EP0426719A1

EP0426719A1 - A hair dye

Info

Publication number: EP0426719A1
Application number: EP89908410A
Authority: EP
Inventors: David Rose; Edgar Lieske; Horst Höffkes
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1988-07-25
Filing date: 1989-07-17
Publication date: 1991-05-15
Also published as: ATE88489T1; KR0129858B1; JP2801716B2; WO1990001050A1; NO179574C; JPH03506031A; EP0353531A1; NO910167L; DE58904125D1; DE3825212A1; NO179574B; FI100658B; KR900701938A; ES2041902T3; FI910319A0; EP0353531B1; DK11491A; DK11491D0; NO910167D0; US5089025A

Abstract

On utilise comme colorants à action directe dans des teintures pour cheveux des composés ayant la formule (I), ou leurs sels, dans laquelle un des groupes R1 ou R2 est un groupe nitro, alors que l'autre groupe est hydrogène, halogène, un groupe amine, un groupe monoalkylamine ou dialkylamine avec des groupes alkyle ayant entre 1 et 4 atomes de carbone, R3 et R4 sont indépendamment l'un de l'autre de l'hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de carbone, A est un groupe >CHR6 ou >C=O-, R6 étant de l'hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de carbone, et R5 est de l'hydrogène ou un groupe alkyle ayant entre 1 et 4 atomes de carbone.As direct-acting dyes in hair dyes are used compounds having formula (I), or their salts, in which one of the groups R 1 or R 2 is a nitro group, while the other group is hydrogen, halogen, a. amine group, a monoalkylamine or dialkylamine group with alkyl groups having between 1 and 4 carbon atoms, R3 and R4 are independently of each other hydrogen or an alkyl group having between 1 and 4 carbon atoms, A is a group> CHR6 or> C = O-, R6 being hydrogen or an alkyl group having between 1 and 4 carbon atoms, and R5 is hydrogen or an alkyl group having between 1 and 4 carbon atoms. carbon.

Description

"Hair dye"

The invention relates to hair colorants containing direct hair dyes.

In addition to the oxidation dyes which result from the oxidative coupling of one or more developer components with one another or with one or more coupler components, the substantive hair dyes play an important role in dyeing hair. The direct dyes have the advantage that they are used without the addition of oxidizing agents. Compounds belonging to the group of nitrobenzene derivatives are predominantly used as direct dyes. They are used either alone or in combination with other substantive dyes such as anthraquinone dyes, indophenols, triphenylmethane dyes, cationic azo dyes or with oxidation dyes.

Hair dyes usually contain such direct hair dyes in a cosmetic carrier. Creams used as cosmetic carriers for the direct hair dyes and for the oxidation dye precursors additionally contained in the hair dye to achieve certain shades, Emulsions, gels, shampoos, aerosols or other preparations that are suitable for use on the hair.

Good hair dyes have to develop the desired color shades with sufficient intensity. You need to have a good ability to draw on human hair without staining the scalp too much. The dyeings thus produced must have a high stability against light, heat, sweat, shampoo and the chemicals used in the permanent waving of the hair. After all, they should be safe from a toxicological and dermatological point of view.

Direct dyes should continue to have good compatibility with other dyes, e.g. with oxidation dye precursors and with the components customary in oxidation hair dyes, since direct dyes and oxidation dyes are often combined to modify the nuances. Good stability against reducing agents and against oxidizing agents is therefore necessary.

Among the direct nitrobenzene derivatives, the nitroanilines and their derivatives play a special role, since some of these dyes develop intense colorations of good lightfastness. Disadvantages of the known direct nitroaniline dyes are, on the one hand, the limited solubility in water, which leads to problems in the formulation of the hair dye, and, on the other hand, the unsatisfactory fastness to washing, that is to say that the hair dyeings bleed out heavily after repeated washing. Furthermore, it is difficult to use certain fashionable shades, in particular red shades, when using direct-pulling dyes achieve. So far, 2-nitro-p-phenylenediamine and its amino-substituted derivatives have generally been used for this. However, most of these compounds are insufficiently soluble or dispersible in water. This often leads to uneven coloring. Particularly in the case of colorants which contain a high concentration of dyes in order to achieve certain shades, but also in the case of preparations with only slightly solubilizing carrier components, there is still the risk that weaker colorations than intended are obtained because the dyes crystallize out and remain in the dyebath instead of to pull up the hair.

