DE2934331A1 - Oxidn. hair dye compsns. - contg. as developer, opt. chlorine-substd. para-phenylenediamine bonded to ring system at nitrogen atom - Google Patents

Abstract

New substd. p-phenylene diamines have formula (I). In (I) X is H or Cl; R is a cyclohexane, morpholine bonded via N or a pinane gp. and n is 1 or 2. (I) are prepd. by (i) reacting p-chloro-nitrobenzene, opt. Cl-substd. in 2-position, with the aminomethyl- or aminoethyl-substd. cyclic cpd., at 100-200 deg.C and then (ii) catalytically hydrogenating the nitro cpd. obtd. (I) and their salts with (in)organic acids are used as developer components in oxidn. hair dyes. (I) yield strong, fast shades, are soluble in water, stable to storage, non-toxic and do not irritate the skin.

Description

"New developer components for oxidation hair colors, their production and use, as well as hair colorants containing them11, are the subject of the invention are new, on a nitrogen atom via lower alkyl radicals to certain ring systems bound p-phenylenediamines.

The preparation of the substituted p-phenylenediamines according to the invention takes place by reaction in the first stage of optionally in the 2-position with chlorine substituted p-chloronitrobenzene with that by an aminomethyl radical or aminoethyl radical substituted cyclic compound at an elevated temperature of 100 - 2000 C and, in the second stage, subsequent catalytic hydrogenation of the nitro compound obtained.

Further objects of the invention are the use of the new substitutes p-Phenylenediamine derivatives as such or in the form of their salts with inorganic ones or organic acids as developer components in oxidation hair colors as well Hair dyes containing the new substituted p-phenylenediamines respectively contain their salts.

The so-called oxidation colors play a role in the coloring of hair, that by oxidative coupling of a developer component with a coupler component develop, because of their intense colors and very good fastness properties a preferred role. Nitrogen bases are usually used as developer substances such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives, heterocyclic ones Hydrazones used. As so-called coupler components, m-phenylenediamine derivatives, Phenols, naphthols, resorcinol derivatives and pyrazolones called.

Good oxidative hair dye components must primarily include the following Meet the prerequisites: You must with the oxidative coupling with the respective Developer or coupler components the desired color nuances in sufficient Develop intensity. They must also have sufficient to very good absorbability on human hair and they are also said to be toxicological and be dermatologically harmless.

The products usually used as developer substances up to now from the compound class of substituted or unsubstituted p-phenylenediamines have the disadvantage that they are sensitized and in a number of people in the wake of which cause allergies. The one to avoid this dermatological Disadvantages of recently proposed developer substances can be in their application technology Properties are not always fully satisfactory.

There was therefore a search for useful oxidation hair dyes the task of finding suitable components, the aforementioned requirements meet in an optimal way.

vs it has now been found that oxidation hair colors which meet the requirements set to a particularly high degree can be obtained if substituted p-phenylenediamines of the general formula are used as developer components in which X represents a hydrogen atom or chlorine atom, R represents a cyclohexane radical, a morpholine radical bonded via N or a pinane radical and n represents the numbers 1 or 2, and their inorganic or organic salts are used in combination with customary coupler substances.

Hair dye based on oxidation dyes with a content of substituted p-phenylenediamines of the above general formula, and their inorganic or organic salts as developer components and the coupler substances customary in oxidation hair dyes are therefore special valuable compositions in the field of oxidation hair colors.

When used as developer components, those according to the invention provide Compounds with the coupler substances generally used for oxidation hair coloring the most varied of very intense color nuances and thus represent an essential one Enrichment of oxidative hair coloring possibilities.

In addition, the substituted according to the invention stand out p-phenylenediamine due to the very good fastness properties of the dyeings achieved with it, due to good solubility in water, good storage stability and toxicological as well as dermatological harmlessness.

The substituted to be used according to the invention as developer components p-Phenylenediamines can be used either as such or in the form of their salts with inorganic or organic acids, such as chlorides, sulfates, phosphates, acetates, Propionate, lactate, citrate can be used.

