DE2942297A1 - 2,4-Di:amino-phenoxy-alkylamine cpds. - are oxidn. hair dye coupler components, prepd. from 2,4-di:nitrophenol with chloro-alkylamine - Google Patents

Abstract

New (2,4-diaminophenoxy)-alkylamines have formula (I), (where R is -(CH2)n-NR1R2 or -CHMeCH2-NR1R2, in which n is integer 1-5; each R1 and R2 is 1-4 C-alkyl, or R1 and R2, together with the N atom, for a morpholine, piperidine or pyrrolidine ring). (I), and their salts with organic or inorganic acids, are used as coupler components in oxidn. hair dyes. (I) form strong, fast brown to black and blue shades; are soluble in water, resist storage, are non-toxic and cause no skin-irritation.

Description

"New coupler components for oxidation hair colors, their

Production and hair colorants containing them11 The invention relates to new (2,4-diaminophenoxy) -alkylamines of the general formula in which R represents one of the radicals - (CH2) -NR1R2 or n -CH (CH3) CH2NR1R2, in which n is an integer from 2-5 and R1 and R2 independently of one another are an alkyl radical with 1-4 carbon atoms or R1 and R2 below Insertion of the nitrogen atom denotes a morpholine, piperiline or pyrrolidine radical.

The preparation of the (2,4-diaminophenoxy) alkylamines according to the invention in the form of their hydrochloric acid salts is carried out by converting 2,4-dinitrophenol into first stage with the corresponding chloroalkylamine to (2,4-dinitrophenoxy) alkylamine, which in the second stage in the usual way to (2,4-diaminophtnoxy) -alkylamine catalytically is reduced.

The invention also relates to the use of the new (2,4-diaminophenoxy) alkylamines as such or in the form of their salts with inorganic or organic acids as coupler components in oxidation hair dyes as well as hair dyes that make the new (2,4-Diaminophenoxy) -alkylamines or their salts contain.

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 arise because of their intense colors and very good fastness properties preferred role. Nitrogen bases are usually used as developer substances such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazol.one 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.

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

It has now been found that oxidation hair dyes which meet the requirements set to a particularly high degree can be obtained if (2,4-diaminophenoxy) alkylamines of the general formula are used as coupler components in which R represents one of the radicals - (CH2) -NR1R2, or n -CH (CH3) CH2NR1R2, in which n is an integer from 2-5 and R1 and R2 independently of one another are an alkyl radical with 1-4 carbon atoms or R1 and R2 including the nitrogen atom denote a morpholine, piperidine or pyrrolidine radical, and their inorganic or organic salts are used in combination with customary developer substances.

(2,4-Diaminophenoxy) -alkylamines of the general formula are of particular importance as coupler components in the R one of the remainders (CH2) 2 N (C2H5) 2 '- (CH2) 3-N (cH3) 2 or -.cH (cH3) cH2N (cH3) 2, as well as their inorganic or organic salts.

Hair dye based on oxidation dyes with a content of (2,4-diaminophenoxy) alkylamines of the above formula and their inorganic or organic salts as coupler components and those in oxidation hair dyes The usual developer substances are therefore particularly valuable compositions in the field of oxidation hair colors.

When used as coupler components, the inventive Compounds with the developer substances generally used for oxidation hair coloring very intense colors ranging from brown to black and thus represent a essential enrichment of the oxidative hair coloring possibilities. In addition The (2,4-diaminophenoxy) alkylamines according to the invention are characterized by very good properties Fastness properties of the dyeings achieved therewith, due to good solubility in water, good storage stability and toxicological and dermatological harmlessness the end.

The (2,4-diaminophenoxy) -alkylamines to be used as coupler components according to the invention can either as such or in the form of their salts with inorganic or organic Traces, such as chlorides, sulfates, phosphates, acetates, propionates, Lactates, citrates are used.

The coupler components to be used according to the invention are 2- (2,4-diaminophenoxy) -N-ethylmorpholine, -N-ethylpyrrolidine, -N-ethylpiperidine, -N, N-dimethyl- aminoethane, -N, -diethylaminoethane, -N, N-dipropylaminoethane, -N, N-dibutylaminoethane, -1-dimethylaminopropane, -1-diethylaminopropane, -1-dipropylaminopropane, -1-dibutylaminopropane, 3- (2> 4-diaminophenoxy) -N-propylmorpholine> -N-propyl-pyrrolidine, -N-propylpiperidine, -N, N-dimethylaminopropane, -N, N-diethylaminopropane, -N, N-dipropylaminopropane, -N, N-dibutylaminopropane, 4- (2,4-diaminophenoxy) -N-butylmorpholine, -N-butylpyrrolidine, -N-butylpiperidine, SN, N-dimethylaminobutane, -N, N-diethylaminobutane, -N, N-dipropylaminobutane, -N, N-dibutylaminobutane, 5- (2,4-diaminophenoxy) -N-pentylmorpholine -N-pentylpyrrolidine, -N-pentylpiperidine, -N, N-dimethylaminopentane, -N, N-diethylaminopentane, -N, N-dipropylaminopentane, -N, N-dibutylaminopentane to be mentioned.

