DE29705264U1 - New triaminobenzene derivatives and dyes containing them for keratin fibers - Google Patents

Description

Description

New triaminobenzene derivatives and dyes containing them for keratin fibres

The present invention relates to new derivatives of 1,2,4-triaminobenzene and their use for coloring keratin material, in particular fur, hair or wool.

Oxidative dyeing processes have become widespread in the dyeing practice for keratin fibers - especially for producing dark color nuances. In these processes, the dyes are produced by oxidative coupling of suitable developer substances and coupler substances in the hair shaft, which results in very intense colors with very good fastness properties. In addition, a variety of different color nuances can be obtained by combining different developer substances and coupler substances.

However, a certain problem that occurs particularly in the coloring of human hair is the creation of blue color shades. This problem is solved in today's hair dyes by using 2,5-diaminotoluene or 2,5-diaminophenylethanol in combination with an m-phenylenediamine derivative. However, this solution is not entirely satisfactory and it is desirable to create blue hair colors without the use of m-phenylenediamine derivatives.

Now it has surprisingly been found that the problem can be solved by the use of new 1,2,4-triaminobenzene derivatives of the general formula (I).

NH-CH ₂ -CH ₂ -SO ₂ -X

(iii)

The radical X represents an NR1R2 or CHR1R2 group, where R1 and R2 can be the same or different and represent hydrogen, an alkyl group with 1 to 4 carbon atoms or a mono- or polyhydroxyalkyl group with 2 to 4 carbon atoms.

The compounds according to formula (I) with X = NR1R2 can be obtained by reacting 2,4-dinitrochlorobenzene with taurine, the subsequent conversion of the sulfonic acid into the sulfochloride, the reaction of the sulfochloride with a suitable amine or ammonia to form the sulfonamide and the final hydrogenation of the nitro groups to form the triamino derivative.

To prepare the compounds of formula (I) with X = CH ₂ -RI, the corresponding aminoethyl alkyl sulfone is reacted with 2,4-dinitrochlorobenzene and the resulting product is hydrogenated to the triamino derivative.

For better handling of the triamino derivatives according to formula (I), they are conveniently converted into their salts with inorganic acids, for example the hydrochlorides or sulfates.

The present invention further relates to hair dyes containing new compounds of formula (I), in particular for human hair. The compounds of formula (I) are present in the hair dye according to the invention in an amount of 0.1 to 10 percent by weight, in particular in an amount of 0.5 to 6 percent by weight.

The compounds of the general formula (I) dye hair into a reddish-brown shade without the addition of developers or couplers.

To produce further color nuances, the hair dye according to the invention can additionally contain other known developer substances and coupler substances, preferably in an amount of 0.1 to 4 percent by weight.

Of the known developer substances, in addition to the compounds of formula (I), 1,4-diaminobenzene, 2-(2',5'-diaminophenyl)-ethanol, 4-aminophenol, 4-amino-3-methylphenol and 4,5-diamino-1-(2-hydroxyethyl)-1 H-pyrazole are particularly suitable as components of the hair dye according to the invention. The developer substances can be used individually or in a mixture with one another. Of the known coupler substances, resorcinol, 4-chlororesorcinol, m-aminophenol derivatives, 5-hydroxy-1,3-benzodioxole, 5-amino-1,3-benzodioxole, 5-((2 ^l -hydroxyethyl)-amino)-1,3-benzodioxole and

5-((2-Hydroxyethyl)-amino)-2-methoxyaniiin comes into consideration.

The compounds according to formula (I) or their salts with inorganic acids color keratin material in combination with m-aminophenol derivatives under the action of an oxidizing agent, for example hydrogen peroxide or atmospheric oxygen, in intense blue shades.

Particularly preferred m-aminophenol derivatives are 3-aminophenol, 5-amino-2-methylphenol, 5-((3-hydroxyethyl)amino)-2-methylphenol and 5-((3-hydroxypropyl)amino)-2-methylphenol.

