DE3313905A1 - Novel 2,4-diaminophenol ethers as couplers for oxidative hair dyes - Google Patents

Abstract

1-Cycloalkoxy-2,4-diaminobenzenes of the general formula <IMAGE> in which R denotes hydrogen or an alkyl group having 1-4 C atoms and n denotes an integer from 4 to 11, with the proviso that not more than 3 R groups are alkyl groups, are novel coupler substances for oxidative hair dyes. The novel couplers yield brilliant shades of high fastness with all customary developer substances and have favourable toxicological properties. Preferably, n = 4 or 5 and R = hydrogen. Combined with developers of the p-phenylenediamine derivative type, predominantly blue shades are produced. The novel couplers are employed in hair dyes in amounts from 0.1 to 3.0 % by weight.

Description

"New 2,4-diaminophenol ethers as couplers for oxidation

HAIRFARE PRODUCTS "The invention relates to new 1-cycloalkyloxy-2,4-diaminobenzenes. These compounds are valuable precursors for oxidation hair dyes.

The so-called oxidation arrows play a role in the coloring of hair, that by oxidative coupling of one or more developer components with one another or arise with one or more coupler components, because of their intense Colors and good fastness properties play a preferred role. As developer substances are usually primary aromatic amines with another in para or Orthopositioned frëin or substituted hydroxyl or amino group, also diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives and tetraaminopyrimidines are used. As so-called coupler substances m-phenylenediamine derivatives, Phenols, naphthols, resorcinol derivatives and pyrazolones are used.

Good oxidation hair dye precursors must primarily include the following Meet the prerequisites: You have to do the desired in the oxidative coupling Develop color nuances with sufficient intensity. These shades of color have to against the effects of heat, light and chemicals, e.g. against those during cold wave treatment of the hair reducing agents used have sufficient stability. They must also be able to lend themselves well to human hair without To stain the scalp too much, and they are said to be toxicological and especially be dermatologically harmless.

These requirements are met by those currently used in oxidation hair dyes Common couplers, in particular special couplers with known developers how p-tolylenediamine give blue nuances, not satisfactorily met. Particularly problematic are the toxicological properties of many couplers e.g.

of the aromatic amine type. Other coupler substances lead to Dyeings with unsatisfactory fastness properties.

2,4-Diaminophenol ethers are used as couplers for oxidation colorants known for a long time. The use of 2.4-diaminoanisole is described, for example, in DE-PS 226 790 and DE-PS 228 245 for the production of oxidation colorants. However, numerous compounds of this class of substances have unfavorable toxicological properties Properties, e.g. sensitizing and mutagenic properties.

In the search for better oxidation dye precursors hence the task of finding suitable coupler substances that are brilliant on the one hand Produce dyeings of high fastness, but on the other hand compared to the known Coupler substances have reduced toxicity.

It has now surprisingly been found that 1-cycloalkyloxy-2,4-diaminobenzenes of the general formula I. in which R is hydrogen or an alkyl group with 1-4 carbon atoms and n is an integer from 4-11, with the proviso that no more than three groups R are alkyl groups, meet the requirements to a high degree. These compounds are new and are excellent couplers for the manufacture of oxidation hair dyes.

The 1-cycloalkyloxy-2,4-diamlnobenzenes are prepared by reacting 2,4-dinitrofluorobenzene with cycloalkanols of the general formula II in which R and n have the meaning given in formula 1, in a manner known per se. The 1-cycloalkyloxy-2,4-dinitrobenzenes obtained in this reaction are catalytically hydrogenated to the 1-cyclealkyloxy-2,4-diaminobenzenes of the general formula I, likewise in a manner known per se.

Suitable new coupler substances according to general formula I are e.g.

1-Cyclopentyloxy-2,4-diaminobenzene 1-Cyclohexyloxy-2,4-diaminobenzene 1 -Cycloheptyloxy-2,4-diaminobenzene 1-Cyclododecyloxy-2,4-diaminobenzene 1- (2'-methyl) -cyclopentyloxy-2,4-diaminobenzene 1- (2l, 4'-dimethyl) -cyclopentyloxy-2,4-diaminobenzene 1- (2'-methyl) -cyclohexyloxy-2,4-diaminobenzene 1- (4'-methyl) -cyclohexyloxy-2,4-diaminobenzene 1- (4'-isopropyl) -cyclohexyloxy-2,4-diaminobenzene 1- (2 ', 4'-dimethyl) -cyclohexyloxy-2t4-diaminobenzene 1- (2', 4 ', 6'-trimethyl) -cyclohexyloxy-24-diaminobenzene Preferred coupler substances according to the invention are 1-cycloalkyloxy-2,4-diaminobenzenes of the general formula I, in which n = 4 or 5. Furthermore, there are such compounds preferred which carry no substituents, i.e. in which R is hydrogen especially 1-cyclopentyloxy-2,4-diaminobenzene and 1-cyclohexyloxy-2,4-diaminobenzene.

