EP0435884A1

EP0435884A1 - 2-(alkoxyalkylaminomethyl)-4-aminophenols and their use in oxidative hair dyes

Info

Publication number: EP0435884A1
Application number: EP19890909743
Authority: EP
Inventors: David Rose; Horst Höffkes; Edgar Lieske
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1988-09-21
Filing date: 1989-09-12
Publication date: 1991-07-10
Also published as: DE3831977A1; EP0364731A1; WO1990003362A1; DK50291A; DK50291D0

Abstract

Lesdits produits correspondent à la formule (I), où R1 représente hydrogène, un groupe alkyle avec 1 à 4 atomes de C, un groupe hydroxyalkyle avec 2 à 4 atomes de C, un groupe aminoalkyle avec 2 à 4 atomes de C, qui peut être substitué sur l'atome d'azote par un ou deux groupes alkyle avec 1 à 4 atomes de C ou dont l'atome d'azote appartient à un anneau de pipéridine, morpholine, pyrrolidine ou pipérazine ou qui est un groupe -CmH2m-O-CnH2n+1, où m est un nombre entier entre 2 et 4 et n est un nombre entier entre 1 et 4. Lesdits produits et leurs sels solubles dans l'eau agissent en tant que développeurs des teintures par oxydation et servent de matières de base pour colorants d'oxydation lors de la fabrication de teintures pour cheveux. Avec les copulateurs habituels, lesdits produits donnent des teintures solides à nuances brunes à rousses.Said products correspond to formula (I), where R1 represents hydrogen, an alkyl group with 1 to 4 C atoms, a hydroxyalkyl group with 2 to 4 C atoms, an aminoalkyl group with 2 to 4 C atoms, which can be substituted on the nitrogen atom by one or two alkyl groups with 1 to 4 C atoms or whose nitrogen atom belongs to a ring of piperidine, morpholine, pyrrolidine or piperazine or which is a group -CmH2m- O-CnH2n + 1, where m is an integer between 2 and 4 and n is an integer between 1 and 4. Said products and their water-soluble salts act as developers of oxidative dyes and serve as materials base for oxidation dyes when making hair dyes. With the usual copulators, said products give solid dyes with brown to red hues.

Description

"2- (Alkoxyalkylaminomethyl) -iJ-aminophenols and their Use in Oxidation Hair Dyes"

The invention relates to new 2- (alkoxyalkyaminomethyl) -4-aminophenols and their salts and to their use as developer components in oxidation hair colorants.

The so-called oxidation hair colorants play a preferred role for dyeing hair because of their intense colors and good fastness properties. Such hair dyes contain oxidation dye precursors in a cosmetic carrier. Developer substances and coupler substances are used as oxidation dye precursors. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.

Good oxidation dye precursors must first and foremost meet the following requirements: in oxidative coupling, they must form the desired color shades with sufficient intensity and authenticity. They must also have a good ability to draw up on human hair, with no noticeable differences between damaged and freshly regrown hair. They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against permanent wave fluids. Finally, they should not stain the scalp too much and, above all, they should be harmless in toxicological and dermatological terms. Primary aromatic amines with a further free or substituted hydroxy or amino group located in para or ortho position, furthermore diaminopyridine derivatives, heterocyclic hydrazone derivatives and 4-aminopyrazolone derivatives are usually used as developer substances. M-Phenylenediamine derivatives, naphthols, resorcinol derivatives and pyrazolones are used as so-called coupler substances.

Of particular importance are the intensity of the color nuances formed in the oxidative coupling and the fastness properties, in particular the light fastness. From DE-OS 35 43 345 4-amino-2-aminomethylphenols were already known as oxidation hair dye precursors in hair dyes. It has now been found that even more intense and durable hair dyeing can be achieved if 2- (alkoxyalkylaminomethyl) -4-aminophenols of the structure described in more detail below are used as the developer component.

