EP1718705A1 - Cationic heteroaryl azine dyes, and dyeing agents containing said compounds - Google Patents

Cationic heteroaryl azine dyes, and dyeing agents containing said compounds

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Publication number
EP1718705A1
EP1718705A1 EP04803447A EP04803447A EP1718705A1 EP 1718705 A1 EP1718705 A1 EP 1718705A1 EP 04803447 A EP04803447 A EP 04803447A EP 04803447 A EP04803447 A EP 04803447A EP 1718705 A1 EP1718705 A1 EP 1718705A1
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EP
European Patent Office
Prior art keywords
methyl
group
amino
hydrazono
anion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP04803447A
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German (de)
French (fr)
Inventor
Markus Speckbacher
Hans-Jürgen BRAUN
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Procter and Gamble Deutschland GmbH
Original Assignee
Wella GmbH
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Filing date
Publication date
Application filed by Wella GmbH filed Critical Wella GmbH
Publication of EP1718705A1 publication Critical patent/EP1718705A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/16—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms
    • C09B23/162—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms
    • C09B23/166—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing two or more nitrogen atoms

Definitions

  • the present invention relates to novel cationic heteroarylazine dyes and colorants for keratin fibers, such as hair, wool or furs, containing these compounds.
  • oxidation dyes which result from the oxidative coupling of one or more developer components with one or more coupler components
  • direct dyes are generally used.
  • oxidation-stable, direct dyes can be added to the oxidative system in order to achieve special color effects.
  • Direct dyes are incorporated into suitable substrates to be applied to the fiber. This process, commonly known as tinting, is easy to use, extremely mild and is characterized by little damage to the keratin fiber, since no ammonia or peroxide is added.
  • the dyes used here have to meet some requirements. For example, they have to be harmless from a toxicological and dermatological point of view and enable the coloring to be achieved in the desired intensity and brilliance.
  • the dyeings obtained must also have good light fastness and resistance to shampooing and good rub fastness.
  • a combination of different non-oxidative dyes is generally required for a direct, non-oxidative colorant for keratin fibers in order to achieve certain nuances. Since the selection of such dyes, which sufficiently meet the requirements mentioned, is limited, there is still a great need for such dyes.
  • the object of the present invention is therefore to provide direct dyes for dyeing keratin fibers, in particular hair, which meet these requirements.
  • cationic heteroarylazine dyes of the general formulas (I) and (II) can be applied very gently to keratin fibers as direct dyes in coloring compositions without the addition of an oxidizing agent. Since these dyes are stable to oxidizing agents, they can also be used in brightening colorants containing oxidizing agents, for example peroxides or persulfates.
  • the present invention therefore relates to cationic heteroarylazine dyes of the general formulas (I) and (II),
  • R1 represents a group of formula (III), (IV), (V) or (VI);
  • E represents an oxygen atom or a sulfur atom
  • Hydroxyalkyl group or a radical of general formula (VII) - R2, R4 and R5 are the same or different and represent hydrogen, a tert-butyl group, / so-propyl group, a C ⁇ -C6 alkyl group, a C ⁇ -C 6;
  • R3 represents a group of formula (VIII), (IX) or (X);
  • R6 represents hydrogen, a straight-chain or branched C 1 -C 6 -alkyl group or a straight-chain or branched C 2 -C -hydroxyalkyl group
  • R7 represents a branched or linear C 1 -C 6 -alkyl group, a C 2 -C -hydroxyalkyl group or a C 4 -C 6 -polyhydroxyalkyl group
  • R8 and R9 are the same or different and are hydrogen, a C.
  • R10 represents hydrogen, a straight-chain or branched C 1 -C 6 -alkyl group or a straight-chain or branched C 2 -C 4 -hydroxyalkyl group;
  • R11 and R12 can be the same or different and are hydrogen, a d-Ce-alkyl
  • Preferred compounds of the general formulas (I) and (II) are 1- (2-hydroxyethyl) -3 - ⁇ (Z) - [(2E) -2- (3-methyl-1,3-benzothiazol-2 (3H) - ylidene) hydrazono] methyl ⁇ pyridinium bromide, 4 - ⁇ (E) - [(2Z) -2- (3,4-dimethyl-1,3-thiazol-2 (3H) -ylidene) hydrazono] methyl ⁇ - 1- (2-hydroxyethyl) pyridinium bromide, 2 - ⁇ (E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) -ylidene) hydrazono] methyl ⁇ - 3- (methyl) -1-methyl-1 H-imidazol-3-ium-methyl sulfate, 3- (2-hydroxyethyl) -1-methyl-2 -
  • Aromatic hydrazone compounds can, for example, according to S. Hünig et al. (Chem. Eur. J. 2000, 6, No. 14, pages 2618-2632) can easily be obtained from hydrazine monohydrate and the corresponding ketones or thioketones.
  • heteroarylazine compounds of the formula (Ia) / (Ila) can be prepared by condensation reactions of the hydrazone with heterocyclic aldehydes in solvents, such as, for example, dilute acetic acid.
  • solvents such as, for example, dilute acetic acid.
  • the residual groups R1, R2, R4, R5 and R7 have the meanings given above, while R1 'represents an unquaternized heterocycle of the formulas (III) to (VI) and X represents an uncharged residual group X " .
  • the cationic heteroarylazine dyes of the general formulas (I) and (II) according to the invention enable uniform coloring of keratin fibers, in particular human hair, with good stability against light, sweat and shampooing.
  • the compounds of the general formula (I) and (II) according to the invention result in an intensive, brilliant coloring of keratin fibers, in particular human hair, but also wool, furs or other fiber materials, under gentle conditions.
  • some compounds of formula (I) or (II) allow (e.g. 1 - (2-hydroxyethyl) -3 - ⁇ (Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 / - /) - ylidene) hydrazono] methyl ⁇ pyridinium bromide or 2 - ⁇ (£) - [(2Z) -2- (3,4-dimethyl-1,3-thiazole-2 (3 - / ) -ylidene) hydrazono] methyl ⁇ -3- (methyl) -1-methyl-1 H-imidazol-3-ium-methyl sulfate) a natural lightening of untreated natural hair without the addition of chemical oxidizing agents.
  • Another object of the present invention is therefore
  • agents (a), (b) and (c) are characterized in that they each contain at least one derivative of the general formula (I) or (II).
  • the cationic heteroarylazine dyes of the general formulas (I) and (II) are preferably present in the colorants according to the invention in a total amount of 0.01 to 10 percent by weight, in particular 0.1 to 8 percent by weight.
  • the colorant (a) according to the invention can also include other known direct-dyeing dyes from the group consisting of nitro dyes, azo dyes, athraquinone dyes and triphenylmethane dyes, such as, for example, 1,4-bis [( 2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene, (HC Blue No. 2), 1- Amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene, (HC Violet No.
  • 1,4-Diamino-9,10-anthraquinone (CI61100, Disperse Violet No. 1), 1-Amino-4- (methylamino) -9,10-anthraquinone (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), N- (6 - ((3-chloro-4- (methylamino) phenyl) imino) -4-methyl-3-oxo-1,4-cyclohexadien-1-yl) urea (HC Red No. 9), 2 - ((4- (Di (2-hydroxyethyl) amino) phenyl) amino) -5 - ((2-hydroxyethyl) amino) -2,5-.
  • HC Green No. 1 2-hydroxy-1,4-naphthoquinone
  • CI75480 Natural Orange No. 6
  • 1,2-dihydro-2- 1,3-dihydro-3 -oxo-2H-indol-2-ylidene) -3H-indol-3-one
  • 1,3-bis (dicyanomethylene) indan di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI42595; Basic Blue No.
  • the abovementioned direct dyes can be present in a total amount of about 0.01 to 4 percent by weight, the total amount of dyes in the colorant according to the invention preferably being about 0.01 to 10 percent by weight, in particular 0.1 to 5 percent by weight.
  • the oxidation coloring agent (c) according to the invention which is mixed with an oxidizing agent (in particular hydrogen peroxide or its addition compounds) before use, also contains oxidation dye precursors in addition to the dyes of the general formulas (I) and (II).
  • an oxidizing agent in particular hydrogen peroxide or its addition compounds
  • oxidation dye precursors in addition to the dyes of the general formulas (I) and (II).
  • the following developer substances and coupler substances and with self-coupling compounds can be mentioned as suitable oxidation dye precursors:
  • Coupler substances N- (3-dimethylaminophenyl) urea, 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino-1 - fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1 - (2nd -hydroxy-ethoxy) -5-methyl-benzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino- 6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimeth
  • (iii) Self-coupling compounds: 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol or 2-propylamino-5-aminopyridine.
  • the total amount of the oxidation dye precursors contained in the colorant (c) according to the invention is about 0.01 to 12 percent by weight, in particular about 0.2 to 6 percent by weight.
  • the colorant (a), (b) or (c) according to the invention can furthermore all known and customary additives for such preparations, for example perfume oils, complexing agents, waxes, preservatives, thickeners, antioxidants, alginates, guar gum, hair-care substances such as cationic Contain polymers or lanolin derivatives, or anionic, nonionic, amphoteric or cationic surface-active substances.
  • perfume oils for example perfume oils, complexing agents, waxes, preservatives, thickeners, antioxidants, alginates, guar gum, hair-care substances such as cationic Contain polymers or lanolin derivatives, or anionic, nonionic, amphoteric or cationic surface-active substances.
  • Amphoteric or nonionic surface-active substances for example betaine surfactants, propoinates and glycinates, for example cocoamphoglycinates or cocoamphdiglacinates, are preferably ethoxylated surfactants with 1 to 1000 ethylene oxide units, preferably with 1 to 300 ethylene oxide units, for example glyceride alkoxylates, for example with 25 ethylene oxide -Units of ethoxylated castor oil, polyglycolamides, ethoxylated alcohols and ethoxylated fatty alcohols (fatty alcohol alkoxylates) and ethoxylated fatty acid sugar esters, in particular ethoxylated sorbitan fatty acid esters, are used.
  • the abovementioned constituents are used in the amounts customary for such purposes, for example the surface-active substances in a concentration of 0.1 to 30 percent by weight, and the care substances in an amount of 0.1 to 5 percent by weight.
  • the colorant (a), (b) or (c) according to the invention can, in particular if it is a hair colorant, in the form of a powder or granules, which, before use, is in an aqueous or aqueous-alcoholic preparation is dissolved, or an aqueous or aqueous-alcoholic solution, a cream, a gel, an emulsion or an aerosol foam, the hair dye both in the form of a one-component preparation and in the form of a multi-component preparation, for example in the form of a two-component preparation, in which the each dye derivative of the general formulas (I) and (II) is packaged separately from the other constituents and the ready-to-use hair dye is only prepared immediately before use by mixing the two components.
  • the colorant (a), (b) or (c) according to the invention has a pH of about 2 to 11, preferably about 5 to 10, and in particular a neutral to basic pH of about 7 to 10.
  • Both organic and inorganic acids or bases are suitable for adjusting the pH value according to the invention.
  • Suitable acids include the following acids: ⁇ -hydroxycarboxylic acids, such as glycolic acid, lactic acid, tartaric acid, citric acid or malic acid, ascorbic acid, gluconic acid lactone, acetic acid, hydrochloric acid or phosphoric acid, and mixtures of these acids.
  • Suitable bases include, in particular, sodium carbonate, sodium hydrogen carbonate, alkanolamines, for example monoethanolamine or triethanolamine, ammonia, aminomethylpropanol and sodium hydroxide and mixtures thereof.
  • the colorant according to the invention can be used with one or more oxidizing agents (brightening; oxidizing coloring agent) or without an oxidizing agent (non-oxidative coloring agent).
  • the dye (a), (b) or (c) according to the invention is generally applied by applying an amount sufficient for hair coloring, depending on the length of the hair, of about 30 to 120 grams of the hair dye to the hair, the hair dye at about 15 up to 45 degrees Celsius for about 1 to 60 minutes, preferably 5 to 30 minutes, then rinse the hair thoroughly with water, if necessary, wash with a shampoo and finally dry.
  • the agent is mixed with an oxidizing agent before use.
  • the coloring agent described above can furthermore contain natural or synthetic polymers or modified polymers of natural origin, which are customary for cosmetic agents, as a result of which hair is set at the same time as the coloring.
  • Such agents are generally referred to as tinting or color strengthening agents.
  • polyvinylpyrrolidone polyvinyl acetate
  • polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid
  • basic polymers of esters of polyacrylic acid polymethylacrylic acid and amino alcohols, for example their salts or quaternizing products
  • polyacrylonitrile and copolymers of such vinyl acetate such as polyvinyl pyrrolidone vinyl acetate
  • chitosan (deacetylated chitin) or chitosan derivatives for example, can be used as natural polymers or modified natural polymers.
  • the aforementioned polymers can be present in the colorant (a) according to the invention in the amounts customary for such agents, in particular in an amount of about 1 to 5 percent by weight.
  • the pH of the tinting or color fixing agent according to the invention is preferably about 6 to 9.
  • the hair dye with additional setting is used in a known and customary manner by moistening the hair with the setting agent, setting (inserting) the hair for the hairstyle and subsequent drying.
  • the colorants (a), (b) and (c) according to the invention enable a uniform, intensive and permanent coloring of keratin fibers (for example human hair, wool or furs) without any noteworthy coloring of the skin or scalp, this coloring also in the case of the colorant ( a) five or more washes without a noticeable fading of the hair color persists.
  • Stage 1 Preparation of nicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3 -) - ylidene) hydrazone 1, 50 g (6.42 mmol) 2,3-dihydro-3-methyl- 2-benzothiazolone hydrazone hydrochloride and 0.69 g (6.42 mmol) 3-pyridinecarboxaldehyde are stirred at room temperature in 10% acetic acid for 30 minutes. The mixture is then made weakly alkaline with 2 N sodium hydroxide solution, the precipitate which has separated out is filtered off with suction, washed with water and dried in vacuo.
  • Step 2 Preparation of 1 - (2-hydroxyethyl) -3 - ⁇ (Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 - /) - ylidene) hydrazono] methyl ⁇ pyridinium bromide 1, 21 g (4.51 mmol) nicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3H) ylidene) hydrazone from stage 1 and 0.85 g (6.76 mmol) of bromoethanol are refluxed in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 1, 20 g (68% of theory), bright yellow powder
  • Stage 1 Preparation of isonicotinaldehyde ((2Z) -3,4-dimethyl-1, 3-thiazole-2 (3H) -ylidene) hydrazone
  • 0.20 g (1, 12 mmol) ⁇ / -Methyl- 5-methyl-2-thiazole hydrazone hydrochloride and 0.12 g (1.12 mmol) of 4-pyridinecarboxaldehyde were stirred at room temperature in 10% acetic acid for 30 minutes. The mixture is then made weakly alkaline with 2 N sodium hydroxide solution, the precipitate which has separated out is filtered off with suction, washed with water and dried in vacuo.
  • Step 2 Preparation of 4 - ⁇ (E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl ⁇ -1- (2- hydroxyethyl) pyridinium bromide
  • Stage 1 Preparation of isonicotinaldehyde-9H-fluoren-9-ylidene hydrazone
  • 1.50 g (7.72 mmol) of 9-fluorenone hydrazone and 0.82 g (7.72 mmol) of 4-pyridinecarboxaldehyde are added at room temperature 10% acetic acid stirred for 30 minutes.
  • the mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the crystals which have precipitated are then filtered off with suction, washed with water and dried in vacuo.
  • the aqueous phase is then extracted with ethyl acetate in order to isolate the product which has not precipitated out.
  • Step 2 Preparation of 4 - [(E) - (9H-fluoren-9-ylidenhydrazono) methyl] - 1-methyl-pyridinium-methylsulfate 0.84 g (2.96 mmol) isonicotinaldehyde-9H-fluoren-9-ylidenhydrazone from step 1 and 0.56 g (4.44 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo.
  • Stage 1 Preparation of isonicotinaldehyde ((2E) -3-methyl-1,3-benzothiazol-2 (3H) -ylidene) hydrazone
  • the mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the crystals which have precipitated are filtered off with suction, washed with water and dried in vacuo.
  • Step 2 Preparation of 1 - (2-hydroxyethyl) -4 - ⁇ (Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono] methyl ⁇ pyridinium -bromide 1.00 g (3.73 mmol) isonicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3H) - ylidene) hydrazone from stage 1 and 0.70 g (5.59 mmol) Bromoethanol is boiled under reflux in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 0.39 g (27% of theory), light red powder
  • Stage 1 Preparation of 1-methyl-1 H-imidazole-2-carbaldehyde ((2E) -3-methyl-1,3-benzothiazol-2 (3H) -ylidene) hydrazone
  • (2E) -3-methyl-1,3-benzothiazol-2 (3H) -ylidene) hydrazone
  • Step 2 Preparation of 3- (2-hydroxyethyl) -1-methyl-2 - ⁇ (Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono ] methyl ⁇ -1 H-imidazol-3-ium bromide 1.00 g (3.68 mmol) 1-methyl-1 H-imidazole-2-carbaldehyde ((2E) -3-methyl-1, 3-benzothiazole -2 (3H) -ylidene) hydrazone from stage 1 and 0.69 g (5.52 mmol) of bromoethanol are boiled under reflux in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 1.03 g (71% of theory), green-yellow powder
  • Stage 1 Preparation of isonicotinaldehyde ⁇ bis [4- (dimethylamino) phenyl] - methylene ⁇ hydrazone
  • isonicotinaldehyde ⁇ bis [4- (dimethylamino) phenyl] - methylene ⁇ hydrazone
  • 1.66 g (5.66 mmol) of bis [4- (dimethylamino) phenyl] - methanone hydrazone 0.63 g (5.88 mmol) of 4-pyridinecarboxaldehyde at room temperature for 30 minutes.
  • the mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the precipitated product is filtered off with suction, washed with water and dried in vacuo.