The new coupler substances according to the invention of the general formula I are suitable for a variety of different developer systems. They generate on the hair intense, deep blue, .to reddish brown color nuances of high purity and of good resistance to light and heat. In addition, they are particularly cheap toxicological properties that make them suitable for use in cosmetic hair dyes make particularly suitable.

The new coupler substances are therefore a valuable asset the oxidative hair coloring options.

Particularly intense and pure blue color nuances are used of the new coupler substances in oxidation dyes together with developer substances obtained from the aromatic diamine type, in particular the p-phenylenediamine derivatives. Such shades of blue are responsible for the creation of browns and blacks Combination with yellow and red nuances and to compensate for the reddening effect in bleaching agents of high application value.

Such preferred developer substances are, for example, p-phenylenediamine, p-toluenediamine, N-methyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, N-hydroxyethyl-p-phenylenediamine, chlorine-p-phenylenediamine, N, N-bis-hydroxyethylamino-p-phenylenediamine, methoxy-pphenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, 2 5-diaminoanisole N-ethyl- (N- (2-hydroxyethyl) -p-phenylenediamine, N-2-methoxyethyl-p-phenylenediamine, N-2-hydroxypropyl-p-phenylenediamine, N-butyl-N-sulfobutyl-p-phenylenediamine or their Salts with inorganic or organic acids.

The 1-cycloalkyloxy-2,4-diaminobenzenes to be used as couplers according to the invention can either as such or in the form of their salts with inorganic or organic Acids, e.g. as chlorides, sulfates, phosphates, acetates, propionates, lactates, citrates can be used.

Another subject of the invention are hair dyes containing Oxidation dye precursors in a cos- metic carrier, thereby characterized in that the oxidation dye precursors are couplers of the general Formula I or their salts in addition to customary coupler substances and customary developer substances are included. The aromatic compounds mentioned should preferably be used as developer substances Diamines, in particular p-phenylenediarain derivatives or salts thereof, may be included.

In addition, however, the hair colorants according to the invention can be used for production other well-known developers and coupler components of the desired color shades contain.

Such developers are e.g. p-aminophenols, diaminopyridine derivatives, heterocyclic hydrazone derivatives, 4-aminopyrazolone derivatives and tetraaminopyrimidines. Further couplers that can be used in the hair dyes according to the invention are, for example, naphthols, Resorcinol derivatives, pyrazolones and m-phenylenediamine derivatives are added. Even Substantive dyes, e.g. nitrophenylenediamine derivatives, can be used for modification the color nuances are added.

The coupler substances to be used according to the invention of the general Formula I are in such hair dyes in amounts depending on the desired shade from 0.01 to 3.0% by weight, based on the total agent.

The coupler substances are used in the hair colorants according to the invention generally in approximately molar amounts, based on the developer substances used, used. Even if the molar use proves to be expedient proves however, it is not disadvantageous to use a certain excess of individual oxidation dye precursors to bring into use.

It is also not necessary that the oxidation dye precursors represent uniform substances, rather both the developer component Mixtures of the developer compounds to be used according to the invention as well as the Coupler component Mixtures of the 1-cycloalkyloxyv2,4-diaminobenzoleder to be used according to the invention represent general formula I and known coupler substances.

The oxidative development of the color can in principle, as in other oxidation hair dyes, too, are done by atmospheric oxygen. Appropriately however, chemical oxidizing agents are used. As such come in particular Hydrogen peroxide or its addition products with urea, melamine and sodium borate and mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulfate into consideration.

The oxidation dye precursors are used to produce the hair colorants according to the invention incorporated into a suitable cosmetic carrier. Such carriers are e.g. creams, Emulsions, gels or even surfactant-containing, foaming solutions, e.g. shampoos or other preparations suitable for use on the hair. Usual Components of such cosmetic preparations are, for example, wetting and emulsifying agents, how anionic, nonionic or ampholytic surfactants, e.g. fatty alcohol sulfates, alkane sulfonates, sC -olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products of fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, Fatty acid alkanolamides and thickeners such as methyl or hydroxyethyl cellulose, Starch, fatty alcohols, paraffin oil, fatty acids, also perfume oils and hair care oils Additives such as water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol.

