EP0618903A1 - Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production - Google Patents

Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production

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Publication number
EP0618903A1
EP0618903A1 EP93921871A EP93921871A EP0618903A1 EP 0618903 A1 EP0618903 A1 EP 0618903A1 EP 93921871 A EP93921871 A EP 93921871A EP 93921871 A EP93921871 A EP 93921871A EP 0618903 A1 EP0618903 A1 EP 0618903A1
Authority
EP
European Patent Office
Prior art keywords
amino
pyrazole
diamino
methoxybenzyl
percent
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.)
Withdrawn
Application number
EP93921871A
Other languages
German (de)
French (fr)
Inventor
Hans Neunhoeffer
Stefan Gerstung
Thomas Clausen
Wolfgang R. Balzer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Deutschland GmbH
Original Assignee
Wella GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wella GmbH filed Critical Wella GmbH
Publication of EP0618903A1 publication Critical patent/EP0618903A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms

Definitions

  • the invention relates to agents for the oxidative coloring of hair on the basis of 4,5-diaminopyrazole derivatives as developer substance and new 4,5-diamino-pyrazole derivatives.
  • Oxidation dyes have become very important in the field of hair coloring.
  • the color is produced by reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent.
  • 2,5-diamino toluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 1,4-diaminobenzene are used as developer substances.
  • Resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol, 5-amino-2-methylphenol and derivatives of m-phenylenediamine are mentioned as preferred coupler substances.
  • Oxidation dyes which are used to dye human hair, have numerous special requirements. For example, they have to be harmless from a toxicological and dermatological point of view and enable dyeing in the desired intensity. Furthermore, good light, permanent wave, acid and rub fastness is required for the hair dyeing achieved. In any case, however, such hair colorations have to be stable over a period of at least 4 to 6 weeks without the influence of light, friction and chemical agents stay. In addition, it is necessary that a wide range of different color shades can be produced by combining suitable developer and coupler components. In order to achieve natural and particularly fashionable shades in the red range, 4-aminophenol in particular, alone or in a mixture with other developer substances, is used in combination with suitable coupling substances.
  • DE-OS 21 41 700 describes a one-step process according to which 5-amino-1-methylpyrazole is to be obtained from N, N-dimethylaminoacrylonitrile and methylhydrazine in a 71 percent yield.
  • This compound can be implemented further according to MA Khan et al., Can. J. Chem. 9_, 3566 (1971) convert to 5-amino-1-methyl-4-nitropyrazole with a yield of 23 percent.
  • the starting compounds such as, for example, ethyl ethoxymethyl-cyanoacetate or N, N-dimethylaminoacrylonitrile, and also certain hydrazine derivatives
  • the starting compounds are not commercially available and likewise have to be prepared by in part complex syntheses.
  • the technically available hydrazine derivatives are classified as toxic and some are classified as carcinogen-suspect substances.
  • the preparation of compounds which are substituted on the 5-position amino group for example alkyl, hydroxyalkyl, benzyl
  • Another disadvantage of this synthesis is that the ring alkylation is introduced in the first reaction step, which means that special starting compounds are required even at the beginning of the synthesis.
  • Substituted pyrazole derivatives such as 5-amino-1-alkyl-4-nitro-pyrazoles or 5-amino-1-benzyl-4-nitro-pyrazoles, as well as compounds substituted on the 5-amino group, can also be prepared by reduction using this process can be converted into the corresponding diamino compounds, or not or only in very poor yields. Furthermore, the harmless hydrazine must also be used in this process.
  • the object was therefore to provide an oxidation colorant based on a developer substance / coupler substance combination, which contains a developer substance for the red range, which is physiologically very well tolerated, with conventional coupler substances, the hair in brilliant red shades dyes with a high depth of color and is technically producible in good yields.
  • a developer substance-coupler substance combination which as the developer substance is a 4,5-diaminopyrazole of the general formula (I)
  • Rl is halogen.
  • Preferred coupler substances are ot-naphthol, resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 2-methylresorcinol, 2-amino-4- (2'-hydroxyethyl) amino anisole, 2,4-diaminophenyl alcohol, m -Phenylene diamine, 5-amino-2-methylphenol, 2,4-diaminophenoxyethanol, 4-amino-2-hydroxyphenoxyethanol, 3-aminophenol, 3-amino-2-methylphenol, 4-hydroxy-l, 2-methylenedioxybenzene, 4 -Amino-l, 2-methylenedioxybenzene, 4- (2 '-hydroxyethyl) - amino-1,2-methylenedioxybenzene, 2,4-diaminobenzyl alcohol, 2,4-diamino-p'henetol, 2,4-diamino-5- methylphenetol, 4-hydroxyindole, 3-amin
  • the coupler and developer substances can each be contained in the hair dye individually or in a mixture with one another.
  • the total amount of the developer substance-coupler substance combination contained in the hair dye composition described here is 0.1 to 5.0 percent by weight, an amount of 0.5 to 4.0 percent by weight being preferred.
  • the developer components are generally used in approximately equimolar amounts, based on the coupler components. However, it is not a disadvantage if the developer components are present in a certain excess or deficit in this regard.
  • the hair dye according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, and also conventional direct dyes, for example triphenylmethane dyes such as Diamond Fuchsine (CI 42 510) and Leather Ruby HF (CI 42 520), aromatic nitro dyes such as 2-nitro-1,4-diaminobenzene, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 2-amino-4,6-di-nitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene and 2-methylamino-5-bis- (2'-hydroxyethyl) amino-nitrobenzene, azo dyes such as Acid Brown 4 (CI 14 805) and disperse dyes such as 1,4-diamino anthraquinone and 1,4,5,8-tetraaminoanthraquinone ent.
  • the hair dye can contain these color components in an amount of about 0.1 to
  • the coupler and developer substances and the other color components can also be in the form of the physiologically tolerable salts with organic or inorganic acids, such as, for example, hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of the salts with bases, for example as alkali phenolates.
  • organic or inorganic acids such as, for example, hydrochloric acid or sulfuric acid
  • aromatic OH groups - in the form of the salts with bases for example as alkali phenolates.
  • the hair dye can also contain other customary cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, and also perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.
  • antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite
  • perfume oils such as ascorbic acid, thioglycolic acid or sodium sulfite
  • complexing agents such ascorbic acid, thioglycolic acid or sodium sulfite
  • wetting agents such ascorbic acid, thioglycolic acid or sodium sulfite
  • perfume oils such ascorbic acid, thioglycolic acid or sodium sulfite
  • complexing agents such ascorbic acid, thioglycolic acid or sodium sulfite
  • wetting agents such ascorbic acid, thioglycolic acid or sodium sulfite
  • the preparation form of the new hair dye can be, for example, a solution, especially an aqueous one or be an aqueous-alcoholic solution.
  • the particularly preferred preparation forms are a cream, a gel or an emulsion.
  • Their composition represents a mixture of the dye components with the additives customary for such preparations.
  • Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol and isopropanol, glycerol, or glycols such as 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic , amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium ammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid ester, also thickeners such as higher fatty alcohols, starch, cellulose derivatives, vaseline, paraffin oil and fatty
  • constituents mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 percent by weight.
  • the hair dye according to the invention can react weakly acidic, neutral or alkaline.
  • it has a pH of 6.0 to 11.5, the basic setting being carried out with ammonia.
  • organic amines for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide are used.
  • inorganic bases such as sodium hydroxide and potassium hydroxide are used.
  • phosphoric acid and acetic acid or other organic acids such as citric acid or tartaric acid, come into consideration.
  • the hair dye described above is mixed with an oxidizing agent immediately before use and an amount sufficient for hair dye treatment, depending on the hair volume, is generally about 60 to 200 g of this mixture Hair on.
  • the main oxidizing agents used to develop hair color are hydrogen peroxide or its addition compounds with urea, melamine or sodium borate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all at higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time. The mixture is allowed to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried.
  • 4,5-diamino-pyrazole derivatives of the general formula (I) used in the oxidation hair colorants according to the invention can be very well prepared by a 3,5-dibromo-4-nitropyrazole of the general formula (II) with a suitable benzyl halide in the presence of Brings sodium hydride to reaction, then the l-benzyl-3,5-dibromo-4-nitropyrazole derivative of the general formula (III) obtained is reacted with an A in and the 5-alkylamino-l-benzyl-3-bromo-4- obtained nitropyrazole derivative of the general formula (IV) catalytically reduced.
  • Nitration of pyrazole with sulfuric acid / nitric acid gives 4-nitro-pyrazole in a yield of 80 percent (R. Wilsontel et al., Chem. Ber. .88. / 1577 (1955)). Milder conditions during the nitration give N-nitro-pyrazole in yields of 84 to 93 percent (HJ Klebe et al., Synthesis 1973, 294); which can also be rearranged to 4-nitro-pyrazole by the action of sulfuric acid (R. Wilsontel et al., Chem. Ber. .88., 1586 (1955)). Bromination of 4-nitro-pyrazole according to the instructions of JPH Juffermanns et al., J. Org. Chem.