Developer components to be used according to the invention are, for example N- (4-aminophenyl) -aminomethyl-cyclohexane, N- (4-amino-2-chlorophenyl) -aminomethyl-cyclohexane, N- (4-aminophenyl) -aminomethyl-morpholine, N- (4-amino-2-chlorophenyl) -aminomethyl-morpholine, N- (4-aminophenyl) -aminomethyl-pinane, N- (4-amino-2-chlorophenyl) -aminomethyl-pinane, N- (4-aminophenyl) -aminoethyl-cyclohexane, N- (4-amino-2-chlorophenyl) -aminoethyl-cyclohexane, N- (4-aminophenyl) -aminoethyl-morpholine, N- (4-amino-2-chlorophenyl) -aminoethyl-morpholine, N- (4-aminophenyl: -aminoethyl-pinane, N- (4-amino-2-chlorophenyl) -aminoethyl-pinane to name.

As examples of those to be used in the colorants according to the invention Coupler components are a-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, pyrocatechol, pyrogallol, 1,5- or 1, i-dihydroxynaphthalene, 5-amino-2-methylphenol, hydroquinone, 2,4-diamino-anisole, m-toluenediamine, 4-aminophenol, Resorcinol, resorcinol monomethylether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 1-phenyl-3-arflinopyrazolone-5, 1-phenyl-555-diketo-pyrazolidine, 1-methyl-7-dimethyl-amino-4-hydroxy-quinolone-2, 1-amino-3-acetacetylamino-4-nitro-benzene or 1-amino-3-cyanoacetylamino-4-nitro-benzene to cite.

The developer components are used in the hair dyes according to the invention generally in approximately molar amounts, based on the coupler substances used, used. If molar use also proves useful, so it is but not disadvantageous if the developer component is in a certain excess or a shortfall is used.

It is also not necessary that the developer component and the coupler substance represent uniform products, rather both the Developer component Mixtures of the substituted to be used according to the invention p-Phenylenediamines as well as the coupler substance ^ -emAsche of the above Represent coupler components.

In addition, the hair dyes of the present invention can be other known ones and customary developer components as well as, where appropriate, customary substantive ones Contain dyes in the mixture, if this is necessary to achieve certain color nuances is.

The oxidative coupling, i.e. the development of the color, can basically as with other oxidation hair dyes, by means of atmospheric oxygen take place. However, chemical oxidizing agents are expediently used. Hydrogen peroxide or its addition products in particular come as such of urea, melamine and sodium borate, as well as mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulphate.

The hair dyes according to the invention are suitable for use in cosmetic preparations such as creams, emulsions, gels or simple solutions incorporated and immediately before application on the hair with one of the mentioned Oxidizing agents added. The concentration of such dyeing preparations of the coupler-developer combination is 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight. Used in the production of creams, emulsions or gels the dye components with the other ingredients customary for such preparations mixed. Such additional components are, for example, wetting agents or emulsifiers of the anionic or nonionic type such as alkylbenzenesulfonates, fatty alcohol sulfates, Alkyl sulfonates, fatty acid alkanolamides, addition products of ethylene oxide with fatty alcohols, Thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil, Fatty acids, also perfume oils and hair care products such as pantothenic acid and cholesterol to call. The additives mentioned are used in those customary for this purpose Amounts used, such as wetting and emulsifying agents in concentrations from 0.5 to 30 percent by weight and thickener in concentrations of 0.1 up to 25 percent by weight, each based on the total preparation.

The application of the hair colorants according to the invention can, independently whether it is a solution, an emulsion, a cream or a gel, in a weakly acidic, neutral or especially alkaline environment at a pH value from 8-10. The application temperatures are in the range of 15 to 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Afterwards the hair is treated with a mild one Shampoo washed and dried.

The colorations that can be achieved with the hair colorants according to the invention show particularly when using different developer and coupler components intense color nuances. The dyeings obtained have good light, wash and rub fastness properties and can easily be removed again with reducing agents.

The following examples are intended to explain the subject matter of the invention in greater detail explain without, however, restricting it to this.

