WO1993016679A1

WO1993016679A1 - p-PHENYLENE DIAMINE DERIVATIVES AS INITIAL PRODUCTS FOR OXIDATION DYES

Info

Publication number: WO1993016679A1
Application number: PCT/EP1993/000351
Authority: WO
Inventors: David Rose; Edgar Lieske; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-02-21
Filing date: 1993-02-13
Publication date: 1993-09-02
Also published as: DE4205329A1

Abstract

p-phenylene diamine derivatives of general formula (I) wherein: R?1 and R2¿ independently of each other represent alkyl groups with 1 - 4 C atoms, X represents a hydrogen atom or a halogen atom, and n is an integer between 2 and 4; and the salts thereof, are useful initial products for oxidation dyes. They are suitable for use as developers together with standard couplers to formulate oxidation hair dyes particularly for shades in the ruby-blue range.

Description

'p-phenylenediamine derivatives as oxidation dye precursors'

The invention relates to the use of p-phenylenediamine derivatives as oxidation dye precursors, in particular as developer components in oxidation colorants for keratin fibers.

The so-called oxidation hair colorants play a preferred role for dyeing keratin fibers, in particular hair, furs and furs, because of their intensive colors and good fastness properties. Such hair colorants contain oxidation dye precursors in an aqueous 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.

As developer substances. Usually primary aromatic amines with a further free or substituted hydroxy or amino group in para or ortho position, furthermore diaminopyridine derivatives, heterocyclic hydrazone derivatives and 4-aminopyrazolone derivatives are used. Metaphenylene diamine derivatives, dihydroxynaphthalenes, naphthols, resorcinol derivatives, meta-aminophenols and pyrazolones are used as so-called coupler substances.

A certain developer substance can form very different color shades when combined with different couplers, but it is often not possible to achieve the multitude of natural hair color shades with the help of a single developer substance. In practice, therefore, a combination of different developer components and coupler components is usually required in order to obtain a single natural-looking hair color. Therefore, there is a constant need for new developer components. Good oxidation dye precursors must first of all meet the following requirements:

In oxidative coupling, they have to develop the desired color shades with sufficient intensity and authenticity. When used in hair dyes, they should have good absorption properties on human hair even at low temperatures below 40 ° C., with no noticeable differences between damaged and freshly regrown hair, and they should be resistant to light, heat and the influence of chemical reducing agents such. B. against perm fluids; after all, they should not stain the scalp too much and, above all, they should be harmless in toxicological and dermatological terms.

p-Phenylenediamine and derivatives of this compound have long been known as oxidation dye precursors. However, many of these compounds are toxicologically and dermatologically questionable because they have allergic properties. There is therefore a high level of interest in oxidation dye precursors which, on the one hand, form intensive colors with high fastness properties, but on the other hand are harmless from a toxicological and dermatological point of view.

The German patent application DE 27 37 291 describes N- (2-alkoxyalkyl) -p-phenylenediamine derivatives, alkoxy being either methoxy or ethoxy and alkyl being either ethyl or propyl, as developer components in oxidation hair colorants.

US Pat. No. 3,884,627 also describes oxidation colorants with substituted p-phenylenediamines. In addition to p-phenylenediamines with a tertiary amino group and unsubstituted benzene nucleus, the publication also describes p-phenylenediamines with a secondary amino group, the benzene nucleus of which necessarily has at least one substituent. However, these types of compounds either have disadvantages with regard to skin compatibility or are less suitable for achieving deeper hair colorations. It has now been found that by using p-phenylenediamine derivatives of the formula I as developer components in oxidation hair colorants, hair colorations with respect to light fastness, heat stability, cold wave fastness and leveling ability can be significantly improved.

The invention relates to the use of p-phenylenediamine derivatives of the formula I.

NH "

in which R ^ and R ^ independently of one another represent alkyl groups with 1 to 4 carbon atoms, X is a hydrogen atom or a halogen atom and n is a whole number between 2 and 4, or their salts as a precursor for producing oxidation colorations .

The compounds of the formula I or their salts, in which R * and R ^ are methyl groups and n is 2, have a particularly favorable coloring behavior. The use of these compounds or their salts as precursors for producing oxidation colorations is therefore a further subject of the invention.

The p-phenylenediamine derivatives of the formula I are oxidation dye precursors of the developer substance type, ie they are able to form dyes under the action of oxidizing agents. However, particularly brilliant and intense colors are formed in the presence of coupler substances. Compounds such as, for example, are particularly suitable as coupler substances. B. α-naphthol, ortho-cresol, meta-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, pyrocatechol, pyrogallol, 1,5- or 1,7-dihydroxynaphthalene, 5-amino- 2-methylphenol, meta-aminophenol, 2,4-diaminoanisole, meta-toluenediamine, resorcinol, resorcinol monomethyl ether, meta-phenylene diamine in, l-phenyl-3- methyl-pyrazolone-5, l-Amι ^{'no-3-nitrobenzene,} 2,4-dichloro-3-aminophenol, 1,3-Bιs- (2,4-diaminophenoxy) propane, 2-Chlorresorcιn, 2-chloro- 6-methyl-3-aminophenol, 2,7-dihydroxynaphthalene, 2-methylresorc n, 2,4-diaminophenol.