It has surprisingly been found that certain 1,2,3,4-tetrahydro-nitroquinoxalines do not have these disadvantages mentioned and therefore meet the requirements imposed on substantive hair dyes to a particular degree.

The invention therefore relates to hair colorants containing direct dyes, characterized in that one or more compounds of the formula (I)

in which one of the groups R ¹ or R ^{2 is} a nitro group, while the second group is hydrogen, halogen, an amino group, a mono- or dialkylamino rib with alkyl ribs with 1 to 4 carbon atoms, an alkyl or alkoxy group, each with 1 to 4 carbon atoms, R ³ and R ^{4 are} independently hydrogen or an alkyl group with 1 to 4 carbon atoms, A is a> CHR ⁶ - or a> C = 0 group, where R ^{6 is} hydrogen or an alkyl group with 1 to 4 carbon atoms, and R ^{5 represents} hydrogen or an alkyl group with 1 to 4 carbon atoms, or their salts are included.

Particularly suitable dyes are 1,2,3,4-tetrahydro-5-nitroquinoxaline and 1,2,3,4-tetrahydro-6-nitroquinoxaline.

The dyes according to the invention are generally obtainable from the correspondingly substituted quinoxalines by customary synthetic processes. So the production of 1,2,3,4-tetrahydro-5-nitroquinoxaline and 1,2,3,4-tetrahydro-6-nitroquinoxaline is carried out by reacting the corresponding quinoxalines with sodium borohydride in methanolic solution in J. Het. Chem, 10, 213 (1973). Compounds of formula (I) are also accessible in other ways. For example, 1,2,3,4-tetrahydro-7-nitro-2-oxoquinoxaline according to J. Chem. Soc. (1961), 5283 by reacting N- (2,4-dinitrophenyl) glycine with a mixture of sodium hydrogen carbonate and sodium sulfide in methanolic solution.

However, the publications mentioned give no indication of the suitability of these compounds for dyeing hair.

New and therefore a further subject of the invention are compounds of formula (I) according to claim 1, characterized by the following substituent combinations (I) to (IV): R ¹ R ² R ³ R ⁴ R ⁵

I: H NO ₂ H CH ₃ H CH ₂

II: H NO ₂ CH ₃ CH ₃ H CH ₂

III: NH ₂ NO ₂ HHH CH ₂

IV: H NO ₂ HH CH ₃ CH ₂

In principle, these compounds are also accessible from the correspondingly substituted quinoxalines; Synthesis instructions are given in the example section.

The dyes of the general formula (I) produce yellow to red-orange shades of high intensity, light and wash fastness on the hair. They also have better solubility in aqueous alkaline media compared to known nitroaniline dyes. From a dermatological and toxicological point of view, the compounds mentioned are harmless and are therefore particularly suitable for use in hair dyes.

The dyes of the invention can be used both themselves and in the form of their water-soluble salts. In this context, salts are considered to be water-soluble if they dissolve in water or aqueous mixtures in an amount sufficient for dyeing hair.

Among the water-soluble salts are primarily the salts of strong bases such as the alkali salts, ∑. B. the sodium or potassium salt or ammonium salts and alkanolammonium salts with 2 to 4 carbon atoms in the alkanol group such as. B. the monoethanolammo nium salt, the triethanolammonium salt or the isopropanolammonium salt to understand.

The hair dye according to the invention can the direct compounds of formula (I) alone or in combination with known direct dyes, for. B. with other nitrobenzene derivatives, anthraquinone dyes, triphenylmethane or azo dyes. In addition, because of their high resistance to reducing agents and oxidizing agents, the substantive dyes according to formula (I) are also very suitable for combination with oxidizing dye precursors, that is to say for modifying the nuances of oxidizing hair dyes. Oxidation hair colorants contain, as dye precursors, developer components which form the oxidation dyes by oxidative coupling with one another or with suitable coupler components. As developer substances such. B. primary aromatic amines with a further, in para or ortho position free or substituted Hyάroxy- or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used as coupler substances.