  • the 3,5-dibromo-4-nitro-pyrazole can be converted to the new 1-benzyl-substituted pyrazoles of the general formula (III), where R1 is a halogen, alkyl or. Represents alkoxy radical.
  • R1 is a halogen, alkyl or. Represents alkoxy radical.
  • These residues can be introduced by various methods, for example the compounds of the general formula (III) can be obtained by reacting the compound (II) with sodium hydride in dimethylformamide by adding the corresponding benzyl halides.
  • the particular advantage of this reaction step lies above all in the isomerically pure preparation of the N-benzyl-substituted pyrazoles of the general formula (III).
  • the compounds of the general formula (IV) can be converted to different 4,5-diaminopyrazoles of the general formula (I) by catalytic reduction, the reduction usually being carried out using hydrogen and customary catalysts (for example palladium / activated carbon catalysts) is and can optionally be hydrogenated in an autoclave under pressure to increase the reaction rate. It is particular with this method Surprisingly, the substituted benzyl radical of the compounds of the general formula (IV) is not removed reductively. In contrast to this, in comparative experiments with compounds of the formula (IV) in which R 1 represents hydrogen, 4,5-diamino-pyrazoles which had a hydrogen atom in the 1-position were obtained after reduction in all cases.
  • customary catalysts for example palladium / activated carbon catalysts
  • the salts of the compounds of formula (I) can be obtained by reaction with organic or inorganic acids or bases.
  • the developer substances of the formula (I) are to be used in the hair dye either as free bases or in the form of their physiologically tolerable salts with inorganic or organic acids, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
  • the compounds of formula (I) are readily soluble in water and they additionally have excellent storage stability, in particular as a constituent of the hair colorants described here.
  • the hair dye according to the invention with a content of 4,5-diaminopyrazole derivatives as developer substances enables hair dyeings with excellent color fastness, in particular with regard to light, washing and rubbing fastness.
  • the hair colorants according to the invention offer possibilities which go far beyond the replacement of the 4-aminophenols normally used. In this way, brilliant red tones can be created with an extraordinary depth of color that cannot be achieved with the usual color components.
  • natural colors can also be produced by the use in combination with suitable coupling components without the need for a further development component of the p-phenylenediamine type.
  • the very good coloring properties of the hair colorants according to the present application are further shown in the fact that these agents enable graying, chemically not previously damaged hair to be colored easily and with good coverage.
  • the present patent application also relates to the new 4,5-diaminopyrazole derivatives of the general formula (I), in particular 4,5-diamino-1- (4'-methoxybenzyl) pyrazole,
  • reaction mixture (250 ml) transferred and stirred during the specified period at 50 bar hydrogen atmosphere and room temperature (20 to 30 degrees Celsius). After the end of the reaction, the reaction mixture is sucked into a glass flask with a water jet pump and immediately filtered through a
  • (4'-Methoxybenzyl) -4-nitropyrazole are mixed in 100 ml of absolute ethanol with 2 spatula tips of palladium-activated carbon catalyst and hydrogenated for 2 hours at 50 bar and room temperature.
  • 50 g of the above hair dye are mixed with 50 g of hydrogen peroxide solution (6 percent) shortly before use and the mixture is then applied to natural blonde hair. After an exposure time; from 30 minutes at 40 degrees Celsius, the hair is rinsed with water and dried. The hair has an intense bright red-orange color.
  • the hair dye solutions are prepared according to Example 5 and applied to 90 percent gray human hair. The resulting colorations are shown in Table 1.

Abstract

Agent pour la teinture oxydante des cheveux, à base d'une combinaison de substance de développement-substance copulante renfermant, comme substance de développement, un dérivé du 4,5-diaminopyrazole de formule générale (I) où R1 représente halogène, alkyle en C1-C4, alkoxy en C1-C4; R2 représente hydrogène, alkyle en C1-C4, hydroxyalkyle en C2-C4, ou ses sels solubles dans l'eau, physiologiquement acceptables, ainsi que nouveaux dérivés du 4,5-diaminopyrazole.Agent for oxidative hair dyeing, based on a developing substance-coupling substance combination containing, as developing substance, a 4,5-diaminopyrazole derivative of general formula (I) where R1 is halogen, C1-alkyl -C4, C1-C4 alkoxy; R2 represents hydrogen, C1-C4 alkyl, C2-C4 hydroxyalkyl, or its water-soluble, physiologically acceptable salts, as well as new derivatives of 4,5-diaminopyrazole.

Description

Beschreibung description
Oxidationshaarfärbemittel mit einem Gehalt an 4,5- Diaminopyrazolderivaten sowie neue 4,5-Diaminopyrazol- derivate und Verfahren zu ihrer HerstellungOxidation hair dye containing 4,5-diaminopyrazole derivatives as well as new 4,5-diaminopyrazole derivatives and process for their preparation
Gegenstand der Erfindung sind Mittel zur oxidativen Färbung von Haaren auf der Basis von 4,5-Diaminopyrazol- derivaten als Entwicklersubstanz sowie neue 4,5-Diamino- pyrazolderivate.The invention relates to agents for the oxidative coloring of hair on the basis of 4,5-diaminopyrazole derivatives as developer substance and new 4,5-diamino-pyrazole derivatives.
Auf dem Gebiet der Haarfärbung haben Oxidationsfarb- stoffe eine wesentliche Bedeutung erlangt. Die Färbung entsteht hierbei durch Reaktion bestimmter Entwickler¬ substanzen mit bestimmten Kupplersubstanzen in Gegenwart eines geeigneten Oxidationsmittels.Oxidation dyes have become very important in the field of hair coloring. The color is produced by reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent.
Als Entwicklersubstanzen werden insbesondere 2,5-Diami- notoluol, 2,5-Diaminophenylethylalkohol, p-Aminophenol und 1,4-Diaminobenzol eingesetzt. Von den vorzugsweise verwendeten Kupplersubstanzen sind Resorcin, 4-Chlor- resorcin, 1-Naphthol, 3-Aminophenol, 5-Amino-2-methyl- phenol und Derivate des m-Phenylendiamins zu nennen.In particular, 2,5-diamino toluene, 2,5-diaminophenylethyl alcohol, p-aminophenol and 1,4-diaminobenzene are used as developer substances. Resorcinol, 4-chlororesorcinol, 1-naphthol, 3-aminophenol, 5-amino-2-methylphenol and derivatives of m-phenylenediamine are mentioned as preferred coupler substances.
An Oxidationsfarbstoffe, die zur Färbung menschlicher Haare verwendet werden, sind zahlreiche besondere Anfor¬ derungen gestellt. So müssen sie in toxikologischer und dermatologischer Hinsicht unbedenklich sein und Färbun¬ gen in der gewünschten Intensität ermöglichen. Ferner wird für die erzielten Haarfärbungen eine gute Licht-, Dauerwell-, Säure- und Reibeechtheit gefordert. Auf jeden Fall aber müssen solche Haarfärbungen ohne Ein¬ wirkung von Licht, Reibung und chemischen Mitteln über einen Zeitraum von mindestens 4 bis 6 Wochen stabil bleiben. Außerdem ist es erforderlich, daß durch Kombi¬ nation geeigneter Entwickler- und Kupplerkomponenten eine breite Palette verschiedener Farbnuancen erzeugt werden kann. Zur Erzielung natürlicher und besonders modischer Nuancen im Rotbereich wird vor allem 4-Amino- phenol, allein oder im Gemisch mit anderen Entwickler¬ substanzen in Kombination mit geeigneten Kupplungs¬ substanzen eingesetzt.Oxidation dyes, which are used to dye human hair, have numerous special requirements. For example, they have to be harmless from a toxicological and dermatological point of view and enable dyeing in the desired intensity. Furthermore, good light, permanent wave, acid and rub fastness is required for the hair dyeing achieved. In any case, however, such hair colorations have to be stable over a period of at least 4 to 6 weeks without the influence of light, friction and chemical agents stay. In addition, it is necessary that a wide range of different color shades can be produced by combining suitable developer and coupler components. In order to achieve natural and particularly fashionable shades in the red range, 4-aminophenol in particular, alone or in a mixture with other developer substances, is used in combination with suitable coupling substances.