The ingredients of the cosmetic carriers are used to produce the hair dyes according to the invention are used in the amounts customary for these purposes; for example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners used in concentrations of 0.1 to 25 wt .-% of the hair dye. The oxidation dye precursors are usually used in amounts of 0.05 to 5.0% by weight of the total colorant mixed into the carrier.

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 about 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. There is no need to wash with a shampoo, if a strong surfactant Carrier such as a coloring shampoo is used became.

The colorations that can be achieved with the hair colorants according to the invention have good light, wash and rub fastness properties.

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

Examples 1. 1-C clo ent lox -2,4-diaminobenzene a) 1-Cylopentyloxy-2,4-dinitrobenzene A mixture consisting of 18.4 g of cyclopentanol (0.2 mol) 37.2 g of 2,4-dinitrofluorobenzene, 25 ml of triethylamine and 60 ml of dimethylformamide were left to stand at 20 ° C. for 5 days. The reaction mixture was then acidified with 10% strength hydrochloric acid and with 500% ml of water diluted. The precipitate formed was filtered off and taken from water / Dimethylformamide recrystallized. It became an olive brown product with a melting point obtained from 53 ° - 57 ° C.

b) 1-cyclopentyloxy-2 .4-diaminobenzene 4 g of 1-cyclopentyloxy-2,4-dinitrobenzene were in 125 ml of ethanol in the presence of 0.2 g of palladium catalyst (5 wt .-% Pd on activated carbon) catalytically hydrogenated. After the hydrogen uptake has ceased the catalyst was filtered off and the filtrate was evaporated to dryness. That Product was obtained in the form of brown crystals with a melting point of 59-61 ° C.

2.1-Cyclohexyloxy-2. 4-diaminobenzene dihydrochloride a) 1-Cyclohexyloxy-2,4-dinitrobenzene The production was carried out analogously to Example 1a) starting from 20 g of cyclohexanol (0.2 Mole). A yellow bl was obtained.

b) 1-Cyclohexyloxy-2,4-diaminobenzene-dihydrochloride The hydrogenation was carried out analogously to Example 1 b), starting from 5 g of 1-cyclohexyloxy-2,4-dinitrobenzene.

After the hydrogen uptake has ended and the catalyst has been separated off the dihydrochloride of 1-cyclohexyloxy-2,4-diaminobenzene was obtained by adding 14 g of 10% strength hydrochloric acid and this isolated by evaporation to dryness. The product has one Melting point of 1200C.

3. 1- (4'-Isopropyl) -cyclohexyloxy-2,4-diaminobenzene dihydrochloride a) 1- (4'-Isopropyl) -cyclohexyloxy-2,4-dinitrobenzene The preparation was carried out analogously Example 1a) starting from 28.4 g of 4-isopropylcyclohexanol (0.2 mol).

A yellow powder with a melting point of 78 ° C. was obtained.

b) 1- (4'-Isopropyl) -cyclohexyloxy-2 .4-diaminobenzene dihydrochloride The hydrogenation and conversion into the dihydrochloride took place analogously to Example 2 b). The product had a melting point of 216-2270 ° C. (with decomposition).

4. 1-Cycloheptyloxy-2,4-diaminobenzene a) 1-Cycloheptyloxy-2,4-dinitrobenzene Production was carried out analogously to Example 1 a), starting from 22.8 g of cycloheptanol (0.2 moles). The product was obtained as a light brown blue.

b) 1-cycloheptyloxy-2. 4-diaminobenzene The production took place analogous to example 1 b). The product fell as brown crystals with a melting point from 56 ° C.

5 1 -cyclooctyloxy-2. 4-diaminobenzene a) 1-cyclooctyloxy-2,4-dinitrobenzene Production was carried out analogously to Example 1 a), starting from 25.6 g of cyclooctanol (0.2 moles). The product was obtained as a light brown oil.

b) 1-Cyclooctyloxy-2,4-diaminobenzene The preparation was carried out analogously Example 1 b). The product was obtained as a light brown oil.

JR (film) spectrum: cm 1: 1665, 1620, 1510, 1465, 1445, 1390, 1330, 1220, 1120, 1090, 1045, 965, 845, 790.

6. 1 -Cyclododecyloxy-2. 4-diaminobenzene a) 1-cyclododecyloxy-2,4-dinitrobenzene Production was carried out analogously to Example 1a), starting from 36.8 g of cyclododecanol (0.2 moles). The product was in the form of yellow crystals with a melting point of 680C isolated.

b) 1-Cyclododecyloxy-2,4-diaminobenzene The hydrogenation was carried out analogously Example 1b>. The product was in the form of light brown crystals with a melting point obtained from 1150C.