  • Step 2 Preparation of 4 - [(E) - ( ⁇ bis [4- (dimethylamino) phenyl] methylene ⁇ - hydrazono) methyl] -1-methylpyridinium methyl sulfate 0.54 g (1.46 mmol) isonicotinaldehyde ⁇ bis [ Stage 1 4- (dimethylamino) phenyl] methylene ⁇ hydrazone and 0.92 g (7.30 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After this Removal of the solvent, the precipitate is filtered off, washed with ethyl acetate and dried in vacuo. Yield: 0.64 g (88% of theory), dark red powder
  • Stage 1 Preparation of nicotinaldehyde ⁇ bis [4- (dimethylamino) phenyl] methylenej-hydrazone
  • the mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the precipitated product is filtered off with suction, washed with water and dried in vacuo.
  • the aqueous phase is then extracted with ethyl acetate in order to isolate the product which has not precipitated out.
  • Step 2 Preparation of 3 - [(E) - ( ⁇ bis [4- (dimethylamino) phenyl] methylene ⁇ - hydrazono) methyl] -1-methylpyridinium methyl sulfate 0.76 g (2.05 mmol) nicotinaldehyde ⁇ bis [ 4- (dimethylamino) phenyl] -methylene ⁇ hydrazone from stage 1 and 1.29 g (10.25 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 0.81 g (79% of theory), red powder
  • Example 8 Preparation of 2 - ⁇ (E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl ⁇ -3- (methyl) - 1-methyl-1 H-imidazole-3 ium methyl sulfate
  • Step 1 (2Z) -3,4-dimethyl-2 - ⁇ (2E) - [(1-methyl-1 H-imidazol-2-yl) methylidenes] hydrazono ⁇ -2,3-dihydro-1,3- thiazole
  • Step 2 Preparation of 2 - ⁇ (E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl ⁇ -3- (methyl) - 1 -methyl-1 / - -imidazole-3-ium-methyl sulfate 1.40 g (5.95 mmol) (2Z) -3,4-dimethyl-2 - ⁇ (2E) - [(1 -methyl-1 H -imidazol-2-yl) methylidenes] hydrazono ⁇ -2,3-dihydro-1,3-thiazole from stage 1 and 7.58 g (59.50 mmol) of dimethyl sulfate are heated under reflux in acetone for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo.
  • the coloring solution is adjusted to a pH of 7 to 10 by adding ammonia.
  • Hair coloring is carried out by applying a sufficient amount of the colorant to the hair (Examples 9-16: bleached natural hair, Example 17: light brown natural hair) after an exposure time of 30 Minutes at 40 ° C, rinse the hair with lukewarm water and then dry.
  • the dyeing results are summarized in Table 1 below.
  • Brightening powder base P 20.0 g potassium persulfate 30.0 g ammonium persulfate 24.0 g sodium silicate 12.5 g magnesium oxide 5.0 g hydroxyethyl cellulose 6.0 g soap pearls 2.0 g disperse silica 0.5 g disodium EDTA ready-to-use coloring agent 0.1 g dye of the general formulas (I) and (II) 5.0 g lightening powder base P 10.0 g hydrogen peroxide (12% in water)
  • the specified components are mixed to a homogeneous mass, so that no dye particles can be recognized. Then a sufficient amount of the aforementioned coloring agent for hair coloring is applied to the hair. After an exposure time of 45 minutes at 40 ° C, the hair is rinsed with lukewarm water and treated with an acid conditioner, rinsed out again and dried.

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  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Disclosed are cationic heteroaryl azine dyes of general formula (I) and (II) as well as dyeing agents for keratin fibers which contain said compounds.

Description

B e s c h r e i b u n g Description
Kationische Heteroarylazinfarbstoffe und diese Verbindungen enthaltende FärbemittelCationic heteroarylazine dyes and colorants containing these compounds
Gegenstand der vorliegenden Erfindung sind neuartige kationische Heteroarylazinfarbstoffe sowie diese Verbindungen enthaltene Färbemittel für Keratinfasern, wie zum Beispiel Haare, Wolle oder Pelze.The present invention relates to novel cationic heteroarylazine dyes and colorants for keratin fibers, such as hair, wool or furs, containing these compounds.
Für das Färben von keratinhaltigen Fasern, kommen im allgemeinen entweder Oxidationsfarbstoffe, die durch oxidative Kupplung einer oder mehrerer Entwicklerkomponenten mit einer oder mehreren Kupplerkomponenten entstehen, oder direktziehende Farbstoffe zur Anwendung. Bei Bedarf können dem oxidativen System oxidationsstabile, direktziehende Farbstoffe zugesetzt werden, um besondere Farbeffekte zu erzielen. Direktziehende Farbstoffe werden in geeignete Trägermassen eingearbeitet, um dann auf die Faser aufgebracht zu werden. Dieses Verfahren, allgemein als Tönung bekannt, ist einfach anzuwenden, ausgesprochen mild und zeichnet sich durch eine geringe Schädigung der Keratinfaser aus, da kein Ammoniak oder Peroxid zugesetzt wird. Die hierbei verwendeten Farbstoffe müssen allerdings einige Anforderungen erfüllen. So müssen sie in toxikologischer und dermatologischer Hinsicht unbedenklich sein und die Erzielung von Färbungen in der gewünschten Intensität und Brillianz ermöglichen. Außerdem müssen die erzielten Färbungen auch eine gute Lichtechtheit und Resistenz gegen Shampoonieren sowie eine gute Reibechtheit besitzen. Für ein direktziehendes, nicht-oxidatives Färbemittel für Keratinfasern wird in der Regel eine Kombination von verschiedenen nicht-oxidativen Farbstoffen benötigt, um bestimmte Nuancierungen zu erreichen. Da die Auswahl an derartigen Farbstoffen, die die genannten Anforderungen hinreichend erfüllen, beschränkt ist, besteht weiterhin ein großer Bedarf an solchen Farbstoffen.For the dyeing of keratin-containing fibers, either oxidation dyes, which result from the oxidative coupling of one or more developer components with one or more coupler components, or direct dyes are generally used. If necessary, oxidation-stable, direct dyes can be added to the oxidative system in order to achieve special color effects. Direct dyes are incorporated into suitable substrates to be applied to the fiber. This process, commonly known as tinting, is easy to use, extremely mild and is characterized by little damage to the keratin fiber, since no ammonia or peroxide is added. The dyes used here, however, have to meet some requirements. For example, they have to be harmless from a toxicological and dermatological point of view and enable the coloring to be achieved in the desired intensity and brilliance. In addition, the dyeings obtained must also have good light fastness and resistance to shampooing and good rub fastness. A combination of different non-oxidative dyes is generally required for a direct, non-oxidative colorant for keratin fibers in order to achieve certain nuances. Since the selection of such dyes, which sufficiently meet the requirements mentioned, is limited, there is still a great need for such dyes.
Aufgabe der vorliegenden Erfindung ist es daher, direktziehende Farbstoffe zum Färben von Keratinfasern, insbesondere von Haaren, bereitzustellen, die diesen Anforderungen genügen.The object of the present invention is therefore to provide direct dyes for dyeing keratin fibers, in particular hair, which meet these requirements.
Überraschenderweise wurde nun gefunden, dass kationische Heteroarylazinfarbstoffe der allgemeinen Formeln (I) und (II) als direktziehende Farbstoffe in Färbemassen ohne Zusatz eines Oxidationsmittels sehr schonend auf Keratinfasern aufgebracht werden können. Da diese Farbstoffe gegenüber Oxidationsmitteln stabil sind, können sie aber auch in Oxidations- mittel, beispielsweise Peroxide oder Persulfate, enthaltenden aufhellenden Färbemitteln verwendet werden.Surprisingly, it has now been found that cationic heteroarylazine dyes of the general formulas (I) and (II) can be applied very gently to keratin fibers as direct dyes in coloring compositions without the addition of an oxidizing agent. Since these dyes are stable to oxidizing agents, they can also be used in brightening colorants containing oxidizing agents, for example peroxides or persulfates.
Gegenstand der vorliegenden Erfindung sind daher kationische Heteroarylazinfarbstoffe der allgemeinen Formel (I) und (II),The present invention therefore relates to cationic heteroarylazine dyes of the general formulas (I) and (II),
worin wherein
R1 eine Gruppe der Formel (III), (IV), (V) oder (VI) darstellt;R1 represents a group of formula (III), (IV), (V) or (VI);
E ein Sauerstoffatom oder ein Schwefelatom darstellt; R2, R4 und R5 gleich oder verschieden sind und für Wasserstoff, eine tert- Butylgruppe, eine /so-Propylgruppe, eine Cι-C6-Alkylgruppe, eine Cι-C6- Hydroxyalkylgruppe oder einen Rest der allgemeinen Formel (VII) stehen;E represents an oxygen atom or a sulfur atom; Hydroxyalkyl group or a radical of general formula (VII) - R2, R4 and R5 are the same or different and represent hydrogen, a tert-butyl group, / so-propyl group, a Cι-C6 alkyl group, a Cι-C 6;
(VII) (VII)
R3 eine Gruppe der Formel (VIII), (IX) oder (X) darstellt;R3 represents a group of formula (VIII), (IX) or (X);
(VIII) (IX) (X) (VIII) (IX) (X)
R6 für Wasserstoff, eine geradkettige oder verzweigte C-ι-C6-Alkylgruppe oder eine geradkettige oder verzweigte C2-C -Hydroxyalkylgruppe steht; R7 eine verzweigte oder lineare Cι-C6-Alkylgruppe, eine C2-C -Hydroxyalkyl- gruppe oder eine C4-C6-Polyhydroxyalkylgruppe darstellt; R8 und R9 gleich oder verschieden sein können und Wasserstoff, eine C.-C6-Alkylaminogruppe, eine CrC6-A/,Λ/-Dialkylaminogruppe, eine Cι-C6-Λ/,Λ/-Dihydroxyalkylaminogruppe, eine Cι-C6-Λ/-hydroxyalkyl-Λ.- alkylaminogruppe, eine CrC6-Alkylcyanogruppe, eine Methoxymethylgruppe, eine te/f-Butylgruppe, eine /so-Propylgruppe, eine Cι-C6-Alkylgruppe, eine CrC6-Alkyloxygruppe oder eine CrCδ-Hydroxyalkylgruppe darstellen; R10 für Wasserstoff, eine geradkettige oder verzweigte Cι-C6-Alkylgruppe oder eine geradkettige oder verzweigte C2-C4-Hydroxyalkylgruppe steht; R11 und R12 gleich oder verschieden sein können und Wasserstoff, eine d-Ce-Alkylaminogruppe, eine Cι-C6-A/,Λ/-Dialkylaminogruppe, eine Cι-C6-/V,Λ/-Dihydroxyalkylaminogruppe, eine C1-C6-A/-hydroxyalkyl-Λ.- alkylaminogruppe, eine C-i-Cθ-Alkylcyanogruppe, eine Methoxymethylgruppe, eine fe/f-Butylgruppe, eine /so-Propylgruppe, eine CrCβ-Alkylgruppe, eine Cι-C6-Alkyloxygruppe oder eine Cι-C6-Hydroxyalkylgruppe darstellen; und X~ ein Anion, vorzugsweise ein Sulfatanion, ein Phosphatanion, ein Hydrogenphosphatanion, ein Oxalatanion, ein Formiatanion, ein Acetatanion, ein Zitratanion, ein Tartratanion, ein Malonatanion, ein Pyruvatanion, ein lodidanion, ein Chloridanion, ein Bromidanion oder ein Methylsulfatanion, darstellt, wobei das Chloridanion, Bromidanion und das Methylsulfatanion besonders bevorzugt sind.R6 represents hydrogen, a straight-chain or branched C 1 -C 6 -alkyl group or a straight-chain or branched C 2 -C -hydroxyalkyl group; R7 represents a branched or linear C 1 -C 6 -alkyl group, a C 2 -C -hydroxyalkyl group or a C 4 -C 6 -polyhydroxyalkyl group; May be R8 and R9 are the same or different and are hydrogen, a C. -C 6 alkylamino group, a CrC 6 -A /, Λ / -dialkylamino group, a Cι-C 6 -Λ /, Λ / -dihydroxyalkylamino group, a Cι-C 6 -Λ / -hydroxyalkyl-Λ.- alkylamino group, a CrC 6 -Alkylcyano group, a methoxymethyl group, a te / f-butyl group, a / so-propyl group, a -C-C 6 alkyl group, a CrC 6 alkyloxy group or a CrC δ -hydroxyalkyl group; R10 represents hydrogen, a straight-chain or branched C 1 -C 6 -alkyl group or a straight-chain or branched C 2 -C 4 -hydroxyalkyl group; R11 and R12 can be the same or different and are hydrogen, a d-Ce-alkylamino group, a Cι-C 6 -A /, Λ / -dialkylamino group, a Cι-C 6 - / V, Λ / -dihydroxyalkylamino group, a C 1 - C 6 -A / -hydroxyalkyl-Λ.- alkylamino group, a CiC θ -alkylcyano group, a methoxymethyl group, a fe / f-butyl group, a / so-propyl group, a CrCβ-alkyl group, a Cι-C 6 -alkyloxy group or a Cι Represent -C 6 hydroxyalkyl group; and X ~ represents an anion, preferably a sulfate anion, a phosphate anion, a hydrogen phosphate anion, an oxalate anion, a formate anion, an acetate anion, a citrate anion, a tartrate anion, a malonate anion, a pyruvate anion, a iodide anion, a chloride anion, a bromidate anion or a methylsion the chloride anion, bromide anion and the methyl sulfate anion are particularly preferred.
Als geeignete kationische Heteroarylazinfarbstoffe der allgemeinen Formeln (I) und (II) können beispielsweise die folgenden Verbindungen genannt werden: 4-{(E)-({Bis[4-(dimethylamino)phenyl]methylen}hydrazono)[4-(dimethyl- amino)phenyl]-methyl}-1 -methylpyridinium-methylsulfat, 1 -(2-Hydroxyethyl)-3- {(Z)-[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3H)-yliden)hydrazono]methyl}- pyridinium-bromid) 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)-yliden)- hydrazono]methyl}-1-(2-hydroxyethyl)pyridinium-bromid, 2-{(E)-[(2Z)-2-(3,4- Dimethyl-1 ,3-thiazol-2(3H)-yliden)hydrazono]methyl}-3-(methyl)-1 -methyl-1 H- imidazol-3-ium-methylsulfat, 3-(2-Hydroxyethyl)-1-methyl-2-{(Z)-[(2E)-2-(3- methyl-1 ,3-benzothiazol-2(3 -/)-yliden)hydrazono]methyl}-1 -/-imidazol-3-ium- bromid, 1 -(2-Hydroxyethyl)-4-{(Z)-[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3H)- yliden)-hydrazono]methyl}pyridinium-bromid, 3-(Methyl)-1-methyl-2-{(Z)-[(2E)- 2-(3-methyl-1 ,3-benzothiazol-2(3H)-yliden)hydrazono]methyl}-1 - -imidazol-3- ium-methylsulfat, 3-{(Z)-(3,4-Dimethoxyphenyl)[(2E)-2-(3-methyl-1 ,3- benzothiazol-2(3/-.)-yliden)-hydrazono]methyl}-1-(2-hydroxyethyl)pyridinium- bromid, 3-{(Z)-[4-(Dimethylamino)phenyl][(2E)-2-(4-methoxybenzyliden)- hydrazono]methyl}-1-methyl-pyridinium-methylsulfat, 2-{(Z)-(2,5-Dimethoxy- phenyl)[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3 -/)-yliden)hydrazono]methyl}-3- (2-hydroxyethyl)-1 -methyl-1 /-/-imidazol-3-ium-bromid, 4-[(E)-({Bis[4- (dimethylamino)phenyl]methylene}hydrazono)methyl]-1-(2-hydroxyethyl)- pyridinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]-methylen}- hydrazono)methyl]-1-(2-hydroxyethyl)quinolinium-bromid, 4-((E)-{[Bis(4- methoxyphenyl)methylen]hydrazono}methyl)-1 -methylpyridinium-methylsulfat, 4-[(E)-({Bis[4-(dimethylamino)phenyl]methylene}hydrazono)methyl]-1- methylpyridinium-methylsulfat, 4-[(E)-({Bis[4-(diethylamino)phenyl]methylen}- hydrazono)methyl]-1 -methylpyridinium-methylsulfat, 4-[(E)-(9H-Fluoren-9- ylidenhydrazono)methyl]-1-methylpyridinium-methylsulfat, 3-[(E)-({Bis[4- (dimethylamino)phenyl]-methylen}hydrazono)methyl]-1-methylpyridinium- methylsulfat, 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)- yliden)hydrazono]methyl}-1 -methylpyridinium-methylsulfat und 4-[(E)-({Bis[4-The following compounds may be mentioned as suitable cationic heteroarylazine dyes of the general formulas (I) and (II): 4 - {(E) - ({bis [4- (dimethylamino) phenyl] methylene} hydrazono) [4- (dimethylamino) phenyl] methyl} -1-methylpyridinium methyl sulfate, 1 - (2-hydroxyethyl) - 3- {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono] methyl} - pyridinium bromide ) 4 - {(E) - [( 2Z) -2- (3,4-dimethyl-1,3-thiazole-2 (3H) -ylidene) - hydrazono] methyl} -1- (2-hydroxyethyl) pyridinium bromide, 2 - {(E) - [ (2Z) -2- (3,4-dimethyl-1,3-thiazol-2 (3H) -ylidene) hydrazono] methyl} -3- (methyl) -1-methyl-1 H -imidazol-3-ium- methyl sulfate, 3- (2-hydroxyethyl) -1-methyl-2 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 - /) - ylidene) hydrazono] methyl} -1 - / - imidazol-3-iumbromide, 1 - (2-hydroxyethyl) -4 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 ( 3H) - ylidene) hydrazono] methyl} pyridinium bromide, 3- (methyl) -1-methyl-2 - {(Z) - [(2E) - 2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono] methyl} -1 - -imidazole-3-ium-methyl sulfate, 3 - {(Z) - (3,4-dimethoxyphenyl) [(2E) -2- (3-methyl-1, 3- benzothiazol-2 (3 /-.)- ylidene) hydrazono] methyl} -1- (2-hydroxyethyl) pyridinium bromide, 3- {(Z) - [4- (Dimethylamino) phenyl] [(2E) -2- (4-methoxybenzylidene) - hydrazono] methyl} -1-methyl-pyridinium-methyl sulfate, 2 - {(Z) - (2.5 -Dimethoxy-phenyl) [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 - /) - ylidene) hydrazono] methyl} -3- (2-hydroxyethyl) -1-methyl-1 / - / - imidazol-3-ium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} hydrazono) methyl] -1- (2-hydroxyethyl) pyridinium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1- (2-hydroxyethyl) quinolinium bromide, 4 - ((E) - {[bis (4- methoxyphenyl) methylene] hydrazono} methyl) -1-methylpyridinium methyl sulfate, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - [( E) - ({bis [4- (diethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - [(E) - (9H-fluoren-9-ylidene hydrazono) methyl] -1-methylpyridinium -methylsulfate, 3 - [(E) - ({bis [4- (dimethylamino) phenyl] -methylene} hydrazono) methyl] -1-methylpyridinium-methylsulfate, 4 - {(E) - [(2Z) -2- ( 3,4-dimethyl-1,3-thiazole-2 (3H) - ylidene) hydrazono] methyl} -1-methylpyridinium methyl sulfate and 4 - [(E) - ({bis [4-
(dimethylamino)phenyl]methyliden}hydrazono)methyl]-1-methylquinolinium- methylsulfat.(dimethylamino) phenyl] methylidene} hydrazono) methyl] -1-methylquinolinium methyl sulfate.
