 g diethanolamides from coconut fatty acids 7.5 g triethanolamine q.s.p. pH = 8.5

water q.s.p 100 g

This dye composition applied for 15 min at 20 ° C on bleached hair gives them a champagne color after rinsing and shampooing.

Example J

The following dye composition is prepared:

dye from Example 6 ... 1.3 g butylglycol 10 g water q.s.p 100 g final pH = 5.

This dye composition applied for 15 min at 20 ° C. to naturally white hair at 95% gives them, after rinsing and shampooing, an Esterel coloring.

Example K

The following dye composition is prepared:

dye of example 14 0.2 g monomethyl ester of diethylene glycol 10 g ammonia at 22 ° B q.s.p pH = 8

water q.s.p 100 g

This dye composition applied for 30 minutes at 30 ° C on bleached hair gives them, after rinsing and shampooing, a sunflower coloring.

Example L

The following dye composition is prepared:

dye from Example 5 0.05 g

ethanol at 96 ° 9 g carboxymethylcellulose 4.5 g ammonia at 22 ° B q.s.p pH = 9

water q.s.p 100 g

This dye composition applied for 25 min at room temperature to bleached hair gives them, after rinsing and shampooing, a light salmon coloring.

Example M

The following dye composition is prepared:

dye from Example 8 0.25 g

■ Ethomeen C25 (fatty coconut amines containing 15 moles of ethylene oxide) 3 g monoethanolamine lauryl ether sulfate to 2 moles of ethylene oxide 10 g 35% hydrochloric acid 3 g water qs .. 100 g when dissolved is complete, the pH is adjusted to 6 using triethanolamine.

This dye composition applied for 20 min at 25 ° C to bleached hair gives them, after rinsing and shampooing, a pineapple color.

Example N

The following dye composition is prepared:

dye from Example 3 0.5 g oleic oxyethylenated alcohol with 2 moles of ethylene oxide 3.2 g oleic oxyethylenated alcohol with 4 moles of ethylene oxide 4.8 g propylene glycol 20 g ammonia at 22 ° B qs pH = 10

water q.s.p 100 g

This dye composition applied for 25 min at 35 ° C to bleached hair gives them, after rinsing and shampooing, a lemon yellow coloring.

Example O

The following dye composition is prepared:

dye from Example 10 0.2 g

ethyl glycol 20 g monomethyl ester of diethylene glycol 8 g triethanolamine q.s.p pH = 7

water q.s.p. 100g

This dye composition applied for 20 min at room temperature to bleached hair gives them, after rinsing and shampooing, a canary yellow coloring.

Example P

The following dye composition is prepared:

dye from Example 11 0.1 g polyvinylpyrrolidone 30%

polymer S

(70% vinyl acetate

sold under code

PVP / VA E 335 by General Aniline and Film

Corporation 2 g

ethanol 40 g triethanolamine q.s.p pH = 7.5

water q.s.p. 100g

This dye composition applied as a styling lotion to bleached hair gives them a cytise coloring.

Example Q

The following dye composition is prepared:

dye from Example 7 0.4 g propylene glycol 20 g nonylphenol with 4 moles of ethylene oxide sold under the name Remcopal334 by the company Gerland 18 g nonylphenol with 9 moles of ethylene oxide sold with the name Remcopal 349 18 g ammonia at 22 ° B qs pH = 10

water q.s.p ... 100 g

This dye composition applied for 20 min at room temperature to bleached hair gives them a champagne color after rinsing and shampooing.

Example R

The following dye composition is prepared:

dye from Example 12. 0.25 g 96 ° alcohol 15 g

Carbopol 934 3.8 g

(PM 2 to 3 million acrylic acid polymer manufactured by Goodrich Chemical Co.

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water q.s.p 100 g lactic acid q.s.p pH = 3

This dye composition applied for 30 min at 30 ° C to naturally white hair at 95% gives them a golden straw shade.

Example S

The following dye composition is prepared:

1-hydroxy 4-Y-aminopropylamino- hydrochloride

anthraquinone ..: ............ - 0.4 g dye from Example 9 0.6 g

(3-nitro 4-N methylamino) phenoxyethanol 0.3 g lauric alcohol to 10.5 moles of ethylene oxide 20 g ammonia at 22 ° B q.s.p pH = 9

water q.s.p ... 100

This dye composition applied for 15 min at 25 ° C to naturally white hair at 95% gives them, after rinsing and shampooing, a bronze coloring with bronze reflections.