To produce the hair dye according to the invention, the substantive hair dye and optionally the oxidation dye precursors are in a suitable cosmetic carrier, for. B. in creams, emulsions, gels or surfactant-containing, foaming solutions, for. B. incorporated in shampoos, aerosols or other preparations that are suitable for use on the hair. Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkane sulfonates, alpha olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acid alkanolamides and thickeners such as. As methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, fatty acids, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol. The constituents of the cosmetic carriers are used to produce the hair colorants according to the invention in amounts customary for these purposes; z. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

The substantive hair dyes of the general formula I are used in the hair colorants according to the invention in a quantity of from 0.01 to 5.0% by weight, preferably from 0.1 to 2% by weight, based on the total hair colorant. In addition, known oxidation hair dye precursors (developer and coupler substances) can be contained in an amount of 0.01 to 5% by weight, preferably 1 to 3% by weight.

If the hair dye according to the invention contains oxidation dye precursors, the addition of a small amount of a reducing agent, e.g. B. from 0.5 to 2.0 wt .-% sodium sulfite to stabilize the oxidation dye precursors. In this case, an oxidizing agent is added to the hair dye before it is applied in order to promote oxidative development of the oxidation dye precursors. Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate and mixtures of such hydrogen peroxide adducts with potassium peroxide sulfate.

The hair colorants according to the invention can be used in a slightly acidic, neutral or alkaline medium, regardless of the type of cosmetic preparation, for example as a cream, gel or shampoo. The hair colorants are preferably used in a pH range from 6 to 10. The application temperatures can be in a range between 15 ° C. and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. The hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used.

With the hair colorants according to the invention, hair colorations of high intensity and good fastness properties, in particular also of good wash fastness and high stability against bleeding and color changes during shampooing, can be achieved. The following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto.

B e i s p i e l e

Manufacturing examples

1.) 1,2,3,4-tetrahydro-2-methyl-6-nitroquinoxaline

1 g of 2-methyl-6-nitroquinoxaline, prepared according to the method described in Coll. Czech. Chem. Comm. 30, 3106 (1965) described synthesis instructions from 4-nitro-1,2-diaminobenzene by reaction with methylglyoxal were dissolved in 30 ml of acetic acid. Sodium borohydride was added to this solution in small portions at +5 ° C. until the starting compound was no longer detectable in the solution by thin layer chromatography. The solution was then diluted with 200 ml of water and extracted twice with chloroform. The organic phase was washed with water and dried. After concentrating to dryness, the residue was dissolved in acetone and precipitated with hydrochloric acid. The yield was 0.6 g (58% of theory). The melting point of the 1,2,3,4-tetrahydro-2-methyl-6-nitroquinoxaline thus obtained was 178 ° C.

2.) 1,2,3,4-tetrahydro-5-amino-6-nitroquinoxaline

According to the synthetic procedure published in J. Chem. Soc., Perkin I, 1975, 1229, 5-amino-6-nitroquinoxaline was prepared by reacting 6-nitroquinoxaline with hydroxylamine in an alkaline medium. The product was reacted with sodium borohydride as in Example 1). That in a yield of 11.5% of theory. Th. 1,2,3,4-tetrahydro-5-amino-6-nitroquinoxaline obtained as brown crystals had a melting point of 213 ° C. 3.) N, N'-dimethyl-1,2,3,4-tetrahydro-6-nitroquinoxaline

To a mixture of 1.08 g (0.006 mol) of the according to the instructions in J. Het. Chem. 10, 213 (1973) 1,2,3,4-tetrahydro-6-nitro-quinoxaline and 1.5 g (0.005 mol) paraformaldehyde in 300 ml acetic acid were 1.52 g (0.024 mol ) Sodium cyanoborohydride added. The solution was then left at room temperature for 24 hours. The solution was then poured into 60 ml of 25% aqueous NaOH solution. The resulting mixture was then extracted three times with methylene chloride. After drying and concentration, 0.35 g (35% of theory) of N, N'-dimethyl-1,2,3,4-tetrahydro-6-nitroquinoxaline was obtained. The melting point of the product was 70 ° C.

4.) 1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxaline

Step 1:

A mixture of 21.75 g (0.14 mol) of 2-fluoro-5-nitroaniline, 56 g (0.74 mol) of 2-methylaminoethanol and 1 g of copper (II) oxide were at 120 ° for 1.5 hours C. heated. After cooling, the catalyst was filtered off and the solution was poured onto ice water. The resulting precipitate was filtered off and dried in vacuo at + 70 ° C. The yield of 1- (N-methyl-N-β-hydroxyethyl) -2-amino-4-nitrobenzene was 25.5 g (96% of theory). The melting point of the product was 111 to 113 ° C.