With these and other known coupler substances, the p-phenylenediamine derivatives of the formula I form a broad spectrum of color shades, of which those in the ruby to blue range are particularly noteworthy because of their good fastness properties. The p-phenylenediamine derivatives of the formula I according to the invention are therefore eminently suitable for use as oxidation dye precursors of the developer type in hair colorants.

The p-phenylenediamine derivatives of the formula I can either as such or in the form of their water-soluble salts with inorganic or organic

Acids, e.g. B. as hydrochlorides, sulfates, phosphates, acetates, propionates, lactates or citrates.

Most of the compounds of formula I are already known, those compounds of general formula I in which R * and R ^ are methyl groups, n is 2 and X represents a fluorine atom or a chlorine atom, and their salts are new; they are therefore themselves the subject of the present invention.

The process for their production is also an object of the invention. For this purpose, methyl-2-methoxyethylamine (CH3-H- (CH2) 2-0CH3), which is known per se from the literature, is reacted with a nitrobenzene derivative of the formula II, where Y represents a fluorine atom, if X is a hydrogen atom or a fluorine atom and Y represents a chlorine atom when X is a chlorine atom and then converts the nitro group into the amino group in the reaction product of the formula III by catalytic hydrogenation. NO,

'(CH ₂ ) _n - OR'

Another object of the invention are hair dyes with a content of oxidation dye precursors in a cosmetic carrier, the oxidation dye precursors being p-phenylenediamine derivatives of the formula I, where R * and R ^ independently of one another are alkyl groups with 1 to 4 carbon atoms, X is a hydrogen atom or is a halogen atom and n is an integer from 2 to 4, or their salts as developer component in an amount of 0.05 to 10 mmol per 100 g of the hair dye and, if appropriate, conventional coupler components.

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 can be used in a molar ratio of 1: 0.5 to 1: 2 .

However, it is not necessary for the compounds of the formula I to be uniform compounds. Rather, mixtures of compounds of the formula I or mixtures of compounds of the formula I with customary developer substances are used.

To modify the hair coloring, the hair dye compositions according to the invention can also be known direct hair dyes, for. B. nitrophenylenediamine derivative, antrachinone dyes or indophenols can be added.

To produce the hair colorants according to the invention, the oxidation dye precursors and optionally direct hair dyes are incorporated into an aqueous cosmetic carrier. Such carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions z. B. shampoos or other preparations that are suitable for use on the hair.

Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides and thickeners, such as. As methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils ,. Fatty acids, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.

The constituents of the cosmetic carriers are used for the production of the hair colorants according to the invention in amounts customary for this purpose; z. For example, 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.

Particularly suitable as a carrier is a gel with a content of 1 to 20% by weight of a soap, preferably ammonium oleate, or an oil-in-water emulsion with a content of 1 to 25% by weight of a fat component with 0.5 up to 30% by weight of an emulsifier from the group of anionic, nonionic, ampholytic or zwitterionic surfactants.

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.

The oxidative development of the coloring can in principle be carried out with atmospheric oxygen, but a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a brightening effect on the hair is desired. Particularly suitable oxidizing agents are hydrogen peroxide or its addition products with urea, melamine or sodium borate, as well as mixtures of such hydrogen peroxide addition products with potassium peroxide disulfate.

A preparation of the oxidizing agent is preferably mixed with the preparation of oxidation dye precursors and carrier immediately before hair coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10.

It is particularly preferred to use the hair dye in a weakly alkaline environment, the application temperatures can be in a range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. eim coloring 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

Synthesis of N-methyl-N- (2-methoxyethyl) -p-phenylenediamine dihydrochloride (developer El)

Step 1: N-methyl-N- (2-methoxyethyl) -4-nitroaniline

A mixture consisting of 7 g (0.05 mol of 4-fluoronitrobenzene),

3.8 g (0.028 mol) of potassium carbonate and 4.46 g (0.05 mol) of methyl-2-methoxyethylamine in 80 ml of acetone were boiled under reflux for four hours. After cooling and filtering off the precipitate, the mixture was evaporated to dryness and the oil was used without purification.

Step 2: N-methyl-N- (2-methoxyethyl) -p-phenylenediamine dihydrochloride

The oil from step 1 was taken up in 200 ml of ethanol and in

In the presence of about 0.5 g Pa / C at about 20 ° C and 1 bar hydrogenated.

