DE4200534A1 - N-benzyl-4-aminophenol derivs. as oxidn. dye developers - for human hair, giving strong, bright shades of good fastness - Google Patents

Abstract

Use of N-benzylamino-phenols of formula (I) or their salts as precursors in oxidn. dyeing is new. Where R1-R7 = H or 1-4C alkyl; up to 3 of R3-R7 can also be Cl or OR8 and the other R gps. H; R8 = H, 1-4C alkyl or 2-4C hydroxyalkyl. (I) and their salts are new where (a) R3 = R5 = H; (b) R3, R5 and R7 = 1-4C alkoxy; (c) R4, R5 and R6 = 1-4C alkoxy; or (d) R4 and R6 = 1-4C alkoxy and R5 = OH, th eother R gps. being H. Pref. deriv. of (I) is N-(2,4-dihydroxybenzyl)-4-aminophenol. USE/ADVANTAGE - (I) are developers for dyeing keratin fibres, esp. human hair. When used with a wide variety of usual couplers they provide bright shades (beige to brown-violet) of good fastness properties. Partic. they give shades of better brightness, colour depth and light fastness than 4-aminophenol itself.

Description

The invention relates to the use of N-Benzylaminophenolderivaten as developer components in Oxidati onsfärbemitteln.

For the dyeing of hair play the so-called oxidation hair dyes because of their intense colors and good fastness a preferred role. Contain such hair dyes Oxidation dye precursors in a cosmetic carrier. When Oxidation dye precursors become developer substances and Coupler substances used. The developer components form un ter the influence of oxidizing agents or atmospheric oxygen un one behind the other or under coupling with one or more couplers components are the actual dyes.

A certain developer substance can be combined with un Different couplers also very different shades form. Nevertheless, often it does not succeed with the help of a single Developer substance to the variety of natural hair color shades come. In practice, a combination is therefore usually different the developer components and coupler components required to  to get a single, natural hair coloring. Therefore be is constantly in demand for new developer components.

Good oxidation dye precursors must first and foremost Meet the requirements: You must in the oxidative coupling the desired color shades in sufficient intensity and real training. You also need to have a good wind up possess human hair, with no noticeable differences between strained and newly regrown hair allowed. They should be resistant to light, heat and the one flow of chemical reducing agent, e.g. B. against perming liquid opportunities. After all, they should not stain the scalp too much, and above all, they should be toxicological and dermatological Regard safe.

As developer substances are usually primary aromatic Amines with another in para or ortho position free or substituted hydroxy or amino group, further Diaminopyridine derivatives, heterocyclic hydrazone derivatives or 4- Aminopyrazolonderivate used. As so-called coupler substances Methaphenylenediamine derivatives, naphthols, resorcinol derivatives and Pyrazolone used.

4-aminophenol has long been a developer component for oxida tion hair dye known. It has now been found that by the Use of N-benzylated 4-aminophenols as developer compo In oxidation hair dyes, the hair coloration in terms of Color brilliance, Därbeintensität and light fastness significantly improved can be.

The invention relates to the use of N-Benzylaminophenolen of the formula I.  

wherein R ¹ to R ^{7 are} independently hydrogen or alkyl groups having 1-4 C atoms and up to three of the groups R ³ to R ^{7 are} also chlorine or a group OR ⁸ and the remaining hydrogen, wherein R ^{8 is} hydrogen, an alkyl group with 1-4 C atoms or a hydroxyalkyl group having 2-4 C atoms, or salts thereof as a developer component in oxidation colorants containing conventional coupler components for dyeing keratin fibers, in particular of human hair.

The N-benzylaminophenols of formula I are Oxidation dye precursors of the type of developer substances, d. H. they are able to color under the action of oxidizing agents to train materials. In the presence of couplers are ever but especially brilliant and intense colors formed. As a Kupp excipients are especially the m-phenylenediamines, m-aminophenols, resorcinols, naphthol-1, 1,5- and 2,7- Dihydroxynaphthalene, hydroxy and aminopyridines, hydroxyquinolines and aminopyrazolones.

With these and other known coupler substances form the N-benzylaminophenols have a wide range of nuances, that of beige until brown violet is enough. The N-benzylaminophenols according to the invention of formula I are therefore ideal for use as  Developer-type oxidation dye precursors in hair dye stuffs.

The N-benzylaminophenols of the formula I can either be used as such or in the form of their salts with inorganic or organic acids, z. As hydrochlorides, sulfates, phosphates, acetates, propionates, Lactates or citrates isolated and used in hair dye become.

It is also not necessary that the N-Benzylaminophenole the Formula I represent uniform chemical compounds. Much more These may also be mixtures of various compounds of the formula I. his.