The 2- (2,4-diaminophenoxy) -N-ethylmorpholine is of particular importance, -N-ethylpyrrolidine, -N, N-diethylaminoethane, -1-dimethylaminopropane and 3- (2,4-diaminophenoxy-N, N-dimethylaminopropane to.

As an example of those to be used in the hair dyes according to the invention Developer components are primary aromatic amines with another in the p-position located functional group such as p-phenylenediamine, p-tolylenediamine, p-aminophenol, N-methyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, chlorine-p-phenylenediamine, N, N-bis-hydroxyethylamino-p-phenylenediamine, Methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, other compounds of the type mentioned, which still have one or more functional groups such as OH groups, NH2 groups, NHR groups, NR2 groups, where R is an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms, also diaminopyridine derivatives, heterocyclic Hydrazone derivatives such as 1-methylpyrrolidone- (2) -hydrazone, 4-amino- pyrazolone derivatives such as 4-amino-1-phenyl-3-carbamoylpyrazolone-5, N-butyl-N-sulfobutyl-p-phenylenediarnine> Tetraaminopyrimidines such as 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-2,6-bismethylaminopyrimidine, 2,5-diamino-4-diethylamino-6-methylaminopyrimidine, in 2,4,5-triamino-6-dimethylaminopyrimidine, 2,4,5-triamino-6-piperidinopyrimidine, 2,4,5-triamino-6-anilino-pyrimidine, 2,4,5-triamino-6-morpholinopyrimidine, 2,4,5-Triarnino-6-B-hydroxy-ethylamino-pyrimidine should be mentioned.

The coupler components according to the invention provide with corresponding Developing substances particularly intensive and in their lightfastness properties protruding brown tones, which is of great importance for their practical applicability is. In addition, with the help of certain developer substances, intensive and achieve lightfast blue tones. To achieve the most powerful and natural Hair color nuances of largely corresponding shades is a full-fledged blue dye as a nuance component of particular importance. In creating more natural Color nuances with the help of blue coupler components result with the usual ones Blue couplers often encounter difficulties. The (2,4-diaminophenoxy) -alkylamines according to the invention can be used here contribute significantly to closing an existing gap.

The coupler components are used in the hair colorants according to the invention generally in approximately molar amounts, based on the developer substances used, used. If molar use also proves useful, so it is but not disadvantageous if the coupler 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 developer compounds to be used according to the invention as well as the coupler substance mixtures of the (2,4-diaminophenoxy) alkylamines to be used according to the invention represent.

In addition, the hair colorants according to the invention can optionally Usual substantive dyes contained in the mixture, if this is to achieve certain color nuances is required.

The oxidative coupling, i.e. the development of the color, can basically as with other oxidation hair dyes, also through 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 and 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 in coupler-developer combinations is 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight.

The dye components are used in the production of creams, emulsions or gels mixed with the other ingredients customary for such preparations.

Such additional components are, for example, network or Emulsifiers of the anionic or nonionic type such as alkylbenzenesulfonates, Fat- alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, addition products from ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, also perfume oils and hair care products like pantothenic acid and cholesterol.

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 to 10. The application temperatures are in the range from 15 to 400 C. After an exposure time of about 30 minutes, the hair dye removed from the hair to be colored by rinsing. Afterwards the hair is treated with a mild one Shampoo washed and dried.

The colorations achievable with the hair colorants according to the invention, in particular brown and blue tones, show when using different developer and coupler components particularly intense color nuances. The colorations achieved have good light, wash and rub fastness properties and are easy to use remove 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 in the following Examples of the different colorations used as coupler components (2,4-diaminophenoxy) -alkylamines according to the invention described.

A) 2- (2,4-Diaminophenoxy) -N-ethylmorpholine trihydrochloride dihydrate Step 1 Production of 2- (2,4-dinitrophenoxy) -N-ethylmorpholine.