The developer substances and coupler substances are generally used in approximately equimolar amounts. However, it is not a disadvantage if the developer substances, based on the amount of coupler substances, are used in an excess or deficiency.

The hair dye according to the invention can also contain self-coupling color precursors, such as 2-amino-5-methylphenol, 2-amino-6-methylphenol or 2-amino-5-ethoxyphenol.

In order to achieve certain color nuances, conventional direct dyes, for example triphenylmethane dyes such as Diamond Fuchsine (Cl. 42 510) or Basic Blue 26 (Cl. 44 045), aromatic nitro dyes such as picramic acid or 2-((hydroxyethyl)-amino)-4,6-dinitrophenol, 4-((2'-hydroxyethyl)-amino)-2-nitroaniline, azo dyes such as Acid Brown 4 (C.I. 14 805) and Acid Blue 135 (C.I. 61 100) can also be included in an amount of 0.01 to 4 percent by weight.

Other suitable dyes that are applied directly to the hair are described, for example, in the book by J.C. Johnson, "Hair Dyes", Noyes Data Corp. Park Ridge USA (1973).

Known and common substances for hair coloring are also described in the book by E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (1957), pages 503 ff. and in the book by H. Janistyn, "Handbook of Cosmetics and Fragrances" (3rd revised edition 1978, ISBN 3-7785-0423-1), pages 454 ff.

The developer and coupler substances as well as the other color components can of course also be used in the form of physiologically acceptable acid addition salts, for example as hydrochloride or sulfate, if they are bases, or, if they contain aromatic hydroxy groups, in the form of salts with inorganic bases, for example as alkali phenolates.

Especially in the case of amino compounds that are sensitive to oxidation, it is advantageous if these are used in the form of their salts in the production of the hair dye.

The total amount of the developer substances, the coupler substances, the self-coupling color precursors and the direct dyes or their salts used in the hair dye according to the invention is about 0.1 to 10.0 percent by weight, preferably 3.0 to 8.0 percent by weight.

In addition, the hair dye may contain other common cosmetic additives, such as antioxidants such as ascorbic acid or sodium sulphite, perfume oils, complexing agents, wetting agents, emulsifiers, thickeners, care substances and others.

The preparation form can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. However, the particularly preferred preparation forms are a cream, a gel or an emulsion. Their composition is a mixture of the dye components with the additives customary for such preparations.

Common additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycols such as glycerin or glycol ethers such as propylene glycol, as well as wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyltrimethylammonium salts, alkyl betaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamines, ethoxylated fatty acid esters, and thickeners such as higher fatty alcohols, starch, cellulose derivatives, Vaseline, paraffin oil and fatty acids, as well as care substances such as lanolin derivatives, cholesterol, betaine and pantothenic acid.

The components mentioned are used in the amounts usual for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in a

Amount of about 0.1 to 25 percent by weight and the care ingredients in an amount of about 0.1 to 5 percent by weight.

Depending on their composition, the hair dyes according to the invention can react slightly acidic, neutral or alkaline. In particular, they have a pH value in the alkaline range between 8.0 and 11.5, whereby the pH is preferably adjusted using ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide can also be used.

For use in the oxidative coloring of hair, the hair dye described above is mixed with an oxidizing agent immediately before use and a sufficient amount of this mixture for the hair coloring treatment, depending on the thickness of the hair, generally about 60 to 200 g, is applied to the hair.

The oxidizing agents used to develop hair color are mainly hydrogen peroxide or its addition compounds with urea, melanin or sodium borate in the form of 3 to 12 percent, preferably 6 percent, aqueous solutions.

If a 6 percent hydrogen peroxide solution is used as an oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidizing agent are used primarily when the dye concentration in the hair dye is higher or when a stronger bleaching of the hair is desired at the same time.

The mixture is left to act on the hair at 15 to 50 ^° C for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, the hair is washed with a shampoo after this rinse and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.