Level 2:

5 g of the product from stage 1 were introduced into 22 ml of phosphorus oxide trichloride at room temperature within 15 minutes. The mixture was then heated on the water bath for 1 hour. After the excess phosohoroxide trichloride has been distilled off ... the residue was mixed with 50 ml of distilled water. The mixture was then extracted with diethyl ether. The orange-colored oil obtained by concentrating the ethereal phase was refluxed with ethanol for 16 hours and evaporated to dryness in vacuo. The residue obtained was dissolved in water and a potassium carbonate solution was added until the mixture reacted alkaline. The resulting precipitate was filtered off and dried in vacuo at 60 ° C. Orange-red crystals of 1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxaline were obtained. The UV spectrum of these crystals recorded with ethanol as the solvent showed maxima at 441 nm, 350 nm and 290 nm.

Hair dye attempts

Hair dye creams of the following composition were produced:

Fatty alcohol C _12-18 10 g

Fatty alcohol C _12-14 + 2 EO sulfate,

Na salt (28%) 25 g

Water 60 g

direct dye 1 g

Ammonium sulfate l g

concentrated ammonia solution up to pH = 9.5

Water ad 100 g

The ingredients were mixed together in order. After the direct dyes had been added, the pH of the emulsion was adjusted to 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water. The coloring cream was applied to strands approx. 5 cm long, 90% gray, but not specially pretreated, and left there for 30 minutes at 27 ° C. After the dyeing process had ended, the hair was rinsed, washed out with a customary shampoo and then dried

The result of the dyeing tests is shown in Table I.

Table I Direct Dye Nuance of Dyed Hair

1,2,3,4-tetrahydro-5-nitroquinoxaline gray red

1,2,3,4-tetrahydro-6-nitroquinoxaline copper

1,2,3,4-tetrahydro-7-nitro-2-oxoquinoxaline olive brown

1,2,3,4-tetrahydro-2-methyl-6-nitroquinoxaline rose gold

1,2,3,4-tetrahydro-5-amino-6-nitroquinoxaline yellow

N, N'-Dimethyl-1,2,3,4-tetrahydro-6-nitroquinoxaline red-orange

1- (N-methyl) -1,2,3,4-tetrahydro-6-nitroquinoxaline red-brown

Claims

P a t e n t a n s r u c h e

Hair dye containing direct dyes, characterized in that one or more compounds of formula (I) as direct dyes,

in which one of the groups R ¹ or R ^{2 is} a nitro group, while the second group is hydrogen, halogen, an amino group, a mono- or dialkylamino group with alkyl groups with 1 to 4 carbon atoms, an alkyl or alkoxy group, each with 1 to 4 carbon atoms , R ³ and R ^{4 are} independently hydrogen or an alkyl group with 1 to 4 carbon atoms, A is a> CHR ⁶ - or a> C = 0 group, where VP "is hydrogen or an alkyl group with 1 to 4 carbon atoms , and R ^{5 represents} hydrogen or an alkyl group having 1 to 4 carbon atoms, or contains salts thereof.

2. Hair dye according to claim 1, characterized in that 1,2,3,4-tetrahydro-5-nitroquinoxaline and / or 1,2,3,4-tetrahydro-6-nitroquinoxaline are contained as direct dyes.

3. Hair dye according to one of claims 1 or 2, characterized in that the substantive dyes according to formula (I) in an amount of 0.01 to 5 wt .-%, in particular from 0.1 to 2 wt .-%, based on the entire hair dye, are included.

4. Hair dye according to one of claims 1 to 3, characterized in that in addition to the compounds of formula (I), further direct hair dyes and / or oxidation dye precursors are also contained.

5. Hair dye according to one of claims 1 to 4, characterized in that these dyes are incorporated into a cosmetic carrier in the form of a cream, an emulsion, a gel, a shampoo or a foam aerosol.

6. Compounds of formula (I) according to claim 1, characterized by the following substituent combinations (I) to (IV):

R ¹ R ² R ³ R ⁴ R ⁵ A

I: H NO ₂ H CH ₃ H CH ₂

II: H NO ₂ CH ₃ CH ₃ H CH ₂

III: NH ₂ NO ₂ HHH CH ₂

IV: H NO ₂ HH CH ₃ CH ₂