Gegen den für den Rotbereich der Farbskala bisher haupt¬ sächlich eingesetzten Entwickler 4-Aminophenol wurden in letzter Zeit Bedenken in bezug auf die physiologische Verträglichkeit erhoben, während die in neuerer Zeit empfohlenen Entwicklersubstanzen, wie zum Beispiel Pyrimidinderivate, in färberischer Hinsicht nicht völlig zufriedenstellen können. Die in der DE-OS 21 60 317 beschriebenen Pyrazolderivate, wie zum Beispiel das 3-Amino-l-phenyl-2-pyrazolon-5, färben Haare nur in sehr geringen, für die Haarfärbepraxis unbrauchbaren, Farb¬ tiefen an.Concerns about the physiological compatibility have recently been raised against the developer 4-aminophenol, which has hitherto been used mainly for the red range of the color scale, while the developer substances recommended in more recent times, such as pyrimidine derivatives, cannot be completely satisfactory in terms of color. The pyrazole derivatives described in DE-OS 21 60 317, such as, for example, 3-amino-1-phenyl-2-pyrazolone-5, dye hair only in very small color depths which are unusable for hair dyeing practice.
In der DE-OS 38 43 892 werden Pyrazolderivate beschrie¬ ben, die mit unterschiedlichen Kupplungssubstanzen intensive Ausfärbungen geben. Die dort beschriebenen Verbindungen sind allerdings nur durch sehr aufwendige Syntheseverfahren und in geringen Ausbeuten erhältlich.DE-OS 38 43 892 describes pyrazole derivatives which give intense colorations with different coupling substances. However, the compounds described there can only be obtained by very complex synthetic processes and in low yields.
Zur Darstellung von l-Methyl-4,5-Diaminopyrazol sind in der Literatur verschiedene Wege beschrieben. Ausgehend von Ethoxymethylen-cyanessigsäure-ethylester und Methyl- hydrazin wird nach H. Dorn et al. , Chem. Ber. _98_, 3368 (1965) in einer Ausbeute von 53 Prozent die 5-Amino-l- methyl-pyrazol-4-carbonsäure enthalten, aus der durch Decarboxylierung in einer Ausbeute von 75 Prozent das 5-Amino-l-methyl-pyrazol entsteht (Gesamtausbeute 40 Prozent). In der DE-OS 21 41 700 ist ein Einstufen¬ verfahren beschrieben, nach dem aus N,N-Dimethylamino- acrylnitril und Methylhydrazin das 5-Amino-l-methyl- pyrazol in 71-prozentiger Ausbeute erhalten werden soll. Zur weiteren Umsetzung läßt sich diese Verbindung nach M.A. Khan et al., Can. J. Chem. 9_, 3566 (1971) mit einer Ausbeute von 23 Prozent zum 5-Amino-l-methyl-4- nitropyrazol umsetzen.Various methods are described in the literature for the preparation of l-methyl-4,5-diaminopyrazole. Starting from ethyl ethoxymethylene cyanoacetate and methyl hydrazine, according to H. Dorn et al. , Chem. Ber. _98_, 3368 (1965) contain the 5-amino-1-methyl-pyrazole-4-carboxylic acid in a yield of 53 percent, from which the 5-amino-1-methyl-pyrazole is formed by decarboxylation in a yield of 75 percent (overall yield 40 percent ). DE-OS 21 41 700 describes a one-step process according to which 5-amino-1-methylpyrazole is to be obtained from N, N-dimethylaminoacrylonitrile and methylhydrazine in a 71 percent yield. This compound can be implemented further according to MA Khan et al., Can. J. Chem. 9_, 3566 (1971) convert to 5-amino-1-methyl-4-nitropyrazole with a yield of 23 percent.
Die katalytische Reduktion dieses Produkts liefert nach V.P. Perevalov et al; Khim. Geterotsicl. Soedin. Q_, 1090 (1985) l-Methyl-4,5-diamino-pyrazol-dihydrochlorid in einer Ausbeute von etwa 79 Prozent. Nach dieser Reaktionsfolge beträgt die Gesamtausbeute an 1-Methyl- 4,5-diamino-pyrazol 13 Prozent über alle Stufen.The catalytic reduction of this product provides according to V.P. Perevalov et al; Khim. Geterotsicl. Soedin. Q_, 1090 (1985) l-methyl-4,5-diamino-pyrazole dihydrochloride in a yield of about 79 percent. According to this reaction sequence, the total yield of 1-methyl-4,5-diamino-pyrazole is 13 percent over all stages.
Bessere Ausbeuten werden erhalten, wenn man 5-Amino-l- methyl-pyrazol nach H. Dorn et al-, Liebigs Ann. Chem., 717 , 118 (1968) mit Isoamylnitrit zum 5-Amino-l-methyl- 4-nitroso-pyrazol umsetzt (Rohausbeute ca. 97 Prozent) und anschließend mit Zinnchlorid zum Endprodukt reduziert (Ausbeute 67 Prozent), so daß die Gesamtausbeute nach diesem Verfahren 46 Prozent über alle Stufen beträgt.Better yields are obtained if 5-amino-1-methyl-pyrazole according to H. Dorn et al., Liebigs Ann. Chem., 717, 118 (1968) with isoamyl nitrite to give 5-amino-l-methyl-4-nitroso-pyrazole (crude yield approx. 97 percent) and then reduced with tin chloride to the end product (yield 67 percent), so that the overall yield using this procedure is 46 percent across all levels.
Eine entsprechende Synthese ist für das l-Benzyl-4,5- diamino-pyrazol in der DE-OS 34 32 983 beschrieben. Ausgehend von Ethoxymethylen-cyanessigsäureethylester und Benzylhydrazin wird 5-Amino-l-benzyl-pyrazol-carbon- säureethylester erhalten, nach Esterspaltung, Decarboxy¬ lierung, Nitrosierung und Reduktion wird das 1-Benzyl- 4,5-diämino-pyrazol in einer Gesamtausbeute von 30 Prozent erhalten. Neben den zum Teil geringen Ausbeuten beinhalten die hier beschriebenen Verfahren noch weitere Nachteile. So ist hier noch nicht berücksichtigt, daß die Ausgangs¬ verbindungen wie zum Beispiel Ethoxymethyl-cyanessig- säureethylester beziehungsweise N,N-Dimethylaminoacryl- nitril, wie auch bestimmte Hydrazinderivate, nicht käuflich erhältlich sind und ebenfalls durch zum Teil aufwendige Synthesen hergestellt werden müssen. Darüber hinaus sind die technischen verfügbaren Hydrazinderivate als giftig und zum Teil als carcinogenverdächtige Substanzen eingestuft. Weiterhin ist die Herstellung von Verbindungen, die an der 5-ständigen Aminogruppe substituiert sind (zum Beispiel Alkyl, Hydroxyalkyl, Benzyl) nach diesem Verfahren beziehungsweise durch Folgeschritte nicht beschrieben. Ein weiterer Nachteil dieser Synthese besteht darin, daß die Ringalkylierung schon im ersten Reaktionsschritt eingebracht wird, das heißt, daß bereits zu Beginn der Synthese spezielle Aus¬ gangsverbindungen benötigt werden.A corresponding synthesis for l-benzyl-4,5-diamino-pyrazole is described in DE-OS 34 32 983. Starting from ethyl ethoxymethylene cyanoacetate and benzylhydrazine, 5-amino-1-benzyl-pyrazole-carbonate is obtained. After ester cleavage, decarboxylation, nitrosation and reduction, the 1-benzyl-4,5-diaminopyrazole is obtained in a total yield of Get 30 percent. In addition to the sometimes low yields, the processes described here have further disadvantages. It has not yet been taken into account here that the starting compounds, such as, for example, ethyl ethoxymethyl-cyanoacetate or N, N-dimethylaminoacrylonitrile, and also certain hydrazine derivatives, are not commercially available and likewise have to be prepared by in part complex syntheses. In addition, the technically available hydrazine derivatives are classified as toxic and some are classified as carcinogen-suspect substances. Furthermore, the preparation of compounds which are substituted on the 5-position amino group (for example alkyl, hydroxyalkyl, benzyl) by this process or by subsequent steps is not described. Another disadvantage of this synthesis is that the ring alkylation is introduced in the first reaction step, which means that special starting compounds are required even at the beginning of the synthesis.
