DE19955915C2 - Tryptophane derivatives and tryptophanase-containing hair colorants and processes for enzymatic hair coloring - Google Patents

Description

The present invention relates to a tryptophane derivative and Tryptophanase-containing hair dye and a method for enzymatic coloring of hair, especially human hair.

JP-PS 2745018 describes a process for dyeing fibers known, in the indigo dyes enzymatically from indole derivatives are to be generated. However, this procedure does not lead to satisfactory color results. In addition, the synthesis of required indole derivatives sometimes quite complex and expensive.

It has now surprisingly been found that tryptophane derivatives according to the general formula (I) in the presence of certain Enzymes under the influence of oxidizing agents or atmospheric oxygen the formation of a large number of colorations even at room temperature Allow hair.

The present invention therefore relates to an agent for coloring hair, in particular human hair, which is characterized in that it consists of a component (A) containing at least one tryptophane derivative, the general formula (I) and a component containing a tryptophanase enzyme ( B), where component (A) and / or (B) additionally contains pyridoxal phosphate, where the pyridoxal phosphate can also be packaged separately,

where in formula (I) X is N or a CR4 group, R is equal Is hydrogen or a C1 to C4 alkyl group, and R1 to R4 are the same or can be different and independently of one another hydrogen, a straight-chain or branched alkyl group with 1 to 6 carbon atoms men, an aryl group, a difluoromethyl group, a trifluoromethyl group pe, a halogen atom (fluorine, chlorine, bromine or iodine), an amino group, a C1 to C6 alkylamino group, an arylamino group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an aryloxy group, a nitro group, a carboxy group, a carboxyalkyl group, a carboxamido group, a carboalkoxy group, a carboaryloxy group or a heterocyclic radical, or R1 and R2 be or R2 and R3 form a methylenedioxy group.

As a tryptophan derivative of the general formula (I), for example are called: L-tryptophan, D, L-tryptophan, L-5-hydroxytryptophan, D, L-5-hydroxytryptophan, D, L-4-fluortryptophan, D, L-5-fluortryptophan, D, L-6-fluortryptophan, D, L-7-fluortryptophan, D, L-5-methoxytryptophan, D, L-4-methyltryptophan, D, L-5-methyltryptophan, D, L-6-methyltryptophan, D, L-7-methyltryptophan, D, L-5,6-dihydroxytryptophan, L-5,6-dihydroxy tryptophan, D, L-7-azatryptophan, 6- (difluoromethyl) -tryptophan, 5,6-methylenedioxy-tryptophan and β-indazolyl-L-alanine, where L-tryptophan, D, L-tryptophan, D, L-4-fluortryptophan, 5,6-methylenedioxy-tryptophan, D, L-5-fluortryptophan, D, L-6-fluortryptophan, D, L-4-methyltryptophan, D, L-5-methyltryptophan, D, L-6-methyltryptophan and D, L-7-methyl tryptophan, and in particular L-tryptophan, D, L-4-fluortryptophan,  5,6-methylenedioxy-tryptophan, L-5-hydroxy-tryptophan, D, L-5-hydroxytryptophan, D, L-5-fluortryptophan, D, L-4-methyltryptophan and D, L-7-methyltryptophan are preferred.

Under "Tryptophanase enzyme" each enzyme or its derivative is ver stand, which is able to implement tryptophan or substit tryptophans in pyruvate, ammonia and the corresponding indole Catalyze derivative. A is preferably used as the tryptophanase enzyme enzyme obtained from E. coli used; depending on the used Tryptophane derivative of the formula (I), however, it is also possible to choose from other bacteria (e.g. Proteus vulgaris, Proteus rettgeri, Bacillus alvei, Enterobacter aerogenes or Symbiobacterium thermophi lum) obtained tryptophanase enzyme to use. The enzyme will preferably in an amount of 5 to 100 units per 1 mmol of substrate (Compound of formula (I), based on the content of L-isomer) puts. By definition, 1 unit stands for the amount of enzyme added to the Ka Analysis of the oxidation of 1 µmol tryptophane derivative per minute required is.

The pyridoxal phosphate, which acts as a cofactor for tryptophanase, can in very small amounts, preferably in an amount of about 1 to 50 mmol per 1 mol of substrate (compound of formula (I), based on the L-isomer content).

To optimize the color result and to create special ones len color effects can the colorant according to the invention (prefer as the component A) compounds from the group of  direct dyes, for example aromatic nitro dyes, Azo dyes, anthraquinone dyes or triphenylmethane dyes, added alone or in a mixture.

