DE3007997A1 - Beta-amino-bis:beta-hydroxy:ethyl-amino-phenoxy-ethanol prepn. - from 2-acetyl-amino-4-amino-phenol in three steps; used as oxidn. hair dye coupler - Google Patents

Abstract

Beta-(2-amino-4-(bis -(beta-hydroxy ethyl)-amino)-phenoxy)- ethanol, (I), is new. (I), as its dihydrochloride, is prepd. is in 3 steps. In 1st step, (1), 2-acetylamino-4-aminophenol is converted to 2-acetylamino-4 -(bis-(beta -hydroxy-ethyl) -amino)- phenol, (A), by reaction with ethylene oxide. In 2nd step, (2) (A) is converted to beta-(2 -acetylamino-4 -(bis-(beta -hydroxyethyl)- amino)-phenoxy)-ethanol, (B), by further reaction with ethylene oxide in the presence of AcONa. In 3rd step, (3), the acetyl gp. is dissociated by boiling with HCl, under the formation of the dihydrochloride of (I). The use of (I), and of its salts with inorganic or organic acids, as coupler components in oxidn. hair dyes is claimed. Fast brown to strong blue-black shades can be achieved. (I) are non-toxic, do not irritate the skin, draw well on hair, and are water-soluble.

Description

New coupler component for oxidation hair colors, their

Production and hair dyes containing them "The subject of the invention is the new compound ß- {2-amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol of the formula The preparation of the new compound according to the invention in the form of its dihydrochloride takes place in 3 stages, starting from 2-acetylamino-4-aminophenol by reaction with ethylene oxide to give 2-acetylamino-4- [bis- (α-hydroxyethyl) -aminoj-phenol, its further Reaction with ethylene oxide in the presence of sodium acetate to form ß- {2-acetylamino-4- [bis- (ß-hydroxyethyl) aminophenoxy} -ethanol and, in the third stage, splitting off the acetyl group by boiling with hydrochloric acid to form the ß- {2- Amino-I1-bis - (- hydroxyethyl) -amino3-phenoxy} -ethanol-dihydrochloride.

The invention also relates to the use of the new compound 6- {2-Amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol as such or in form their salts with inorganic or organic acids as coupler components in oxidation hair dyes and hair dyes that contain the new compound or its 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 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-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.

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 can be used which provide the Requirements are met to a particularly high degree, if one is used as a coupler component 6- {2-Amino-4-E is- (ß-hydroxyethyl) amine -phenoxy} -ethanol, as well as its inorganic or organic salts are used in combination with customary developer substances.

Hair dye based on oxidation dyes with a content of ß- {2-amino-4-2bis (ß-hydroxyethyl) aminophenoxy} ethanol and its inorganic or organic salts as a coupler component and those customary in oxidation hair dyes Developer substances therefore make particularly valuable compositions on the Area of oxidation hair colors.

When used as a coupler component, the inventive Combination with the developer substances generally used for oxidation hair coloring very intense colors ranging from brown to black-blue and thus represents a essential enrichment of the oxidative hair coloring possibilities.

The coupler component according to the invention is also distinguished by very good fastness properties of the dyeings achieved therewith, by a good solubility in water, good storage stability and toxicological as well as dermatological Harmlessness.

The compound to be used according to the invention as a coupler component B- (2-Amino-4-Fbis- (B-hydroxyethyl) -amine07-.

phenoxy} -ethanol can either be used as such or in the form of their salts with inorganic or organic acids such as chlorides, sulfates, Phosphates, acetates, propionates, lactates, citrates can be used.

As examples of those to be used in the hair colorants 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-Nethyl-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, carry, 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-aminopyrazolone derivatives such as 4-Amino-1-phenyl-3-carbamoylpyrazolone-5, N-butyl-N-sulfobutyl-p-phenylenediamine, Tetraaminopyrimidines such as 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-2,6-bismethylaminopyrimidine, 2,5-diamino-4-diethylamino-6-methylaminopyrimidine, 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-triamino-6-B-hydroxy-ethylamino-pyrimidine should be mentioned.

The coupler component according to the invention provides corresponding Developing substances particularly intensive and in their lightfastness properties prominent brown tones, which is of great importance for their practical applicability is. In addition, with the help of certain developers, substances can also be used achieve intense and lightfast blue tones. To achieve as strong and as possible the natural hair color nuances going to corresponding color tones is a full-fledged blue dye as a shading component of particular importance. When creating natural color nuances with the help of Blaükuppler components difficulties often arise with the usual blue couplers.

Here the coupler component according to the invention can make a significant contribution to to fill an existing gap.

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 the molar use also proves to be 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 substance is a uniform Product represents, rather the developer substance can be a mixture of different Be developer connections.

In addition, the hair colorants according to the invention can optionally Usual substantive dyes contained in the mixture, if this is necessary to achieve this 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. Hydrogen peroxide or its addition products are particularly suitable as such of urea, melamine and sodium borate and mixtures of such hydrogen peroxide addition compounds with potassium peroxide disulphate.

The Ilaar stains 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, Fatty alcohol sulfates, alkyl sulfonates, fatty acid alkanolamides, addition products of Ethylene oxide to fatty alcohols, thickeners such as methyl cellulose, starch, higher Fatty alcohols, paraffin oil, fatty acids, perfume oils and hair care products such as To mention 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 of 0.5 to 30 percent by weight and thickeners in concentrations of 0.1 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 approx. 30 minutes the hair dye is removed from the hair to be colored by rinsing. Afterwards will the hair was washed with a mild shampoo and dried.