Favorable application properties are those benzylaminophenols of the formula I in which the two groups R ¹ and R ^{2 are} hydrogen or R ^{1 is} hydrogen and R ^{2 is} methyl and in which up to three of the groups R ³ to R ^{7 is} a group OR ⁸ and the others Are hydrogen, wherein R ^{8 is} hydrogen, an alkyl group having 1-4 C atoms or a hydroxyalkyl group having 2-4 C atoms.

A series of N-Benzylaminophenolen of formula I are known from the literature, for. By S. Huneck et al., Plant Growth Regula tion, S 75, Springer Verlag (1984).

Not known from the literature is a group of N-Benzylaminophenolen of formula I, but have particularly favorable performance properties egg. These new N-Benzylaminophenole of formula I, in which
R ³ and R ^{5 are} hydroxy groups or
R ³ , R ⁵ and R ^{7 are} alkoxy groups having 1-4 C atoms or
R ⁴ , R ⁵ and R ^{6 are} alkoxy groups having 1-4 C atoms or
R ⁴ and R ^{6 are} alkoxy groups having 1-4 C atoms and
R ^{5 is} a hydroxy group,
and the other groups R are each hydrogen, are a further object of the invention.

Particularly suitable has N- (2,4-dihydroxybenzyl) -4-ami Nophenol, which in addition to its positive toxicological Characteristics characterized in that it as a developer component hair dyes produced in Oxidationshaarfärbemitteln that regard Color brilliance, color intensity and light fastness those with 4-Ami nophenol as a developer component produced significantly superior are.

These new N-benzyl-4-aminophenols can be prepared by known Synthetic method z. B. thereby, that the corre sponding 4-aminophenols of the formula II with the corresponding Reacting benzaldehyde derivatives of the formula III and the gebil catalytically hydrogenated Azomethine of formula IV (detailed Rule in the example section).

Another patent object is therefore the method of manufacture ment of N-Benzylaminophenole of formula I, in which

R ³ and R ^{5 are} hydroxy groups or
R ³ , R ⁵ and R ^{7 are} alkoxy groups having 1-4 C atoms or
R ⁴ , R ⁵ and R ^{6 are} alkoxy groups having 1-4 C atoms or
R ⁴ and R ^{6 are} alkoxy groups having 1-4 C atoms and
R ^{5 is} a hydroxy group,
and the remaining groups R are each hydrogen.

Another patent object is a hair dye with a content oxidation dye precursors in a cosmetic carrier, the oxidation dye precursors N-Benzylaminophenole the Formula I as a developer component in an amount of 0.05-10 mmol per 100 g of the hair dye in addition to conventional coupler components contain.

For the preparation of the hair dye according to the invention are Oxidation dye precursors in a suitable cosmetic  Carrier incorporated. Such carriers are z. As creams, emulsions, Gels or surfactant-containing foaming solutions, eg. Shampoos, Foam aerosols or other preparations necessary for the applications are suitable on the hair.

Usual components of such cosmetic preparations are, for. B .:

• - wetting and emulsifying and anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, Alkanesulfonates, α-olefinsulfonates, fatty alcohol polyglycol ether
• Ethylene oxide addition products to fatty alcohols, to fatty acids, to alkylphenols, to sorbitan fatty acid esters, on Fatty acid partial glycerides and fatty acid alkanolamides
• - Thickener, z. Fatty alcohols, fatty acids, paraffin oils, Fatty acid esters and other fat components in emulsified form
• - Water-soluble polymeric thickeners, such as. Methyl or hydroxyethyl cellulose, starch, vegetable gums, water-soluble, synthetic polymers, water-soluble Biopolymers (eg xanthan gum)
• - hair-care additives, such as. B. water-soluble cationic Polymers, protein derivatives, pantothenic acid, vitamins, plants extracts, cholesterol and sugar
• - Electrolyte and buffer salts, pH adjusters, complexing agents and Perfume oils
• - Reducing agent for stabilizing the dye, for. B. Na triumsulfate or ascorbic acid.

The ingredients of the cosmetic carriers are used to prepare the hair products according to the invention in amounts customary for this purpose used; z. B. become emulsifiers in concentrations of 0.5 to 30% by weight and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.

Particularly suitable as a carrier is a gel with a content of 1 to 20% by weight of a soap, preferably ammonium oleate or an oil in-water emulsion containing from 1 to 25% by weight of a Fat component and 0.5 to 30 wt .-% of an emulsifier from the Group of anionic, nonionic, ampholytic or zwitterionic surfactants.

The oxidation dye precursors are in amounts of from 0.2 to 5 Wt .-%, preferably 1 to 3 wt .-%, of the total colorant in the carrier mixed.