In diesem Fall wäre es günstiger ein in 4- und 5-Stellung substituiertes Pyrazolderivat am Ringstick¬ stoff zu alkylieren, wodurch man durch Wahl verschiede¬ ner Alkylierungsmittel erst am Ende der Synthese zu unterschiedlichen Derivaten gelangt. Ein Verfahren zur Herstellung von l-Methyl-4,5-diamino-pyrazol ist in der DE-OS 38 43 892 beschrieben. Danach liefert die Alkylie- rung von 3(5)-Amino-4-nitro-pyrazol - das durch Cycli- sierung von 2-Chloracrylnitril mit Hydrazin (G. Ege, Angew. Chem., 86, 237 (1974)) und anschließender Acety- lierung der Aminogruppe, Nitrierung und Abspaltung der Schutzgruppe in einer Gesamtausbeute von etwa 41 Prozent gebildet wird - mit Dimethylsulfat in einer Ausbeute von 70 Prozent ein Isomerengemisch, aus dem nach chromatogra¬ phischer Trennung das gewünschte 5-Amino-l-methyl-4- nitro-pyrazol in einer Ausbeute von 25 Prozent und das isomere 3-Amino-l-methyl-4-nitro-pyrazol in einer Ausbeute von 45 Prozent erhalten werden. Nach Reduktion der Nitroverbindungen wurden die entsprechenden Diamino-Verbindungen isoliert.In this case, it would be more favorable to alkylate a pyrazole derivative substituted in the 4- and 5-position on the ring nitrogen, as a result of which, by choosing different alkylating agents, different derivatives are only obtained at the end of the synthesis. A process for the preparation of l-methyl-4,5-diamino-pyrazole is described in DE-OS 38 43 892. Thereafter, the alkylation of 3 (5) -amino-4-nitro-pyrazole - that by cyclization of 2-chloroacrylonitrile with hydrazine (G. Ege, Angew. Chem., 86, 237 (1974)) and subsequent Acety- lation of the amino group, nitration and cleavage of the protective group is formed in a total yield of about 41 percent - with dimethyl sulfate in a yield of 70 percent an isomer mixture from which the desired 5-amino-1-methyl-4 after chromatographic separation - nitro-pyrazole in a yield of 25 percent and the isomeric 3-amino-1-methyl-4-nitro-pyrazole in a yield of 45 percent. After reduction of the nitro compounds, the corresponding diamino compounds were isolated.
Die Umsetzung von 3(5)-Amino-4-nitropyrazol mit Benzyl- bromid ist ebenfalls in der DE-OS 38 43 892 beschrieben, wobei die Bildung des gewünschten 5-Amino-l-benzol-4- nitro-pyrazols nicht erfolgt; man erhält vielmehr ein Gemisch, aus dem nach chromatographischer Trennung etwa 18 Prozent l-Benzyl-3-benzylamino-4-nitro-pyrazol und 78 Prozent 3-Amino-l-benzyl-4-nitro-pyrazol erhalten werden.The reaction of 3 (5) -amino-4-nitropyrazole with benzyl bromide is also described in DE-OS 38 43 892, the formation of the desired 5-amino-1-benzene-4-nitro-pyrazole not taking place; rather, a mixture is obtained from which about 18 percent l-benzyl-3-benzylamino-4-nitro-pyrazole and 78 percent 3-amino-l-benzyl-4-nitro-pyrazole are obtained after chromatographic separation.
Auch nach diesem Verfahren lassen sich substituierte Pyrazolderivate, wie 5-Amino-l-alkyl-4-nitro-pyrazole beziehungsweise 5-Amino-l-benzyl-4-nitro-pyrazole sowie auch an der 5-Aminogruppe substituierte Verbindungen, die durch Reduktion in die entsprechenden Diamino-Verbindun¬ gen überführt werden können, nicht oder nur in sehr schlechten Ausbeuten darstellen. Weiterhin muß auch bei diesem Verfahren das nicht unbedenkliche Hydrazin verwendet werden.Substituted pyrazole derivatives, such as 5-amino-1-alkyl-4-nitro-pyrazoles or 5-amino-1-benzyl-4-nitro-pyrazoles, as well as compounds substituted on the 5-amino group, can also be prepared by reduction using this process can be converted into the corresponding diamino compounds, or not or only in very poor yields. Furthermore, the harmless hydrazine must also be used in this process.
Es bestand daher die Aufgabe, ein Oxidationsfärbemittel auf der Basis einer Entwicklersubstanz/Kupplersubstanz- Kombination zur Verfügung zu stellen, in dem eine Ent¬ wicklersubstanz für den Rotbereich enthalten ist, welche physiologisch sehr gut verträglich ist, mit üblichen Kupplersubstanzen das Haar in brillianten roten Farbtönen mit einer hohen Farbtiefe färbt und technisch in guten Ausbeuten herstellbar ist. Hierzu wurde nun gefunden, daß durch ein Mittel zur oxi- dativen Färbung von Haaren auf der Basis einer Entwicklersubstanz-Kupplersubstanz-Kombination, welche als Entwicklersubstanz ein 4,5-Diaminopyrazol der allgemeinen Formel (I),The object was therefore to provide an oxidation colorant based on a developer substance / coupler substance combination, which contains a developer substance for the red range, which is physiologically very well tolerated, with conventional coupler substances, the hair in brilliant red shades dyes with a high depth of color and is technically producible in good yields. For this purpose, it has now been found that by means of an oxidative dyeing of hair on the basis of a developer substance-coupler substance combination, which as the developer substance is a 4,5-diaminopyrazole of the general formula (I),
in der Rl gleich Halogen. Alkyl mit 1 bis 4 Kohlenstoff¬ atomen oder Alkoxy mit 1 bis 4 Kohlenstoffatomen darstellt und R2 Wasserstoff, Alkyl mit 1 bis 4 Kohlen¬ stoffatomen oder Hydroxyalkyl mit 2 bis 4 Kohlenstoff¬ atomen bedeutet, oder dessen physiologisch verträgliche, wasserlösliche Salze enthält, diese Aufgabe in hervor¬ ragender Weise gelöst wird.in the Rl is halogen. Alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R 2 is hydrogen, alkyl with 1 to 4 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms, or its physiologically compatible, water-soluble salts are used for this task is solved in an outstanding manner.
In dem Haarfärbemittel sollen die Entwicklersubstanzen der Formel (I), von denen das 4,5-Diamino-l-(4 '-methoxy¬ benzyl)-pyrazol, das 4,5-Diamino-l-(4 '-methylbenzyl)- pyrazol, das 4,5-Diamino-l-(3'-methoxybenzyl)-pyrazol und das 4,5-Diamino-l-(4'-chlorbenzyl)-pyrazol bevorzugt ist, in einer Menge von 0,01 bis 3,0 Gewichtsprozent, vor¬ zugsweise in einer Menge von 0,1 bis 2,5 Gewichtspro¬ zent, enthalten sein. Obwohl die vorteilhaften Eigenschaften der hier beschriebenen neuen Entwicklersubstanzen es nahelegen, diese als alleinige Entwicklersubstanz zu verwenden, ist es selbstverständlich auch möglich, die Entwicklersub¬ stanzen der Formel (I) gemeinsam mit bekannten Entwick¬ lersubstanzen, wie zum Beispiel 1, 4-Diaminobenzol, 2,5- Diaminotoluol oder 2,5-Diaminophenylethylalkohol, einzu¬ setzen.In the hair dye, the developer substances of the formula (I), of which 4,5-diamino-1- (4'-methoxybenzyl) -pyrazole, 4,5-diamino-1- (4'-methylbenzyl) - pyrazole, the 4,5-diamino-l- (3'-methoxybenzyl) -pyrazole and the 4,5-diamino-l- (4'-chlorobenzyl) -pyrazole is preferred, in an amount of 0.01 to 3, 0 percent by weight, preferably in an amount of 0.1 to 2.5 percent by weight. Although the advantageous properties of the new developer substances described here suggest that they be used as the sole developer substance, it is of course also possible to use the developer substances of the formula (I) together with known developer substances, such as, for example, 1,4-diaminobenzene, 2,5-diaminotoluene or 2,5-diaminophenylethyl alcohol.
Als Kupplersubstanzen kommen vorzugsweise o-t-Naphthol, Resorcin, 4-Chlorresorcin, 4,6-Dichlor- resorcin, 2-Methylresorcin, 2-Amino-4-(2 '-hydroxyethyl)- amino-anisol, 2,4-Diaminophenylalkohol, m-Phenylendia- min, 5-Amino-2-methylphenol, 2,4-Diaminophenoxyethanol, 4-Amino-2-hydroxyphenoxyethanol, 3-Aminophenol, 3-Amino- 2-methylphenol, 4-Hydroxy-l,2-methylendioxybenzol, 4-Amino-l,2-methylendioxybenzol, 4-(2 '-Hydroxyethyl)- amino-1,2-methylendioxybenzol, 2,4-Diaminobenzylalkohol, 2,4-Diamino-p'henetol, 2,4-Diamino-5-methylphenetol, 4-Hydroxyindol , 3-Amino-5-hydroxy-2 ,6-dimethoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin in Betracht.Preferred coupler substances are ot-naphthol, resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 2-methylresorcinol, 2-amino-4- (2'-hydroxyethyl) amino anisole, 2,4-diaminophenyl alcohol, m -Phenylene diamine, 5-amino-2-methylphenol, 2,4-diaminophenoxyethanol, 4-amino-2-hydroxyphenoxyethanol, 3-aminophenol, 3-amino-2-methylphenol, 4-hydroxy-l, 2-methylenedioxybenzene, 4 -Amino-l, 2-methylenedioxybenzene, 4- (2 '-hydroxyethyl) - amino-1,2-methylenedioxybenzene, 2,4-diaminobenzyl alcohol, 2,4-diamino-p'henetol, 2,4-diamino-5- methylphenetol, 4-hydroxyindole, 3-amino-5-hydroxy-2, 6-dimethoxypyridine and 3,5-diamino-2,6-dimethoxypyridine.