The colorations that can be achieved with the hair dyes 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.

EXAMPLE First, the production of the inventive Compound B- (2-Amino-II-Tb.is- (B-hydroxyethyl) -aminoJ-phenoxy) -ethanol in the form of their dihydrochloride.

Step 1: 2-Acetylamino-4- [bis (ß-hydroxethyl) amino] -phenol 18.8 g (0.113 Mol) 2-acetylamino-4-aminophenol were with 10 g (0.227 mol) ethylene oxide in 200 ml of ethanol treated for 5 hours at 800 C in the autoclave. After cooling it was concentrated to dryness. The 2-acetylamino-4- ßbis - (- ydroxyethyl) -amino-phenol was preserved as a brown bl.

Step 2: ß- {2-Acetylamino-4- [bis- (ß-hydroxyethyl) -amino] ~ phenoxy ) ethanol 31 g (0.12 mol) of 2-acetylamino-4- [bis- (β-hydroxyethyl) -amino] -phenol with 6 g (0.14 mol) of ethylene oxide in 200 ml of ethanol in the presence of 0.5 g (0.006 mol) Sodium acetate heated to 800 ° C. in an autoclave for 5 hours. After cooling down was filtered and concentrated to dryness.

The mass spectrum of the residue showed a molecular ion peak at 298 (cal. 298).

Step 3: ß- {2-Amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol-dihydrochloride 10 g of the substance from stage 2 were mixed with 40 ml of concentrated hydrochloric acid for 3 hours boiled under reflux for a long time. After concentration to dryness, 12 g of the desired Product obtained as a red-brown bl. The mass spectrum showed one molecular ion at 256 (calc. 256). Thin-layer chromatography on silica gel plates (F-60, Merck) with mobile phase n-butanol-ethanol-water-ammonia 9: 1: 0> 5: 0.5 showed a major product with Rf = 0.4.

The compound of the invention was used in the following examples for the different colors as a coupler component in combination with different ones Developing substances used.

The following compounds served as developer substances: E il: pvTolBylenediamine E 2: 2,4,5,6-tetraaminopyrimidine E 3: p-phenylenediamine E 4: 2-chloro-p-phenylenediamine E 5: 2,5-diaminoanisole E 6: N, N-bis (ß-hydroxyethyl) -amino-p-phenylenediamine E 7: p-aminopherol E 8: N, N-dimethyl-p-phenylenediamine E 9: N-methyl-p-phenylenediamine E 10: N-ethyl-N-β-hydroxyethyl-p-phenylenediamine E 11: 2-methylamino-4,5,6 triaminopyrimidine The hair colorants according to the invention were used in the form of an oreme 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 fatty alcohol sulfate (sodium salt) chain length 012 -C18 and 75 parts by weight of water each 0.01 mole of those listed in the table below Developer substances and ß- {2-Amino-4- [bis- (B-hydrsxyethyP) -amino? -Phenoxy) -ethanol incorporated Thereafter, the pH of the emulsion was adjusted using ammonia adjusted to 9.5 and the emulsion made up to 100 parts by weight with water. The oxidative coupling was carried out with 1 auger hydrogen peroxide solution as the oxidizing agent carried out, with 100 parts by weight of the emulsion 10 parts by weight of hydrogen peroxide solution were given.

The respective coloring cream with the addition of oxidizing agents was applied 90% gray, not specially pretreated human hair is applied and there Leave for 30 minutes. After completing the dyeing process, the hair was finished with a Washed out conventional shampoos and then dried. The received The colorations are shown in Table 1 below.

Table 1 Example developer nuance of colored hair, 9% H2O2 solution 1 E1 blue-gray 2 E 2 brown orange 3 E 3 black-blue 4 E 4 purple-gray 5 E 5 blue-gray 6 E 6 dark blue 7 E 7 dark ruby 8 E 8 dark blue 9 E 9 blue-gray 10 E 10 durAel blue Ii E 11 brown

Claims (5)

"New coupler component for oxidation hair colors, their production and hair dyes containing them11 Claims: 1. ß- (2-Amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol. 2. Process for the preparation of ß- {2-Amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol according to claim 1 in the form of its dihydrochloride in 3 stages, starting from 2-acetylamino-4-aminophenol by reaction with ethylene oxide to form 2-acetylamino-4- [bis- (ß-hydroxyethyl) -amino] -phenol, its further reaction with ethylene oxide in the presence of sodium acetate to form ß-f2-acetylamino-II-is- ( -hydroxyethyl) -amino-phenoxy} -ethanol and in the third stage splitting off of the acetyl group by boiling with hydrochloric acid to form the ß- (2-amino-4- [bis- (ß-hydroxyethyl) -amino] - phenoxy} ethanol dihydrochloride. 3. Use of ß- (2-amino-4- [bis- (ß-hydroxyethyl) -amino] -phenoxy} -ethanol according to claims 1 and 2 and their salts with inorganic or organic acids as a coupler component in oxidation hair colors. 4. Hair dye based on oxidation dyes with a content of B-C2-amino-4- bis (B-hydroxyethyi) -amino3-phenoxy} -ethanol according to claim 1 - 3 and its salts with inorganic or organic acids as a coupler component and the developer substances common in oxidation hair colors. 5. Hair dye according to claim 4, characterized by £ a content of developer-coupler combination in an amount of 0.2 to 5 percent by weight, based on the total hair dye.