The oxidative development of the staining can basically be done with air oxygen take place. However, preferred is a chemical Oxidati Onsmittel used, especially if in addition to the coloring a lightening effect on the hair is desired. As oxidizing agent in particular hydrogen peroxide or its Addition products of urea, melamine or sodium borate and Mixtures of such hydrogen peroxide addition products with Potassium peroxide disulfate into consideration.

A preparation of the oxidizing agent is preferred immediately before hair dyeing with the preparation Oxidation dye precursors and carriers mixed. That here The resulting ready-to-use hair dye preparation should be preferred have a pH in the range of 6 to 10.  

Particularly preferred is the application of the hair dye in one weak alkaline environment. The application temperatures can be in range between 15 and 40 ° C. After a Einwir kinkzeit of about 30 minutes, the hair dye by Off Rinse away from the hair to be dyed. The rinsing with egg A shampoo is omitted if a strong surfactant-containing carrier, eg. B. a dyeing shampoo was used.

The following examples are intended to illustrate the subject matter of the invention but without limiting it.

Examples 1. Production examples Synthesis of N- (2,4-dihydroxybenzyl) -4-aminophenol: (E1)

11.5 g (0.05 mol) of N- (2,4-dihydroxybenzylidene) -4-aminophenol taken up in 400 ml of ethanol and catalytically with platinum (5% strength Carbon) hydrogenated as a catalyst. After recording the calculation th amount of hydrogen is stopped, concentrated to dryness and recrystallized twice from acetonitrile. Yield: 5.2 g (45%), Melting point: 148 ° C.

Synthesis of N- (2,4,6-trimethoxybenzyl) -4-aminophenol: (E6) a) N- (2,4,6-trimethoxybenzylidene) -4-aminophenol

9.8 g of 2,4,6-trimethoxybenzaldehyde ge in about 50 ml of ethanol dissolves and filters. 5.4 g of 4-aminophenol are dissolved in 300 ml Ethanolamine and filtered. While stirring, the two solutions combined. After a short time the product starts to fail. After standing overnight, filtered off with suction and washed with cold ethanol rule. Yield: 13.8 g (96%), m.p. 275 ° C.

b) N- (2,4,6-trimethoxybenzyl) -4-aminophenol

11.5 g (0.03 mol) of N- (2,4,6-trimethoxybenzylidene) -4-aminophenol are taken up in 200 ml of ethanol and catalytically with platinum (5% on carbon) hydrogenated as a catalyst. After recording the calculated amount of hydrogen is broken off, to dryness  concentrated and recrystallized from ethanol. Yield: 7.3 g (84%), Melting point: 120 to 122 ° C.

Synthesis of N- (3,4,5-trimethoxybenzyl) -4-aminophenol: (E5) a) N- (3,4,5-trimethoxybenzylidene) -4-aminophenol

19.6 g of 3,4,5-trimethoxybenzaldehyde ge in about 50 ml of ethanol dissolves and filters. 10.9 g of 4-aminophenol are dissolved in 250 ml Ethanolamine and filtered. While stirring, the two solutions combined. After a short time the product starts to fail. After standing overnight, it is filtered off with suction and recrystallized from ethanol Siert. Yield: 5.4 g (19%), mp 187 ° C.

b) N- (3,4,5-trimethoxybenzyl) -4-aminophenol:

5.4 g (0.019 mol) of N- (2,4,6-trimethoxybenzylidene) -4-aminophenol are taken up in 250 ml of ethanol and catalytically with platinum (5% on carbon) as a catalyst. After recording the Calculated amount of hydrogen is stopped, concentrated and the crystallized product separated. Yield: 4.3 g (79%), Melting point: 122 to 126 ° C.

Synthesis of N- (3,5-dimethoxy-4-hydroxybenzyl) -4-aminophenol: (E8) a) N- (3,5-Dimethoxy-4-hydroxybenzylidene) -4-aminophenol:

9.1 g of 3,5-dimethoxy-4-hydroxy-benzaldehyde are dissolved in about 50 ml Dissolved ethanol and filtered. 5.4 g of 4-aminophenol are dissolved in 50 ml Ethanolamine and filtered. While stirring, the two solutions combined. After a short time the product starts to fail.  

After standing overnight, it is filtered off with suction and recrystallized from ethanol Siert. Yield: 11.9 g (44%), m.p .: 208 ° C.

b) N- (3,5-Dimethoxy-4-hydroxybenzyl) -4-aminophenol:

5.4 g (0.02 mol) of N- (3,5-dimethoxy-4-hydroxybenzylidene) -4-amino phenol are taken up in 150 ml of ethanol and catalytically with Raney nickel hydrogenated as a catalyst. After recording the calculation Neten amount of hydrogen is broken off, concentrated and the back was recrystallized from methanol. Yield: 0.5 g (9%), Melting point: 153-154 ° C.