EXAMPLES First, the preparation of the inventive substituted p-phenylenediamines described.

A) N- (4-Amino-2-chlorophenyl) aminomethyl-cyclohexane dihydrochloride Stage 1 N- (4-nitro-2-chlorophenyl) aminomethylcyclohexane.

A mixture of 19.2 g (0.1 mol) 3,4-dichloronitrobenzene and 3D, 9 g (0.3 mol) of aminomethylcyclohexane would be heated up to 1100.degree. After the exothermic The reaction was further heated to 1500 C for 30 minutes. The reaction mixture obtained was poured onto 500 ml of ice water and the precipitated product was recrystallized from ethanol. There were 24 g, that is 89% of theory, of N- (4-nitro-2-chlorophenyl) aminomethylcyclohexane obtained in the form of yellow crystals with a melting point of 73-760 ° C.

Stage 2 N- (4-Amino-2-chlorophenyl) -aminoethyl-cyclohexane dihydrochloride.

24 g of N- (4-nitro-2-chlorophenyl) -aminoethylcyclohexane were in 100 ml of ethanol in the presence of Raney nickel (approx. 1 g) hydrogenated at 250 ° C. and 1 atm. When the uptake of hydrogen had ended, the catalyst was filtered off and diluted with Acidified hydrochloric acid. The resulting precipitate was filtered off with suction and dried at 700.degree. The compound N- (4-amino-2-chlorophenyl) -amino- methylcyclohexane dihydrochloride was obtained in the form of white crystals with a melting point of 242 ° C.

3) N- (4-aminophenyl) -aminomethyl-cyclohexane-dihydrochloride stage 1 N- (4-nitrophenyl) aminomethylcyclohexane.

A mixture of 9.2 g (0.06 mol) p-chloronitrobenzene and 20.3 g (0.18 Mol) aminomethylcyclohexane was heated to 1800 C for 3 hours. The received The mixture was poured onto 500 ml of ice water and the precipitate was filtered off with suction. That N- (4-nitrophenyl) aminomethylcyclohexane obtained after recrystallization from ethanol had a melting point of 1010 C.

Step 2 N- (4-aminophenyl) aminomethylcyclohexane dihydrochloride.

According to the information from stage 2, A, that obtained in stage 1 was obtained Catalytically reduced N- (4-nitrophenyl) aminomethylcyclohexane.

The N- (4-aminophenyl) -amlnomethylcyclohexanedihydrochloride was in Shape of slightly reddish colored crystals with a melting point of 2320 C obtained.

C) N- (4-aminophenyl) -aminoethylmorpholine dihydrochloride step 1 N- (8-itrophenyl) -aminoethylmorpholine.

According to the information in stage 1, B), a mixture of p-chloronitrobenzene and aminoethylcyclohexane produce the desired product N- (4-nitrophenyl) -aminoethylmorpholine obtained in the form of yellow crystals with a melting point of 124-1260 ° C.

Step 2 N- (4-aminophenyl) -aminoethylmorpholine dihydrochloride.

The desired product was selected according to the information in stage 1, A) by catalytic reduction of N- (4-nitrophenyl) aminoethylmorpholine in shape white crystals with a melting point of 1240 C.

D) N- (4-aminophenyl) aminomethylpinane dihydrochloride, step 1 N- (4-nitrophenyl) aminomethylpinane.

The product was manufactured according to the information in Step 1, B) from 3.2 g (0.02 mol) p-chloronitrobenzene and 7.8 g (0.05 mol) (+) - 3- (aminomethyl) -pinane.

The compound is a brown oil.

Step 2 N- (4-aminophenyl) aminomethylpinane dihydrochloride.

By catalytic reduction according to the information in stage 2, A) the N- (4-aminophenyl) was obtained from the brown oil obtained in the first stage -aminomethylpinane dihydrochloride after recrystallization from ethanol in the form of white Crystals with a melting point of 2050 C obtained.

The abovementioned substituted ones described in their preparation p-Phenylenediamines A - D were used as developer components in the following examples used.