Die Kuppler- und Entwicklersubstanzen können in dem Haarfärbemittel jeweils einzeln oder im Gemisch mitein¬ ander enthalten sein.The coupler and developer substances can each be contained in the hair dye individually or in a mixture with one another.
Die Gesamtmenge der in dem hier beschriebenen Haarfärbe¬ mittel enthaltenen Entwicklersubstanz-Kupplersubstanz- Kombination beträgt 0,1 bis 5,0 Gewichtsprozent, wobei eine Menge von 0,5 bis 4,0 Gewichtsprozent bevorzugt ist. Die Entwicklerkomponenten werden im allgemeinen in etwa äquimolaren Mengen, bezogen auf die Kupplerkompo¬ nenten, eingesetzt. Es ist jedoch nicht nachteilig, wenn die Entwicklerkσmponenten diesbezüglich in einem gewissen Überschuß oder Unterschuß vorhanden sind. Weiterhin kann das erfindungsgemäße Haarfärbemittel zusätzlich andere Farbkomponenten, beispielsweise 6-Amino-2-methylphenol und 2-Amino-5-methylphenol, sowie ferner übliche direktziehende Farbstoffe, zum Beispiel Triphenylmethanfarbstoffe wie Diamond Fuchsine (C.I. 42 510) und Leather Ruby HF (C.I. 42 520), aromatische Nitrofarbstoffe wie 2-Nitro-l,4-diaminobenzol, 2-Amino- 4-nitrophenol, 2-Amino-5-nitrophenol, 2-Amino-4,6-di- nitrophenol, 2-Amino-5-(2 '-hydroxyethyl)amino-nitrobenzol und 2-Methylamino-5-bis-(2 '-hydroxyethyl)amino-nitroben¬ zol, Azofarbstoffe wie Acid Brown 4 (C.I. 14 805) und Dispersionsfarbstoffe wie beispielsweise 1,4-Diamino- anthrachinon und 1,4,5,8-Tetraaminoanthrachinon ent¬ halten. Die Haarfärbemittel können diese Farbkomponenten in einer Menge von etwa 0,1 bis 4,0 Gewichtsprozent enthalten.The total amount of the developer substance-coupler substance combination contained in the hair dye composition described here is 0.1 to 5.0 percent by weight, an amount of 0.5 to 4.0 percent by weight being preferred. The developer components are generally used in approximately equimolar amounts, based on the coupler components. However, it is not a disadvantage if the developer components are present in a certain excess or deficit in this regard. Furthermore, the hair dye according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, and also conventional direct dyes, for example triphenylmethane dyes such as Diamond Fuchsine (CI 42 510) and Leather Ruby HF (CI 42 520), aromatic nitro dyes such as 2-nitro-1,4-diaminobenzene, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 2-amino-4,6-di-nitrophenol, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene and 2-methylamino-5-bis- (2'-hydroxyethyl) amino-nitrobenzene, azo dyes such as Acid Brown 4 (CI 14 805) and disperse dyes such as 1,4-diamino anthraquinone and 1,4,5,8-tetraaminoanthraquinone ent. The hair dye can contain these color components in an amount of about 0.1 to 4.0 percent by weight.
Selbstverständlich können die Kuppler- und Entwickler¬ substanzen sowie die anderen Farbkomponenten, sofern es Basen sind, auch in Form der physiologisch verträglichen Salze mit organischen oder anorganischen Säuren, wie beispielsweise Salzsäure oder Schwefelsäure, beziehungs¬ weise - sofern sie aromatische OH-Gruppen besitzen - in Form der Salze mit Basen, zum Beispiel als Alkalipheno- late, eingesetzt werden.Of course, the coupler and developer substances and the other color components, if they are bases, can also be in the form of the physiologically tolerable salts with organic or inorganic acids, such as, for example, hydrochloric acid or sulfuric acid, or - if they have aromatic OH groups - in the form of the salts with bases, for example as alkali phenolates.
Darüberhinaus können in dem Haarfärbemittel noch weitere übliche kosmetische Zusätze, beispielsweise Antioxidan- tien wie Ascorbinsäure, Thioglykolsäure oder Natrium¬ sulfit, sowie Parfümöle, Komplexbildner, Netzmittel, Emulgatoren, Verdicker und Pflegestoffe enthalten sein.In addition, the hair dye can also contain other customary cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, and also perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.
Die Zubereitungsform des neuen Haarfärbemittels kann beispielsweise eine Lösung, insbesondere eine wäßrige oder wäßrig-alkoholische Lösung sein. Die besonders bevorzugten Zubereitungsformen sind jedoch eine Creme, ein Gel oder eine Emulsion. Ihre Zusammensetzung stellt eine Mischung der Farbstoffkomponenten mit den für solche Zubereitungen üblichen Zusätzen dar.The preparation form of the new hair dye can be, for example, a solution, especially an aqueous one or be an aqueous-alcoholic solution. However, the particularly preferred preparation forms are a cream, a gel or an emulsion. Their composition represents a mixture of the dye components with the additives customary for such preparations.
Übliche Zusätze in Lösungen, Cremes, Emulsionen oder Gelen sind zum Beispiel Lösungsmittel wie Wasser, niedere aliphatische Alkohole, beispielsweise Ethanol, Propanol und Isopropanol, Glycerin, oder Glykole wie 1,2- Propylenglykol, weiterhin Netzmittel oder Emulgatoren aus den Klassen der anionischen, kationischen, amphoteren oder nichtionogenen oberflächenaktiven Substanzen wie Fettalkoholsulfate, oxethylierte Fettalkoholsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Alkyltrimethyl- ammoniumsalze, Alkylbetaine, oxethylierte Fettalkohole, oxethylierte Nonylphenole, Fettsäurealkanolamide, oxethylierte Fettsäureester, ferner Verdicker wie höhere Fettalkohole, Stärke, Cellulosederivate, Vaseline, Paraffinöl und Fettsäuren sowie außerdem Pflegestoffe wie kationische Harze, Lanolinderivate, Cholesterin, Pantothensäure und Betain. Die erwähnten Bestandteile werden in den für solche Zwecke üblichen Mengen verwen¬ det, zum Beispiel die Netzmittel und Emulgatoren in Konzentrationen von etwa 0,5 bis 30 Gewichtsprozent, die Verdicker in einer Menge von etwa 0,1 bis 25 Gewichts¬ prozent und die Pflegestoffe in einer Konzentration von etwa 0,1 bis 5,0 Gewichtsprozent.Usual additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol and isopropanol, glycerol, or glycols such as 1,2-propylene glycol, furthermore wetting agents or emulsifiers from the classes of the anionic, cationic , amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium ammonium salts, alkylbetaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid ester, also thickeners such as higher fatty alcohols, starch, cellulose derivatives, vaseline, paraffin oil and fatty acids as well Care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The constituents mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 percent by weight.
Je nach Zusammensetzung kann das erfindungsgemäße Haar¬ färbemittel schwach sauer, neutral oder alkalische reagieren. Insbesondere weist es einen pH-Wert von 6,0 bis 11,5 auf, wobei die basische Einstellung mit Ammoniak erfolgt. Es können aber auch organische Amine, zum Beispiel Monoethanolamin und Triethanolamin, oder auch anorganische Basen wie Natriumhydroxid und Kalium¬ hydroxid Verwendung finden. Für eine pH-Einstellung im sauren Bereich kommen zum Beispiel Phosphorsäure sowie Essigsäure oder andere organische Säuren,wie zum Beispiel Zitronensäure oder Weinsäure, in Betracht.Depending on the composition, the hair dye according to the invention can react weakly acidic, neutral or alkaline. In particular, it has a pH of 6.0 to 11.5, the basic setting being carried out with ammonia. But organic amines, for example monoethanolamine and triethanolamine, or else inorganic bases such as sodium hydroxide and potassium hydroxide are used. For a pH adjustment in the acidic range, for example phosphoric acid and acetic acid or other organic acids, such as citric acid or tartaric acid, come into consideration.
Für die Anwendung zur oxidativen Färbung von Haaren vermischt man das vorstehend beschriebene Haarfärbe¬ mittel unmittelbar vor dem Gebrauch mit einem Oxida- tionsmittel und trägt eine für die Haarfärbebehandlung ausreichende Menge, je nach Haarfülle, im allgemeinen etwa 60 bis 200 g, dieses Gemisches auf das Haar auf.For use in the oxidative dyeing of hair, the hair dye described above is mixed with an oxidizing agent immediately before use and an amount sufficient for hair dye treatment, depending on the hair volume, is generally about 60 to 200 g of this mixture Hair on.