Example T

The following dye composition is prepared:

dye from Example 5 1.5 g

1-methylamino 4-Y-aminopropylaminoanthraquinone 0.1 g

ethylglycol 25 g carboxymethylcellulose 4 g ammonia at 22 ° B q.s.p pH = 9

water q.s.p 100 g

This dye composition applied for 20 minutes at 25 ° C on bleached hair gives them, after rinsing and shampooing, a steel blue gray coloring.

Example U

The following dye composition is prepared:

dye from Example 15 0.25 g dye from Example 10 0.30 g nitroparaphenylenediamine 0.1%

N-methylamine 1-y-aminopropylamino-4-anthra-

quinone 0.1%

ethylglycol 25 g carboxymethylcellulose 4 g ammonia q.s.p pH = 7

water q.s.p 100 g

This composition applied to naturally white hair at 95% for 20 min at 30 ° C. gives them, after rinsing and shampooing, a silver gray coloring with eucalyptus reflections.

Example V

The following dye composition is prepared:

dye from Example 2. 0.05 g

2-N-P-hydroxyethylamino 5- [4 '- (N, N-ethylacetyl-

aminoethylamino) anilino] benzoquinone 1.4 0.025 g

N - [(hydroxy 4) -phenyl] 2-methyl-5-amino benzo-

quinone-imine 0.05 g

N - [(hydroxy-4 'chloro-3') - phenyl] (hydroxy-4 "-

3-chloro) 2-anilino benzoquinone-imine 0.05 g f polyvinylpyrrolidone 60%

copolymer • <

(. vinyl acetate 40%

sold under the code PVP / VA S. 630 by the General

Aniline and Film Corporation 2 g isopropanol 35 g triethanolamine q.s.p pH = 8

water q.s.p 100 g

This dye composition applied as a styling lotion to colored hair gives them a pinkish beige shade.

Example W

The following dye composition is prepared:

dye from Example 18 1 g carboxymethylcellulose 3.3 g ammonia at 22 ° B q.s.p. .... pH = 10

water q.s.p 100 g

This dye composition applied to bleached hair for 10 minutes at 25 ° C. gives them, after rinsing and shampooing, a powerful orange coloring.

Examples in oxidation dyeing

Example I

The following dye composition is prepared;

dye from Example 14 0.5 g.

deparatoluylenediamine dihydrochloride ................ 0.75 g 2-methyl 5-methoxyparaphenylene dihydrochloride

diamine 04- g

6-hydroxyphenomorpholine 0.2 g meta-aminophenol 0.5 g a-naphthol 0.1 g 3-chloro-4-amino phenol hydrochloride ........... 0.3 g butylglycol 5 g lauric alcohol oxyethylenated to 10.5 moles of ethylene oxide 5 g ammonia at 22 ° B 8 "g water qs 100 g the final pH is equal to 10.

At the time of application, 70 g of hydrogen peroxide at 20 volumes are added. This dye composition applied for 20 min at 30 ° C to bleached hair gives them, after rinsing and shampooing, a dark brown coloring with slight purplish reflections.

Example II

The following dye composition is prepared:

dye from Example 13 .... 0.8 g

(2-nitro-5-N, N-diethylamino) phenyl ß-carboxy-

methyl ether 0 ^ 4 g 4- (N-ß-hydroxyethylamino) aniline sulfate 0.3 g

2,6-dimethyl 3-aminophenol: ... 0.1 g

2,6-diaminopyridine 0,05 g sodium lauryl sulfate 19% starting oxyethylenated alcohol 20 g

Trilon B 0.2 g ammonia at 22 ° B • ... ■ •. 10 g water q.s. 100: g

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

This dye composition applied during. 25 minutes at 30 ° C on naturally white hair at 95% gives them, after rinsing and shampooing, a very light brown chestnut color.

Example III

The following dye composition is prepared:

dye from Example 3 0.3 g

1-methoxy 3-nitro 4- (N-p-hydroxyethylamino) benzene 0.5 g

(3-nitro 4-amino) phenoxyethanol 0.5 g.