The hair dye according to the invention enables hair coloring with excellent fastness properties, in particular with regard to light, wash and rub fastness, which can be easily removed again with reducing agents. In terms of coloring options, the hair dye according to the invention offers a wide range of different color nuances depending on the type and composition of the color components. The great color intensity and the color purity of the achievable colors are remarkable. With the help of the hair dye described, it is also possible to color gray and chemically undamaged hair without any problems and with very good coverage. The colorings obtained are uniform and very well reproducible, regardless of the different structure of the hair.

The following examples are intended to explain the subject matter of the invention in more detail.

Manufacturing examples

Example 1 : Preparation of 2-[(2,4-diaminophenyl)amino]-ethanesulfonic acid amide dihydrochloride

Step 1: 2-((2,4-Dinitrophenyl)amino)ethanesulfonic acid sodium salt

The product is prepared according to the procedure of Example 59 of US Patent 3,629,330.

NHCH ₂ CH ₂ SO ₃ ^{Na +} ,NO,

+ H ₂ N-CH ₂ CH ₂ SO ₃ H

20.26 g (0.1 mol) of 2,4-dinitrobenzene, 14.0 g (0.112 mol) of taurine, 10.0 g of sodium hydrogen carbonate, 80 ml of water and 40 ml of ethanol are heated under reflux for 5 hours. The mixture is filtered hot and then slowly cooled to room temperature. The precipitated product is filtered off with suction, washed with a little water and dried over calcium chloride. 23.8 g (0.076 mol, 76% of theory) of a yellow product are obtained which melts between 160 and 162 ⁰ C.

Step 2: 2-((2,4-Dinitrophenyl)amino)ethanesulfonic acid chloride

NHCH ₂ CH ₂ SO ₃ " Na ⁺

NHCH ₂ CH ₂ SO ₂ Cl

_POCl3

Sulfolane/Acetonitrile

40.0 g (0.137 mol) 2-((2,4-dinitrophenyl)aminoethanesulfonic acid sodium salt
from step 1, 90 ml of acetonitrile, 90 ml of sulfolane and 70 ml of phosphorus oxychloride are heated to 75 ⁰ C for 45 minutes. The brown reaction mixture is then cooled to 0 ⁰ C and 400 ml
Water under ice cooling. The dropwise addition rate of the
The water is adjusted so that the temperature of the reaction mixture does not rise above 10 ⁰ C. After stirring for one hour at 10 ⁰ C, the yellow product is filtered off with suction, washed with water and dried over calcium chloride. 33.3 g (0.11 mol, 78% of theory) of yellow powder with a melting point between 120 and 122 ⁰ C are obtained.

Step 3: 2-((2,4-Dinitrophenyl)amino)ethanesulfonic acid amide

NHCH ₂ CH ₂ SO ₂ Cl

_NH3 / _H2O

NHCH ₂ CH ₂ SO ₂ NH ₂

To 90 ml of aqueous ammonia solution (32% ammonia content) are added at ⁰ ° C 30.0 g (0.097 mol) of 2-((2,4-dinitrophenyl)amino)ethanesulfonic acid-

Chloride from stage 2 is added in portions. The yellow suspension is stirred for 7 hours at room temperature and then filtered and washed with water. After drying over calcium chloride, 23.8 g (0.082 mol, 84% of theory) of a yellow powder with a melting point of 174 to 177 ⁰ C are obtained (literature melting point according to US Pat. No. 3,629,330, Example 60: 165-169 ⁰ C).

Step 4 and 5: 2-[(2,4-diaminophenyl)amino]ethanesulfonic acid amide and its conversion into the dihydrochloride

NHCH ₂ CH ₂ SO ₂ ]OT ₂

2 H ₂ /Pd(10% on activated carbon)

Ethanol

NHCH ₂ CH ₂ SO ₂ NH ₂

HCl ethanol

NHCH ₂ CH ₂ SO ₂ NH ₂

10.0 g (0.035 mol) of 2-((2,4-dinitrophenyl)amino)ethanesulfonic acid amide from step 3 are hydrogenated in 1.2 l of ethanol with the addition of a palladium/activated carbon catalyst (10% Pd). After stirring for 20 hours under a hydrogen atmosphere, the catalyst is filtered off. When the ethanol is distilled off, a gray powder with a melting point between 133 and 135 ^° C remains.