Als Oxidationsmittel zur Entwicklung der Haarfärbung kommen hauptsächlich Wasserstoffperoxid oder dessen Additionsverbindungen an Harnstoff, Melamin oder Natriumborat in Form einer 3- bis 12-prozentigen, vor¬ zugsweise 6-prozentigen, wäßrigen Lösung, aber auch Luftsauerstoff in Betracht. Wird eine 6-prozentige Wasserstoffperoxid-Lösung als Oxidationsmittel verwen¬ det, so beträgt das Gewichtsverhältnis zwischen Haar¬ färbemittel und Oxidationsmittel 5:1 bis 1:2, vorzugs¬ weise jedoch 1:1. Größere Mengen an Oxidationsmittel werden vor allem bei höheren Farbstoffkonzentrationen im Haarfärbemittel oder wenn gleichzeitig eine stärkere Bleichung des Haares beabsichtigt ist verwendet. Man läßt das Gemisch bei 15 bis 50 Grad Celsius etwa 10 bis 45 Minuten lang, vorzugsweise 30 Minuten lang, auf das Haar einwirken, spült sodann das Haar mit Wasser aus und trocknet es. Gegebenenfalls wird im Anschluß an diese Spülung mit einem Shampoo gewaschen und eventuell mit einer schwachen organischen Säure, wie zum Beispiel Zitronensäure oder Weinsäure, nachgespült. Anschließend wird das Haar getrocknet. Die in den erfindungsgemäßen Oxidationshaarfärbemitteln verwendeten 4,5-Diamino-pyrazolderivate der allgemeinen Formel (I) lassen sich sehr gut darstellen, indem man ein 3,5-Dibrom-4-nitropyrazol der allgemeinen Formel (II) mit einem geeigneten Benzylhalogenid in Gegenwart von Natriumhydrid zur Reaktion bringt, anschließend das erhaltene l-Benzyl-3,5-dibrom-4-nitropyrazolderivat der aligemeinen Formel (III) mit einem A in umsetzt und das so erhaltene 5-Alkylamino-l-benzyl-3-brom-4-nitropyrazol- derivat der allgemeinen Formel (IV) katalytisch reduziert.The main oxidizing agents used to develop hair color are hydrogen peroxide or its addition compounds with urea, melamine or sodium borate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5: 1 to 1: 2, but preferably 1: 1. Larger amounts of oxidizing agent are used above all at higher dye concentrations in the hair dye or when more bleaching of the hair is intended at the same time. The mixture is allowed to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, this rinse is washed with a shampoo and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried. The 4,5-diamino-pyrazole derivatives of the general formula (I) used in the oxidation hair colorants according to the invention can be very well prepared by a 3,5-dibromo-4-nitropyrazole of the general formula (II) with a suitable benzyl halide in the presence of Brings sodium hydride to reaction, then the l-benzyl-3,5-dibromo-4-nitropyrazole derivative of the general formula (III) obtained is reacted with an A in and the 5-alkylamino-l-benzyl-3-bromo-4- obtained nitropyrazole derivative of the general formula (IV) catalytically reduced.
(II) (III) (IV) (I)(II) (III) (IV) (I)
Das als Ausgangsmaterial benötigte 3,5-Dibrom-4-nitro- prazol (II) ist in der Literatur beschrieben und läßt sich leicht auf folgendem Weg darstellen:The 3,5-dibromo-4-nitro-prazole (II) required as starting material is described in the literature and can be easily prepared in the following way:
Nitrierung von Pyrazol mit Schwefelsäure/Salpetersäure liefert 4-Nitro-pyrazol in einer Ausbeute von 80 Prozent (R. Hüttel et al. , Chem. Ber. .88./ 1577 (1955)). Durch mildere Bedingungen bei der Nitrierung erhält man N-Nitro-pyrazol in Ausbeuten von 84 bis 93 Prozent (H.J. Klebe et al., Synthesis 1973, 294); das sich durch Ein¬ wirken von Schwefelsäure ebenfalls zum 4-Nitro-pyrazol umlagern läßt (R. Hüttel et al., Chem. Ber. .88., 1586 (1955)). Bromierung von 4-Nitro-pyrazol nach der Vor¬ schrift von J.P.H. Juffermanns et al., J. Org. Chem. 51, 4656 (1986) liefert dann das 3,5-Dibrom-4-nitro- pyrazol (II) . Nach dem erfindungsgemäßen Verfahren läßt sich das 3,5-Dibrom-4-nitro-pyrazol zu den neuen 1-Benzyl-sub- stituierten Pyrazolen der allgemeinen Formel (III) umsetzen, wobei Rl einen Halogen-, Alkyl- beziehungsweise. Alkoxyrest darstellt. Die Einführung dieser Reste kann dabei nach verschiedenen Verfahren erfolgen, so können zum Beispiel die Verbindungen der allgemeinen Formel (III) durch Umsetzung der Verbindung (II) mit Natriumhydrid in Dimethylformamid durch Zugabe der entsprechenden Benzylhalogenide erhalten werden. Der besondere Vorteil dieses Reaktionsschrittes liegt vor allem in der isomerenreinen Darstellung der N-Benzyl-substituierten Pyrazole der allgemeinen Formel (III).Nitration of pyrazole with sulfuric acid / nitric acid gives 4-nitro-pyrazole in a yield of 80 percent (R. Hüttel et al., Chem. Ber. .88. / 1577 (1955)). Milder conditions during the nitration give N-nitro-pyrazole in yields of 84 to 93 percent (HJ Klebe et al., Synthesis 1973, 294); which can also be rearranged to 4-nitro-pyrazole by the action of sulfuric acid (R. Hüttel et al., Chem. Ber. .88., 1586 (1955)). Bromination of 4-nitro-pyrazole according to the instructions of JPH Juffermanns et al., J. Org. Chem. 51, 4656 (1986) then gives 3,5-dibromo-4-nitro-pyrazole (II). According to the process of the invention, the 3,5-dibromo-4-nitro-pyrazole can be converted to the new 1-benzyl-substituted pyrazoles of the general formula (III), where R1 is a halogen, alkyl or. Represents alkoxy radical. These residues can be introduced by various methods, for example the compounds of the general formula (III) can be obtained by reacting the compound (II) with sodium hydride in dimethylformamide by adding the corresponding benzyl halides. The particular advantage of this reaction step lies above all in the isomerically pure preparation of the N-benzyl-substituted pyrazoles of the general formula (III).
Durch Austausch eines Bromatoms in der Verbindung (III) erhält man die Pyrazolderivate der allgemeinen Formel ( IV) , in der Rl die vorstehend angegebene Bedeutung besitzt, während R einen Cι-C4-Alkyl-, C2-C4-Hydroxy- alkyl-oder Benzylrest darstellt. Der Austausch des Brom¬ atoms erfolgt hierbei durch Einwirkung einer wäßrigen oder alkoholischen Lösung des entsprechenden Alkyl-, Hydroxyalkyl-oder Benzylamins . Bei diesem Reaktions¬ schritt wird ausschließlich das Bromatom in 5-Stellung ausgetauscht, so daß auch in diesem Reaktionsschritt nur isomerenreine Verbindungen entstehen.By exchanging a bromine atom in the compound (III), the pyrazole derivatives of the general formula (IV) are obtained, in which Rl has the meaning given above, while R is a C 1 -C 4 -alkyl, C2-C4-hydroxyalkyl or benzyl radical represents. The exchange of the bromine atom takes place here by the action of an aqueous or alcoholic solution of the corresponding alkyl, hydroxyalkyl or benzylamine. In this reaction step, only the bromine atom in the 5-position is exchanged, so that only isomerically pure compounds are formed in this reaction step.
Durch katalytische Reduktion lassen sich die Verbindun¬ gen der allgemeinen Formel (IV) zu unterschiedlichen 4,5-Diaminopyrazolen der allgemeinen Formel (I) umwan¬ deln, wobei die Reduktion üblicherweise mit Wasserstoff und gebräuchlichen Katalysatoren (beispielsweise Palladium/Aktivkohle-Katalysatoren) durchgeführt wird und zur Erhöhung der Reaktionsgeschwindigkeit gegebenenfalls im Autoklaven unter Druck hydriert werden kann. Bei diesem Verfahren ist es insbesondere überraschend, daß der substituierte Benzylrest der Verbindungen der allgemeinen Formel (IV) nicht reduktiv entfernt wird. Im Gegensatz hierzu wurden bei Vergleichs¬ versuchen mit Verbindungen der Formel (IV), bei denen Rl Wasserstoff darstellt, nach Reduktion in allen Fällen 4,5-Diamino-pyrazole, die in der 1-Position ein Wasser¬ stoffatom trugen, erhalten.The compounds of the general formula (IV) can be converted to different 4,5-diaminopyrazoles of the general formula (I) by catalytic reduction, the reduction usually being carried out using hydrogen and customary catalysts (for example palladium / activated carbon catalysts) is and can optionally be hydrogenated in an autoclave under pressure to increase the reaction rate. It is particular with this method Surprisingly, the substituted benzyl radical of the compounds of the general formula (IV) is not removed reductively. In contrast to this, in comparative experiments with compounds of the formula (IV) in which R 1 represents hydrogen, 4,5-diamino-pyrazoles which had a hydrogen atom in the 1-position were obtained after reduction in all cases.