4- (N-ethyl, N-carbamylethyl) aminoaniline 0.9. g resorcin 0.5 g a-naphthol <3.2 g.

lauric alcohol with 10.5 moles of ethylene oxide ...... 4.7 g butylglycol 4.7 g ammonia at 22 ° B 5 g water q.s.p. 100g

The final pH is 10.

At the time of use, 60 g of hydrogen peroxide are added to 20 volumes.

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This dye composition applied 20 min at 30 ° C to colored hair gives them, after rinsing and shampooing, a coffee color.

Example IV

The following dye composition is prepared:

dye from Example 2 0.5 g

(3-nitro 4-amino) phenoxyethanol 0.15 g 3-methoxy-4-N-P-hydroxyethylamino- sulfate

aniline. 0.15 g 3-methyl sulfate 4-N-P-acetylaminoethylamino-

aniline 0.17 g para-aminophenol 0.5 g

2-methyl 5-N-P-hydroxyethylIamino'phenol 0.2 g

2-methyl 5-ureidophenol 0.5 g sulfated with 4-N-methylaminophenol. 0.1 g sodium lauryl sulfate at 19% starting oxyethylenated alcohol 20 g

TrilônB 10 g ammonia at 22 ° B 10 g water q.s.p 100 g

The final pH is 10.

At the time of use, 40 g of hydrogen peroxide are added to 20 volumes.

This dye composition applied to bleached hair 15 min at 25 ° C gives them, after rinsing and shampooing, a golden beige color.

Example V

The following dye composition is prepared:

dye from Example 5 • • 0.02 g dye from Example 9 0.02 g

2-methyl 4- (N-ethyl, N-mesylaminoethyl) aminoaniline 0.8 g resorcin ...... 0.15 g

2-methyl 5- (N-P-hydroxyethylamino) phenol 0.1 g sodium lauryl sulfate to 10 moles of starting oxyethylenated alcohol, - 20 g

Trilon B ....... 0.2 g 40% sodium bisulfite solution 1 g ammonia at 22 ° B 10 g 40% sodium bisulfite solution 1 g water q.s.p 100 g

The final pH is 10.5.

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

The dye composition applied for 30 min at 25 ° C to bleached hair gives them, after rinsing and shampooing, a silver gray coloring with maluves reflections.

Example VI

The following dye composition is prepared:

dye from Example 9, ........ 0.30 g

1-methoxy 3-nitro 4-N-P-hydroxyethylaminobenzene. 0.30 g 2,6-dimethyl-3-methoxypara- dihydrochloride

phenylenediamine ...... 0.20 g para-aminophenol ...... * Y .. "0.15 g 2,4-diaffiinoanisolated dihydrochloride. 0.10 g reorder 0.15 g ammonium lauryl sulfate ., 7 g propylene glycol i ..... 25 g ammonia at 22 ° B 5 g water qs 100 g

The final pH is 9.5.

At the time of use. 25 g of hydrogen peroxide are added to 20 volumes.

The dye composition applied for 30 min at 25 ° C to naturally white hair at 95% gives them, after rinsing and shampooing, a light mahogany coloring.

Example VII

The following dye composition is prepared:

dye from Example 9 0.30 g

1-methoxy 3-nitro 4-N-P-hydroxyethylamino-

benzene 0.30 g 4-N-di-P-hydroxyethylaminoaniline sulfate 0.20 g para-aminophenol 0.15 g 2,4-diaminoanisole dihydrochloride 0.10 g resorcin 0.15 g ammonium lauryl sulfate 7 g propylene glycol 25 g ammonia at 22 ° B 5 g water qs 100 g

The final pH is 9.5.

At the time of use, 25 g of hydrogen peroxide are added to 20 volumes.

The dye composition applied for 20 minutes at 30 ° C on bleached hair gives them, after rinsing and shampooing, a very golden light brown coloring.