Examples of nitro dyes are picramic acid, 4- (2 ', 3'-dihydroxypropyl) - amino-3-nitro-trifluoromethylbenzene, 4, N-ethyl-N- (2'-hydroxyethyl) amino-1- (2'-hydroxyethyl) amino-2-nitro-benzene, 2-chloro-6-ethylamino-4- nitrophenol, 1-hydroxy-2-β-hydroxyethylamino-4,6-dinitrobenzene, 4- (2'-hydroxyethyl) amino-3-nitro-chlorobenzene, 2-amino-6-chloro-4-nitrophenol and 4- (2'-hydroxyethyl) amino-3-nitro-methylbenzene.

Examples of azo dyes are 1- (2'-methoxyphenylazo) -2-hydroxy-7- trimethyl-ammonium-naphthalene (Basic Red 76), 4- (4'-sulfo-1-phenylazo) - 1- (4 "-sulfophenyl) -3-carboxy-5-hydroxypyrazolone (Acid Yellow 23), 4-amino-4'-bis [2" -hydroxyethyl] amino-azobenzene (Disperse Black 9) and 1- (4th '-Aminophenylazo) -2-hydroxy-7-trimethyl-ammonium-naphthalene (Basic Brown 16).

Examples of anthraquinone dyes are 1-methylamino-4- (2'-hydroxyethyl) amino-anthraquinone (Disperse Blue 3), 1-amino-4-hydroxy anthraquinone (Disperse Red 15), 2-methoxy-1,4-diamino-anthraquinone (Disperse Red 11), 1,4-diamino-anthraquinone (Disperse Violet 1), 1-amino-4-methylamino-anthraquinone (Disperse Violet 4), 1,4-bis (2 ', 3'-dihydroxypropyl) amino- anthraquinone, 1-methylamino-4- (amino-n- propyltrimethylammonium) anthraquinone (Basic Blue 22), 1,4-bis (2-hydroxyethyl) amino-5,8-dihydroxyanthraquinone (Disperse Blue 7) and 1-methylamino-4-aminopropylaminoanthraquinone (HC Blue 8th).

Examples of triphenylmethane dyes are 4 - [[4-diethylamino] phenyl] [4- (ethylamino) -1-naphthalinyl] methylene] -2,5- cyclohexadien-1-ylidene] -N-ethylethanamine (Basic Blue 7) and 4 ', 4', 4 "-triamino-3-methyltriphenylcarbenium chloride (Basic Violet 14, Fuchsin ON). It is also possible to use conventional developer substances and couplers  substances, for example, o-, m- or p-diaminobenzene and its deri vate, resorcinol and its derivatives or m- or p-aminobenzene and its Derivatives.

The amount of direct dyes and / or added Developer substances / coupler substances is preferably 0.01 to 5 Percent by weight, in particular 0.1 and 4 percent by weight.

Components (A) and (B) as well as the ready-to-use colorant can, for example, a solution, especially an aqueous or be aqueous-alcoholic solution, or in the form of a cream, a gel, an emulsion, a powder or granules. Your together The composition represents a mixture of the components with those for such Preparations are common additives.

Common cosmetic additives are, for example, solvents such as What ser; lower aliphatic monohydric or polyhydric alcohols, the Esters and ethers, for example alkanols, in particular with 1 to 4 Carbon atoms in the alkyl chain, such as ethanol, n-propanol or Isopropanol, butanol, isobutanol; di- or trihydric alcohols, especially those with 2 to 6 carbon atoms, for example Ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerin, diethylene glycol, Dipropylene glycol, polyalkylene glycols, such as triethylene glycol, polyethylene glycol, tripropylene glycol and polypropylene glycol; lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether;  Ketones and keto alcohols, especially those with 3 to 7 carbon atoms in the molecule, for example acetone, methylethylke clay, diethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, cyclopenta non, cyclohexanone and diacetone alcohol; Ethers such as dibulyl ether, tetra hydrofuran, dioxane or diisopropyl ether; Esters such as ethyl formate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, phenylace tat, ethylene glycol monoethyl ether acetate or hydroxyethyl acetate; Amides such as dimethylformamide, dimethylacetamide or N-methyl pyrrolidone; as well as urea, tetramethyl urea and thiodiglycol; further hin wetting agents or emulsifiers from the classes of anionic, katio African, amphoteric, non-ionic or zwitterionic surface-active substances, such as fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetai ne, α-olefin sulfonates, ethoxylated fatty alcohols, ethoxylated nonylpheno oils, fatty acid alkanolamines, ethoxylated fatty acid esters, fatty alcohol polygly colether sulfates, alkyl polyglucosides; Thickeners like higher fats alcohol, starch, cellulose derivatives, petroleum jelly, paraffin oil, fatty acids and other fat components in emulsified form; water soluble polymers Thickeners, for example natural gums, guar gum, Xanthan gum, locust bean gum, pectin, dextran, agar-agar, Amy loose, amylopectin, dextrins, clays or fully synthetic hydrocolloids like Polyvinyl alcohol; also care substances such as lanolin derivatives, cholesterol, Pantothenic acid, water-soluble cationic polymers, protein derivatives, Provitamins, vitamins, plant extracts, sugar and betaine; Auxiliaries such as electrolytes, antioxidants, fatty amides, sequestering agents, film-based agents and preservatives.

