DE3016882A1 - Oxidn. hair dye compsn. - contg. 3-amino-2-methyl-phenol deriv. coupler component and standard developer to yield red to violet shades - Google Patents

Abstract

New 3-amino-2-methyl-phenol derivs. are of formula (I) (where R1 and R2 are H, 1-4C alkyl, 2-4C hydroxyalkyl contg. 1-2 OH qps., aminoalkyl contg. 1-4C in alkylene chain and opt. substd. by 1-2 alkyl or hydroxyalkyl, gps. in amine gp., or 3-6C alkoxyalkyl. R1 and R2 together can form an alkylene gp. opt. contg. an-NH- or ether bridge and forming a heterocyclic 5- or 6-membered ring with the amine-N atom). (I), their alkali- or alkaline earth salts or their salts with inorganic or organic acids are used as coupler components in oxidn. hair dye compsns. contg. standard developers. (I) form strong, fast red to violet shades; are water-soluble, storage-resistance, non-toxic and do not irritate the skin. Oxidn. hair dye compsns. contg. 3-(N-(2,3-dihydroxypropyl)- amino-2-methyl-phenol, (Ia), or 3-(N-(2-hydroxyethyl)- amino-2-methyl-phenol, (Ib), and/or their alkali or alkaline earth salts or their salts with inorganic or organic acids, as coupler components are claimed.

Description

"New coupler component for oxidation hair colors, their

Production as well as hair dyes containing these "oxidation dyes, such as by oxidative coupling of a developer component with a coupler component arise, play because of their intense color nuances and their very good fastness properties a preferred role in coloring hair. As developer substances are usually Nitrogen bases such as p-phenylenediamine derivatives, diaminopyridines, 4-aminopyrazolone derivatives or heterocyclic hydrazones are used. M-Phenylenediamine derivatives serve as coupler components, Phenols, naphthols, resorcinol derivatives and pyrazolones.

Useful components for oxidation hair dyes are required that they in the oxidative coupling with the intended coupler or developer substances develop the desired color nuances with sufficient intensity. You must also have a sufficient to very good ability to be absorbed by human hair.

In addition, they should be toxicologically and dermatologically harmless be.

The search for useful oxidation dyes therefore existed the task of finding suitable components that meet the above requirements meet in an optimal way.

It has been found that one arrives at oxidation hair colors that the The requirements set are met to a particularly high degree if one is used as coupler components the new compounds described below in combination with conventional developers substances used.

The invention relates to 3-amino-2-ynethylphenol derivatives of the formula I, in which R1 and R2 are independently a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a hydroxyalkyl radical with 2 to -4 carbon atoms and 1 to 2 OH groups, an aminoalkyl radical with 1 to 4 carbon atoms in the alkylene chain, which is connected to its amino group with 1 up to 2 alkyl radicals or hydroxyalkyl radicals, or an alkoxyalkyl radical with a total of 3 to 6 carbon atoms, or in which R1 and R2 together represent an alkylene radical which optionally contains an -NH- or ether bridge and the amine nitrogen atom has a heterocyclic 5- or 6 -linked ring forms.

The invention further relates to a method for producing the 3-Amino-2-methylphenol derivatives of the formula I, in which 3-amino-2-methylphenol in a manner known per se with the corresponding alkyl-hydroxyalkyl, aminoalkyl or alkoxyalkyl halides or sulfates or with ethylene oxide, propylene oxide or Glycid to the compounds of formula I converts. / 3 Subject of Finally, hair dyes based on oxidation dyes are invention a content of compounds of the formula I, their ammonium, alkali or alkaline earth metal salts or their salts with inorganic or organic acids as coupler components and the developer substances common in oxidation hair colors.

When used as coupler components, those according to the invention provide Compounds of the formula I with those generally used for oxidation hair coloring Very intense color tones ranging from red to purple and developing substances thus represent an essential enrichment of the oxidative hair coloring possibilities represent.