Im Falle der Verbindungen der allgemeinen Formel (IV), bei denen R3 einen Benzylrest oder einen tertiären Butylrest darstellt, gelangt man nach reduktiver Entfernung dieser Reste zu 4,5-Diamino-pyrazol-derivaten, die nach wie vor in 1-Stellung einen substituierten Benzylrest tragen.In the case of the compounds of the general formula (IV) in which R3 represents a benzyl radical or a tertiary butyl radical, after reductive removal of these radicals 4,5-diamino-pyrazole derivatives are obtained which still have a substituted one in the 1-position Wear benzyl residue.
Prinzipiell könnte man zu entsprechenden Verbindungen der Formel (IV) auch gelangen, wenn bei der Herstellung der Verbindungen der allgemeinen Formel (III), das sich in 5-Stellung befindliche Bromatom gegen eine Aminogruppe ausgetauscht werden könnte. Diese Reaktion wurde aber bei den üblichen Reaktionsbedingungen nicht beobachtet, auch bei erhöhtem Druck gelingt die Einführung einer Aminogruppe nicht in präparativen Ausbeuten.In principle, corresponding compounds of the formula (IV) could also be obtained if, in the preparation of the compounds of the general formula (III), the bromine atom located in the 5-position could be replaced by an amino group. However, this reaction was not observed under the usual reaction conditions; even at elevated pressure, it is not possible to introduce an amino group in preparative yields.
Die Salze der Verbindungen der Formel (I) sind durch Um¬ setzung mit organischen oder anorganischen Säuren oder Basen erhältlich.The salts of the compounds of formula (I) can be obtained by reaction with organic or inorganic acids or bases.
Die Entwicklersubstanzen der Formel (I) sollen in dem Haarfärbemittel entweder als freie Basen oder in Form ihrer physiologisch verträglichen Salze mit anorganischen oder organischen Säuren, wie zum Beispiel Salzsäure, Schwefelsäure, Phosphorsäure, Essigsäure, Propionsäure, Milchsäure oder Zitronensäure, eingesetzt werden. Die Verbindungen der Formel (I) sind gut in Wasser löslich und sie weisen zusätzlich eine ausgezeichnete Lager¬ stabilität, insbesondere als Bestandteil der hier beschriebenen Haarfärbemittel, auf.The developer substances of the formula (I) are to be used in the hair dye either as free bases or in the form of their physiologically tolerable salts with inorganic or organic acids, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid. The compounds of formula (I) are readily soluble in water and they additionally have excellent storage stability, in particular as a constituent of the hair colorants described here.
Das erfindungsgemäße Haarfärbemittel mit einem Gehalt an 4,5-Diaminopyrazolderivaten als Entwicklersubstanzen ermöglicht Haarfärbungen mit ausgezeichneter Farbecht¬ heit, insbesondere was die Licht-, Wasch- und Reibeecht¬ heit anbetrifft.The hair dye according to the invention with a content of 4,5-diaminopyrazole derivatives as developer substances enables hair dyeings with excellent color fastness, in particular with regard to light, washing and rubbing fastness.
Hinsichtlich der färberischen Eigenschaften bieten die erfindungsgemäßen Haarfärbemittel Möglichkeiten, die weit über einen Ersatz der üblicherweise verwendeten 4-Aminophenole hinausgehen. So lassen sich brillante Rottöne mit außerordentlicher Farbtiefe erzeugen, wie sie mit den gängigen Farbkomponenten nicht zu erzielen sind. Neben dieser Anwendung im hochmodischen Bereich können aber auch durch die Verwendung in Kombination mit geeigneten Kupplungskomponenten natürliche Farbtöne erzeugt werden, ohne daß eine weitere Entwicklungs¬ komponente vom Typ der p-Phenylendiamine erforderlich wäre.With regard to the coloring properties, the hair colorants according to the invention offer possibilities which go far beyond the replacement of the 4-aminophenols normally used. In this way, brilliant red tones can be created with an extraordinary depth of color that cannot be achieved with the usual color components. In addition to this application in the highly fashionable field, natural colors can also be produced by the use in combination with suitable coupling components without the need for a further development component of the p-phenylenediamine type.
Die sehr guten färberischen Eigenschaften der Haarfärbe¬ mittel gemäß der vorliegenden Anmeldung zeigen sich weiterhin darin, daß diese Mittel eine Anfärbung von ergrauten, chemisch nicht vorgeschädigten Haaren problemlos und mit guter Deckkraft ermöglichen.The very good coloring properties of the hair colorants according to the present application are further shown in the fact that these agents enable graying, chemically not previously damaged hair to be colored easily and with good coverage.
Gegenstand der vorliegenden Patentanmeldung sind ferner die neuen 4,5-Diaminopyrazolderivate der allgemeinen Formel ( I) , wobei insbesondere 4,5-Diamino-l-(4 '-methoxybenzyl)-pyrazol,The present patent application also relates to the new 4,5-diaminopyrazole derivatives of the general formula (I), in particular 4,5-diamino-1- (4'-methoxybenzyl) pyrazole,
4,5-Diamino-1-(3'-methoxybenzyl)-pyrazol,4,5-diamino-1- (3'-methoxybenzyl) pyrazole,
4,5-Diamino-l-(4'-methylbenzyl)-pyrazol,4,5-diamino-1- (4'-methylbenzyl) pyrazole,
4,5-Diamino-l-(4'-chlorbenzyl)-pyrazol,4,5-diamino-l- (4'-chlorobenzyl) pyrazole,
4-Amino-l-(4'-methoxybenzyl)-5-methylamino-pyrazol und4-amino-1- (4'-methoxybenzyl) -5-methylamino-pyrazole and
4-Amino-5-(2'-hydroxyethyl)amino-l-(4 '-methoxybenzyl)- pyrazol zu nennen sind.4-Amino-5- (2'-hydroxyethyl) amino-1- (4'-methoxybenzyl) pyrazole are mentioned.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf zu beschrän¬ ken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto.
HerstellungsbeispieleManufacturing examples
Beispiel 1: Synthese von l-Benzyl-3,5-dibrom-4-nitro- pyrazolen der allgemeinen Formel (III)Example 1: Synthesis of l-benzyl-3,5-dibromo-4-nitro-pyrazoles of the general formula (III)
Allgemeine VorschriftGeneral rule
Zu 1,75 g (70,0 mmol) Natriumhydrid (96 % in 150 ml absolutem Dimethylformamid (DMF)) werden über einen Zeit¬ raum von 1 Stunde 19,0 g (70,0 mmol) 3,5-Dibrom-4-nitro- pyrazol in 90 ml absolutem DMF getropft. Man beobachtet eine Erwärmung der Reaktionslösung und starke Gasent¬ wicklung. Sobald sich die Gasentwicklung gelegt hat, liegt eine klare orangene Lösung vor. Nun werden 70,0 mmol Benzylhalogenid in 30 ml DMF zugetropft und es wird 3 Stunden auf 80 "Celsius erhitzt. Das Lösungs¬ mittel wird im Vakuum abdestilliert und der Rückstand aus Methylenchlorid umkristallisiert.To 1.75 g (70.0 mmol) of sodium hydride (96% in 150 ml of absolute dimethylformamide (DMF)) 19.0 g (70.0 mmol) of 3,5-dibromo-4 are added over a period of 1 hour -nitro-pyrazole dropped in 90 ml of absolute DMF. A heating of the reaction solution and strong gas evolution are observed. As soon as the gas evolution has subsided, there is a clear orange solution. 70.0 mmol of benzyl halide in 30 ml of DMF are then added dropwise and the mixture is heated at 80 ° C. for 3 hours. The solvent is distilled off in vacuo and the residue is recrystallized from methylene chloride.