Example VIII

The following dye composition is prepared:

dye from Example 6 0.35 g

(3-nitro 6-N-p-hydroxyethylamino) phenoxyethanol .. 0.3 g 3-nitro 4-N-p-hydroxyethylamino-N, N- (methyl-

hydroxyethyljaniline 0.5 g 2.5 diamino 4-methylphenol dihydrochloride 0.075 g ammonium lauryl sulfate 10 g ammonia q.s.p pH = 9

water q.s.p 100 g

This dye composition applied for 20 min at room temperature to bleached hair gives them, after rinsing and shampooing, a golden bronze coloring.

Example IX

The following dye composition is prepared:

dye from Example 5 0.2 g

4-N, N- (ethylcarbamylmethylamino) aniline 3.1 g trihydroxybenzene 2 g alcohol at 96 ° 30 g triethanolamine q.s.p pH = 8

water q.s.p 100 g

This dye composition applied for 30 min at 25 ° C on bleached hair gives them, after rinsing and shampooing, a hazelnut color.

Example X

The following dye composition is prepared:

dye from Example 6 4 g (3-nitro 6-amino) phenyl hydrochloride,

P-N, N-diethylaminoethyl ether 0.5 g 2,5-diamino 4-methylphenol dihydrochloride 1%

ethylglycol 10 g C12-C14 ammonium alkyl sulfate

70% of C12 and 30% of C14 13.5 g ammonia at 22 ° B 10 g water q.s.p 100 g

The pH is equal to 9.5.

This dye composition applied for 10 minutes at room temperature to bleached hair gives them a light brown coloring with light bronze reflections.

5

10

15

20

25

30

35

40

45

50

55

60

65

Example XI

The following dye composition is prepared:

dye from example 13

(3-nitro 4-N-methylamino) phenoxyethanol

2,6-diamino-4-N, N-diethylamino- hydrochloride

phenol

2,6-diaminohydroquinone dihydrochloride

4,4'-diamino 3,3 ', 5,5'-tetramethyldiphenylamine

17,616,840

propylene glycol 25 g diethanolamides from coconut fatty acids 7 g ammonia at 22 ° B 5 g

0> 15 g water q.s.p 100 g

0.25 g 5

At the time of use, 25 g of hydrogen peroxide are added to 0.20 g of 20 volumes.

0.15 g This dye composition applied for 25 min at 30 ° C 0.20 g on bleached hair gives them a mahogany color.

R

Claims (23)