The invention relates to 2- (alkoxyalkylaminomethyl) -4-am_- nophenols of the formula (I)

NH in the R is hydrogen, an alkyl group with 1 to 4 carbon atoms, a hydroxyalkyl group with 2 to 4 carbon atoms, an aminoalkyl group with 2 to 4 carbon atoms which are linked to nitrogen by one or two alkyl groups with 1 to 4 carbon atoms. Atoms can be substituted or their nitrogen atom a piperidine, morpholine, pyrrolidine or

Piperazin-Rinq belongs to or a group -C H_ -OC H_, - ° - ^{^} ^ m 2m n 2n + 1, and wherein m is an integer from 2-4 and n is an integer from 1-4 and their water-soluble Salts. Of the Compounds of the formula (I) are of greatest importance to those in which R is hydrogen.

The compounds of formula (1) are new. However, they can be prepared in a conventional manner by adding 2-chloromethyl-4-nitrophenol with an amine of the formula (II)

in which R, m and n have the same meaning as in formula (I), brings them to reaction and in the resulting 2- (alkoxyalkylaminomethyl) -4-nitrophenol the nitro group is catalytically hydrogenated to the amino group.

The new compounds of the formula (I) or their salts are suitable for use as oxidation dye precursors of the developer type in hair colorants. They are able to form dyes under the action of oxidizing agents. However, particularly intensive and brilliant dyes are formed by oxidative coupling in the presence of coupler substances.

Another subject matter of the invention are hair colorants containing oxidation dye precursors in a cosmetic carrier, the oxidation dye precursors containing 2- (alkoxyalkylaminomethyl) -4-aminophenols of the formula (I) or their water-soluble salts as developer components in addition to customary developer or coupler components and, if appropriate direct hair dyes included. Among the numerous known coupler substances for the new developers of the formula (1) are, in particular, those with phenolic hydroxyl groups and those of the bis- (2,4-diaminophenyl) alkane and bis- (2,4-diami) type - Suitable nophenoxy) alkanes, as in DE-OS 32 35 615 and DE-OS 28 52 272 are described. A further, particularly preferred embodiment of the invention is therefore hair dye of the abovementioned type which, as coupler component, contains phenols, naphthols, resorcinols and / or 1,3-bis- (2,4-diaminophenyl) alkanes or 1,3- Contain bis- (2,4-diaminophenoxy) alkanes. Such hair dyes provide particularly intense colors in the range of red-brown to olive-brown shades.

The 2- (alkoxyalkylaminomethyl) -4-aminophenols of the formula (I) according to the invention can be used either as such or in the form of their water-soluble salts with inorganic or organic acids, for. B. isolated as hydrochlorides, sulfates, phosphates, acetates, propionates, lactates or citrates and used in hair dyes. -

In the hair colorants according to the invention, the developer substances and the coupler substances are generally used in equimolar amounts, but a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer substances and coupler substances in a molar ratio of 1: 0.5 to 1: 2 can be used. The 2-alkoxy-alkylaminomethyl) -4-aminophenols of the formula (1) according to the invention or their salts can be used in an amount of 0.05 to 10 millimoles per 100 g of the hair dye. It is not necessary for the compounds of the formula (1) to be uniform compounds. Rather, mixtures of the compounds can also be used.

In order to modify the hair coloration, known direct hair dyes, e.g. B. Nitrophenylenediamine derivatives, anthraquinone dyes or indophenols can be added. To produce the hair colorants according to the invention, the oxidation dye precursors and any direct dyes are incorporated into a suitable cosmetic carrier. Such carriers are, for example, creams, emulsions, gels or also surfactant-containing, foaming solutions, for example shampoos or other preparations which are suitable for use on the hair. Standard ingredients are TION such cosmetic Zube¬ such as wetting agents and emulsifiers such as anionic, nonionic or amphoiytische surfactants, for example fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide adducts with fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty repartialglyceride, Fettsäurealkanola ide as well as thickeners such as methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, fatty acids, furthermore perfume oils and hair care additives such as water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.

The components of the cosmetic carriers are used to manufacture the hair dye according to the invention! used in amounts customary for this purpose, e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant. The oxidation dye precursors are mixed into the carrier in amounts of 0.2 to 5% by weight, preferably 1 to 3% by weight, of the total colorant.