The components mentioned are in the usual for such purposes Amounts used, for example the wetting agents and emulsifiers in concentrations  from about 0.5 to 30 percent by weight, the thickeners in one Amount from about 0.1 to 25 percent by weight and the care substances in one Concentration from about 0.1 to 5.0 percent by weight.

The use of the colorant according to the invention can vary that way. So the components (A) and (B) before the Application to be mixed together and immediately or after an incubation period of 15 to 45 minutes on the hair to be dyed be applied. The mixture is left to add a suitable 2-electron oxidoreductase enzyme / substrate mixture, such as 6lucose oxidase (EC 1.1.3.4) / D-glucose, alcohol Oxidase (EC 1.1.3.13) / ethanol, pyruvate oxidase (EG 1.2.3.3) / pyruvate; Oxalate oxidase (EC 1.2.3.4) / oxalate, cholesterol oxidase (EC 1.1.3.6) / Cholesterol, uricase (EC 1.7.3.3) / uric acid, lactate oxidase / lactic acid and xanthine oxidase (EC 1.1.3.22) / xanthine - under the influence of air at about 15 to 50 ° C for about 10 to 45 minutes, preferably 30 to 40 minutes long, on the hair, for example human hair, rinses then wash the hair with water and dry it. Following this conditioner, the hair can be sham poo washed and / or with a weak organic acid such as for example citric acid, glycolic acid, lactic acid, malic acid, Ascorbic acid or tartaric acid.

However, it is also possible to use components (A) and (B) before the start application with an oxidizing agent, for example a 1- to 12 percent aqueous solution of hydrogen peroxide or its ad ditionsverbindungen, mix and then on the hair bring to. After an exposure time of another 10 to 45 minutes, preferably 30 to 40 minutes, at a temperature of 15 to 50 ° C,  preferably 30 to 45 ° C, the hair is rinsed with water and ge dries. Following this rinse the hair can be washed with a shampoo and / or with a weak one organic acid such as citric acid, glycolic acid, milk acid, malic acid, ascorbic acid or tartaric acid. If necessary, the oxidation can also be carried out in the presence of an enzyme, for example a peroxidase.

The colorant is used at a pH of around 6 to 9.5, preferably 7.2 to 9.5, and in particular 8 to 9.5.

The dyeing treatment is preferably carried out in the presence of a potassium salt and / or an ammonium salt, preferably potassium phosphate, the amount of potassium salt and / or ammonium salt used preferably 50 to 100 mmol per 10 mmol substrate (compound of Formula (I), based on the content of L-isomer).

The colorant / dyeing process according to the invention leads to dyeings with excellent fastness properties, especially with regard to light, Fastness to washing and rubbing. Regarding the dyeing possible the dye according to the invention offers depending on the type and Concentration of the compounds of general formula (I) a variety different color shades. The large color is remarkable intensity and the color purity of the achievable colors. Finally is with the help of the hair dye described, a dyeing of gray and chemically not damaged hair easily and with very good coverage possible. The colorations obtained here are regardless of the different structure of the hair, evenly and very reproducible.  

The following examples are intended to illustrate the subject matter of the invention refine without restricting it to it.

Examples example 1 Hair dye

Component (A):
1 mmol L-5-hydroxy-tryptophan
0.005 mmol pyridoxal phosphate
10 mmol potassium phosphate buffer
ad 100 ml water

Component (B):
25 ml tryptophanase extract (tryptophanase from E. coli) with an enzyme content of 1 unit per milliliter

Components (A) and (B) are mixed together (pH = 9.5) and allowed to stand in the air for 30 minutes at 35 to 40 ° C. Subsequently the mixture is applied to light blonde hair. After an ent 30 minutes at 35 to 40 ° C, the hair is washed out with water rinsed and dried. The hair has a brown color.  