9.2 g (0.05 mol) 2,4-dinitrophenol, moistened with 0.6 g water, were suspended in 40 ml of diethylene glycol dimethyl ether. To the suspension were at about 250 ° C. 6.9 g (0.05 mol) of potassium carbonate were added.

The suspension was then heated to 1000 C and 9.3 g (0.05 mol) N- (2-chloroethyl morpholine hydrochloride was added. This was followed by a period of 5 hours heated to 1400 C. After cooling, the resulting precipitate was filtered off with suction, washed with sodium hydroxide solution and then with water. After drying that had 2- (2,4-Dinitrophenoxy) -N-ethylmorpholine obtained a melting point of 2570 C.

Step 2 Production of 2- (2,4-diaminophenoxy) -N-ethylmorpholine trihydrochloride dihydrate.

4.6 g of 2- (2,4-dinitrophenoxy) -N-ethylmorpholine were dissolved in 50 ml of ethanol hydrogenated in the presence of 5% palladium on charcoal at 1 atm and 250.degree. After finished The uptake of hydrogen was filtered off from the catalyst.

The solution was acidified with concentrated hydrochloric acid and used to Concentrated to dryness. 2- (2,4-Diaminophenoxy) -N-ethylmorpholine trihydrochloride dihydrate became obtained in the form of dark red crystals with a melting point of 250 ° C.

B) 2- (2,4-Diaminophenoxy) -N-ethylpyrrolidine trihydrochloride monohydrate Stage 1 2- (2,4-dinitrophenoxy) -N-ethylpyrrolidine was completely prepared analogous to the information in Example A, stage 1, except that instead of chloroethyl) morpholine hydrochloride, 8.6 g (0.05 mol) of N- (2-chloroethyl) pyrrclidine hydrochloride were added. After this Drying, the product obtained had a melting point of 241 ° C.

Step 2 Preparation of 2- (2,4-diaminophenoxy) -N-ethylpyrrolidine trihydrochloride monohydrate.

According to the information under Example A), level 2, 14.3 g 2- (2,4-dinitrophenoxy) -N-ethylpyrrolidine catalytically hydrogenated at 250 ° C. and 1 atm and worked up. 14.9 g of 2- (2,4-diaminophenoxy) -N-ethylpyrrolidine trihydrochloride monohydrate were obtained obtained with a melting point of 2250 ° C. (decomposition).

C) 3- (2'4-Diaminophenoxy) -NN-dirr'ethvlaminonroan trihydrochloride.

Stage 1 The production of 3- (2,4-Dinitrophenoxy) -N, N-dimethylaminopropane was carried out completely analogously to the information in Example A), stage 1, only that instead of N- (2-chloroethyl) morpholine hydrochloride, 7.9 g (0.05 mol) 3-dimethylaminopropyl chloride were given.

After drying, the product obtained had a melting point from 160 - 1650 C.

Stage 2 3- (2,4-Diaminophenoxy) -N, N-dimethylaminopropane trihydrochloride.

According to the information under Example A), stage 2, 8.5 g 3- (2,4-Dinitrophenoxy) -N, N-dimethylaminopropane catalytically hydrogenated at 250 ° C. and 1 atm and worked up. There were 7.6 g of 3- (2,4-diaminophenoxy) -N, N-dimethylaminopropane trihydrochloride obtained from 0 melting point 195 C.

D) 2- (2,4-diaminophenoxy) -1-dimethylaminopropane trihydrochloride 1.5 hydrate.

Stage 1 2- (2,4-Dinitrophenoxy) -1-dimethylaminopropane.

The production was carried out completely analogously to the information in Example A), Step 1, except that instead of N- (2-chloroethyl) morpholine hydrochloride, 7.9 g (0.05 Mol) 1-dimethylamino-2-propyl chloride hydrochloride were added.

After drying, the product had a melting point of 0 of 237 C.

Stage 2 2- (2,4-diaminophenoxy) -1-dimethylaminopropane trihydrochloride.

According to the information under Example A), stage 2, 6.4 g 2- (2,4-Dinitrophenoxy) -1-dimethylaminopropane catalytically reduced at 250 C and 1 atm and worked up. 2.8 g of 2- (2,4-diaminophenoxy) -1-dimethylaminopropane trihydrochloride were obtained obtained with a melting point of 1880 C.

E) 2- (2, -diaminophenoxy) -N'N-diethylaminoethane trihydrochloride stage 1 2- (2,4-Dinitrophenoxy) -N, N-diethylaminoethane.