Technical application test To test the new coupler components according to Example 1 - 6, these were in hair coloring cream emulsions of the following composition used: fatty alcohol C12-18 10 g fatty alcohol C12-14 + 2EO sulfate, sodium salt (28 $ ig) 25 g water 60 g developer substance 0.0075 mol coupler substance 0.0075 mol inhibitor (Na2SO3) 1.0 g conc. Ammonia solution up to pH = 9.5 water ad 100 g The components were mixed together in sequence. After adding the developer substance and the coupler substance was first adjusted to the pH value with concentrated ammonia solution the emulsion adjusted to 9.5, then made up to 100 g with water.

The oxidative coupling was carried out with 3% hydrogen peroxide solution carried out as an oxidizing agent. For this purpose, 10 g of the coloring cream were mixed with 5 g of hydrogen peroxide solution (3%) added and mixed.

The coloring cream was standardized, however, to 90% gray Human hair that has not been specially treated is applied and left there for 30 minutes Leave 270C. After completing the dyeing process, the hair was rinsed with a Washed out conventional shampoos and then dried.

The following compounds were used as developer substances: E 1: p-toluenediamine E 2: 2.5-diamino anisole E 3: N-methyl-p-phenylenediamine E 4: N-2-methoxyethyl-p-phenylenediamine E 5: N-ethyl-N- ß-hydroxyethyl-p-phenylenediamine E 6: N, N-bis- (ß-hydroxyethyl) -p-phenylenediamine E 7: 2-chloro-p-phenylenediamine E 8: N-2-hydroxypropyl-p-phenylenediamine E 9: 2.4.5.6-Tetraamino-pyrimidine E 10: p-aminophenol The following compounds were used as coupler substances according to the invention: K 1: 1-cyclopentyloxy-2.4-diaminobenzene K 2: 1-cyclohexyloxy-2.4-diaminobenzene K 3: 1- (4 ' -Isopropyl) -cyclohexyloxy-2.4-diaminobenzene K 4: 1-Cycloheptyloxy-2.4-diaminobenzene K 5: 1-cyclododecyloxy-2.4-diaminobenzene The results of the dyeing tests are compiled in Table I: TABLE 1 Example No. Developer Coupler shade of the colored Hair P 1 E 1 K 1 blue-black P 2 E 1 K 2 blue-black P 3 E 1 K 3 brown-gray p 4 E 2 K 3 dark purple P 5 E 3 K 3 black-blue P 6 E 4 K 3 dark purple P 7 E 5 K 3 ink blue P 8 E 6 K 3 dark blue P 9 E 7 K 4 dark purple P 10 E 8 K 5 dark purple P 11 E 9 K 4 blue-green P 12 E 9 K 1 blue-green P 13 E 10 K 3 red-brown

Claims (8)

Patent claims 1. 1-Cycloalkyloxy-2,4-diaminobenzenes of the general formula lormYl1Oa1lkYlOXY2 4-diaminobenzenes of the general formula in which R is hydrogen or an alkyl group with 1-4 carbon atoms and n is an integer from 4-11, with the proviso that no more than three radicals R are alkyl groups. 2. 1-Cycloalkyloxy-2,4-diaminobenzenes according to Claim 1, characterized in that that n = 4 or 5. 3. 1-cycloalkyloxy-2,4-diaminobenzenes according to claim 1 or 2, characterized characterized in that R is hydrogen. 4. A process for the preparation of 1-cycloalkyloxy-2,4-diaminobenzenes according to claim 1-3, characterized in that 2 »4-dinitrofluorobenzene with cycloalkanols of the general formula II in a manner known per se in which R and n have the meaning given in claim 1, converts them to the 1-cycloalkyloxy-2 # 4-dinitrobenzenes and hydrogenates them catalytically to the 1-cycloalkyloxy-2,4-diaminobenzenes. 5. Use of the 1-cycloalkyloxy-2,4-diaminobenzenes according to claim 1 - 3 or their salts with inorganic or organic acids in oxidation dyes as coupler substances together with customary developer substances. 6. Use according to claim 5, characterized in that the developer substances aromatic diamines, in particular p-phenylenediamine derivatives, are used. 7. Hair dyes containing oxidation dye precursors in a cosmetic carrier, characterized in that the oxidation dye precursors Coupler substances of the general formula I according to Claim 1 in an amount of 0.01 - 3.0% by weight, based on the total agent, in addition to conventional coupler substances and usual developer substances are included. 8. Hair dye according to claim 7, characterized in that as Developing substances aromatic diamines, especially p-phenylene diamine derivatives are included.