2. Application examples

Hair dyes according to the invention were in the form of a hair dye cream emulsion prepared in the following composition:

Fatty alcohol C₁₂ to C₁₈ | 10 g Fatty alcohol C₁₂ to C₁₄ + 2 EO sulfate, sodium salt 28% 25 g water 60 g Developer component according to table (1) 7.5 mmol Coupler component according to Table (1) 7.5 mmol Na₂SO₃ (inhibitor) 1.0 g concentrated ammonia solution to pH = 9.5 water ad 100 g

The ingredients were mixed together in order. To Addition of the developer components and the inhibitor was initially  with concentrated ammonia solution, the pH of the emulsion to 9.5 adjusted, then made up to 100 g with water.

The oxidative development of the staining was with 3% water stoffperoxidlösung performed as an oxidation solution. For this purpose were 100 g of the emulsion with 50 g of hydrogen peroxide solution (3%) ver sets and mixes.

The staining cream was standardized to about 5 cm long strands, 90% gray but not particularly pre-treated human hair applied and left there for 30 minutes at 27 ° C. After completion the dyeing process, the hair was rinsed, with a usual Washed shampoo and then dried.

The developer components were the compounds according to the invention used:

N- (2,4-dihydroxybenzyl) -4-aminophenol E1 N- (4-methoxybenzyl) -4-aminophenol E2 N- (2-hydroxybenzyl) -4-aminophenol E3 N-benzyl-4-aminophenol E4 N- (3,4,5-trimethoxybenzyl) -4-aminophenol E5 N- (2,4,6-trimethoxybenzyl) -4-aminophenol E6 N- (4-chlorobenzyl) -4-aminophenol E7 N- (3,5-dimethoxy-4-hydroxybenzyl) -4-aminophenol E8

As coupler components, the following compounds were used:

1-naphthol K1 5-Amino-4-chloro-2-methylphenol K2 1,5-dihydroxynaphthalene K3 2,4-dichloro-3-aminophenol K4 3-aminophenol K5 resorcinol K6 1,3-bis (2,4-diaminophenoxy) -propane K7 2-chloro-3-amino-6-methylphenol K8 5-amino-2-methylphenol K9

Table 1 gives an overview of the obtained shades of human hair with hair dye, the N-benzyl-4-aminophenols as developer components and conventional coupler components enthal th.

Table 1

Claims (5)

1. Use of N-Benzylaminophenolen of the formula I. wherein R ¹ to R ^{7 are} independently hydrogen or alkyl groups having 1-4 carbon atoms and up to three of the groups R ³ to R ^{7 are} also chlorine or a group OR ⁸ and the remaining hydrogen, wherein R ^{8 is} hydrogen, a Alkyl group having 1-4 C-atoms or a hydroxyalkyl group having 2-4 C-atoms, or salts thereof as precursors for the production of Oxida tion dyeings. 2. Use of N-Benzylaminophenolen of the formula I or salts thereof according to claim 1, characterized in that R ¹ and R ^{2 are} hydrogen and up to three of the groups R ³ to R ^{7 is} a group OR ⁸ and the remaining hydrogen or that R ^{1 is} hydrogen and R ^{2 is} methyl and up to three of the groups R ³ to R ^{7 are} a group OR ⁸ and the remaining hydrogen, where R ^{8 is} hydrogen, an alkyl group having 1-4 C atoms or a hydroxyalkyl group having 2- 4 C atoms is. 3. N-Benzylaminophenole of the formula I or their salts, wherein R ³ and R ^{5 are} hydroxy groups or R ³ , R ⁵ and R ^{7 are} alkoxy groups having 1-4 C-atoms or R ⁴ , R ⁵ and R ⁶ alkoxy groups with 1 4 are C atoms or R ⁴ and R ^{6 are} alkoxy groups having 1-4 C atoms and R ^{5 is} a hydroxy group and the remaining R groups are each hydrogen. 4. A process for the preparation of N-Benzylaminophenolen of the formula I according to claim 3, wherein R ¹ to R ⁷ in the formulas II, III and IV have the same meaning as in formula I, claim 3, by reacting an aminophenol of the formula II a benzaldehyde of the formula III an azomethine of the formula IV, characterized in that this azomethine is catalytically hydrogenated. 5. hair dye containing oxidation dye precursors in a cosmetic carrier, characterized in that as Oxidation dye precursors N-Benzylaminophenols of the formula I according to claims 1-3 or their salts as developer components  in an amount of 0.05-10 mmol per 100 g of the hair dye Are included in addition to conventional coupler components.