The above-mentioned substance was produced in a completely analogous manner the information in Example A), stage 1, except that instead of Ni2-chloroethyl) morpholine hydrochloride 8.6 g (0.05 mol) of 2-diethylaminoethyl chloride hydrochloride were added. To after drying, the substance had a melting point of 2470 C.

Step 2 2- (2,4-Diaminophenoxy) -N, N-diethylaminoethane trihydrochloride.

According to the information under Example A), stage 2, 7 g of 2- (2,4-dinitrophenoxy) -N, N-diethylaminoethane were used Catalytically hydrogenated at 250 ° C. and 1 atm and worked up. There were 6.4 g of the above-mentioned substance with a melting point of 2300 ° C.

The following substances were used as developer components: E 1: p-toluenediamine E 2: 2,4,5,6-tetraaminopyrimidine E 3: 2,5-diaminoaniso3 E 4: p-phenylenediamine E. 5: N-ethyl-N-S-hydroxyethyl-p-phenylenediamine E 6: N, N-dimethyl-p-phenylenediamine E 7: N, N-bis-B-hydroxyethyl-p-phenylenediamine E 8: 2-methylamino-4,5,6-triamino-pyrimine E 9: 2-chloro-p-phenylenediamine E 10: 1-phenyl-3-carbamoyl-4-aminopyrazolone-5 E 11: p-aminophenol E 12: N-butyl-N-sulfobutyl-p-phenylenediamine E 13: N-methyl-p-phenylenediamine the Hair colorants according to the invention were used in the form of a cream emulsion. This was done in an emulsion of 10 parts by weight of fatty alcohols of 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 mol of those listed in the table below Incorporated developer substances and (2,4-diaminophenoxy) -alkylamines. 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 carried out with 1% of a hydrogen peroxide solution carried out as an oxidizing agent, with 100 parts by weight of the emulsion 10 parts by weight Hydrogen peroxide solution were given. The respective coloring cream with the addition of Oxidizing agents was applied to human hair that was 90% gray and not specially treated applied and left there for 30 minutes. After the dyeing process was finished the hair was washed out with a standard shampoo and then dried. The colorations obtained are shown in Table 1 below.

Table 1 At- developer coupler obtained hue with game | 1 Siger H20 2 solution 1 E 1 A brown 2 E 2 A olive 3 E 3 A dark brown 4 E 4 A olive brown 5 E 5 A dark brown 6 E 6 A dark brown 7 E 1 C black 8 E 2 C dark green 9 E 3 C blue-gray 10 E 7 C dark blue 11 E 8 C dark green 12 E 9 C violet gray 13 E 10 C violet gray 14 E 11 C red-brown 15 E 6 C dark blue 16 E 5 C dark blue 17 E 1 E dark brown 18 E 2 E honey yellow 19 E 1 D red-brown 20 E 2 D light brown 21 E 11 B teak colored 22 E 12 B brown 23 E 13 B dark brown 24 E 10 brown fawn

Claims (6)

"New coupler components for oxidation hair dyes, their production and hair dyes containing them" Patent claims: t9 2,4-diaminophenoxy) -alkylamines of the general formula in which R represents one of the radicals - (CH2) n-NR1R2, or -CH (CH3) CH2NR1, in which n is an integer from 2-5 and R1 and R2 are, independently of one another, an alkyl radical with 1-4 carbon atoms, or R1 and R2, including the nitrogen atom, denotes a morpholine, piperidine or pyrrolidine radical. 2. (2,4-Diaminophenoxy) -alkylamines according to the general formula according to Claim 1. in which R is one of the radicals Represents - (CH2) 2N (C2H5) 2, - (CH2) 3N (CH3) '2 or -CH (CH3) CH2N (CH2) 2. 3. Process for the preparation of the (2,4-diaminophenoxy) -alkylamines according to Claims 1 and 2 in the form of their hydrochloric acid salts by reacting 2,4-dinitrophenol in the first stage with the corresponding chloroalkylamine to (2,4-dinitrophenoxy) alkylamine and its catalytic reduction in the usual manner in the second stage. 4. Use of the (2,4-diaminophenoxy) alkylamines according to Claim 1 to 3 and their salts with inorganic or organic acids as coupler components in oxidation hair colors. 5. Hair dye based on oxidation dyes with a content an (2,4-diaminophenoxy) -alkylamines according to Claims 1-4 and their salts with inorganic ones or organic acids as coupler components and those customary in oxidation hair dyes Developer substances. 6. Hair dye according to claim 5, characterized by a content of developer-coupler combination in an amount of 0.2-5 percent by weight, preferably 1 - 3 percent by weight, based on the total hair dye.