Bevorzugte Verbindungen der allgemeinen Formeln (I) und (II) sind 1-(2-Hydroxyethyl)-3-{(Z)-[(2E)-2-(3-methyl-1,3-benzothiazol-2(3H)- yliden)hydrazono]methyl}pyridinium-bromid, 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3- thiazol-2(3H)-yliden)hydrazono]methyl}-1-(2-hydroxyethyl)pyridinium-bromid, 2-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)-yliden)hydrazono]methyl}-3- (methyl)-1 -methyl-1 H-imidazol-3-ium-methylsulfat, 3-(2-Hydroxyethyl)-1 - methyl-2-{(Z)-[(2£)-2-(3-methyl-1 ,3-benzothiazol-2(3/-/)-yliden)hydrazono]- methyl}-1 H-imidazol-3-ium-bromid, 1 -(2-Hydroxyethyl)-4-{(Z)-[(2E)-2-(3- methyl-1,3-benzotniazol-2(3/-/)-yliden)-hydrazono]methyl}pyridinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]methylen}hydrazono)methyl]-1-(2- hydroxyethyl)pyridinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]- methylen}-hydrazono)methyl]-1-(2-hydroxyethyl)quinolinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]methylen}hydrazono)methyl]-1- methylpyridinium-methylsulfat, 4-[(E)-({Bis[4-(diethylamino)phenyl]methylen}- hydrazono)methyl]-1-methylpyridinium-methylsulfat, 4-[(E)-(9H-Fluoren-9- ylidenhydrazono)methyl]-1-methylpyridinium-methylsulfat, 3-[(E)-({Bis[4- (dimethylamino)phenyl]methylen}hydrazono)-methyl]-1 -methylpyridinium- methylsulfat, 4-{(£)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)- yliden)hydrazono]methyl}-1 -methylpyridinium-methylsulfat und 4-[(E)-({Bis[4- (dimethylamino)phenyl]methyliden}hydrazono)methyl]-1-methylquinolinium- methylsulfat. Die erfindungsgemäßen kationischen Heteroarylazinfarbstoffe der allgemeinen Formeln (I) und (II) sind durch Standardoperationen aus kommerziell erhältlichen oder leicht herstellbaren Komponenten zugänglich.Preferred compounds of the general formulas (I) and (II) are 1- (2-hydroxyethyl) -3 - {(Z) - [(2E) -2- (3-methyl-1,3-benzothiazol-2 (3H) - ylidene) hydrazono] methyl} pyridinium bromide, 4 - {(E) - [(2Z) -2- (3,4-dimethyl-1,3-thiazol-2 (3H) -ylidene) hydrazono] methyl} - 1- (2-hydroxyethyl) pyridinium bromide, 2 - {(E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) -ylidene) hydrazono] methyl} - 3- (methyl) -1-methyl-1 H-imidazol-3-ium-methyl sulfate, 3- (2-hydroxyethyl) -1-methyl-2 - {(Z) - [(2 £) -2- (3rd -methyl-1, 3-benzothiazol-2 (3 / - /) - ylidene) hydrazono] - methyl} -1 H-imidazol-3-ium bromide, 1 - (2-hydroxyethyl) -4 - {(Z) - [(2E) -2- (3-methyl-1,3-benzotniazol-2 (3 / - /) - ylidene) hydrazono] methyl} pyridinium bromide, 4 - [(E) - ({bis [4 - (dimethylamino) phenyl] methylene} hydrazono) methyl] -1- (2-hydroxyethyl) pyridinium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] - methylene} hydrazono) methyl] -1- (2-hydroxyethyl) quinolinium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - [(E) - ({bis [4- (diethylamino ) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - [(E) - (9H-fluoren-9-ylidene hydrazono) methyl] -1-methylpyridinium methyl sulfate, 3 - [(E) - ( {Bis [4- (dimethylamino) phenyl] methylene} hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - {(£) - [(2Z) -2- (3,4-dimethyl-1,3-thiazole -2 (3H) - ylidene) hydrazono] methyl} -1-methylpyridinium methyl sulfate and 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylidene} hydrazono) methyl] -1-methylquinolinium methyl sulfate. The cationic heteroarylazine dyes of the general formulas (I) and (II) according to the invention are accessible by standard operations from commercially available or easily manufactured components.
Aromatische Hydrazonverbindungen können beispielsweise nach S. Hünig et al. (Chem. Eur. J. 2000, 6, No. 14, Seiten 2618-2632) leicht aus Hydrazinmonohydrat und den entsprechenden Ketonen beziehungsweise Thioketonen erhalten werden.Aromatic hydrazone compounds can, for example, according to S. Hünig et al. (Chem. Eur. J. 2000, 6, No. 14, pages 2618-2632) can easily be obtained from hydrazine monohydrate and the corresponding ketones or thioketones.
Durch Kondensationsreaktionen der Hydrazone mit heterozyklischen Aldehyden in Lösungsmitteln, wie beispielsweise verdünnter Essigsäure, lassen sich die entsprechenden Heteroarylazinverbindungen der Formel (la)/(lla) herstellen. Ein allgemeiner Syntheseweg ist in Schema 1 dargestellt.The corresponding heteroarylazine compounds of the formula (Ia) / (Ila) can be prepared by condensation reactions of the hydrazone with heterocyclic aldehydes in solvents, such as, for example, dilute acetic acid. A general synthetic route is shown in Scheme 1.
Schema 1 :Scheme 1:
(la) oder (la) or
(Ha) Der kationische Farbstoff der Formel (I) oder (II) wird im abschließenden Schritt gemäß Schema 2, durch Quatemisierung des heterozyklischen Stickstoffatoms in R1' mit einem Alkylierungsmittel der allgemeinen Formel X-R7 erhalten. (Ha) The cationic dye of the formula (I) or (II) is obtained in the final step according to scheme 2, by quaternization of the heterocyclic nitrogen atom in R1 'with an alkylating agent of the general formula X-R7.
Schema 2:Scheme 2:
(la) (D (la) (D
oderor
(Na) (M) (Na) (M)
In Schema 1 und 2 haben die Restgruppen R1, R2, R4, R5 und R7 die vorstehend angegebene Bdeutung, während R1' für einen nicht- quaternisierten Heterozyklus der Formel (III) bis (VI) und X für eine ungeladene Restgruppe X" steht. Die erfindungsgemäßen kationischen Heteroarylazinfarbstoffe der allgemeinen Formel (I) und (II) ermöglichen eine gleichmäßige Färbung von Keratinfasern, insbesondere menschlichen Haaren, mit einer guten Stabilität gegen Licht, Schweiß und Shampoonieren. Die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) und (II) ergeben eine intensive, brillante Färbung von Keratinfasern, insbesondere von menschlichen Haaren, aber auch Wolle, Pelzen oder anderen Fasermaterialien, unter schonenden Bedingungen.In Schemes 1 and 2, the residual groups R1, R2, R4, R5 and R7 have the meanings given above, while R1 'represents an unquaternized heterocycle of the formulas (III) to (VI) and X represents an uncharged residual group X " . The cationic heteroarylazine dyes of the general formulas (I) and (II) according to the invention enable uniform coloring of keratin fibers, in particular human hair, with good stability against light, sweat and shampooing. The compounds of the general formula (I) and (II) according to the invention result in an intensive, brilliant coloring of keratin fibers, in particular human hair, but also wool, furs or other fiber materials, under gentle conditions.
Bei besonderer Anregung, beispielsweise durch UV-Licht läßt sich zudem häufig eine ausgeprägte Festkörperfluoreszenz der gefärbten Faser beobachten.With special excitation, for example by UV light, a pronounced solid-state fluorescence of the dyed fiber can often be observed.
Außerdem ermöglichen einige Verbindungen der Formel (I) oder (II) (zum Beispiel 1 -(2-Hydroxyethyl)-3-{(Z)-[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3/-/)- yliden)hydrazono]methyl}-pyridinium-bromid oder 2-{(£)-[(2Z)-2-(3,4- Dimethyl-1 ,3-thiazol-2(3 -/)-yliden)hydrazono]methyl}-3-(methyl)-1 -methyl-1 H- imidazol-3-ium-methylsulfat) eine natürliche Aufhellung von unbehandeltem Naturhaar ohne Zusatz von chemischen Oxidationsmitteln.In addition, some compounds of formula (I) or (II) allow (e.g. 1 - (2-hydroxyethyl) -3 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 / - /) - ylidene) hydrazono] methyl} pyridinium bromide or 2 - {(£) - [(2Z) -2- (3,4-dimethyl-1,3-thiazole-2 (3 - / ) -ylidene) hydrazono] methyl} -3- (methyl) -1-methyl-1 H-imidazol-3-ium-methyl sulfate) a natural lightening of untreated natural hair without the addition of chemical oxidizing agents.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daherAnother object of the present invention is therefore
(a) ein Mittel zum nicht-oxidativen Färben von Keratinfasern, insbesondere menschlichen Haaren,(a) an agent for the non-oxidative dyeing of keratin fibers, in particular human hair,
(b) ein Mittel zum gleichzeitigen Aufhellen und Färben von Keratinfasern, das neben dem Farbstoff der Formel (I) und (II) ein Oxidationsmittel enthält, und(b) an agent for simultaneously lightening and dyeing keratin fibers, which contains an oxidizing agent in addition to the dye of the formula (I) and (II), and
(c) ein oxidatives Färbemittel für Keratinfasern auf der Basis mindestens einer Oxidationsfarbstoffvorstufe, wobei die Mittel (a), (b) und (c) dadurch gekennzeichnet sind, dass sie jeweils mindestens ein Derivat der allgemeinen Formel (I) oder (II) enthalten.(c) an oxidative colorant for keratin fibers based on at least one oxidation dye precursor, wherein the agents (a), (b) and (c) are characterized in that they each contain at least one derivative of the general formula (I) or (II).
Die kationischen Heteroarylazinfarbstoffe der allgemeinen Formeln (I) und (II) sind in den erfindungsgemäßen Färbemitteln vorzugsweise in einer Gesamtmenge von 0,01 bis 10 Gewichtsprozent, insbesondere 0,1 bis 8 Gewichtsprozent, enthalten.The cationic heteroarylazine dyes of the general formulas (I) and (II) are preferably present in the colorants according to the invention in a total amount of 0.01 to 10 percent by weight, in particular 0.1 to 8 percent by weight.
Das erfindungsgemäße Färbemittel (a) kann neben den Farbstoffen der allgemeinen Formel (I) und (II) zusätzlich noch weitere bekannte direktfärbende Farbstoffe aus der Gruppe bestehend aus Nitrofarbstoffen, Azofarbstoffen, Athrachinonfarbstoffen und Triphenylmethanfarbstoffen, wie zum Beispiel, 1,4-Bis[(2-hydroxyethyl)amino]-2-nitrobenzol, 1-(2-Hydroxy- ethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]-benzol, (HC Blue No. 2), 1-Amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzol, (HC Violet No. 1), 4-[Ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzol- hydrochlorid (HC Blue No. 12), 1-[(2,3-Dihydroxypropyl)amino]-4-[methyl-(2- hydroxyethyl)amino]-2-nitrobenzol (HC Blue No. 10), 1-[(2,3-Dihydroxy- propyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzol-hydrochlorid (HC Blue No. 9), 1-(3-Hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2- nitrobenzol, (HC Violet No. 2); 1-Amino-4-[(2-hydroxyethyl)amino]-2- nitrobenzol (HC Red No. 7), 2-Amino-4,6-dinitro-phenol, 1 ,4-Diamino-2- nitrobenzol (CI76070), 4-Amino-2-nitro-diphenylamin (HC Red No. 1), 1-Amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzol-hydrochlorid (HC Red No. 13), 1 -Amino-5-chlor-4-[(2-hydroxyethyl)amino]-2-nitrobenzol, 4-Amino-1 -[(2- hydroxyethyl)amino]-2-nitrobenzol (HC Red No. 3), 4-Amino-2-nitro-1-((prop- 2-en-1-yl)amino)-benzol, 4-Amino-3-nitrophenol, 4-[(2-Hydroxyethyl)amino]-3- nitrophenol, 4-[(2-Nitrophenyl)amino]phenol (HC Orange No. 1), 1-[(2-Amino- ethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzol (HC Orange No. 2), 4-(2,3-Dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzol, (HC Orange No. 3), 1-Amino-5-chlor-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzol (HC Red No. 10), 5-Chlor-1 ,4-[di(2,3-dihydroxypropyl)amino] -2-nitrobenzol (HC Red No. 11), 2-[(2-Hydroxyethyl)amino]-4,6-dinitro-phenol, 4-Ethylamino- 3-nitrobenzoesäure, 2-[(4-Amino-2-nitrophenyl)amino]-benzoesäure, 2-Chlor- 6-ethylamino-4-nitrophenol, 2-Amino-6-chlor-4-nitrophenol, 4-[(3-Hydroxy- propyl)amino]-3-nitrophenol, 2,5-Diamino-6-nitropyridin, 3-Amino-6- (methylamino)-2-nitropyridin, 1 ,2,3,4-Tetrahydro-6-nitrochinoxalin, 7-Amino- 3,4-dihydro-6-nitro-2H-1,4-benzoxazin (HC Red No. 14), 1 ,2-Diamino-4- nitrobenzol (CI76020), 1-Amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzol (HC Yellow No. 5), 1-(2-Hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzol, (HC Yellow No. 4), 1-[(2-Hydroxyethyl)amino]-2-nitrobenzol (HC Yellow No. 2), 2-[(2-Hydroxyethyl)amino]-1 -methoxy-5-nitrobenzol, 2-Amino-3- nitrophenol, 1 -Amino-2-methyl-6-nitrobenzol, 1 -(2-Hydroxyethoxy)-3- methylamino-4-nitrobenzol, 2,3-(Dihydroxypropoxy)-3-methylamino-4- nitrobenzol, 2-[(2-Hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-Aminoethyl)amino]-1-methoxy-4-nitrobenzol-hydrochlorid, (HC Yellow No.9), 1 -[(2-Ureidoethyl)amino]-4-nitrobenzol, 4-[(2,3-Dihydroxypropyl)- amino]-3-nitro-1-trifluormethyl-benzolt (HC Yellow No. 6), 1 -Chlor-2,4-bis[(2- hydroxyethyl)amino]-5-nitrobenzol (HC Yellow No. 10), 4-[(2-Hydroxyethyl)- amino]-3-nitro-1 -methylbenzol, 1 -Chlor-4-[(2-hydroxyethyl)amino]-3- nitrobenzol (HC Yellow No. 12), 4-[(2-Hydroxyethyl)amino]-3-nitro-1- trifluormethyl-benzol, (HC Yellow No. 13), 4-[(2-Hydroxyethyl)amino]-3-nitro- benzonitril (HC Yellow No. 14), 4-[(2-Hydroxyethyl)amino]-3-nitro-benzamid (HC Yellow No. 15), 2,4-Dinitro-1-hydroxy-naphthalin, 1 ,4-Di[(2,3-dihydroxy- propyl)amino]-9,10-anthrachinon, 1 ,4-Di[(2-hydroxyethyl)amino]-9,10- anthrachinon (CI61545, Disperse Blue 23), 1-Amino-4-hydroxy-9,10- anthrachinon (CI60710, Disperse Red 15), 1-Hydroxy-4-[(4-methyl-2- sulfophenyl)amino]-9,10-anthrachinon, 7-Beta-D-glucopyranosyl-9,10- dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracencarbonsäure (CI75470, Natural Red 4), 1-[(3-Aminopropyl)amino]-9,10-anthrachinon (HC Red No. 8), 1,4-Diamino-9,10-anthrachinon (CI61100, Disperse Violet No. 1), 1-Amino-4-(methylamino)-9,10-anthrachinon (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), N-(6-((3-Chlor-4-(methylamino)phenyl)imino)-4- methyl-3-oxo-1,4-cyclohexadien-1-yl)hamstoff (HC Red No. 9), 2-((4-(Di(2- hydroxyethyl)amino)phenyl)amino)-5-((2-hydroxyethyl)amino)-2,5- . cyclohexadien-1 ,4-dion (HC Green No. 1), 2-Hydroxy-1 ,4-naphthochinon (CI75480, Natural Orange No. 6), 1 ,2-Dihydro-2-(1 ,3-dihydro-3-oxo-2H-indol- 2-yliden)-3H-indol-3-on (CI73000), 1,3-Bis(dicyanomethylen)indan, Di[4- (diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium-chlorid (CI42595; Basic Blue No. 7), Di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]- carbenium-chlorid (CI44045; Basic Blue No. 26), Basic Blue No. 77, 8-Amino-2-brom-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]- 1(4H)-naphthalinon-chlorid (CI56059; Basic Blue No. 99), Tri(4-amino-3- methylphenyl)carbenium-chlorid (CI42520; Basic Violet No. 2), Di(4- aminophenyl)(4-amino-3-methylphenyl)carbenium-chlorid (CI42510; Basic Violet No. 14), 1-[(4-Aminophenyl)azo]-7-(trimethylammonio)-2-naphthol- chlorid (CM 2250; Basic Brown No. 16), 3-[(4-Amino-2,5-dimethoxyphenyl)- azo]-N,N,N-trimethylbenzolaminium-chlorid (CH 12605, Basic Orange No. 69), 1-[(4-Amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol-chlorid (Basic Brown No. 17), 1-[(4-Amino-3-nitrophenyl)azo]-7-(trimethylammonio)- 2-naphthol-chlorid (CI12251; Basic Brown No. 17), 2-((4-Aminophenyl)azo)- 1 ,3-dimethyl-1H-imidazol-3-ium-chlorid (Basic Orange No. 31 ), 3,7-Diamino- 2,8-dimethyl-5-phenylphenazinium-chlorid (CI50240; Basic Red No. 2), 1 ,4-Dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1 ,2,4-triazolium-chlorid (CM 1055; Basic Red No. 22), 1,3-Dimethyl-2-((4-dimethylamino)phenyl)azo- 1 H-imidazol-3-ium-chlorid (Basic Red No. 51), 2-Hydroxy-1-[(2-methoxy- phenyl)azo]-7-(trimethylammonio)-naphthalin-chlorid (CM 2245; Basic Red No. 76), 3-Methyl-1 -phenyl-4-[(3-(trimethylammonio)phenyl)azo]-pyrazol-5- on-chlorid (CI12719; Basic Yellow No. 57), 1-Methyl-4-((methyl-phenyl- hydrazono)methyl)-pyridinium-methylsulfat (Basic Yellow No. 87), 1-(2-Morpholiniumpropylamino)-4-hydroxy-9,10-anthrachinon-methylsulfat, 1-[(3-(Dimethyl-propylaminium)propyl)amino]-4-(methylamino)-9,10- anthrachinon-chlorid,1-[Di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)- azo]-benzol (CM 1210, Disperse Red No. 17), 1-[Di(2-hydroxyethyl)amino]-4- [(4-nitrophenyl)azo]-benzol, (Disperse Black No. 9), 4-[(4-Aminophenyl)azo]- 1-[di(2-hydroxyethyl)amino]-3-methylbenzol, (HC Yellow No. 7), 2,6-Diamino-3-[(pyridin-3-yl)azo]-pyridin und 2-((4-(Ethyl(2-hydroxyethyl)- amino)-2-methylphenyl)azo)-5-nitro-1 ,3-thiazol (CM 11935; Disperse Blue No. 106), alleine oder im Gemisch miteinander enthalten.In addition to the dyes of the general formulas (I) and (II), the colorant (a) according to the invention can also include other known direct-dyeing dyes from the group consisting of nitro dyes, azo dyes, athraquinone dyes and triphenylmethane dyes, such as, for example, 1,4-bis [( 2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene, (HC Blue No. 2), 1- Amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene, (HC Violet No. 1), 4- [ethyl- (2-hydroxyethyl) amino] -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 12), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl- (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue No. 10), 1 - [(2,3-Dihydroxy-propyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 9), 1- (3-hydroxypropylamino ) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, (HC Violet No. 2); 1-amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitro-phenol, 1,4-diamino-2-nitrobenzene (CI76070) , 4-amino-2-nitro-diphenylamine (HC Red No. 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red No. 13), 1-amino -5-chloro-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 3), 4-amino- 2-nitro-1 - ((prop-2-en-1-yl) amino) benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] -3- nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange No. 1), 1 - [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange No. 2), 4- (2,3-Dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2-nitrobenzene, (HC Orange No. 3), 1-amino-5-chloro-4 - [(2, 3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 10), 5-chloro-1,4, 4- [di (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 11), 2 - [(2-Hydroxyethyl) amino] -4,6-dinitro-phenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino -4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol, 2,5-diamino-6-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 1, 2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14) , 1, 2-diamino-4-nitrobenzene (CI76020), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1- (2-hydroxyethoxy) -2- [(2-hydroxyethyl) amino] -5-nitrobenzene, (HC Yellow No. 4), 1 - [(2-hydroxyethyl) am ino] -2-nitrobenzene (HC Yellow No. 2), 2 - [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1 - (2-hydroxyethoxy) - 3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow No. 11), 3 - [( 2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride, (HC Yellow No.9), 1 - [(2-ureidoethyl) amino] -4-nitrobenzene, 4 - [(2,3-dihydroxypropyl) - amino] -3-nitro-1-trifluoromethyl-benzene t (HC Yellow No. 6), 1-chloro-2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 10) , 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow No. 12), 4- [ (2-hydroxyethyl) amino] -3-nitro-1-trifluoromethyl-benzene, (HC Yellow No. 13), 4 - [(2-hydroxyethyl) amino] -3-nitro-benzonitrile (HC Yellow No. 14), 4 - [(2-Hydroxyethyl) amino] -3-nitro-benzamide (HC Yellow No. 15), 2,4-dinitro-1-hydroxy-naphthalene, 1,4-di [(2,3-dihydroxy- propyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI61545, Disperse Blue 23), 1-amino-4-hydroxy-9,10- anthraquinone (CI60710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7-beta-D-glucopyranosyl-9,10-dihydro-1- methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI75470, Natural Red 4), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red No. 8), 1,4-Diamino-9,10-anthraquinone (CI61100, Disperse Violet No. 1), 1-Amino-4- (methylamino) -9,10-anthraquinone (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), N- (6 - ((3-chloro-4- (methylamino) phenyl) imino) -4-methyl-3-oxo-1,4-cyclohexadien-1-yl) urea (HC Red No. 9), 2 - ((4- (Di (2-hydroxyethyl) amino) phenyl) amino) -5 - ((2-hydroxyethyl) amino) -2,5-. cyclohexadiene-1,4-dione (HC Green No. 1), 2-hydroxy-1,4-naphthoquinone (CI75480, Natural Orange No. 6), 1,2-dihydro-2- (1,3-dihydro-3 -oxo-2H-indol-2-ylidene) -3H-indol-3-one (CI73000), 1,3-bis (dicyanomethylene) indan, di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (CI42595; Basic Blue No. 7), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] - carbenium chloride (CI44045; Basic Blue No. 26), Basic Blue No. 77, 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] - 1 (4H) -naphthalenone chloride (CI56059; Basic Blue No. 99), Tri (4-amino-3-methylphenyl) carbenium chloride (CI42520; Basic Violet No. 2), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI42510; Basic Violet No. 14) , 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (CM 2250; Basic Brown No. 16), 3 - [(4-amino-2,5-dimethoxyphenyl) - azo ] -N, N, N-trimethylbenzolaminium chloride (CH 12605, Basic Orange No. 69), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (Basic Brown No. 17), 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonio) - 2-naphthol chloride (CI12251; Basic Brown No. 17), 2 - ((4-aminophenyl) azo) - 1,3-dimethyl-1H-imidazol-3-ium chloride (Basic Orange No. 31), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI50240; Basic Red No. 2), 1,4-Dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1, 2,4-triazolium chloride (CM 1055; Basic Red No. 22), 1,3-dimethyl-2 - (( 4-dimethylamino) phenyl) azo-1 H-imidazol-3-ium chloride (Basic Red No. 51), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) naphthalene -chloride (CM 2245; Basic Red No. 76), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] -pyrazole-5-one chloride (CI12719; Basic Yellow No. 57 ), 1-methyl-4 - ((methylphenylhydrazono) methyl) pyridinium methyl sulfate (Basic Yellow No. 87), 1- (2-morpholinium propylamino) -4-hydroxy-9,10-anthraquinone methyl sulfate, 1 - [(3- (dimethyl-propylaminium) propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride, 1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [( 4-nitrophenyl) azo] benzene (CM 1210, Disperse Red No. 17), 1- [di (2-hydroxyethyl) amino] -4- [(4-nitrophenyl) azo] benzene, (Disperse Black No. 9), 4 - [(4-Am inophenyl) azo] - 1- [di (2-hydroxyethyl) amino] -3-methylbenzene, (HC Yellow No. 7), 2,6-diamino-3 - [(pyridin-3-yl) azo] pyridine and 2 - ((4- (ethyl (2-hydroxyethyl) amino) -2-methylphenyl) azo) -5- nitro-1, 3-thiazole (CM 11935; Disperse Blue No. 106), alone or in a mixture with each other.
Das erfindungsgemäße Färbemittel (b), das sich durch einen Gehalt an einem Oxidationsmittel, vorzugsweise Wasserstoffperoxid und/oder Persulfaten beziehungsweise Perboraten, und insbesondere Persulfaten oder einer Mischung aus Wasserstoffperoxid und Persulfaten, auszeichnet, kann neben den Farbstoffen der allgemeinen Formel (I) und (II) zusätzlich noch weitere oxidationsstabile direktfärbende Farbstoffe, wie zum Beispiel 3-(2',6'-Diaminopyridyl-3'-azo)-pyridin (= 2,6-Diamino-3-((pyridin-3- yl)azo)pyridin, 2-((4-(Ethyl(2-hydroxyethyl)-amino)-2-methylphenyl)azo-5- nitro-1 ,3-thiazol (Disperse Blue 106), N,N-Di(2-hydroxyethyl)-3-methyl-4-((4- nitrophenyl)azo)-anilin (Disperse Red 17, Cl 11210), 3-Diethylamino-7-(4- dimethylaminophenylazo)-5-phenyl-phenaziniumchlorid (Cl 11050), 4-(2-Thiazolylazo)-resorcin, 4-(((4-Phenylamino)azo)benzosulfonsäure- natriumsalz (Orange IV), 1-((3-Aminopropyl)amino)-9,10-anthracendion (HC Red No. 8), 3'(3")4,5,5',5",6,7-Octabromphenolsulfonphtalein (Tetrabromphenol Blue), 1 -((4-Amino-3,5-dimethylphenyl)-(2,6-dichlorphenyl)- methylen)-3,5-dimethyl-4-imino-2,5-cyclohexadien-Phosphorsäure (1:1) (Basic Blue 77), 3',3",5',5"-Tetrabrom-m-kresolsulfonphthalein, 2,4-Dinitro-1- naphthol-7-sulfonsäure-Dinatriumsalz (Acid Yellow 1 , Cl 10316), 4-[2'-Hydroxy-1 '-naphthyl)azo]-benzosulfonsäure-Natriumsalz (Acid Orange 7, Cl 15510), 3',6'-Dihydroxy-2',4',5',7'-tetraiodospiro-[isobenzo-furan-1(3H), 9'(9H)-xanthen]-3-on-Dinatriumsalz (Acid Red 51, Cl 45430), 6-Hydroxy-5-((2- methoxy-5-methyl-4-sulfophenyl)azo)-2-Naphthalin-sulfonsäuredinatriumsalz (FD&C Red 40, Cl 16035), 2,4-Dinitro-1-naphthol-Natriumsalz (Acid Yellow 24; Cl 10315), 2\4\5\7'-tetrabrom-4,5,6,7-tetrachlor-3\6'-dihydroxy- Spiro(isobenzofuran-1(3H), 9'[9H]xanthen]-3-on-dinatriumsalz (Acid Red 92; Cl 45410) , 4-(2-Hyd roxy- 1 -naphthylazo)-3-methy l-benzolsu Ifonsäu re- natriumsalz (Acid Orange 8, Cl 15575), 2-Amino-1 ,4-naphthalindion, Dithizon (1 ,5-Diphenylthiocarbazon), N-(2-Hydroxyethyl))-2-nitro-4-trifluormethyl)anilin (HC Yellow 13), N-(2-hydroxyethyl)-4-nitro-anilin und 4-Chlor-N-(2,3- dihydroxypropyl)-2-nitro-anilin, enthalten.The colorant (b) according to the invention, which is characterized by a content of an oxidizing agent, preferably hydrogen peroxide and / or persulfates or perborates, and in particular persulfates or a mixture of hydrogen peroxide and persulfates, can, in addition to the dyes of the general formula (I) and ( II) additionally further oxidation-stable direct-coloring dyes, such as, for example, 3- (2 ', 6'-diaminopyridyl-3'-azo) pyridine (= 2,6-diamino-3 - ((pyridin-3-yl) azo) pyridine, 2 - ((4- (ethyl (2-hydroxyethyl) amino) -2-methylphenyl) azo-5- nitro-1,3-thiazole (Disperse Blue 106), N, N-di (2-hydroxyethyl) -3-methyl-4 - ((4-nitrophenyl) azo) aniline (Disperse Red 17, Cl 11210), 3 -Diethylamino-7- (4-dimethylaminophenylazo) -5-phenyl-phenazinium chloride (Cl 11050), 4- (2-thiazolylazo) -resorcinol, 4 - (((4-phenylamino) azo) benzosulfonic acid sodium salt (Orange IV), 1 - ((3-aminopropyl) amino) -9,10-anthracendione (HC Red No. 8), 3 ' ( 3 " ) 4,5,5', 5", 6,7-octabromophenolsulfonphthaline (tetrabromophenol blue), 1 - ((4-Amino-3,5-dimethylphenyl) - (2,6-dichlorophenyl) - methylene) -3,5-dimethyl-4-imino-2,5-cyclohexadiene-phosphoric acid (1: 1) (basic Blue 77), 3 ', 3 ", 5', 5" tetrabromo-m-cresolsulfonphthalein, 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (Acid Yellow 1, Cl 10316), 4- [2 '-Hydroxy-1' -naphthyl) azo] -benzenesulfonic acid sodium salt (Acid Orange 7, Cl 15510), 3 ', 6'-dihydroxy-2', 4 ', 5', 7'-tetraiodospiro- [isobenzo-furan -1 (3H), 9 '(9H) -xanthene] -3-one disodium salt (Acid Red 51, Cl 45430), 6-hydroxy-5 - ((2-methoxy-5-methyl-4-sulfophenyl) azo ) -2-naphthalene sulfonic acid disodium salt (FD&C Red 40, Cl 16035), 2,4-dinitro-1-naphthol sodium salt (Acid Yellow 24; Cl 10315), 2 \ 4 \ 5 \ 7'-tetrabromo-4,5,6,7-tetrachlor-3 \ 6'-dihydroxy-Spiro (isobenzofuran-1 (3H), 9 '[9H] xanthene] -3 -on-disodium salt (Acid Red 92; Cl 45410), 4- (2-hydroxyoxy-1-naphthylazo) -3-methyl l-benzenesu ifonic acid, sodium salt (Acid Orange 8, Cl 15575), 2-amino-1 , 4-naphthalenedione, dithizone (1,5-diphenylthiocarbazone), N- (2-hydroxyethyl)) - 2-nitro-4-trifluoromethyl) aniline (HC Yellow 13), N- (2-hydroxyethyl) -4-nitro- aniline and 4-chloro-N- (2,3-dihydroxypropyl) -2-nitro-aniline.
Die vorgenannten direktziehenden Farbstoffe können in einer Gesamtmenge von etwa 0,01 bis 4 Gewichtsprozent enthalten sein, wobei der Gesamtgehalt an Farbstoffen in dem erfindungsgemäßen Färbemittel vorzugsweise etwa 0,01 bis 10 Gewichtsprozent, insbesondere 0,1 bis 5 Gewichtsprozent, beträgt.The abovementioned direct dyes can be present in a total amount of about 0.01 to 4 percent by weight, the total amount of dyes in the colorant according to the invention preferably being about 0.01 to 10 percent by weight, in particular 0.1 to 5 percent by weight.