When the uptake of H2 had ended, the catalyst was filtered off.

After acidification with hydrochloric acid, the mixture was evaporated to dryness.

Colorless crystals, melting point: decomposition from 178 ° C.

N-methyl-N- (2-methoxyethyl) -2-chloro-p-phenylenediamine dihydrochloride (developer E2)

Step 1: N-methyl-N- (2-methoxyethyl) -2-chloro-4-nitroaniline

9.6 g (0.05 mol) of 3,4-dichloronitrobenzene and 8.9 g (0.1 mol) of methyl-2-methoxyethylamine were stirred at 120 ° C. for seven hours. After cooling, 100 ml of a H2O / HCl mixture were added and extracted 5 times with 50 ml of ether each time. After the solvent had been removed, an oil remained which was immediately used further. Stage 2: N-methyl-N- (2-methoxyethyl) -2-chloro-p-phenylenediamine dihydrochloride as in Example 1, stage 2.

Beige crystals, melting point: decomposition from 150 ° C.

N-methyl-N- (2-methoxyethyl) -2-fluoro-p-phenylenediamine dihydrochloride (developer E3)

Step 1: N-methyl-N- (2-methoxyethyl) -2-fluoro-4-nitroaniline

8.0 g (0.05 mol) of 3.4 difluoronitrobenzene and 8.9 g (0.1 mol) of methyl-2-methoxyethylamine were stirred at 120 ° C. for seven hours. After cooling, 100 ml of a H2θ / HCl mixture were added and extracted 5 times with 50 ml of ether each time. After removing the solvent, yellow crystals remained, melting point: 62 to 63 ° C.

Stage 2: N-methyl-N- (2-methoxyethyl) τ2-fluoro-p-phenylenediamine dihydrochloride as in Example 1, stage 2,

Beige crystals, very hygroscopic.

2. Application example

Hair colorants according to the invention were produced in the form of a hair color cream emulsion of the following composition: Fatty alcohol C12-14 10.0 g

Fatty alcohol C12-1 ⁺ EO-sulfate,

Na salt (28 »ig) 25.0 g water 60.0 g

Developer component E (El - E3) 7.5 mmol coupler component K (Kl - K9) 7.5 mmol Na2Sθ3 (inhibitor) 1.0 g concentrated NH3 solution to pH = 9.5 water ad 100 g

The constituents were mixed with one another in succession; after the developer components and the inhibitor had been added, the concentrated ammonia solution was first adjusted to pH 9.5 in the emulsion and then made up to 100 g with water.

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

The coloring cream was applied to strands approx. 5 cm long, 90% gray, but not specially pretreated, and left there for 30 minutes at 27 ° C. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried.

The developer components E1 to E3 according to the invention were used as developer components.

The following compounds were used as coupler components: Resorcinol class

5-Amino-2-methylphenol K2 l, 3-bis (2,4-diaminophenoxy) propane K3

1-naphthol K4

2-chloro-3-amino-6-methylphenol K5

2,7-dihydroxynaphthalene K6

4-chloro-5-amino-2-methylphenol K7

2,4-dichloro-3-aminophenol K8

2-methylresorcinol K9

The color shades achieved are shown in Table 1.

Table 1

Developer components Coupler components Nuance of the colored hair

El El El El El El

E2 E2

E3 E3 E3 E3 E3 E3

Claims

1. Use of p-phenylenediamines of the formula I.

R ' ^:

in which R * and R ^ independently of one another represent alkyl groups with 1 - 4 carbon atoms, X is a hydrogen atom or a halogen atom and n is an integer from 2 to 4, or their salts as precursors for producing oxidation colorations.

2. Use of p-phenylenediamine derivatives of the formula I or their salts according to claim 1, characterized in that Rl and R ^< - methyl groups and n is 2.

3. p-phenylenediamine derivatives of the formula I or their salts, where R * and R ^ are methyl groups, n is 2 and X represents a fluorine atom or a chlorine atom.

4. A process for the preparation of p-phenylenediamine derivatives of the formula I or salts thereof according to claim 3, where Rl, 2, n and X have the same meaning as in formula I, claim 3, characterized in that methyl-2-methoxyethylamine with a nitrobenzene derivative of the formula II NO,

wherein Y represents a fluorine atom if X is a hydrogen or a fluorine atom and Y represents a chlorine atom if X is a chlorine atom, and then in the reaction product of the formula III O,

Λ N '^ (CH ₂ ) _n - OR "converted the nitro group into the amino group by catalytic hydrogenation.

Hair colorants containing oxidation dye precursors in an aqueous cosmetic carrier, characterized in that p-phenylenediamine derivatives of the formula I according to Claims 1 to 3 or their salts as developer components in an amount of 0.05 to 10 mmol per 100 g of the hair dye and, if appropriate, customary as oxidation dye precursors Coupler components are included.