The 3-amino-2-methylphenol derivatives according to the invention are also notable due to the very good fastness properties of the dyeings achieved with aamit, due to good Solubility in water, good storage stability as well as toxicological and dermatological Harmlessness.

Hair dye based on oxidation dyes with a content of 3-amino-2-methylphenol derivatives of the formula I or their salts as coupler components and the developer substances customary in oxidation hair dyes are therefore particularly important valuable compositions in the field of oxidation hair colors.

The coupler components 3- N- (2,3-dihydroxypropyl) are of particular importance -amino-2-methylphenol and 3- N- (2-hydroxyethyl)] -amino-2-methylphenol, their ammonium salts, Alkali salts, alkaline earth salts or salts with inorganic or organic acids to be measured.

As examples of 3-amino-2-methylphenol derivatives according to the invention of formula I should be mentioned: 3- (N-methyl) -, 3- (N-ethyl) -, 3- (N-iso-propyl) -, 3- (N-n-butyl) -, 3- (N, N-dimethyl) -, 3- (N, N-di-npropyl) -, 3- [N- (2-hydroxyethyl) 7 -, 3- LM- (2-hydroxypropyl)] -, 3- EN- (2,3-dihydroxypropyl £ j-, 3- [N, N-di- (2-hydroxyethyl)] -, 3- [N, N-di- (2,3-dihydroxypropyl 3- [N- (2-aminoethyl)] -, 3- [N- (3-aminopropyl] -, 3- {N- [2- (N ', N-dimethylaminoethyl)} -, 3- {N- [2- (N'-2-hydroxyethylaminoethyl)]} -, 3- [N- (2-methoxyethyl)] -, 3- [N- (2-ethoxyethyl) -, 3- [N- (2-butoxyethyl)] - and 3- [N- (2-ethoxybutyl)] - amino-2-methylphenol and 3-pyrrolidino, 3-piperidino, 3-piperazino and 3-morpholino-2-methylphenol.

As a starting material for the production of the compounds of Formula I serving 3-amino-2-methylphenol is a known compound whose Production of Noelting in the reports of the German Chemical Society 37 (1904), pages 1020-1021.

The 3-amino-2-methylphenol derivatives according to the invention to be used as coupler components can either as such, in the form of their alkali salts, especially in the form of their Sodium or potassium salts, in the form of their alkaline earth salts or in the form of their salts with physiologically harmless inorganic or organic acids, such as used as chlorides, sulfates, phosphates, acetates, propionates, lactates and citrates will.

As examples of developer components that are used in the invention Hair dyes are primary aromatic amines with a further functional groups in the p-position such as p-phenylenediamine, p-tolylenediamine, Monochlorophenylenediamine, p-dimethylaminoaniline, p-aminophenol, p-diaminoanisole or other compounds of the type mentioned, which continue to 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 - 4 carbon atoms, also contain diaminopyridine derivatives, heterocyclic hydrazone derivatives and 4-aminopyrazolone derivatives such as 4-amino-1-phenyl-3-carbamoylpyrazolone-5 to cite.

Tetraaminopyrimidines of the general formula are further developer components which can advantageously be combined with the 3-amino-2-methylphenol derivatives in which R1 - R6 is hydrogen, an alkyl radical with 1 - 4 carbon atoms, the radical - (CH2) nX, in which n = 1 - 4 and X is a hydroxyl group, a halogen atom, an -NH2-, -NHR'- and -NR 'R't group, where R' and R "can denote alkyl radicals with 1-4 halogen atoms or are closed with the nitrogen atom to form a heterocyclic ring which can contain a further nitrogen atom or oxygen atom, Ri and R2 or R3 and R4, or R5 and R6 with the respective nitrogen atom can represent a heterocyclic 5- or 6-membered ring with one or two nitrogen atoms or one nitrogen atom and one oxygen atom, as well as their inorganic or organic salts.

The tetraaminopyrimidines to be used as developer components can either as such or in the form of their salts with inorganic or organic Acids, such as chlorides, sulfates, phosphates, acetates, propionates, Lactates, citrates are used.