Das erfindungsgemäße Oxidationsfärbemittel (c), das vor der Anwendung mit einem Oxidationsmittel (insbesondere Wasserstoffperoxid oder dessen Additionsverbindungen) vermischt wird, enthält neben den Farbstoffen der allgemeinen Formel (I) und (II) zusätzlich Oxidationsfarbstoffvorstufen. Als geeignete Oxidationsfarbstoffvorstufen können beispielsweise die folgenden Entwicklersubstanzen und Kupplersubstanzen und mit sich selbst kuppelnden Verbindungen genannt werden:The oxidation coloring agent (c) according to the invention, which is mixed with an oxidizing agent (in particular hydrogen peroxide or its addition compounds) before use, also contains oxidation dye precursors in addition to the dyes of the general formulas (I) and (II). The following developer substances and coupler substances and with self-coupling compounds can be mentioned as suitable oxidation dye precursors:
(0 Entwicklersubstanzen: 1 ,4-Diamino-benzol (p-Phenylendiamin), 1 ,4-Diamino-2-methyl-benzol (p-Toluylendiamin), 1 ,4-Diamino-2,6-dimethyl~ benzol, 1 ,4-Diamino-3,5-diethyl-benzol, 1 ,4-Diamino-2,5-dimethyl-benzol, 1 ,4-Diamino-2,3-dimethyl-benzol, 2-Chlor-1 ,4-diaminobenzol, 1 ,4-Diamino-2- (thiophen-2-yl)benzol, 1 ,4-Diamino-2-(thiophen-3-yl)benzol, 1 ,4-Diamino-2- (pyridin-3-yl)benzol, 2,5-Diamino-biphenyl, 1 ,4-Diamino-2-methoxymethyl- benzol, 1 ,4-Diamino-2-aminomethyl-benzol, 1 ,4-Diamino-2-hydroxymethyl- benzol, 1 ,4-Diamino-2-(2-hydroxyethoxy)-benzol, 2-(2-(Acetylamino)ethoxy)- 1 ,4-diamino-benzol, 4-Phenylamino-anilin, 4-Dimethylamino-anilin, 4-Diethylamino-anilin, 4-Dipropylamino-anilin, 4-[Ethyl(2-hydroxyethyl)- amino]-anilin, 4-[Di(2-hydroxyethyl)amino]-anilin, 4-[Di(2-hydroxyethyl)amino]- 2-methyl-anilin, 4-[(2-Methoxyethyl)amino]-anilin, 4-[(3-Hydroxypropyl)amino]- anilin,4-[(2,3-Dihydroxypropyl)amino]-anilin, 1 ,4-Diamino-2-(2-hydroxyethyl)- benzol, 1 ,4-Diamino-2-(1-methylethyl)-benzol, 1 ,3-Bis[(4-aminophenyl)(2- hydroxyethyl)amino]-2-propanol, 1,4-Bis[(4-Aminophenyl)amino]-butan, 1 ,8-Bis(2,5-diaminophenoxy)-3,6-dioxaoctan, 4-Amino-phenol, 4-Amino-3- methyl-phenol, 4-Amino-3-(hydroxymethyl)-phenol, 4-Amino-3-fluor-phenol, 4-Methylamino-phenol, 4-Amino-2-(aminomethyl)-phenol, 4-Amino-2- (hydroxymethyl)-phenol, 4-Amino-2-fluor-phenol, 4-Amino-2-[(2-hydroxy- ethyl)-amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2- (methoxymethyl)-phenol, 4-Amino-2-(2-hydroxyethyl)-phenol, 5-Amino- salicylsäure, 2,5-Diamino-pyridin, 2,4,5,6-Tetraamino-pyrimidin, 2,5,6-Triamino-4-(1 H)-pyrimidon, 4,5-Diamino-1-(2-hydroxyethyl)-1 H-pyrazol, 4,5-Diamino-1 -(1 -methylethyl)-1 H-pyrazol, 4,5-Diamino-1 -[(4-methylphenyl)- methyl]-1 H-pyrazol, 1 -[(4-Chlorphenyl)methyl]-4,5-diamino-1 H-pyrazol, 4,5-Diamino-1 -methyl-1 H-pyrazol, 2-Amino-phenol, 2-Amino-6-methyl- phenol, 2-Amino-5-methyl-phenol, allein oder im Gemisch miteinander. (ii) Kupplersubstanzen: N-(3-Dimethylamino-phenyl)-hamstoff, 2,6-Diamino-pyridin, 2-Amino-4-[(2-hydroxyethyl)amino]-anisol, 2,4-Diamino- 1 -fluor-5-methyl-benzol, 2,4-Diamino-1 -methoxy-5-methyl-benzol, 2,4-Diamino-1 -ethoxy-5-methyl-benzol, 2,4-Diamino-1 -(2-hydroxy-ethoxy)-5- methyl-benzol, 2,4-Di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzol, 2,3-Diamino-6-methoxy-pyridin, 3-Amino-6-methoxy-2-(methylamino)-pyridin, 2,6-Diamino-3,5-dimethoxy-pyridin, 3,5-Diamino-2,6-dimethoxy-pyridin, 1 ,3-Diamino-benzol, 2,4-Diamino-1-(2-hydroxy-ethoxy)-benzol, 1 ,3-Diamino- 4-(2,3-dihydroxypropoxy)-benzol, 2,4-Diamino-1,5-di(2-hydroxyethoxy)- benzol, 1 -(2-Aminoethoxy)-2,4-diamino-benzol, 2-Amino-1 -(2-hydroxyethoxy)- 4-methylamino-benzol, 2,4-Diaminophenoxy-essigsäure, 3-[Di(2-hydroxy- ethyl)amino]-anilin, 4-Amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzol, 5-Methyl-2-(1-methylethyl)-phenol, 3-[(2-Hydroxyethyl)amino]-anilin, 3-[(2-Aminoethyl)-amino]-anilin, 1 ,3-Di(2,4-diaminophenoxy)-propan, Di(2,4- diamino-phenoxy)-methan, 1 ,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis(2- hydroxy-ethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethylamino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl- phenol, 5-Amino-4-methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl- phenol, 3-Amino-2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino-2- methyl-phenol, 3-Amino-2-chlor-6-methyl-phenol, 3-Amino-phenol, 2-[(3-Hydroxyphenyl)amino]-acetamid, 5-[(2-Hydroxyethyl)amino]-4-methoxy- 2-methyl-phenol, 5-[(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-Hydroxy- ethyl)amino]-phenol, 3-[(2-Methoxyethyl)amino]-phenol, 5-Amino-2-ethyl- phenol, 5-Amino-2-methoxy-phenol, 2-(4-Amino-2-hydroxyphenoxy)-ethanol, 5-[(3-Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-Dihydroxypropyl)amino]- 2-methyl-phenol, 3-[(2-Hydroxyethyl)-amino]-2-methyl-phenol, 2-Amino-3- hydroxy-pyridin, 5-Amino-4-chlor-2-methyl-phenol, 1 -Naphthol, 2-Methyl-1- naphthol, 1 ,5-Dihydroxy-naphthalin, 1 ,7-Dihydroxy-naphthalin, 2,3-Dihydroxy- naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1 -naphthol-acetat, 1 ,3-Dihydroxy-benzol, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor-1 ,3-dihydroxy- benzol, 1 ,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1 ,5-Dichlor-2,4-dihydroxy- benzol, 1 ,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxy-phenol, 3,4-Methylendioxy-anilin, 5-[(2-Hydroxyethyl)amino]-1 ,3-benzodioxol, 6-Brom-1-hydroxy-3,4-methylendioxy-benzol, 3,4-Diamino-benzoesäure, 3,4-Dihydro-6-hydroxy-1 ,4(2H)-benzoxazin, 6-Amino-3,4-dihydro-1 ,4(2H)- benzoxazin, 3-Methyl-1-phenyl-5-pyrazolon, 5,6-Dihydroxy-indol, 5,6-Dihydroxy-indolin, 5-Hydroxy-indol, 6-Hydroxy-indol, 7-Hydroxy-indol, 2,3-lndolindion, allein oder im Gemisch miteinander. (iii) Mit sich selbst kuppelnde Verbindungen: 2-Amino-5-methylphenol, 2-Amino-6-methylphenol, 2-Amino-5-ethoxyphenol oder 2-Propyl- amino-5-aminopyridin. Die Gesamtmenge der in dem erfindungsgemäßen Färbemittel (c) enthaltenen Oxidationsfarbstoffvorstufen beträgt etwa 0,01 bis 12 Gewichtsprozent, insbesondere etwa 0,2 bis 6 Gewichtsprozent.(0 developer substances: 1, 4-diamino-benzene (p-phenylenediamine), 1, 4-diamino-2-methyl-benzene (p-toluenediamine), 1, 4-diamino-2,6-dimethyl ~ benzene, 1, 4-diamino-3,5-diethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2- (thiophene-2-yl) benzene, 1,4-diamino-2- (thiophene-3-yl) benzene, 1,4-diamino-2- (pyridin-3-yl) benzene , 2,5-diamino-biphenyl, 1,4-diamino-2-methoxymethyl-benzene, 1,4-diamino-2-aminomethyl-benzene, 1,4-diamino-2-hydroxymethyl-benzene, 1,4-diamino -2- (2-hydroxyethoxy) benzene, 2- (2- (acetylamino) ethoxy) - 1, 4-diamino-benzene, 4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline, 4- Dipropylamino aniline, 4- [ethyl (2-hydroxyethyl) amino] aniline, 4- [di (2-hydroxyethyl) amino] aniline, 4- [di (2-hydroxyethyl) amino] -2-methyl aniline , 4 - [(2-methoxyethyl) amino] aniline, 4 - [(3-hydroxypropyl) amino] aniline, 4 - [(2,3-dihydroxypropyl) amino] aniline, 1, 4-diamino-2- (2-hydroxyethyl) benzene, 1,4-diamino-2- (1-me ethylethylbenzene, 1,3-bis [(4-aminophenyl) (2-hydroxyethyl) amino] -2-propanol, 1,4-bis [(4-aminophenyl) amino] butane, 1,8-bis ( 2,5-diaminophenoxy) -3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methylphenol, 4-amino-3- (hydroxymethyl) phenol, 4-amino-3-fluorophenol . 4-methylamino-phenol, 4-amino-2- (aminomethyl) phenol, 4-amino-2- (hydroxymethyl) phenol, 4-amino-2-fluoro-phenol, 4-amino-2 - [(2- hydroxyethyl) amino] methylphenol, 4-amino-2-methylphenol, 4-amino-2- (methoxymethyl) phenol, 4-amino-2- (2-hydroxyethyl) phenol, 5-amino - salicylic acid, 2,5-diamino-pyridine, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4- (1 H) -pyrimidone, 4,5-diamino-1- (2nd -hydroxyethyl) -1 H-pyrazole, 4,5-diamino-1 - (1-methylethyl) -1 H-pyrazole, 4,5-diamino-1 - [(4-methylphenyl) methyl] -1 H-pyrazole , 1 - [(4-chlorophenyl) methyl] -4,5-diamino-1 H-pyrazole, 4,5-diamino-1-methyl-1 H-pyrazole, 2-amino-phenol, 2-amino-6- methyl-phenol, 2-amino-5-methyl-phenol, alone or as a mixture with one another. (ii) Coupler substances: N- (3-dimethylaminophenyl) urea, 2,6-diamino-pyridine, 2-amino-4 - [(2-hydroxyethyl) amino] anisole, 2,4-diamino-1 - fluoro-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1 - (2nd -hydroxy-ethoxy) -5-methyl-benzene, 2,4-di [(2-hydroxyethyl) amino] -1,5-dimethoxy-benzene, 2,3-diamino-6-methoxy-pyridine, 3-amino- 6-methoxy-2- (methylamino) pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1, 3-diamino-benzene, 2, 4-diamino-1- (2-hydroxy-ethoxy) -benzene, 1,3-diamino-4- (2,3-dihydroxypropoxy) -benzene, 2,4-diamino-1,5-di (2-hydroxyethoxy) - benzene, 1 - (2-aminoethoxy) -2,4-diamino-benzene, 2-amino-1 - (2-hydroxyethoxy) - 4-methylamino-benzene, 2,4-diaminophenoxyacetic acid, 3- [di ( 2-hydroxyethyl) amino] aniline, 4-amino-2-di [(2-hydroxyethyl) amino] -1-ethoxybenzene, 5-methyl-2- (1-methylethyl) phenol, 3- [ (2-hydroxyethyl) amino] aniline, 3 - [(2-aminoethyl) amino] aniline, 1,3-di (2,4-diaminophenoxy) propane, di (2nd , 4-diamino-phenoxy) methane, 1, 3-diamino-2,4-dimethoxy-benzene, 2,6-bis (2-hydroxy-ethyl) aminotoluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4- ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro 6-methylphenol, 3-aminophenol, 2 - [(3-hydroxyphenyl) amino] acetamide, 5 - [(2-hydroxyethyl) amino] -4-methoxy-2-methylphenol, 5 - [( 2-hydroxyethyl) amino] -2-methylphenol, 3 - [(2-hydroxyethyl) amino] phenol, 3 - [(2-methoxyethyl) amino] phenol, 5-amino-2-ethylphenol , 5-Amino-2-methoxyphenol, 2- (4-amino-2-hydroxyphenoxy) ethanol, 5 - [(3-hydroxypropyl) amino] -2-methylphenol, 3 - [(2,3- Dihydroxypropyl) amino] - 2-methylphenol, 3 - [(2-hydroxyethyl) amino] -2-methylphenol, 2-amino-3-hydroxy-pyridine, 5-amino-4-chloro-2-methyl -phenol, 1-naphthol, 2-methyl-1-naphthol, 1, 5-dihydroxy-naphthalene, 1, 7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2,7-dihydroxy-naphthalene, 2-methyl -1-naphthol acetate, 1, 3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 2- Chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2- methyl-benzene, 3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline, 5 - [(2-hydroxyethyl) amino] -1, 3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy -benzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4, (2H) -benzoxazine, 6-amino-3,4-dihydro-1,4, (2H) -benzoxazine, 3rd -Methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole, 2,3-indole-indione , alone or in a mixture with each other. (iii) Self-coupling compounds: 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-ethoxyphenol or 2-propylamino-5-aminopyridine. The total amount of the oxidation dye precursors contained in the colorant (c) according to the invention is about 0.01 to 12 percent by weight, in particular about 0.2 to 6 percent by weight.
Das erfindungsgemäße Färbemittel (a), (b) oder (c) kann weiterhin alle für derartige Zubereitungen bekannten und üblichen Zusatzstoffe, beispielsweise Parfümöle, Komplexbildner, Wachse, Konservierungsstoffe, Verdicker, Antioxidantien, Alginate, Guar Gum, haarpflegende Substanzen, wie zum Beispiel kationische Polymere oder Lanolinderivate, oder anionische, nichtionische, amphotere oder kationische oberflächenaktive Substanzen enthalten. Vorzugsweise werden amphotere oder nichtionische oberflächenaktive Substanzen, beispielsweise Betaintenside, Propoinate und Glycinate, wie zum Beispiel Cocoamphoglycinate oder Cocoamphdiglacinate, ethoxylierte Tenside mit 1 bis 1000 Ethylenoxid-Einheiten, vorzugsweise mit 1 bis 300 Ethylenoxid-Einheiten, wie zum Beispiel Glyceridalkoxylate, beispielsweise mit 25 Ethylenoxid-Einheiten ethoxyliertes Rizinusöl, Polyglycolamide, ethoxylierte Alkohole und ethoxylierte Fettalkohole (Fettalkoholalkoxylate) und ethoxylierte Fettsäurezuckerester, insbesondere ethoxylierte Sorbitanfettsäureester, eingesetzt. Die vorgenannten Bestandteile werden in den für solche Zwecke üblichen Mengen verwendet, zum Beispiel die oberflächenaktiven Substanzen in einer Konzentration von 0,1 bis 30 Gewichtsprozent, und die Pflegestoffe in einer Menge von 0,1 bis 5 Gewichtsprozent.The colorant (a), (b) or (c) according to the invention can furthermore all known and customary additives for such preparations, for example perfume oils, complexing agents, waxes, preservatives, thickeners, antioxidants, alginates, guar gum, hair-care substances such as cationic Contain polymers or lanolin derivatives, or anionic, nonionic, amphoteric or cationic surface-active substances. Amphoteric or nonionic surface-active substances, for example betaine surfactants, propoinates and glycinates, for example cocoamphoglycinates or cocoamphdiglacinates, are preferably ethoxylated surfactants with 1 to 1000 ethylene oxide units, preferably with 1 to 300 ethylene oxide units, for example glyceride alkoxylates, for example with 25 ethylene oxide -Units of ethoxylated castor oil, polyglycolamides, ethoxylated alcohols and ethoxylated fatty alcohols (fatty alcohol alkoxylates) and ethoxylated fatty acid sugar esters, in particular ethoxylated sorbitan fatty acid esters, are used. The abovementioned constituents are used in the amounts customary for such purposes, for example the surface-active substances in a concentration of 0.1 to 30 percent by weight, and the care substances in an amount of 0.1 to 5 percent by weight.
Das erfindungsgemäße Färbemittel (a), (b) oder (c) kann, insbesondere wenn es ein Haarfärbemittel ist, in Form eines Pulvers oder Granulates, das vor der Anwendung in einer wäßrigen oder wäßrig-alkoholischen Zubereitung gelöst wird, oder aber einer wäßrigen oder wäßrig-alkoholischen Lösung, einer Creme, eines Gels, einer Emulsion oder eines Aerosolschaumes vorliegen, wobei das Haarfärbemittel sowohl in Form eines Einkomponentenpräparates als auch in Form eines Mehrkomponentenpräparates, beispielsweise in Form eines Zweikomponentenpräparates, bei dem das jeweilige Farbstoffderivat der allgemeinen Formeln (I) und (II) getrennt von den übrigen Bestandteilen abgepackt wird und die Herstellung des gebrauchsfertigen Haarfärbemittels erst unmittelbar vor der Anwendung durch Vermischen der beiden Komponenten erfolgt, konfektioniert sein kann.The colorant (a), (b) or (c) according to the invention can, in particular if it is a hair colorant, in the form of a powder or granules, which, before use, is in an aqueous or aqueous-alcoholic preparation is dissolved, or an aqueous or aqueous-alcoholic solution, a cream, a gel, an emulsion or an aerosol foam, the hair dye both in the form of a one-component preparation and in the form of a multi-component preparation, for example in the form of a two-component preparation, in which the each dye derivative of the general formulas (I) and (II) is packaged separately from the other constituents and the ready-to-use hair dye is only prepared immediately before use by mixing the two components.
Das erfindungsgemäße Färbemittel (a), (b) oder (c) weist einen pH von etwa 2 bis 11, vorzugsweise etwa 5 bis 10, und insbesondere einem neutralen bis basischen pH-Wert von etwa 7 bis 10, auf. Zur Einstellung des erfindungsgemäßen pH-Wertes sind sowohl organische als auch anorganische Säuren oder Basen geeignet. Als geeignete Säuren sind insbesondere die folgenden Säuren zu nennen: α-Hydroxycarbonsäuren, wie zum Beispiel Glycolsäure, Milchsäure, Weinsäure, Zitronensäure oder Äpfelsäure, Ascorbinsäure, Gluconsäurelacton, Essigsäure, Salzsäure oder Phosphorsäure, sowie Mischungen dieser Säure. Als geeignete Basen sind inbesondere Natrium- carbonat, Natriumhydrogencarbonat, Alkanolamine, beispielsweise Mono- ethanolamin oder Triethanolamin, Ammoniak, Aminomethylpropanol und Natriumhydroxid sowie deren Mischungen zu nennen.The colorant (a), (b) or (c) according to the invention has a pH of about 2 to 11, preferably about 5 to 10, and in particular a neutral to basic pH of about 7 to 10. Both organic and inorganic acids or bases are suitable for adjusting the pH value according to the invention. Suitable acids include the following acids: α-hydroxycarboxylic acids, such as glycolic acid, lactic acid, tartaric acid, citric acid or malic acid, ascorbic acid, gluconic acid lactone, acetic acid, hydrochloric acid or phosphoric acid, and mixtures of these acids. Suitable bases include, in particular, sodium carbonate, sodium hydrogen carbonate, alkanolamines, for example monoethanolamine or triethanolamine, ammonia, aminomethylpropanol and sodium hydroxide and mixtures thereof.