To convert it into the dihydrochloride, a concentrated solution of the free base in ethanol (C « 0.1 mol/l) is mixed with a sufficient amount of hydrochloric acid gas. The dihydrochloride is precipitated with diethyl ether, filtered off with suction and dried in vacuo. 6.3 g (0.021 mol, 59% of theory) of a slightly pink powder with a melting point between 218 and 220 ⁰ C are obtained.

Elemental analysis calc.: %C %H %N (C ₈ H ₁₅ CI ₂ N ₄ O ₂ S) found: 31.69 5.32 18.48 31.80 5.66 18.12

Example 2: Preparation of 1,3-diamino-4-((2-methylsulfonyl)ethyl)amino)benzene

Step 1: 2,4-Dinitro-N-(2-(methylsulfonyl)ethyl)aniline

NHCH ₂ CH ₂ SO ₂ CH,

NaHCO ₃ + H ₂ N-CH ₂ -CH ₂ -SO ₂ -CH ₃ ►

&khgr; HCl
202.55 159.64 289.27

In a three-necked flask with a capacity of 250 ml, equipped with a reflux condenser and internal thermometer, 8.94 g (56 mmol) of 1-amino-2-

(methylsulfonylethane hydrochloride* ¹ 9.2 g (0.11 mol) of sodium hydrogen carbonate and 100 ml of absolute ethanol are heated to 40 ⁰ C. 10.13 g (50 mmol) of 1-chloro-2,4-dinitrobenzene are added in portions to this mixture. The mixture is boiled under reflux for 8 hours.

After cooling, the crude product is filtered off with suction, suspended in water, filtered off with suction again and washed with water. The residue (13.3 g) is boiled under reflux in 150 ml of ethanol. The yellow, insoluble precipitate is filtered off while still warm and washed with warm ethanol. After drying over calcium chloride, 12.7 g (44 mmol, 88% of theory) of a yellow powder with a melting point of 162 to 163 ^° C are obtained.

Elemental analysis calc.: %C %H %N (C ₉ H ₁₁ N ₃ O ₆ S) found: 37.37 3.83 14.53 37.24 3.83 14,45

¹ manufactured according to specification in
SM Liebowitz, JB Lombardini and ClAllen Biochemical Pharmacology 1989, (38), 399-406, 401

Step 2: 1,3-Diamino-4-((2-(methylsulfonyl)ethyl)amino)benzene

NHCH ₂ CH ₂ SO ₂ CH ₃

289.27

H2/Pd(10%C)

EEE

NHCH ₂ CH ₂ SO ₂ CH ₃

229.30

2.025 g (7 mmol) of 2,4-dinitro-N-[2-(methylsulfonyl)ethyl]aniline are hydrogenated with 0.5 g of a palladium/activated carbon catalyst (10 percent) in 300 ml of ethyl acetate (EA). After seven hours, acetone is added until the reaction product dissolves. The catalyst is removed by filtration and the clear solution is concentrated to a small volume. At 0 ⁰ C, a light brown precipitate forms, which is filtered off, washed with a little ethyl acetate and dried in a desiccator under vacuum.

0.84 g (3.7 mmol; 52% of theory) of light brown powder is obtained, melting between 125 and 128.5 ^° C.