616 840 2 1. Dye composition for human hair, characterized in that it contains in aqueous or hydroalcoholic solution, of pH between 3 and 11.5, from 0.001 to 5% by weight of one or more compounds of formula: ^ Ô-N ° 2 m in which Z represents a substituted lower alkyl radical chosen from the group carbalkoxyaminoalkyle, alkoxyalkyle, N, N-dialkyl-carbamylalkyle, acylaminoalkyle, ureidoalkyle, mesylaminoalkyle and - (CH2) n — N® — Xe, n being an integer from 1 to 6 and Xe is an ankmic residue, the valences of the nitrogen atom N® which are represented free being saturated by hydrogen atoms and / or unsubstituted or substituted alkyl or aryl radicals , Ri and Rî, identical or different, represent a hydrogen atom, a lower alkyl radical or a substituted lower alkyl radical, identical or different from Z and the functional groups NO2 and NR1R2 can occupy on the nucleus all positions relative to OZ. 2. Composition according to claim 1, characterized in that in the compounds of formula (I '), Ri and R2, identical or different, are chosen from the group formed by hydroxyalkyl, amino-alkyl, carbamylalkyl and carboxyalkyl. 3. Composition according to one of claims 1 or 2, characterized in that it contains other direct dyes. 4. Composition according to claim 3, characterized in that it contains azo dyes, anthraquinone dyes, nitro dyes from the benzene series, indoanilines, indophenols or indamines. 5. Composition according to one of claims 1 or 2, characterized in that it contains from 20 to 75% and preferably from 25 to 50% by weight of a lower aliphatic alcohol comprising 1 to 4 carbon atoms. 6. Composition according to claim 5, characterized in that the alcohol is ethanol or isopropanol. 7. Composition according to one of claims 5 or 6, constituting a hair styling lotion, characterized in that it contains a cosmetic resin in the proportion of 1 to 3% and preferably from 1 to 2% in by weight, and 20 to 75% and preferably 25 to 50% by weight of a lower aliphatic alcohol having 1 to 4 carbon atoms. 8. Composition according to claim 7, characterized in that the cosmetic resin which it contains is polyvinylpyrroli-done, an ero-tonic acid-vinyl acetate or vinyl-pyrrolidone-vinyl acetate copolymer, methylvinylether-maleic anhydride copolymer and its ethyl, isopropyl and butyl esters and the maleic anhydride-butylvinyl ether copolymer. 9. Composition according to claim 1, characterized in that it contains one or more bases and / or oxidation couplers. 10. Composition according to claim 9, characterized in that one uses as oxidation dye at least one oxidation base chosen from paraphenylenes diamines, para-aminophenols and pyridine derivatives. 11. Composition according to Claim 10, characterized in that the paraphenylenes diamines are primary, secondary or tertiary amines corresponding to the general formula: in which Ru and R12, identical or different, denote hydrogen, a lower straight or branched chain alkyl group, mono- or polyhydroxylated alkylene, piperidinoalkyl, carbamylalkyl, morpholinoalkyl, acylaminoalkyl, 5-mesylaminoalkyl, sulfoalkyl, sulfonamidoalkyl, groups in which the alkyl radical preferably contains 1 to 4 carbon atoms, Ru and Ri 2 can also together form a heterocyclic group with five or six members, such as morpholine or piperidine. Ri3, Ri4, Ri5 and Ri6 mean independently of one another a hydrogen or halogen atom, a lower alkyl or lower alkoxy group, preferably having 1 to 4 carbon atoms. 12. Composition according to claim 10, characterized in that the paraphenylenediamine is chosen from the group consisting of paraphenylenediamine, paratoluylenediamine, methoxyparaphenylenediamine, chloroparaphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,5-dimethylenediamine , 2-methyl-5-methoxy-paraphenylenediamine, 2,6-dimethyl-5-methoxy-paraphenylenediamine, N, N-dimethyl-paraphenylenediamine, 3-methyl-4-amino, N- (diethyl) -anifine, N , N- (di-P-hydroxyethyl) paraphenylenediamine, 3-methyl-4-amino, N- {di-P-hydroxyethyl) aniline, 3-chloro-4-amino, N- {di-P-hydroxyetbyl) aniline, amino-4 N, N- (ethyl, carbamylethyljaniline, methyl-3 amino-4 N, N- {ethyl, carba-methyl) aniline, amino-4 N, N- {ethyl, piperidinoethyl ) aniline, amino-4 N, N- (ethyl, morpholinoethyl) aniline, methyl-3 amino-4 N, N- (ethyl, morpholinoethyl) aniline, amino-4 N, N- (ethyl, acetyl -aminoethyl) aniline, 3-methyl-4-amino, N- (ethyl, acetylami no-30 ethyl) aniline, amino-4 N, N- (ethyl, mesylaminoethyl) aniline, methyl-2 amino-4 N, N- (ethyl, mesylaminoethyl) anihine, amino-4 N, N- (ethyl, p-sulfoethyl) aniline, methyl-3 amino-4 N, N- (ethyl, P-sulfoethyl) aniline, N - [(amino-4 ') - phenyl ] morpho-line, N - [(amino-4 ') - phenyl] piperidine, methyl-3, amino-4 N-methylaniline, chloro-2 amino-4 N- (ethyl) aniline, methyl- 2 amino-4 N- (P-hydroxyethyl) aniline. 