For the combination with the coupler components according to the invention to be used 3-amino-2-methylphenol derivatives suitable developer substances represent for example 2,4,5,6-tetraamino-, 4,5-diamino-2,6-bismethylamino-, 2,5-diamino-4,6-bismethylamino-, 4,5-diamino-6-butylamino-2-dimethylamino, 2, 5-diamino-4-diethylamino-6-methylamino, 4,5-diamino-6-diethylamino-2-dimethylamino-, 4,5-diamino-2-diethylamino-6-methylamino-, 4, 5-diamino-2-dimethylamino-6-ethylamino, 4, 5-diamino-2-dimethylamino-6-isopropylamino, 4,5-diamino-2-dimethylamino-6-methylamino-, 4,5-diamino-6-dimethylamino-2-methylamino-, 4,5-diamino-2-dimethylamino-6-propylamino-, 2,4,5-triamino-6-dimethylamino-, 4,5, 6-triamino-2-dimethylamino, 2,4, 5-triamino-6-methylamino, 4,5, 6-triamino-2-methylamino, 4th , 5-diamino-2-dimethylamino-6-piperidino, 4,5-diamino-6-methylamino-2-piperidino, 2,4,5-triamino-6-piperidino, 2,4,5-triamino-6-anilino, 2,4,5-triamino-6-benzylamino, 2,4,5-triamino-6-benzylideneamino-, 4,5,6-triamino-2-piperidino-, 2,4,6-trismethylamino-5-amino-, 2,4,5-triamino-6-di-n-propylamino, 2,4,5-triamino-6-morpholino, 2,5,6-triamino-4-dimethylamino, 4,5,6-triamino-2-morpholino-, 2,4,5-triamino-6-ß-hydroxyethylamino-, 4,5,6-triamino-2-B-amino-ethylamino-, 2,5,6-triamino-4-ß-methylamino-ethylamino-, 2,5-diamino-4,6-bis-y-diethylamino-propylamino-, 4,5-diamino-2-methylamino-6-ß-hydroxy-ethylamino-, 5-amino-2,4,6-triethylamino-, 2) 4-bis-ß-hydroxyethylamino-6-anilino-5-aminopyrimidine.

The coupler component is 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 the developer component Represent mixtures of the developer compounds to be used according to the invention.

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, by means of atmospheric oxygen take place.

However, chemical oxidizing agents are expediently used. In particular, hydrogen peroxide or its addition products 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 for use in corresponding 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 to produce creams, emulsions or gels mixed with the other ingredients customary for such preparations. as such additional ingredients are, for example, wetting or emulsifying agents from anionic or nonionic type such as alkylbenzene sulfonates, fatty alcohol sulfates, Alkyl sulfonates, fatty acid alkanolamides, addition products of ethylene oxide with fatty alcohols, Thickeners such as ethyl cellulose, starch, higher fatty alcohols, paraffin oil, fatty acids, also to mention perfume oils and hair care products such as pantothenic acid and cholesterol. The additives mentioned are used in the amounts customary for this purpose used, such as wetting and emulsifying agents in concentrations of 0.5 to 30 percent by weight and thickener in concentrations of 0.1 to 25 percent by weight, each based on the entire 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 becomes removed from the hair to be colored by rinsing. Afterwards the hair is treated with a mild one Shampoo washed and dried.

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 production of the colorings 3-Amino-2-ynethylphenol derivatives according to the invention used as coupler components described.

A) 3- [N- (2,3-dihydroxypropyl)] - amino-2-methylphenol (K1) 61.5 g of 3-amino-2-methylphenol, 43.5 g glycid (85 percent by weight) and 0.5 g tetramethylammonium chloride in 500 ml of methanol were heated to 600 ° C. for 6 hours with stirring. After cooling down the volatile components were removed from the reaction mixture with the aid of a rotary evaporator distilled off. 109 g of dark, oily reaction product were obtained. Mass spectrum: Molecular mass found 197 (calculated 197).