A preferred form of use for the 2- (alkoxyalkylaminomethyl) -4-aminophenols of the formula (I) according to the invention are cream coloring agents in the form of an oil-in-water emulsion with an amount of

1 to 10 millimoles per 100 g of developer component. , 1 to 10 millimoles per 100 g of coupler components, up to 10% by weight! an AlkyKC _Q -C) sulfal or alkyl (C -C, _} ether sulfate surfactant,

IU! O 5 to 20% by weight of a fatty alcohol mixture with 12 to 18

C atoms, 0.1 to 2% by weight of an oxidation inhibitor, preferably from the

Group alkali sulfite, alkali ascorbate or

Alkali dithionite and ammonia in an amount to adjust the pH of the emulsion to a value between 8 and 10.

The alkyl sulfate or alkyl ether sulfate surfactant mentioned can be present as alkali, ammonium or alkanolammonium salt with 2 or 3 carbon atoms in the alkanol group, for. B. as sodium, triethanolammonium or isopropanolammonium salt. As alkyl-C ₁ f.-C _{1 (} ether sulfate surfactant, a sulfuric acid monoester salt of an adduct of 1 to 10 moles of ethylene oxide with a C. .. C. fatty alcohol can be used.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on the hair is desired. Particularly suitable oxidizing agents are hydrogen peroxide or its addition products with urea, melamine or sodium borate and mixtures of such hydrogen peroxide addition products with potassium peroxodisulfate.

The use of the hair dye according to the invention can, regardless of the type of cosmetic preparation, for. B. as a cream, gel or shampoo, in a weakly acidic, neutral or alkaline mixture. The use of the hair dye in a pH range from 8 to 10 is preferred. The application temperatures can be in a range between 15 ° C. and 40 ° C. After an exposure time of approx. The hair dye is removed from the hair to be colored by rinsing for 30 minutes. The hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a color shampoo was used.

The following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto.

EXAMPLES

1. Manufacturing examples

1.1. N- (2-Hydroxy-5-aminobenzyl) -2-methoxyethylamine dihydrochloride stage 1

A mixture consisting of 18.8 g (0.1 mol) of 2-chloromethyl-4-nitrophenol and 65.0 g (0.87 mol) of 2-methoxyethylamine was boiled under reflux for 3 hours. After concentrating to dryness, the mixture was slurried with water and suctioned off. After washing with water, the mixture was dried at 70 ° C. in vacuo. Yield: 19.4 g (85.7% of theory); Melting point 160-162 ° C.

Level 2

9.1 g (0.04 mol) of the substance from stage 1 were dissolved in 300 ml of ethano! catalytically reduced (Pd / coal). When the H_ uptake had ended, the catalyst was filtered off and the solution was acidified with dilute hydrochloric acid. Were after Einen¬ gen 7.3 g (68% of theory) ^• receive. Yellow crystals; Melting point 120 ° C (dec.).

1.2. N- (2-Hydroxy-5-ammobenzy!) - 1-methoxy-isopropylamine-dϊhydrochloride

step 1

According to Example 1.1, stage 1, a mixture of

2-chloro-methy! -4-nitrophenol 94 g (0.05 mol) and 2-amino-

1-methoxypropane 35.7 g (0.4 mol) heated to 130 ° C for 3 hours.

Yield: 9.5 g (78.6% of theory) of yellow powder,

Melting point: 188-195 ° C Level 2

According to Example 1.1, stage 2, 9.0 g (0.038 mol of substance obtained in stage 1) were catalytically reduced in ethanol.

Yellow crystals; Melting point 175-181 ° C;

Yield: 8.6 g (81% of theory)

1.3. N- (2-Hydroxy-5-aminobenzyl) -3-ethoxypropylamine dihydrochloride stage 1

Analogously to Example 1.1, stage 1, starting from 41.3 g (0.4 mol) of 3-ethoxypropylamine and 9.4 g (0.05 mol) of 2-chloromethyl-4-nitrophenol.

Yield: 8.0 g (63% of theory); yellow crystals, melting point: 175 - 181 ° C

Level 2

Analogously to Example 1.1, stage 2, 7.6 g (0.03 mol) of the substance obtained in stage 1 were catalytically reduced in ethanol. Yield: 6.1 g (68.5% of theory); yellow crystals, melting point: 60 73 ° C

1.4. N- (2-Hydroxy-5-aminobenzyl) -3-isopropoxypropylamine dihydrochloride stage 1

Analogously to Example 1.1, stage 1, starting from 46.99 g (0.4 mol) of 3-isopropoxypropylamine and 9.4 g (0.05 mol) of 2-chloromethyl-4-nitrophenol.