The following substances were used as coupler components: K1 «-naphthol K2 2-methylresorcinol K3 m-aminophenol K4 1,7-dihydroxynaphthalene K5 1,5-dihydroxynaphthalene K6 2,4-diaminophenol K7 3,5-diamino-2-methoxy-ethylbenzene K8 1-ethoxy-2-bis- (β-hydroxy-ethyl) -amino-4-aminobenzene K9 4-chlororesorcinol KlO 2,4-dichloro-3-aminophenol K11 1-phenyl-3-ethylureido-pyrazolone-5 K12 1,3-bis (2,4-diaminophenoxy) propane.

The hair colorants according to the invention were in the form of a cream emulsion used. In an emulsion of 10 parts by weight of fatty alcohols the Chain length C12-C18, 10 parts by weight of fatty alcohol sulfate (sodium salt, chain length C12-C18 and 75 parts by weight of water each 0.01 moles of those in the table below listed developer substances and coupler substances incorporated. After that it was the pH of the emulsion is adjusted to 9.5 using ammonia and the emulsion with Water made up to 100 parts by weight. The oxidative coupling was with 1% Hydrogen peroxide solution carried out as the oxidizing agent, being 100 parts by weight 10 parts by weight of hydrogen peroxide solution were added to the emulsion. The respective Coloring cream with the addition of oxidizing agents was reduced to 90% gray, not specially pretreated human hair is applied and left there for 30 minutes. After completing the dyeing process, the hair was washed with a conventional shampoo washed out and then dried.

The colorations obtained are shown in Table 1 below.

Table 1 Example of the coupler nuance of the colored hair, game curlers 1% H2O2 solution 1 A K 1 blue-gray 2 A K 2 brown 3 A K 3 gray-brown 4 A K 4 gray-blue 5 A K 5 ink blue 6 A K 6 brown 7 A K 7 mahogany 8 A K 8 dark blue 9 B K 1 ink blue 10 B K 2 violet brown 11 B K 3 aubergine 12 B K 4 dark blue 13 B K 9 brown 14 B K 7 red brown 15 C K 1 dark blue 16 C K 2 brown 17 C K 3 magenta 18 C K 4 blue 19 C K 5 blue-gray 20 C K 6 brown 21 C -K 7 red-brown 22 C K 8 dark blue 23 C K 9 dark brown 24 C KlO blue-violet 25 C K11 violet-brown 26 C K12 dark blue 27 D K 1 gray-blue 28 D K 2 brown

Claims (9)

"New developer components for oxidation hair dyes, their production and use, as well as hair dyes containing them" Patent claims: 9 Substituted p-phenylenediamines of the general formula in which X represents a hydrogen atom or chlorine atom, R represents a cyclohexane radical, a morpholine radical bonded via N or a pinane radical and n represents the numbers 1 or 2. 2. N- (4-amino-2-chlorophenyl) aminomethyl-cyclohexane according to claim 1. 3. N- (4-aminophenyl) aminomethyl-cyclohexane according to claim 1. 4. N- (4-aminophenyl) -aminoethyl-morpholine according to claim 1. 5. N- (4-aminophenyl) aminomethyl-pinane according to claim 1. 6. Process for the preparation of the substituted p-phenylenediamines according to claim 1-5 by reaction in the first stage of optionally in 2-position p-chloronitrobenzene substituted by chlorine with that by a minomethyl radical or aminoethyl radical substituted corresponding cyclic compound in a elevated temperature of 100 - 2000 C and in the second stage subsequent catalytic Hydrogenation of the nitro compound obtained. 7. Use of the substituted p-phenylenediamines according to Claim 1 to 6, as well as their salts with inorganic or organic acids as developer components In oxidation hair dyes. 8. Hair dye based on oxidation dyes with a content of substituted p-phenylenediamines according to claims 1-7 and their salts with inorganic or organic acids as developer components and those in oxidation hair colors usual coupler substances. 9. Hair dye according to claim 8, characterized by a content of developer-coupler combinations in an amount of 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight, based on the total hair dye.