13. Composition according to Claim 10, characterized in that the paraaminophenol is chosen from the group consisting of: paraaminophenol, 2-methyl-4-amino-phenol, 3-methyl 40. 4-amino-phenol, 2-chloro-4-amino phenol, 3-chloro-4-amino phenol, 2,6-dimethyl-4-amino phenol, 3,5-dimethyl-4-amino phenol, 2-dimethyl, 3 amino-4 phenol, dimethyl-2,5 amino-4 phenol. 14. Composition according to claim 10, characterized in that the derivative of pyridine is 2,6-diamino pyridine. 15. Composition according to Claim 9, characterized in that the said couplers correspond to the general formula: 55 in which R17 and Ris, identical or different, signify hydroxy, - NHR where R can be a hydrogen atom, an acyl, ureido, carbalkoxy, carbamylalkyl or alkyl group; R17 and Ris can also mean hydrogen and alkyl, provided that at least one of the substituents Ri 7 and RiS denotes OH. 60 Ri9 and R20 may denote hydrogen, branched or unbranched alkyl, alkoxy, halogen, amino optionally substituted by an alkyl, acylamino or ureido group. 16. Composition according to Claim 15, characterized in that the couplers are resorcinol, metaaminophenol, 65 diamino-2,4 anisole, 2-methyl-5 ureido-phenol, 2,6-dimethyl-5 amino-phenol , 2-methyl-5-acetylamino-phenol, 2,6-dimethyl-5-amino-phenol, 2-methyl. -5-acetylamino-phenol, 2,6-dimethyl 5-acetylamino-phenol, 3-amino-4-methoxy phenol. 3 616840 17. Composition according to Claim 9, characterized in that the said couplers are heterocyclic compounds such as hydroxy-6 phenomorpholine or a-naphthol. 18. Composition according to one of claims 9 to 17, characterized in that it is used in mixture with an oxidant. 19. Composition according to Claim 18, characterized in that the oxidizing agent used is hydrogen peroxide or a peroxide or a persalt. 20. Composition according to one of the preceding claims, characterized in that the proportion of the oxidation bases is between 0.03 and 2% and that that of the coupler is between 0.015 and 2% by weight. 21. Process for the preparation of the compounds of general formula: (I ') 22. The method of claim 21, characterized in that Ri and R2, identical or different, are chosen from hydroxyalkyl, aminoalkyl, carbamylalkyl and carboxyalkyl groups. in which Z represents a substituted lower alkyl radical chosen from the group carbalkoxyaminoalkyle, alkoxyalkyle, N, N-dialkylcarbamylalkyle, acylaminoalkyle, ureidoalkyle, mesylaminoalkyle and - (CH2) „- N®-Xe, n being an integer from 1 to 6 and Xe is an anionic residue, the valences of the nitrogen atom N® which are represented free being saturated by hydrogen atoms and / or unsubstituted or substituted alkyl or aryl radicals, Ri and R2, identical or different, represent a hydrogen atom, a lower alkyl radical or a substituted lower alkyl radical, identical or different from Z and the functional groups NO2 and NRiR2 can occupy all positions with respect to OZ on the nucleus, characterized in that it consists in reacting an alkylating agent of formula XZ, in which X represents a halogen atom and Z a substituted alkyl radical chosen from the group carbalkoxyaminoalkyle, alkoxyalkyle, N, N-dialkylcarbamylalkyle, acylaminoal kyle, ureidoalkyle, mesylaminoalkyle and - (CH2) „- N® — Xe where n is a number from 1 to 6 and Xe is an anionic residue, the valences of the nitrogen atom N® which are represented free being saturated with hydrogen atoms and / or unsubstituted or substituted alkyl or aryl radicals, on an alkaline salt of the compound of formula (II): qjj , P ~ NO. (ii) in which Y represents the group N having the meanings already given, or AT / \ laughed , Ri and R2 r2 an N group OCH3 and, in the latter case, to transform the group N in NHRi grouping \ Ri French patent No. 2132214 discloses dye compositions for hair which contain several substituted nitro-aminophenols. In its French patent application No. 74.36651, the proprietor describes dye compositions for human hair, which contain in solution at least one etheroxide of general formula: (I) COCHa In which Z represents a substituted lower alkyl radical, Ri and R2, which may be identical or different, may be a hydrogen atom, a lower alkyl radical or a substituted lower alkyl radical which may be identical to or different from Z and the functional groups NO2 and NRiR2 may occupy on the core all positions with respect to port to OZ. In this patent application No. 74.36651, the holder has shown the importance in the compounds of general formula (I) of the different meanings taken by the radical Z with regard to the properties of the compounds obtained. The licensee has now discovered that the compounds of formula (I) in which the radical Z is a substituted lower alkyl radical chosen from the group carbalkoxyaminoalkyle, alkoxyalkyle, N, N-dialkylcarbamylalkyle, acylaminoalkyle, ureidoalkyle, mesylaminoalkyle and - (CH2) „ - N® - Xe, also have a good affinity for the hair and give good uniformity to partially sensitized hair,