Example 2 Hair dye

Component (A):
1 mmol of 5,6-methylenedioxy tryptophan
10 mmol potassium phosphate buffer
ad 100 ml water

Component (B):
5 ml tryptophanase extract (tryptophanase from E. coli) with an enzyme content of 1 unit per milliliter
0.005 mmol pyridoxal phosphate

Components (A) and (B) are mixed with a 3% hydrogen pero xid solution mixed in a ratio of 1: 1 (pH = 8-9) and on light blonde hair applied. After an exposure time of 30 minutes at 35 to 40 ° C the hair is rinsed with water and dried. The hair has one Preserved brown color.

Example 3 Hair dye

Component (A):
1 mmol L-5-hydroxy-tryptophan
0.0025 mmol pyridoxal phosphate
10 mmol potassium phosphate buffer
ad 100 ml water

Component (B):
25 ml tryptophanase extract (tryptophanase from E. coli) with an enzyme content of 1 unit per milliliter
0.0025 mmol pyridoxal phosphate

Components (A) and (B) are mixed with 10 mmol hydrogen peroxide (in Form of a 6% aqueous solution) and 15 units of peroxidase ver mixes (pH = 8-9) and applied to light blonde hair. After a one The hair works with water for 30 minutes at 35 to 40 ° C rinsed and dried. The hair has a brown color.

The enzyme concentrations are in the present application in "units" - the standard set by the International Union of Biochemistry unit proposed for all enzymes international unit - specified.

Claims (7)

1. Hair dye composition, characterized in that it consists of a component (A) containing at least one tryptophane derivative of the general formula (I) and a component (B) containing a tryptophanase enzyme and component (A) and / or (B) additionally contains pyridoxal phosphate, where the pyridoxal phosphate can also be packaged separately,
and in formula (I) X is N or a CR4 group, R is hydrogen or a C1 to C4 alkyl group, and R1 to R4 can be the same or different and independently of one another hydrogen, a straight-chain or branched alkyl group with 1 to 6 carbon atoms, an aryl group, a difluoromethyl group, a trifluoromethyl group, a halogen atom, an amino group, a C1 to C6 alkylamino group, an arylamino group, a hydroxy group, an alkoxy group with 1 to 4 carbon atoms, an aryloxy group, a nitro group , a carboxy group, a carboxyalkyl group, a carboxamido group, a carboalkoxy group, a carboaryloxy group or a heterocyclic radical, or R1 and R2 or R2 and R3 form a methylenedioxy group. 2. Composition according to claim 1, characterized in that the Tryptophane derivative is selected from L-tryptophan, D, L-tryptophan, L-5-hydroxytryptophan, D, L-5-hydroxytryptophan, D, L-4-fluortryptophan, D, L-5-fluortryptophan, D, L-6-fluortryptophan, D, L-7-fluortryptophan,  D, L-5-methoxytryptophan, D, L-4-methyltryptophan, D, L-5-methyl tryptophan, D, L-6-methyltryptophan, D, L-7-methyltryptophan, D, L-5,6-dihydroxytryptophan, L-5,6-dihydroxytryptophan, D, L-7-aza tryptophan, 6- (difluoromethyl) tryptophan, 5,6-methylenedioxy tryptophan and β-indazolyl-L-alanine. 3. Means according to claim 1 or 2, characterized in that as Tryptophanase enzyme is a tryptophanase obtained from E. coli is used. 4. Agent according to one of claims 1 to 3, characterized in that it also contains a direct dye. 5. A method of dyeing hair, characterized in that components (A) and (B) of the composition according to one of claims 1 be mixed up to 4 before use and immediately or but after an incubation period of 15 to 45 minutes towards the Coloring hair are applied to the mixture after an on Exposure time from 10 to 45 minutes when exposed to air at 15 to 50 ° C is rinsed with water and the hair is then dried. 6. A method of dyeing hair, characterized in that components (A) and (B) of the composition according to one of claims 1 to 4 mixed with an oxidizing agent before use and then applied to the hair to be dyed, after a Exposure time of 10 to 45 minutes at 15 to 50 ° C with the hair Rinsed water and then dried. 7. The method according to claim 6, characterized in that a Peroxidase is added.