Das erfindungsgemäße Färbemittel kann je nach Einsatzzweck mit einem oder mehreren Oxidationsmitteln (Aufhellung; Oxidationsfärbemittel) oder ohne ein Oxidationsmittel (nicht-oxidative Färbemittel) verwendet werden. Die Anwendung des erfindungsgemäßen Färbemittels (a), (b) oder (c) erfolgt in der Regel indem man eine für die Haarfärbung ausreichende Menge, je nach Haarlänge etwa 30 bis 120 Gramm, des Haarfärbemittels auf das Haar aufträgt, das Haarfärbemittel bei etwa 15 bis 45 Grad Celsius etwa 1 bis 60 Minuten, vorzugsweise 5 bis 30 Minuten, einwirken läßt, das Haar anschließend gründlich mit Wasser ausspült, gegebenenfalls mit einem Shampoo wäscht und abschließend trocknet.Depending on the intended use, the colorant according to the invention can be used with one or more oxidizing agents (brightening; oxidizing coloring agent) or without an oxidizing agent (non-oxidative coloring agent). The dye (a), (b) or (c) according to the invention is generally applied by applying an amount sufficient for hair coloring, depending on the length of the hair, of about 30 to 120 grams of the hair dye to the hair, the hair dye at about 15 up to 45 degrees Celsius for about 1 to 60 minutes, preferably 5 to 30 minutes, then rinse the hair thoroughly with water, if necessary, wash with a shampoo and finally dry.
Erforderlichenfalls wird das Mittel vor der Anwendung mit einem Oxidations- mittel vermischt.If necessary, the agent is mixed with an oxidizing agent before use.
Das vorstehend beschriebene Färbemittel kann weiterhin, sofern keine Oxidationsmittel der Färbemasse zugesetzt werden, für kosmetische Mittel übliche natürliche oder synthetische Polymere beziehungsweise modifizierte Polymere natürlichen Urprungs enthalten, wodurch gleichzeitig mit der Färbung eine Festigung der Haare erreicht wird. Solche Mittel werden im allgemeinen als Tönungsfestiger oder Farbfestiger bezeichnet. Von den für diesen Zweck in der Kosmetik bekannten synthetischen Polymeren seien beispielsweise Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol oder Polyacrylverbindungen wie Polyacrylsäure oder Polymethacrylsäure, basische Polymerisate von Estern der Polyacrylsäure, Polymethylacrylsäure und Aminoalkohole, beispielsweise deren Salze oder Quatemisierungsprodukte, Polyacrylnitril, Polyvinylacetate sowie Copolymerisate aus derartigen Verbindungen, wie zum Beispiel Polyvinylpyrrolidon-Vinylacetat, erwähnt; während als natürliche Polymere oder modifizierte natürliche Polymere beispielsweise Chitosan (entacetyliertes Chitin) oder Chitosanderivate, eingesetzt werden können. Die vorgenannten Polymere können in dem erfindungsgemäßen Färbemittel (a) in der für solche Mittel üblichen Mengen, insbesondere in einer Menge von etwa 1 bis 5 Gewichtsprozent, enthalten sein. Der pH-Wert des erfindungsgemässen Tönungsfestigers oder Farbfestigers beträgt vorzugsweise etwa 6 bis 9.Provided that no oxidizing agents are added to the coloring composition, the coloring agent described above can furthermore contain natural or synthetic polymers or modified polymers of natural origin, which are customary for cosmetic agents, as a result of which hair is set at the same time as the coloring. Such agents are generally referred to as tinting or color strengthening agents. Of the synthetic polymers known for this purpose in cosmetics are, for example, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid, basic polymers of esters of polyacrylic acid, polymethylacrylic acid and amino alcohols, for example their salts or quaternizing products, polyacrylonitrile and copolymers of such vinyl acetate such as polyvinyl pyrrolidone vinyl acetate; while chitosan (deacetylated chitin) or chitosan derivatives, for example, can be used as natural polymers or modified natural polymers. The aforementioned polymers can be present in the colorant (a) according to the invention in the amounts customary for such agents, in particular in an amount of about 1 to 5 percent by weight. The pH of the tinting or color fixing agent according to the invention is preferably about 6 to 9.
Die Anwendung des Haarfärbemittels mit zusätzlicher Festigung erfolgt in bekannter und üblicher Weise durch Befeuchten des Haares mit dem Festiger, Festlegen (Einlegen) des Haares zur Frisur und anschließende Trocknung.The hair dye with additional setting is used in a known and customary manner by moistening the hair with the setting agent, setting (inserting) the hair for the hairstyle and subsequent drying.
Die erfindungsgemäßen Färbemittel (a), (b) und (c) ermöglichen eine gleichmäßige, intensive und dauerhafte Färbung von Keratinfasern (beispielsweise menschlichen Haaren, Wolle oder Pelzen) ohne nennenswerte Anfärbung der Haut beziehungsweise Kopfhaut, wobei diese Färbung auch im Falle des Färbemittels (a) fünf und mehr Haarwäschen ohne ein merkliches Verblassen der Haarfarbe überdauert.The colorants (a), (b) and (c) according to the invention enable a uniform, intensive and permanent coloring of keratin fibers (for example human hair, wool or furs) without any noteworthy coloring of the skin or scalp, this coloring also in the case of the colorant ( a) five or more washes without a noticeable fading of the hair color persists.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne diesen hierauf zu beschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.
B e i s p i e l eExample
Beispiel 1 : Darstellung von 1 -(2-Hydroxyethyl)-3-{(Z)-[(2E)-2-(3-methyl-1 ,3- benzothiazol-2(3 - )-yliden)hydrazono]methyl}pyridinium-bromidExample 1: Preparation of 1 - (2-hydroxyethyl) -3 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 -) -ylidene) hydrazono] methyl} pyridinium bromide
Stufe 1 : Darstellung von Nicotinaldehyd((2E)-3-methyl-1 ,3-benzothiazol- 2(3 -)-yliden)hydrazon 1 ,50 g (6,42 mmol) 2,3-Dihydro-3-methyl-2-benzothiazolon-hydrazon- hydrochlorid und 0,69 g (6,42 mmol) 3-Pyridincarboxaldehyd werden bei Raumtemperatur in 10%iger Essigsäure 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, der ausgefallene Niederschlag abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet.Stage 1: Preparation of nicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3 -) - ylidene) hydrazone 1, 50 g (6.42 mmol) 2,3-dihydro-3-methyl- 2-benzothiazolone hydrazone hydrochloride and 0.69 g (6.42 mmol) 3-pyridinecarboxaldehyde are stirred at room temperature in 10% acetic acid for 30 minutes. The mixture is then made weakly alkaline with 2 N sodium hydroxide solution, the precipitate which has separated out is filtered off with suction, washed with water and dried in vacuo.
Ausbeute: 1 ,21 g (70% der Theorie), blassgelbe Nadeln 1H-NMR (CDCI3/300 MHz): δ = 3,64 (s, 3H, Methyl), 7,05-7,13 (m, 2H, Phenyl), 7,28-7,37 (m, 2H, Phenyl), 7,46 (d, J= 8,4 Hz, 1 H, Pyridyl), 8,15 (d, J= 11 ,4 Hz, 1 H, Pyridyl), 8,39 (s, 1 H, Olefin), 8,59 (d, J= 8,4 Hz, 1H, Pyridyl), 8,90 (s, 1 H, Pyridyl).Yield: 1, 21 g (70% of theory), pale yellow needles 1 H-NMR (CDCl 3/300 MHz): δ = 3.64 (s, 3H, methyl), 7.05-7.13 (m, 2H, phenyl), 7.28-7.37 (m, 2H, phenyl), 7.46 (d, J = 8.4 Hz, 1 H, pyridyl), 8.15 (d, J = 11, 4 Hz, 1 H, pyridyl), 8.39 (s, 1 H, olefin), 8.59 (d, J = 8.4 Hz, 1H, pyridyl), 8.90 (s, 1 H, pyridyl).
Stufe 2: Darstellung von 1 -(2-Hydroxyethyl)-3-{(Z)-[(2E)-2-(3-methyl-1 ,3- benzothiazol-2(3 -/)-yliden)hydrazono]methyl}pyridinium-bromid 1 ,21 g (4,51 mmol) Nicotinaldehyd((2E)-3-methyl-1 ,3-benzothiazol- 2(3H)yliden)-hydrazon aus Stufe 1 und 0,85 g (6,76 mmol) Bromethanol werden 2 Stunden lang in Acetonitril unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 1 ,20 g (68 % der Theorie), leuchtend gelbes PulverStep 2: Preparation of 1 - (2-hydroxyethyl) -3 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 - /) - ylidene) hydrazono] methyl } pyridinium bromide 1, 21 g (4.51 mmol) nicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3H) ylidene) hydrazone from stage 1 and 0.85 g (6.76 mmol) of bromoethanol are refluxed in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 1, 20 g (68% of theory), bright yellow powder
Schmelzpunkt: 181 °C Beispiel 2: Darstellung von 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3/-/)- yliden)-hydrazono]methyl}-1-(2-hydroxyethyl)pyridinium-bromidMelting point: 181 ° C Example 2: Preparation of 4 - {(E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3 / - /) - ylidene) hydrazono] methyl} -1- (2-hydroxyethyl) pyridinium bromide
Stufe 1 : Darstellung von lsonicotinaldehyd((2Z)-3,4-dimethyl-1 ,3-thiazol- 2(3H)-yliden)hydrazon Analog Beispiel 1 werden 0,20 g (1 ,12 mmol) Λ/-Methyl-5-methyl-2- thiazolhydrazon-hydrochlorid und 0,12 g (1,12 mmol) 4-Pyridincarboxaldehyd bei Raumtemperatur in 10 % Essigsäure 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, der ausgefallene Niederschlag abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet.Stage 1: Preparation of isonicotinaldehyde ((2Z) -3,4-dimethyl-1, 3-thiazole-2 (3H) -ylidene) hydrazone Analogously to Example 1, 0.20 g (1, 12 mmol) Λ / -Methyl- 5-methyl-2-thiazole hydrazone hydrochloride and 0.12 g (1.12 mmol) of 4-pyridinecarboxaldehyde were stirred at room temperature in 10% acetic acid for 30 minutes. The mixture is then made weakly alkaline with 2 N sodium hydroxide solution, the precipitate which has separated out is filtered off with suction, washed with water and dried in vacuo.
Ausbeute: 0,18g (70 % der Theorie), orange-gelbe Nadeln 1H-NMR .CDCI3/300 MHz,: δ = 2,17 (s, 3H, Methyl), 3,39 (s, 3H, Methyl), 6,16 (s, 1 H, Thiazol), 7,58 (d, J= 6,0 Hz, 2H, Pyridyl), 8,21 (s, 1 H, Olefin), 8,56 (d, J= 6,0 Hz, 2H, Pyridyl).Yield: 0.18 g (70% of theory), orange-yellow needles 1 H-NMR .CDCI 3/300 MHz ,: δ = 2.17 (s, 3H, methyl), 3.39 (s, 3H, methyl ), 6.16 (s, 1 H, thiazole), 7.58 (d, J = 6.0 Hz, 2H, pyridyl), 8.21 (s, 1 H, olefin), 8.56 (d, J = 6.0 Hz, 2H, pyridyl).
Stufe 2: Darstellung von 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)- yliden)-hydrazono]methyl}-1-(2-hydroxyethyl)pyridinium-bromidStep 2: Preparation of 4 - {(E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl} -1- (2- hydroxyethyl) pyridinium bromide
0,15 g (0,64 mmol) lsonicotinaldehyd((2Z)-3,4-dimethyl-1 ,3-thiazol-2(3H)- yliden)-hydrazon aus Stufe 1 und 0,12 g (0,96 mmol) Bromethanol werden 2 Stunden lang in Acetonitril unter Rückfluss erhitzt. Nach dem Abziehen des Lösungs-mittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 0,11 g (49 % der Theorie), rotes Pulver0.15 g (0.64 mmol) isonicotinaldehyde ((2Z) -3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazone from stage 1 and 0.12 g (0.96 mmol ) Bromoethanol is refluxed in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 0.11 g (49% of theory), red powder
Schmelzpunkt: 169 °C Beispiel 3: Darstellung von 4-[(E)-(9H-Fluoren-9-ylidenhydrazono)methyl]- 1-methyl-pyridinium-methylsulfatMelting point: 169 ° C Example 3: Preparation of 4 - [(E) - (9H-Fluoren-9-ylidenhydrazono) methyl] - 1-methyl-pyridinium-methylsulfate
Stufe 1 : Darstellung von lsonicotinaldehyd-9H-fluoren-9-ylidenhydrazon Analog Beispiel 1 werden 1 ,50 g (7,72 mmol) 9-Fluorenon-hydrazon und 0,82 g (7,72 mmol) 4-Pyridincarboxaldehyd bei Raumtemperatur in 10%iger Essigsäure 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, die ausgefallenen Kristalle werden sodann abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet. Die wäßrige Phase wird anschließend mit Essigester extrahiert, um nicht ausgefallenes Produkt zu isolieren.Stage 1: Preparation of isonicotinaldehyde-9H-fluoren-9-ylidene hydrazone Analogously to Example 1, 1.50 g (7.72 mmol) of 9-fluorenone hydrazone and 0.82 g (7.72 mmol) of 4-pyridinecarboxaldehyde are added at room temperature 10% acetic acid stirred for 30 minutes. The mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the crystals which have precipitated are then filtered off with suction, washed with water and dried in vacuo. The aqueous phase is then extracted with ethyl acetate in order to isolate the product which has not precipitated out.
Ausbeute: 1 ,95 g (89 % der Theorie), dunkelgelbes Pulver 1H-NMR (dg-DMSO/300 MHz): δ = 7,32-7,44 (m, 2H, Fluoren), 7,54-7,60 (m, 2H, Fluoren), 7,83-7,92 (m, 2H, Fluoren), 7,02-7,05 (m, 1H, Fluoren), 8,56 (d, J= 6,9 Hz, 2H, Pyridyl), 8,81 (s, 1H, Olefin), 8,12 (d, J= 6,9 Hz, 2H, Pyridyl).Yield: 1.95 g (89% of theory), dark yellow powder 1 H-NMR (dg-DMSO / 300 MHz): δ = 7.32-7.44 (m, 2H, fluorene), 7.54-7 , 60 (m, 2H, fluorene), 7.83-7.92 (m, 2H, fluorene), 7.02-7.05 (m, 1H, fluorene), 8.56 (d, J = 6, 9 Hz, 2H, pyridyl), 8.81 (s, 1H, olefin), 8.12 (d, J = 6.9 Hz, 2H, pyridyl).
Stufe 2: Darstellung von 4-[(E)-(9H-Fluoren-9-ylidenhydrazono)methyl]- 1 -methyl-pyridinium-methylsulfat 0,84 g (2,96 mmol) lsonicotinaldehyd-9H-fluoren-9-ylidenhydrazon aus Stufe 1 und 0,56 g (4,44 mmol) Dimethylsulfat werden 45 Minuten lang in Aceton unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet.Step 2: Preparation of 4 - [(E) - (9H-fluoren-9-ylidenhydrazono) methyl] - 1-methyl-pyridinium-methylsulfate 0.84 g (2.96 mmol) isonicotinaldehyde-9H-fluoren-9-ylidenhydrazone from step 1 and 0.56 g (4.44 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo.
Ausbeute: 1 ,02 g (84 % der Theorie), hellgelbes PulverYield: 1.02 g (84% of theory), light yellow powder
Schmelzpunkt: 224 °C Beispiel 4: Darstellung von 1-(2-Hydroxyethyl)-4-{(Z)-[(2E)-2-(3-methyl-1 ,3- benzothiazol-2(3 -)-yliden)hydrazono]methyl}pyridinium-bromidMelting point: 224 ° C Example 4: Preparation of 1- (2-hydroxyethyl) -4 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 -) - ylidene) hydrazono] methyl} pyridinium bromide
Stufe 1 : Darstellung von lsonicotinaldehyd((2E)-3-methyl-1 ,3- benzothiazol-2(3H)-yliden)hydrazon Analog Beispiel 1 werden 2,00 g (8,56 mmol) 2,3-Dihydro-3-methyl-2- benzothiazolon-hydrazon-hydrochlorid und 0,92 g (8,56 mmol) 4-Pyridin- carboxaldehyd bei Raumtemperatur in 10% Essigsäure 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, die ausgefallenen Kristalle abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet.Stage 1: Preparation of isonicotinaldehyde ((2E) -3-methyl-1,3-benzothiazol-2 (3H) -ylidene) hydrazone Analogously to Example 1, 2.00 g (8.56 mmol) of 2,3-dihydro-3 -methyl-2-benzothiazolone-hydrazone hydrochloride and 0.92 g (8.56 mmol) of 4-pyridine-carboxaldehyde at room temperature in 10% acetic acid for 30 minutes. The mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the crystals which have precipitated are filtered off with suction, washed with water and dried in vacuo.
Ausbeute: 2,05 g (89 % der Theorie), blassgelbe Nadeln 1H-NMR (CDCI3/300 MHz): δ = 3,66 (s, 3H, Methyl), 7,07-7,15 (m, 2H, Phenyl), 7,30-7,36 (m, 1H, Phenyl), 7,46-7,49 (m, 1H, Phenyl), 7,63 (d, J= 2,1 Hz, 2H, Pyridyl), 8,31 (s, 1H, Olefin), 8,66 (d, J= 2,1 Hz, 2H, Pyridyl).Yield: 2.05 g (89% of theory), pale yellow needles 1 H-NMR (CDCI3 / 300 MHz): δ = 3.66 (s, 3H, methyl), 7.07-7.15 (m, 2H , Phenyl), 7.30-7.36 (m, 1H, phenyl), 7.46-7.49 (m, 1H, phenyl), 7.63 (d, J = 2.1 Hz, 2H, pyridyl ), 8.31 (s, 1H, olefin), 8.66 (d, J = 2.1 Hz, 2H, pyridyl).