B) 3- [N- (2-Hydroxyethyl)] - amino-2-methylphenol (K2) 37 g of 3-amino-2-methylphenol and 38 g of 2-bromoethanol in 1000 ml of anhydrous ethanol were added for 8 hours Heated to reflux. After cooling, the reaction mixture was put on a rotary evaporator evaporated to dryness. The residue was dissolved in water. A small amount insoluble matter was filtered off. The filtrate was made with sodium hydrogen carbonate neutralized and extracted with ether.

After evaporation of the ether extract, 36 g of oily residue remained, which slowly crystallized when left to stand.

Analysis: CgH13NO2 calculated: 54.65 IC; 7.84% H; 8.38% N found: 64.6% C; 7.91 gH; 8.32% N.

The following substances were used as developer components: E 1: tetraaminopyrimidine sulfate E 2: p-tolylene diammonium sulfate E 3: 2-chlorophenylenediamine E 4: N-methyl-p-phenylenediamonium chloride.

The hair colorants according to the invention were in the form of a cream emulsion used. The alcohols were in an emulsion of 10 parts by weight of fat Chain length C12-C18, 10 parts by weight of fatty alcohol sulfate (sodium salt) chain length C12-Cl8 and 75 parts by weight of water each 0.01 mol of that 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 Dye cream with additional oxidizing agent turned gray to 90%, not specially pretreated human hair is applied and left there for 30 minutes. After completing the dyeing process, the hair was washed with a standard shampoo washed out and then dried. The colorations obtained are as follows Table 1 can be found.

Table 1 Example a) Coupler b) Developer with 1% H2O2 solution Color obtained 1 K1 E 1 dark purple 1 K1 E 1 dark purple 2 K1 E 2 ruby red 3 K1 E 3 dark brown 4 Kl E 4 violet gray 5 K2 E 1 matt violet 6 K2 E 2 reddish brown

Claims (6)

'New coupler components for oxidation hair dyes, their production and hair dyes containing them "Patent claims: -ffi) 3-Amino-2-methYlphenol derivatives of the formula I, in which R1 and R2 independently represent a hydrogen atom, an alkyl radical with 1 to 4 carbon atoms, a hydroxyalkyl radical with 2 to 4 carbon atoms and 1 to 2 OH groups, an aminoalkyl radical with 1 to 4 carbon atoms in the alkylene chain, which is connected to its amino group with 1 to 2 alkyl radicals or hydroxyalkyl radicals, or an alkoxyalkyl radical with a total of 3 to 6 carbon atoms, or in which R1 and R2 together represent an alkylene radical, which optionally contains an -NR- or ether bridge and with the amine nitrogen atom a heterocyclic 5- or 6 -linked ring forms. 2. Process for the preparation of the 3-amino-2-methylphenol derivatives Formula I according to Claim 1, characterized in that 3-amino-2-methylphenol in a manner known per se with the corresponding alkyl-hydroxyalkyl, aminoalkyl or alkoxyalkyl halides or sulfates or with ethylene oxide, propylene oxide or Glycid to the compounds of formula I converts. 3. Hair dye based on oxidation dyes with a content of compounds of the formula I according to Claim 1, their alkali metal or alkaline earth metal salts or their salts with inorganic or organic acids as coupler components and the usual developer substances in oxidation hair dyes. 4. Hair dye based on oxidation dyes according to claim 3 containing 3-0N- (2,3-dihydroxypropyl) 3 -amino-2-methylphenol and / or its alkali or alkaline earth salts or their salts with inorganic or organic Acids as coupler components. 5. Hair dye based on oxidation dyes according to claim 3 containing 3-N- (2-hydroxyethyl7-amino-2-methylphenol and / or its Alkali or alkaline earth salts or their salts with inorganic or organic Acids as coupler components. 6. Hair dye according to claims 3 to 5, with a content of Developer and coupler combination in an amount of 0.2 to 5 percent by weight, preferably 1 to 3 percent by weight, based on the total hair dye.