Elemental analysis calc.: %C %H %N (C ₉ H ₁₅ N ₃ O ₂ S) found: 47.14 6.59 18.33 47.35 6.64 18.0

Examples of hair dyes I Example 3: Hair dye solution

10.0 g lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous solution)
10.0 g isopropanol
0.3 g ascorbic acid
10.0 g ammonia (25% aqueous solution) 0.0025 mol dye precursor according to general formula (I)

or a known color precursor according to the list below
ad 100 g demineralized water

For hair dyeing, 10 g of hair dye solution containing a color precursor as per example 1 or 2 are mixed with 10 g of a dye solution containing a known hair color developer or hair color coupler and immediately before use, 20 g of hydrogen peroxide (6% aqueous solution) are added and applied to the hair. After an exposure time of 20 minutes at a slightly elevated temperature, the hair is rinsed, shampooed and dried. The dyeing results are summarized in Table 1 below.

Table 1 : Hair dyeing results according to Example 3

Added developer/coupler Color prepress
according to example 1 Color prepress
according to example 2 p-Phenylenediamine blue green blue green 2,5-Diaminotoluene! blue green blue green 2,5-Diaminophenylethanol blue green blue green 4-Aminophenol grey-green Gray 3-methyl-4-aminophenol grey-green grey-green 4,5-Diamino-1-(2-hydroxyethyl)-1 H-pyrazole yellow-green Resorcin Gray grey-brown 2-Amino-4-((2-hydroxyethyl)amino)anisole blue green blue green 5-Amino-2-methylphenol blue blue 3-Aminophenol blue-grey blue-grey

Example 4: Colorant in cream form

15.0 G Cetyl alcohol 3.5 G Lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous Solution 0.4 G Sodium sulphite 1.0 G Color precursor according to example 1 0.4 G 5-Amino-2-methylphenol 4.0 G Ammonia (25% aqueous solution) 75.7 G Water fully demineralized

Immediately before use, 50 g of the above hair dye are mixed with 50 g of hydrogen peroxide solution (6% aqueous solution) and applied to bleached hair. After a contact time of 30 minutes at 40 ⁰ C, the hair is rinsed with water, shampooed and dried. The hair is dyed dark blue.

All percentages contained in this application are, unless otherwise stated, percentages by weight.

Claims (8)

nclaims 1. 1,2,4-Triaminobenzene derivatives of the general formula (I) NH-CH ₂ -CH ₂ -SO ₂ -X (I) wherein the radical X represents an NR1R2 or CHR1R2 group, where R1 and R2 can be the same or different from one another and independently represent a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a mono- or polyhydroxyalkyl group having 2 to 4 carbon atoms. 2. Compounds according to claim 1, characterized in that the compound of formula (I) is selected from1,3-diamino-4-[(2-methylsulfonyl)-ethyl]-aminobenzene
and 2-[(2,4-diaminophenyl)amino]ethanesulfonamide dihydrochloride. 3. Colorant, characterized in that it contains a compound of the formula (I) according to claim 1 or 2. 4. Agent according to claim 3, characterized in that it contains the compound of formula (I) in an amount of 0.1 to 10 percent by weight. 5. Agent according to claim 3 or 4, characterized in that it additionally contains at least one dye from the group of developer substances, coupler substances, dye precursors and direct dyes. 6. Agent according to claim 5, characterized in that the dye is selected from 1,4-diaminobenzene, 2-(2',5'-diaminophenyl)ethanol, 4-aminophenol, 4-amino-3-methylphenol, resorcinol, 4-chlororesorcinol, m-aminophenol derivatives, 5-hydroxy-1,3-benzodioxole, 5-amino-1,3-benzodioxole, 5-((2'-hydroxyethyl)amino)-1,3-benzodioxole, 5-((2-hydroxyethyl)amino)-2-methoxyaniline, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol, triphenylmethane dyes, aromatic nitro dyes and azo dyes. 7. Agent according to one of claims 3 to 6, characterized in that the m-aminophenol derivative is selected from 3-aminophenol, 5-amino-2-methylphenol, 5-((3-hydroxyethyl)amino)-2-methylphenol and 5-((3-hydroxypropyl)amino)-2-methylphenol. 8. Agent according to one of claims 3 to 7, characterized in that it is a hair dye.