Stufe 2: Darstellung von 1 -(2-Hydroxyethyl)-4-{(Z)-[(2E)-2-(3-methyl-1 ,3- benzothiazol-2(3H)-yliden)hydrazono]methyl}pyridinium-bromid 1 ,00 g (3,73 mmol) lsonicotinaldehyd((2E)-3-methyl-1 ,3-benzothiazol-2(3H)- yliden)hydrazon aus Stufe 1 und 0,70 g (5,59 mmol) Bromethanol werden 2 Stunden in Acetonitril unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 0,39 g (27% der Theorie), hellrotes PulverStep 2: Preparation of 1 - (2-hydroxyethyl) -4 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono] methyl} pyridinium -bromide 1.00 g (3.73 mmol) isonicotinaldehyde ((2E) -3-methyl-1, 3-benzothiazol-2 (3H) - ylidene) hydrazone from stage 1 and 0.70 g (5.59 mmol) Bromoethanol is boiled under reflux in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 0.39 g (27% of theory), light red powder
Schmelzpunkt: 175 °C Beispiel 5: Darstellung von 3-(2-Hydroxyethyl)-1-methyl-2-{(Z)-[(2E)-2-(3- methyl-1 ,3-benzothiazol-2(3 -/)-yliden)hydrazono]methyl}-1 H- imidazol-3-ium-bromidMelting point: 175 ° C Example 5: Preparation of 3- (2-hydroxyethyl) -1-methyl-2 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 - /) - ylidene ) hydrazono] methyl} -1 H-imidazol-3-ium bromide
Stufe 1 : Darstellung von 1 -Methyl-1 H-imidazol-2-carbaldehyd((2E)-3- methyl-1,3-benzothiazol-2(3H)-yliden)hydrazon Analog Beispiel 1 werden 1 ,27 g (5,45 mmol) 2,3-Dihydro-3-methyl-2- benzothiazolon-hydrazon-hydrochlorid und 0,60 g (5,45 mmol) 1-Methyl-2- imidazol-carboxaldehyd bei Raumtemperatur in 40 ml einer Mischung aus HCI und Ethanol (1 :2) 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, das ausgefallene Produkt abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet. Ausbeute: 1 ,19 g (81 % der Theorie), farblose Nadeln 1H-NMR (CPCIa/300 MHz): δ = 3,62 (s, 3H, Methyl), 4,01 , (s, 3H, Methyl), 6,98-7,12 (m, 3H, Phenyl), 7,28 (m, 1 H, Phenyl), 7,33 (d, J= 8,7 Hz, 1 H, Imidazolyl), 7,42 (d, J= 8,4 Hz, 1 H, Imidazolyl), 8,46 (s, 1 H, Olefin).Stage 1: Preparation of 1-methyl-1 H-imidazole-2-carbaldehyde ((2E) -3-methyl-1,3-benzothiazol-2 (3H) -ylidene) hydrazone Analogously to Example 1, 1.27 g (5th , 45 mmol) 2,3-dihydro-3-methyl-2-benzothiazolone hydrazone hydrochloride and 0.60 g (5.45 mmol) 1-methyl-2-imidazole-carboxaldehyde at room temperature in 40 ml of a mixture of HCl and ethanol (1: 2) stirred for 30 minutes. The mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the precipitated product is filtered off with suction, washed with water and dried in vacuo. Yield: 1.19 g (81% of theory), colorless needles 1 H-NMR (CPCIa / 300 MHz): δ = 3.62 (s, 3H, methyl), 4.01, (s, 3H, methyl) , 6.98-7.12 (m, 3H, phenyl), 7.28 (m, 1H, phenyl), 7.33 (d, J = 8.7 Hz, 1H, imidazolyl), 7.42 (d, J = 8.4 Hz, 1H, imidazolyl), 8.46 (s, 1H, olefin).
Stufe 2: Darstellung von 3-(2-Hydroxyethyl)-1 -methyl-2-{(Z)-[(2E)-2-(3- methyl-1 ,3-benzothiazol-2(3H)-yliden)hydrazono]methyl}-1 H- imidazol-3-ium-bromid 1 ,00 g (3,68 mmol) 1 -Methyl-1 H-imidazol-2-carbaldehyd((2E)-3-methyl-1 , 3- benzothiazol-2(3H)-yliden)hydrazon aus Stufe 1 und 0,69 g (5,52 mmol) Bromethanol werden 2 Stunden in Acetonitril unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 1 ,03 g (71 % der Theorie), grüngelbes PulverStep 2: Preparation of 3- (2-hydroxyethyl) -1-methyl-2 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) hydrazono ] methyl} -1 H-imidazol-3-ium bromide 1.00 g (3.68 mmol) 1-methyl-1 H-imidazole-2-carbaldehyde ((2E) -3-methyl-1, 3-benzothiazole -2 (3H) -ylidene) hydrazone from stage 1 and 0.69 g (5.52 mmol) of bromoethanol are boiled under reflux in acetonitrile for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 1.03 g (71% of theory), green-yellow powder
Schmelzpunkt: 242 °CMelting point: 242 ° C
Beispiel 6: Darstellung von 4-[(E)-({Bis[4-(dimethylamino)phenyl]methylen}- hydrazono)methyl]-1-methylpyridinium-methylsulfatExample 6: Preparation of 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate
Stufe 1 : Darstellung von lsonicotinaldehyd{bis[4-(dimethylamino)phenyl]- methylen}hydrazon In 40 ml 10%iger Essigsäure werden 1,66 g (5,66 mmol) Bis[4-(dimethyl- amino)phenyl]-methanon-hydrazon und 0,63 g (5,88 mmol) 4-Pyridin- carboxaldehyd bei Raumtemperatur 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, das ausgefallene Produkt abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet. Die wäßrige Phase wird anschließend mit Essigester extrahiert, um nicht ausgefallenes Produkt zu isolieren. Ausbeute: 1 ,98 g (91 % der Theorie), orange Nadeln 1H-NMR (CDCIa/300 MHz): δ = 3,05 (s, 12H, 4 Methylgruppen), 6,73 (d, J= 8,7 Hz, 4H, Phenyl), 7,32 (d, J= 8,7 Hz, 2H, Phenyl), 7,58 (d, J= 5,7 Hz, 2H, Pyridyl), 7,65 (d, J= 9,0 Hz, 2H, Phenyl), 8,63 (d, J= 5,4 Hz, 2H, Pyridyl).Stage 1: Preparation of isonicotinaldehyde {bis [4- (dimethylamino) phenyl] - methylene} hydrazone In 40 ml of 10% acetic acid, 1.66 g (5.66 mmol) of bis [4- (dimethylamino) phenyl] - methanone hydrazone and 0.63 g (5.88 mmol) of 4-pyridinecarboxaldehyde at room temperature for 30 minutes. The mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the precipitated product is filtered off with suction, washed with water and dried in vacuo. The aqueous phase is then extracted with ethyl acetate in order to isolate the product which has not precipitated out. Yield: 1.98 g (91% of theory), orange needles 1 H-NMR (CDCIa / 300 MHz): δ = 3.05 (s, 12H, 4 methyl groups), 6.73 (d, J = 8, 7 Hz, 4H, phenyl), 7.32 (d, J = 8.7 Hz, 2H, phenyl), 7.58 (d, J = 5.7 Hz, 2H, pyridyl), 7.65 (d, J = 9.0 Hz, 2H, phenyl), 8.63 (d, J = 5.4 Hz, 2H, pyridyl).
Stufe 2: Darstellung von 4-[(E)-({bis[4-(dimethylamino)phenyl]methylen}- hydrazono)methyl]-1-methylpyridinium-methylsulfat 0,54 g (1,46 mmol) lsonicotinaldehyd{bis[4-(dimethylamino)phenyl]- methylen}-hydrazon der Stufe 1 und 0,92 g (7,30 mmol) Dimethylsulfat werden 45 Minuten lang in Aceton unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 0,64 g (88 % der Theorie), dunkelrotes PulverStep 2: Preparation of 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate 0.54 g (1.46 mmol) isonicotinaldehyde {bis [ Stage 1 4- (dimethylamino) phenyl] methylene} hydrazone and 0.92 g (7.30 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After this Removal of the solvent, the precipitate is filtered off, washed with ethyl acetate and dried in vacuo. Yield: 0.64 g (88% of theory), dark red powder
Schmelzpunkt: 202 °CMelting point: 202 ° C
Beispiel 7: Darstellung von 3-[(E)-({Bis[4-(dimethylamino)phenyl]methylen}- hydrazono)methyl]-1-methylpyridinium-methylsulfatExample 7: Preparation of 3 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate
Stufe 1 : Darstellung von Nicotinaldehyd{bis[4-(dimethylamino)phenyl]- methylenj-hydrazon Analog Beispiel 6 werden 1 ,66 g (5,66 mmol) Bis[4-(dimethylamino)phenyl]- methanon-hydrazon und 0,63 g (5,88 mmol) 3-Pyridincarboxaldehyd bei Raumtemperatur 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, das ausgefallene Produkt abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet. Die wäßrige Phase wird anschließend mit Essigester extrahiert, um nicht ausgefallenes Produkt zu isolieren.Stage 1: Preparation of nicotinaldehyde {bis [4- (dimethylamino) phenyl] methylenej-hydrazone Analogously to Example 6, 1.66 g (5.66 mmol) of bis [4- (dimethylamino) phenyl] methanone hydrazone and 0, 63 g (5.88 mmol) of 3-pyridinecarboxaldehyde stirred at room temperature for 30 minutes. The mixture is then made slightly alkaline with 2 N sodium hydroxide solution, the precipitated product is filtered off with suction, washed with water and dried in vacuo. The aqueous phase is then extracted with ethyl acetate in order to isolate the product which has not precipitated out.
Ausbeute: 2,04 g (94 % der Theorie), orange-gelbe Nadeln 1H-NMR (CDCI3/300 MHz): δ = 2,98 (s, 12H, 4 Methylgruppen), 6,96 (d, J= 8,6 Hz, 4H, Phenyl), 7,30 (d, J= 8,7 Hz, 2H, Phenyl), 7,46-7,52 (m, 1H, Pyridyl), 7,62 (d, J= 8,7 Hz, 2H, Phenyl), 8,12-8,41 (m, 2H, Pyridyl), 8,66 (s, 1 H, Pyridyl). Stufe 2: Darstellung von 3-[(E)-({Bis[4-(dimethylamino)phenyl]methylen}- hydrazono)methyl]-1-methylpyridinium-methylsulfat 0,76 g (2,05 mmol) Nicotinaldehyd{bis[4-(dimethylamino)phenyl]-methylen}- hydrazon aus Stufe 1 und 1,29 g (10,25 mmol) Dimethylsulfat werden 45 Minuten lang in Aceton unter Rückfluss gekocht. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet. Ausbeute: 0,81 g (79 % der Theorie), rotes PulverYield: 2.04 g (94% of theory), orange-yellow needles 1 H-NMR (CDCl 3/300 MHz): δ = 2.98 (s, 12H, 4 methyl groups), 6.96 (d, J = 8.6 Hz, 4H, phenyl), 7.30 (d, J = 8.7 Hz, 2H, phenyl), 7.46-7.52 (m, 1H, pyridyl), 7.62 (d, J = 8.7 Hz, 2H, phenyl), 8.12-8.41 (m, 2H, pyridyl), 8.66 (s, 1H, pyridyl). Step 2: Preparation of 3 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium methyl sulfate 0.76 g (2.05 mmol) nicotinaldehyde {bis [ 4- (dimethylamino) phenyl] -methylene} hydrazone from stage 1 and 1.29 g (10.25 mmol) of dimethyl sulfate are refluxed in acetone for 45 minutes. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo. Yield: 0.81 g (79% of theory), red powder
Schmelzpunkt: 193 °CMelting point: 193 ° C
Beispiel 8: Darstellung von 2-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)- yliden)hydrazono]methyl}-3-(methyl)-1 -methyl-1 H-imidazol-3- ium-methylsulfatExample 8: Preparation of 2 - {(E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl} -3- (methyl) - 1-methyl-1 H-imidazole-3 ium methyl sulfate
Stufe 1: (2Z)-3,4-Dimethyl-2-{(2E)-[(1 -methyl-1 H-imidazol-2- yl)methylidene]hydrazono}-2,3-dihydro-1,3-thiazol Analog Beispiel 1 werden 3,00 g (11 ,13 mmol) Λ/-Methyl-5-methyl-2- thiazolhydrazon-hydrochlorid und 1,38 g (12,24 mmol) 1-Methyl-2- imidazolcarboxaldehyd bei Raumtemperatur in 10 %iger Essigsäure 30 Minuten lang gerührt. Anschließend wird der Ansatz mit 2 N Natronlauge schwach alkalisch eingestellt, der ausgefallene Niederschlag abgesaugt, mit Wasser gewaschen und im Vakuum getrocknet. Ausbeute: 1 ,50g (58 % der Theorie), braunes Pulver 1H-NMR .CDC /300 MHz): δ = 2,17 (s, 3H, Methyl), 3,45 (s, 3H, Methyl), 4,01 (s, 3H, Methyl), 5,77 (s, 1H, Thiazol), 6,95 (m, 1H, Imidazol), 7,14 (m, 1H, Imidazol), 8,43 (s, 1H, Olefin). Stufe 2: Darstellung von 2-{(E)-[(2Z)-2-(3,4-Dimethyl-1 ,3-thiazol-2(3H)- yliden)hydrazono]methyl}-3-(methyl)-1 -methyl-1 /- -imidazol-3- ium-methylsulfat 1 ,40 g (5,95 mmol) (2Z)-3,4-Dimethyl-2-{(2E)-[(1 -methyl-1 H-imidazol-2- yl)methylidene]hydrazono}-2,3-dihydro-1 ,3-thiazol aus Stufe 1 und 7,58 g (59,50 mmol) Dimtehylsulfat werden 2 Stunden lang in Aceton unter Rückfluss erhitzt. Nach dem Abziehen des Lösungsmittels wird der ausgefallene Niederschlag abgesaugt, mit Essigester gewaschen und im Vakuum getrocknet.Step 1: (2Z) -3,4-dimethyl-2 - {(2E) - [(1-methyl-1 H-imidazol-2-yl) methylidenes] hydrazono} -2,3-dihydro-1,3- thiazole Analogously to Example 1, 3.00 g (11.13 mmol) of Λ / -methyl-5-methyl-2-thiazole hydrazone hydrochloride and 1.38 g (12.24 mmol) of 1-methyl-2-imidazole carboxaldehyde at room temperature 10% acetic acid stirred for 30 minutes. The mixture is then made weakly alkaline with 2 N sodium hydroxide solution, the precipitate which has separated out is filtered off with suction, washed with water and dried in vacuo. Yield: 1.50 g (58% of theory), brown powder 1 H-NMR .CDC / 300 MHz): δ = 2.17 (s, 3H, methyl), 3.45 (s, 3H, methyl), 4 , 01 (s, 3H, methyl), 5.77 (s, 1H, thiazole), 6.95 (m, 1H, imidazole), 7.14 (m, 1H, imidazole), 8.43 (s, 1H) , Olefin). Step 2: Preparation of 2 - {(E) - [(2Z) -2- (3,4-dimethyl-1, 3-thiazol-2 (3H) - ylidene) hydrazono] methyl} -3- (methyl) - 1 -methyl-1 / - -imidazole-3-ium-methyl sulfate 1.40 g (5.95 mmol) (2Z) -3,4-dimethyl-2 - {(2E) - [(1 -methyl-1 H -imidazol-2-yl) methylidenes] hydrazono} -2,3-dihydro-1,3-thiazole from stage 1 and 7.58 g (59.50 mmol) of dimethyl sulfate are heated under reflux in acetone for 2 hours. After the solvent has been stripped off, the precipitate which has separated out is filtered off with suction, washed with ethyl acetate and dried in vacuo.
Ausbeute: 2,04 g (95 % der Theorie), gelbgrünes PulverYield: 2.04 g (95% of theory), yellow-green powder
Schmelzpunkt: 186 °CMelting point: 186 ° C
Beispiele 9 - 17: Färbemittel (ohne Oxidationsmittel)Examples 9-17: Colorants (without oxidizing agents)
2,5 mmol Farbstoff der allgemeinen Formel (I) und (II) 5,0 g Ethanol 4,0 g Decylpolyglucose 0,2 g Ethylendiaminotetraessigsäure-Dinatriumsalz-Hydrat ad 100,0 g Wasser, vollentsalzt2.5 mmol of dye of the general formula (I) and (II) 5.0 g of ethanol 4.0 g of decyl polyglucose 0.2 g of ethylenediaminotetraacetic acid disodium salt hydrate ad 100.0 g of water, fully desalinated
Die Färbelösung wird durch Zugabe von Ammoniak auf einen pH-Wert von 7 bis 10 eingestellt.The coloring solution is adjusted to a pH of 7 to 10 by adding ammonia.
Die Haarfärbung erfolgt, indem man eine für die Haarfärbung ausreichende Menge des Färbemittels auf das Haar (Beispiele 9-16: gebleichtes Naturhaar, Beispiel 17: hellbraunes Naturhaar) aufträgt, nach einer Einwirkzeit von 30 Minuten bei 40 °C das Haar mit lauwarmen Wasser spült und sodann trocknet. Die Färbeergebnisse sind in der nachfolgenden Tabelle 1 zusammengefasst.Hair coloring is carried out by applying a sufficient amount of the colorant to the hair (Examples 9-16: bleached natural hair, Example 17: light brown natural hair) after an exposure time of 30 Minutes at 40 ° C, rinse the hair with lukewarm water and then dry. The dyeing results are summarized in Table 1 below.