Yield: 7.5 g (56% of theory); yellow crystals, melting point: 180 - 187 ° C

Level 2

Analogously to Example 1.1, stage 2, 7.3 g of substance obtained in stage 1 were catalytically reduced in ethanol. Yield: 6.7 g (80% of theory); beige crystals, melting point: 75 - 85 ° C 2. Examples of use

Hair colorants according to the invention were produced in the form of a hair color cream emulsion of the following composition:

Fatty alcohol _{1 2} _ 10, 0 g fatty alcohol + 2 EO sulfate,

Na salt, 28% 25.0 g

Water 60.0 g

Developer according to Example 1.1-1.4.7.5 mmol

Coupler component 7.5 mmol

Na-SO- (inhibitor) 1.0 g concentrated ammonia solution up to pH = 9.5

Water ad 100 g

The components were mixed together in succession. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.

The oxidative development of the color was carried out with 3% hydrogen peroxide solution as the oxidizing agent. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3%) and mixed.

The coloring cream was adjusted to approx. 5 cm long strands of standardized, 90% gray, but not particularly pretreated human hair applied and left there at 27 ° C. for 30 minutes. After the dyeing process had ended, the hair was rinsed, washed out with a customary shampoo and then dried. The following compounds were used as couplers:

K1 resorcinol

K2 m-aminophenol

K3 5-amino-2-methylphenol

K4 5-amino-4-chloro-2-methylphenol

K5 5-amino-6-chloro-2-methylphenol

K6 1,3-bis (2,4-diaminophenoxy) propane

K7 1-naphthol

K8 1,5-dihydroxy-naphthalene

K9 1-phenyl-3-aminopyrazolone-5

The results of the dyeing tests can be found in Table I.

TABLE

Claims

PATENT CLAIMS

1. 2- (alkoxyalkylaminomethyl) -4-aminophenols of the formula

NH- 1 -_ in the R is hydrogen, an alkyl group with 1 - 4 C atoms, a hydroxyalkyl group with 2 - 4 C atoms, an aminoalkyl group with 2 - 4 C atoms, which are attached to the nitrogen atom by one or two alkyl groups can be substituted with 1 - 4 carbon atoms or their nitrogen atom belongs to a piperidine, morpholine, pyrrolidine or piperazine ring or a group

-C H_ -O-C H-,. and where m is an integer from 2 to 4 m 2m n 2n + 1 = and n is an integer from 1 to 4 and their water-soluble salts.

2. 2- (alkoxyalkyl-aminomethyI) -4-aminophenoIe of formula I according to claim 1, characterized in that R = hydrogen.

3. Use of the 2- (alkoxyalkylaminoalkyl) -4-aminophenols of the formula I as claimed in claim 1 or 2 or their salts as oxidation dye precursors of the developer type in hair colorants.

4. Hair dye containing oxidation dye precursors in a cosmetic carrier, characterized in that as oxidation dye precursors 2- [A ikoxy alkyl -am inomethyl) - 4-aminophenols of the formula I according to claim 1 or 2 or their water-soluble salts as developer component in addition usual developer and coupler components and if necessary. direct hair dyes are included.

5. Hair dye according to claim 4, characterized in that the coupler components are phenols, naphthols, resorcinols and / or 1,3-bis (2,4-diaminophenyl) alkanes or 1,3-bis (2,4-daminophenoxy) - aIkane are included.

6. Hair dye according to claim 4 or 5, characterized gekennzeich¬ net that developer substances and coupler substances in the molar ratio 1: 0, 5 to 1: 2 are included, that the content of oxidation dye precursors 0, 2 to 0, 5 wt. % of the hair dye and the content of 2- (alkoxyalkylaminomethy!) - 4-aminophenol of the formula I, according to claim 1 or its salts, is 0.05 to 10 millimoles per 100 g of the hair dye.