Tabelle 1:Table 1:
Beispiel 18 + 19: Färbemittel zum gleichzeitigen Aufhellen und Färben (mit Oxidationsmittel)Examples 18 + 19: Colorants for simultaneous lightening and coloring (with oxidizing agent)
Aufhellende Pulverbasis P: 20,0 g Kaliumpersulfat 30,0 g Ammoniumpersulfat 24,0 g Natriumsilicat 12,5 g Magnesiumoxid 5,0 g Hydroxyethylcellulose 6,0 g Seifenperlen 2,0 g Disperse Kieselsäure 0,5 g Dinatrium-EDTA gebrauchsfertiges Färbemittel 0,1 g Farbstoff der allgemeinen Formeln (I) und (II) 5,0 g aufhellende Pulverbasis P 10,0 g Wasserstoffperoxid (12% in Wasser)Brightening powder base P: 20.0 g potassium persulfate 30.0 g ammonium persulfate 24.0 g sodium silicate 12.5 g magnesium oxide 5.0 g hydroxyethyl cellulose 6.0 g soap pearls 2.0 g disperse silica 0.5 g disodium EDTA ready-to-use coloring agent 0.1 g dye of the general formulas (I) and (II) 5.0 g lightening powder base P 10.0 g hydrogen peroxide (12% in water)
Die angegebenen Komponenten werden zu einer homogenen Masse vermischt, so dass keine Farbstoffpatikel mehr zu erkennen sind. Dann wird eine für die Haarfärbung ausreichende Menge des vorgenannten Färbemittels auf das Haar aufgetragen. Nach einer Einwirkzeit von 45 Minuten bei 40 °C wird das Haar mit lauwarmen Wasser ausgespült und mit einem sauren Konditioner behandelt, erneut ausgespült und getrocknet.The specified components are mixed to a homogeneous mass, so that no dye particles can be recognized. Then a sufficient amount of the aforementioned coloring agent for hair coloring is applied to the hair. After an exposure time of 45 minutes at 40 ° C, the hair is rinsed with lukewarm water and treated with an acid conditioner, rinsed out again and dried.
Die Färbeergebnisse sind in der nachfolgenden Tabelle 2 zusammengefasst.The dyeing results are summarized in Table 2 below.
Tabelle 2:Table 2:
Beispiel 20 ■ 25: Oxidationshaarfärbemittel Example 20 ■ 25: Oxidation hair dye
Es wird die folgende cremeförmige Farbträgermasse hergestellt:The following cream-like ink is produced:
23,0 g Cetylalkohol 10,0 g Laurylalkohol-diglycolethersulfat-Natriumsalz (28%ige wäßrige Lösung) 0,3 g Ascorbinsäure 0,4 g Natriumsulfit 0,4 g Isopropylalkohol x g Farbstoff der Formel (l)/(ll) gemäß Tabelle 3 Y g Entwicklersubstanz(en) gemäß Tabelle 3 z g Kupplersubstanzen gemäß Tabelle 3 ad 100,0 g Wasser, vollentsalzt23.0 g cetyl alcohol 10.0 g lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous solution) 0.3 g ascorbic acid 0.4 g sodium sulfite 0.4 g isopropyl alcohol xg dye of the formula (I) / (II) according to Table 3 Y g developer substance (s) according to Table 3 zg coupler substances according to Table 3 ad 100.0 g water, fully desalinated
Es werden die folgenden Farbstoffe der allgemeinen Formel (I) und (II) sowie Entwicklersubstanzen und Kupplersubstanzen eingesetzt (siehe Tabelle 3)The following dyes of the general formulas (I) and (II) and developer substances and coupler substances are used (see Table 3)
Vor der Anwendung werden 20 g der obengenannten Farbträgermasse mit 20 g einer 6%igen Wasserstoffperoxid-Emulsion vermischt. Das so erhaltene gebrauchsfertige Oxidationshaarfärbemittel wird auf das Haar aufgetragen und nach einer Einwirkzeit von 30 Minuten bei 40 °C mit Wasser ausgespült, sodann mit einem sauren Konditioner behandelt und getrocknet.Before use, 20 g of the above-mentioned coloring material are mixed with 20 g of a 6% hydrogen peroxide emulsion. The ready-to-use oxidation hair dye thus obtained is applied to the hair and rinsed with water after a contact time of 30 minutes at 40 ° C., then treated with an acidic conditioner and dried.
Die eingesetzten Farbstoffe sowie das Ergebnis der Färbebehandlung ist in der nachfolgenden Tabelle 3 zusammengefaßt. Tabelle 3:The dyes used and the result of the dyeing treatment are summarized in Table 3 below. Table 3:
Alle Prozentangaben stellen -soweit nicht anders angegeben- Gewichtsprozent dar. Unless stated otherwise, all percentages represent percentages by weight.

Claims

Patentansprüche claims
1. Kationische Heteroarylazinfarbstoffe der allgemeinen Formel (I) und (II),1. cationic heteroarylazine dyes of the general formula (I) and (II),
(l) (H) (l) (h)
worinwherein
R1 eine Gruppe der Formel (III), (IV), (V) oder (VI) darstellt;R1 represents a group of formula (III), (IV), (V) or (VI);
(III) (IV) (V) (VI) (III) (IV) (V) (VI)
E ein Sauerstoffatom oder ein Schwefelatom darstellt; R2, R4 und R5 gleich oder verschieden sind und für Wasserstoff, eine tert- Butylgruppe, eine /so-Propylgruppe, eine C-i-Cδ-Alkylgruppe, eine Ci-Cβ- Hydroxyalkylgruppe oder einen Rest der allgemeinen Formel (VII) stehen;E represents an oxygen atom or a sulfur atom; R2, R4 and R5 are the same or different and represent hydrogen, a tert-butyl group, a / so-propyl group, a C-i-Cδ-alkyl group, a Ci-Cβ-hydroxyalkyl group or a radical of the general formula (VII);
(VII) R3 eine Gruppe der Formel (VIII), (IX) oder (X) darstellt; (VII) R3 represents a group of formula (VIII), (IX) or (X);
(VIII) (IX) (X) (VIII) (IX) (X)
R6 für Wasserstoff, eine geradkettige oder verzweigte Cι-C6-Alkylgruppe oder eine geradkettige. oder verzweigte C2-C4-Hydroxyalkylgruppe steht; R7 eine verzweigte oder lineare C C6-Alkylgruppe, eine C2-C4-Hydroxyalkyl- gruppe oder eine C4-C6-Polyhydroxyalkylgruppe darstellt; R8 und R9 gleich oder verschieden sein können und Wasserstoff, eine d-Cβ-Alkylaminogruppe, eine Cι-C6-A/.A-Dialkylaminogruppe, eine CrC6-Λ/,/\/-Dihydroxyalkylaminogruppe, eine Cι-C6-V-hydroxyalkyl-Λ/- alkylaminogruppe, eine Cι-C6-Alkylcyanogruppe, eine Methoxymethylgruppe, eine terf-Butylgruppe, eine /'so-Propylgruppe, eine Cι-C6-Alkylgruppe, eine C-ι-C6-Alkyloxygruppe oder eine Cι-C6-Hydroxyalkylgruppe darstellen; R10 für Wasserstoff, eine geradkettige oder verzweigte Ci-Cβ-Alkylgruppe oder eine geradkettige oder verzweigte C2-C4-Hydroxyalkylgruppe steht; R11 und R12 gleich oder verschieden sein können und Wasserstoff, eine Cι-C6-Alkylaminogruppe, eine C Cβ-N, /V-Dialkylaminogruppe, eine Cι-C6-V,Λ/-Dihydroxyalkylaminogruppe, eine Cι-C6-Λ/-hydroxyalkyl-/V- alkylaminogruppe, eine Ci-Cβ-Alkylcyanogruppe, eine Methoxymethylgruppe, eine terf-Butylgruppe, eine /so-PropylgrUppe, eine C-i-Cβ-Alkylgruppe, eine Cι-C6-Alkyloxygruppe oder eine Cι-C6-Hydroxyalkylgruppe darstellen; und X~ ein Anion darstellt. R6 for hydrogen, a straight-chain or branched C 1 -C 6 -alkyl group or a straight-chain. or branched C 2 -C 4 hydroxyalkyl group; R7 represents a branched or linear CC 6 alkyl group, a C 2 -C 4 hydroxyalkyl group or a C 4 -C 6 polyhydroxyalkyl group; R8 and R9 may be the same or different and are hydrogen, a d-Cβ-alkylamino group, a -CC 6 -A / . A-dialkylamino group, a CrC 6 -Λ /, / \ / - dihydroxyalkylamino group, a Cι-C 6 -V-hydroxyalkyl-Λ / - alkylamino group, a Cι-C 6 alkylcyano group, a methoxymethyl group, a terf-butyl group, a / ' so-propyl group, a -C 6 alkyl group, a C 1 -C 6 alkyloxy group or a -C 6 -hydroxyalkyl group; R10 represents hydrogen, a straight-chain or branched Ci-Cβ-alkyl group or a straight-chain or branched C 2 -C 4 -hydroxyalkyl group; R11 and R12 can be the same or different and are hydrogen, a C 6 -C 6 -alkylamino group, a C Cβ-N, / V-dialkylamino group, a Cι-C6-V, Λ / -dihydroxyalkylamino group, a Cι-C 6 -Λ / -hydroxyalkyl- / V- alkylamino group, a Ci-Cβ-alkylcyano group, a methoxymethyl group, a terf-butyl group, a / so-propyl group, a Ci-Cβ-alkyl group, a Cι-C 6 alkyloxy group or a Cι-C 6 - Represent hydroxyalkyl group; and X ~ represents an anion.
2. Kationische Heteroarylazinfarbstoffe gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Anion ein Sulfatanion, ein Phosphatanion, ein Hydrogenphosphatanion, ein Oxalatanion, ein Formiatanion, ein Acetatanion, ein Zitratanion, ein Tartratanion, ein Malonatanion, ein Pyruvatanion, ein lodidanion, ein Chloridanion, ein Bromidanion oder ein Methylsulfatanion ist.2. Cationic heteroarylazine dyes according to claim 1, characterized in that the anion is a sulfate anion, a phosphate anion, a hydrogen phosphate anion, an oxalate anion, a formate anion, an acetate anion, a citrate anion, a tartrate anion, a malonate anion, a pyruvate anion, a chloridide anion is a bromide anion or a methyl sulfate anion.
3. Kationische Heteroarylazinfarbstoffe gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie ausgewählt sind aus 1-(2-Hydroxyethyl)-3- {(Z)-[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3H)-yliden)hydrazono]methyl}- pyridinium-bromid, 4-{(E)-[(2Z)-2-(3,4-Dimethyl-1,3-thiazol-2(3H)-yliden)- hyd razono] methyl}- 1 -(2-hyd roxyethyl)pyrid in iu m-bromid , 2-{(E)-[(2Z)-2-(3 ,4- Dimethyl-1 ,3-thiazol-2(3H)-yliden)hydrazono]methyl}-3-(methyl)-1 -methyl-1 H- imidazol-3-ium-methylsulfat, 3-(2-Hydroxyethyl)-1-methyl-2-{(Z)-[(2E)-2-(3- methyl-1 ,3-benzothiazol-2(3/-/)-yliden)hydrazono]-methyl}-1H-imidazol-3-ium- bromid, 1 -(2-Hydroxyethyl)-4-{(Z)-[(2E)-2-(3-methyl-1 ,3-benzothiazol-2(3H)- yliden)-hydrazono]methyl}pyridinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)- phenyl]methylen}hydrazono)methyl]-1-(2-hydroxyethyl)pyridinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]-methylen}-hydrazono)methyl]-1-(2- hydroxyethyl)quinolinium-bromid, 4-[(E)-({Bis[4-(dimethylamino)phenyl]- methylen}hydrazono)methyl]-1-methylpyridinium-methylsulfat, 4-[(E)-({Bis[4- (diethylamino)phenyl]methylen}-hydrazono)methyl]-1-methylpyridinium- methylsulfat, 4-[(E)-(9H-Fluoren-9-ylidenhydrazono)methyl]-1-methyl- pyridinium-methylsulfat, 3-[(E)-({Bis[4-(dimethylamino)phenyl]-methylen}- hydrazono)-methyl]-1-methylpyridinium-methylsulfat, 4-{(E)-[(2Z)-2-(3,4- Dimethyl-1 ,3-thiazol-2(3 -/)-yliden)hydrazono]methyl}-1-methylpyridinium- methylsulfat und 4-[(E)-({Bis[4- (dimethylamino)phenyl]methyliden}hydrazono)methyl]-1-methylquinolinium- methylsulfat.3. Cationic heteroarylazine dyes according to claim 1 or 2, characterized in that they are selected from 1- (2-hydroxyethyl) -3- {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazole -2 (3H) -ylidene) hydrazono] methyl} - pyridinium bromide, 4 - {(E) - [(2Z) -2- (3,4-dimethyl-1,3-thiazole-2 (3H) -ylidene ) - hyd razono] methyl} - 1 - (2-hyd roxyethyl) pyride in iu m-bromide, 2 - {(E) - [(2Z) -2- (3, 4-dimethyl-1, 3-thiazole- 2 (3H) -ylidene) hydrazono] methyl} -3- (methyl) -1-methyl-1 H -imidazol-3-ium-methyl sulfate, 3- (2-hydroxyethyl) -1-methyl-2 - {(Z ) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3 / - /) - ylidene) hydrazono] -methyl} -1H-imidazol-3-iumbromide, 1 - (2nd -Hydroxyethyl) -4 - {(Z) - [(2E) -2- (3-methyl-1, 3-benzothiazol-2 (3H) - ylidene) hydrazono] methyl} pyridinium bromide, 4 - [(E ) - ({bis [4- (dimethylamino) - phenyl] methylene} hydrazono) methyl] -1- (2-hydroxyethyl) pyridinium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] -methylene} -hydrazono) methyl] -1- (2-hydroxyethyl) quinolinium bromide, 4 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} hydrazono) me thyl] -1-methylpyridinium methyl sulfate, 4 - [(E) - ({bis [4- (diethylamino) phenyl] methylene} hydrazono) methyl] -1-methylpyridinium methyl sulfate, 4 - [(E) - (9H -Fluoren-9-ylidenhydrazono) methyl] -1-methylpyridinium methyl sulfate, 3 - [(E) - ({bis [4- (dimethylamino) phenyl] methylene} - hydrazono) methyl] -1-methylpyridinium- methyl sulfate, 4 - {(E) - [(2Z) -2- (3,4-dimethyl-1,3-thiazol-2 (3 - /) - ylidene) hydrazono] methyl} -1-methylpyridinium methyl sulfate and 4 - [(e) - ({bis [4- (dimethylamino) phenyl] methylidene} hydrazono) methyl] -1-methylquinolinium methyl sulfate.
4. Mittel zum nicht-oxidativen Färben von Keratinfasern, dadurch gekennzeichnet, dass es einen kationischen Heteroarylazinfarbstoff gemäß einem der Ansprüche 1 bis 3 enthält.4. Agent for the non-oxidative dyeing of keratin fibers, characterized in that it contains a cationic heteroarylazine dye according to any one of claims 1 to 3.
5. Mittel nach Anspruch 4, dadurch gekennzeichnet, dass es mindestens ein für kosmetische Mittel übliches natürliches Polymer, synthetisches Polymer oder modifiziertes Polymer natürlichen Ursprungs enthält und in Form eines Tönungsfestigers oder Farbfestigers vorliegt.5. Composition according to claim 4, characterized in that it contains at least one natural polymer, synthetic polymer or modified polymer of natural origin customary for cosmetic compositions and is in the form of a tinting or color strengthening agent.
6. Mittel zum gleichzeitigen Aufhellen und Färben von Keratinfasern, dadurch gekennzeichnet, dass es (a) ein Oxidationsmittel sowie6. Means for simultaneous lightening and dyeing of keratin fibers, characterized in that it is (a) an oxidizing agent as well
(b) mindestens einen kationischen Heteroarylazinfarbstoff gemäß einem der Ansprüche 1 bis 3 enthält.(b) contains at least one cationic heteroarylazine dye according to any one of claims 1 to 3.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, dass das Oxidationsmittel ausgewählt ist aus Wasserstoffperoxid, Persulfaten, Perboraten und Mischungen dieser Verbindungen.7. Composition according to claim 6, characterized in that the oxidizing agent is selected from hydrogen peroxide, persulfates, perborates and mixtures of these compounds.
8. Mittel zum oxidativen Färben von Keratinfasern auf der Basis von Oxidationsfarbstoffvorstufen, dadurch gekennzeichnet, dass es mindestens einen kationischen Heteroarylazinfarbstoff gemäß einem der Ansprüche 1 bis 3 enthält. 8. Agent for the oxidative dyeing of keratin fibers based on oxidation dye precursors, characterized in that it contains at least one cationic heteroarylazine dye according to one of claims 1 to 3.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, dass es 0,01 bis 12 Gewichtsprozent mindestens einer Oxidationsfarbstoffvorstufe enthält.9. Composition according to claim 8, characterized in that it contains 0.01 to 12 percent by weight of at least one oxidation dye precursor.
10. Mittel nach einem der Ansprüche 4 bis 9, dadurch gekennzeichnet, dass der kationische Heteroarylazinfarbstoff gemäß einem der Ansprüche 1 bis 3 in einer Gesamtmenge von 0,01 bis 10 Gewichtsprozent enthalten ist.10. Agent according to one of claims 4 to 9, characterized in that the cationic heteroarylazine dye according to one of claims 1 to 3 is contained in a total amount of 0.01 to 10 percent by weight.
11. Mittel nach einem der Ansprüche 4 bis 10, dadurch gekennzeichnet, dass es ein Haarfärbemittel ist. 11. Agent according to one of claims 4 to 10, characterized in that it is a hair dye.
EP04803447A 2004-02-28 2004-12-02 Cationic heteroaryl azine dyes, and dyeing agents containing said compounds Withdrawn EP1718705A1 (en)

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BE793207A (en) * 1971-12-23 1973-06-22 Ciba Geigy PROCESS FOR PREPARING CATIONIC DYES IN THE FORM OF CONCENTRATED AQUEOUS SOLUTIONS
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