I. 3,5-Dibrom-l-(4'-methoxybenzol,-4-nitro-pyrazol Benzylhalogenid: 4-MethoxybenzylchloridI. 3,5-dibromo-1- (4'-methoxybenzene, -4-nitro-pyrazole benzyl halide: 4-methoxybenzyl chloride
Nach der allgemeinen Vorschrift erhält man 21,7 g (79 Prozent der Theorie) 3,5-Dibrom-l-(4 '-methoxybenzyl)-4- nitro-pyrazol mit einem Schmelzpunkt von 115 bis 118 Grad Celsius.According to the general procedure, 21.7 g (79 percent of theory) of 3,5-dibromo-l- (4'-methoxybenzyl) -4-nitro-pyrazole with a melting point of 115 to 118 degrees Celsius are obtained.
iH-NMR (60 MHz), DMSO-d6:<f= 3,78 (s; 3H; OCH3) ; 5,30 (s; 2H; -CH2-) und 7,07 ppm (m; 4H; Ph-H)iH-NMR (60 MHz), DMSO-d6: <f = 3.78 (s; 3H; OCH3); 5.30 (s; 2H; -CH2-) and 7.07 ppm (m; 4H; Ph-H)
MS (70 eV) :m/e= 393 (M+) II . 3,5-Dibrom-l-( 3 '-methoxybenzyl)-4-nitro-pyrazol Benzylhalogenid: 3-MethoxybenzylchlσridMS (70 eV): m / e = 393 (M + ) II. 3,5-dibromo-1- (3'-methoxybenzyl) -4-nitro-pyrazole benzyl halide: 3-methoxybenzylchloride
Nach der allgemeinen Vorschrift erhält man 26 g (96 Pro¬ zent der Theorie) 3,5-Dibrom-l-(3 '-methoxybenzyl)-4-ni- tropyrazol mit einem Schmelzpunkt von 130 Grad Celsius.According to the general procedure, 26 g (96 percent of theory) of 3,5-dibromo-l- (3 '-methoxybenzyl) -4-nitropyrazole with a melting point of 130 degrees Celsius are obtained.
iH-NMR (MHz), DMS0-d6:cT= 3,74 (s; 3H; OCH3) ; 5,48 (s; 2H; -CH2)- 6,76-6,93 ( ; 3H; 3H; Ph-H) und 7,30 pp (dd; J=8Hz; 1H; Ph-5H)iH-NMR (MHz), DMS0-d6: cT = 3.74 (s; 3H; OCH 3 ); 5.48 (s; 2H; -CH2) - 6.76-6.93 (; 3H; 3H; Ph-H) and 7.30 pp (dd; J = 8Hz; 1H; Ph-5H)
MS (70 eV):m/e= 393 (M+)MS (70 eV): m / e = 393 (M + )
III. 3,5-Dibrom-l-(4 '-Methylbenzyl .-4-nitro-pyrazol Benzylhalogenid: 4-MethylbenzylchloridIII. 3,5-dibromo-1- (4 '-methylbenzyl. -4-nitro-pyrazole benzyl halide: 4-methylbenzyl chloride
Nach der allgemeinen Vorschrift erhält man 18 g (68 Pro¬ zent der Theorie) 3,5-Dibrom-l-(4 '-methylbenzyl)-4-nitro- pyrazol mit einem Schmelzpunkt von 108 Grad Celsius.According to the general procedure, 18 g (68 percent of theory) of 3,5-dibromo-1- (4'-methylbenzyl) -4-nitropyrazole with a melting point of 108 degrees Celsius are obtained.
iH-NMR (300 MHz, DMSO-dg) '.< = 2,28 (s; 3H; -CH3);iH-NMR (300 MHz, DMSO-dg) '. <= 2.28 (s; 3H; -CH3);
5,45 (s; 2H; -CH2-) und 7,18 ppm (m; 4H; Ph-H)5.45 (s; 2H; -CH2-) and 7.18 ppm (m; 4H; Ph-H)
MS (70 eV):m/e= 375 (M+) IV. 3 ,5-Dibrom-l- (4 '-Chlorbenzyl )-4-nitro-pyrazol Benzylhalogenid: 4-ChlorbenzylchloridMS (70 eV): m / e = 375 (M + ) IV. 3,5-dibromo-1- (4'-chlorobenzyl) -4-nitro-pyrazole benzyl halide: 4-chlorobenzyl chloride
Nach der allgemeinen Vorschrift erhält man 25 g (91 Pro¬ zent der Theorie) 3,5-Dibrom-l-(4 '-chlorbenzyl )-4-nitro- pyrazol mit einem Schmelzpunkt von 109 Grad Celsius.According to the general procedure, 25 g (91 percent of theory) of 3,5-dibromo-1- (4'-chlorobenzyl) -4-nitro-pyrazole are obtained with a melting point of 109 degrees Celsius.
iH-NMR (300 MHz, DMSO-dß):«^ 5,51 (s; 2H; -CH2) ;iH-NMR (300 MHz, DMSO-dß): ^5.51 (s; 2H; -CH2);
7,28 (d; J=8,4 Hz; 2H; Ph-3H und Ph-5H) und 7,75 ppm (d; J=8,4 Hz; 2H; Ph-2H und Ph-6H)7.28 (d; J = 8.4 Hz; 2H; Ph-3H and Ph-5H) and 7.75 ppm (d; J = 8.4 Hz; 2H; Ph-2H and Ph-6H)
MS (70 eV) :m/e= 395 (M+)MS (70 eV): m / e = 395 (M +)
Beispiel 2: Synthese von 5-Alkylamino-l-benzyl-3-brom- 4-nitro-pyrazolen der allgemeinen Formel (IV)Example 2: Synthesis of 5-alkylamino-1-benzyl-3-bromo-4-nitro-pyrazoles of the general formula (IV)
I• Darstellung von 3-Brom-l-f4 '-methoxybenzyl)-5- methylamino-4-nitropyrazolI • Preparation of 3-bromo-l-f4 '-methoxybenzyl) -5-methylamino-4-nitropyrazole
3,93 g (10,0 mmol) 3,5-Dibrom-l-(4 '-methoxybenzyl )-4- nitropyrazol werden unter Rühren mit 100 ml einer 40- prozentigen wäßrigen Methylaminlösung (1,28 mol) ver¬ setzt. Man beobachtet eine Farbänderung der Reaktions¬ lösung nach gelb. Die Reaktionsmischung wird über Nacht bei 60 Grad Celsius gerührt. Man extrahiert die gelb-orange Lösung, aus der bereits eine gelbe Substanz auskristallisiert ist, dreimal mit je 200 ml Essigester, trocknet über Calciumchlorid und filtriert den öligen Rückstand über Kieselgel mit Methylenchlorid. Ausbeute: 2,54 g (75 Prozent der Theorie) 3-Brom-l-( 4 '- methoxybenzyl )-5-methylamino-4-nitropyrazol in Form gelber Kristalle mit einem Schmelzpunkt von 144 bis 147 Grad Celsius.3.93 g (10.0 mmol) of 3,5-dibromo-l- (4'-methoxybenzyl) -4-nitropyrazole are mixed with 100 ml of a 40 percent aqueous methylamine solution (1.28 mol) with stirring. A change in color of the reaction solution to yellow is observed. The reaction mixture is stirred at 60 degrees Celsius overnight. The yellow-orange solution, from which a yellow substance has already crystallized, is extracted three times with 200 ml of ethyl acetate each time, dried over calcium chloride and the oily residue is filtered through silica gel with methylene chloride. Yield: 2.54 g (75 percent of theory) of 3-bromo-1- (4'-methoxybenzyl) -5-methylamino-4-nitropyrazole in the form of yellow crystals with a melting point of 144 to 147 degrees Celsius.
iH-NMR (60 MHz, HZ; - NH; mit D2O aus¬ tauschbar), 7,00 (m; 4H; Ph-H), 5,33 (s; 2H; -CH2PH-OCH3) 3,72 (s; 3H; -OCH3) und 3,05 ppm (d; 3H; J=6Hz; -CH3)iH-NMR (60 MHz, HZ; - NH; exchangeable with D2O), 7.00 (m; 4H; Ph-H), 5.33 (s; 2H; -CH2PH-OCH3) 3.72 (s; 3H; -OCH3) and 3.05 ppm ( d; 3H; J = 6Hz; -CH3)
MS (70 eV) :m/e= 342 (M+)MS (70 eV): m / e = 342 (M + )
II. Synthese von 3-Brom-5-(2 '-hydroxyethylamino , -1- (4 '-methoxybenzyl . -4-nitropyrazolII. Synthesis of 3-bromo-5- (2 '-hydroxyethylamino, -1- (4' -methoxybenzyl. -4-nitropyrazole
4,00 g (10,0 mmol) 3,5-Dibrom-l-(4 '-methoxybenzyl)-4- nitropyrazol werden in 30 ml Ethanol mit 0,61 g (10,0 mmol) Ethanolamin versetzt und bei 70 Grad Celsius über Nacht gerührt. Ein angefertigtes Dunnschichtchromatogramm zeigt, daß eine ungefähr 50-prozentige Umsetzung erfolgt ist. Es werden weitere 0,60 g (10,0 mmol) Ethanolamin zugesetzt und 2 Stunden bei 70 Grad Celsius gerührt. Nun ist im Dunnschichtchromatogramm (Lauf ittel: Methylen¬ chlorid) neben wenig Edukt ein einziges Reaktionsprodukt zu finden. Man gießt die Reaktionsmischung auf Wasser, wobei eine gelbe Substanz kristallisiert, die abgesaugt wird. Ausbeute: 3,39 g (91 Prozent der Theorie) 3-Brom-5-(2-hy- droxyethylamino)-1-(4-methoxybenzyl)-4-nitropyrazol mit einem Schmelzpunkt von 112 Grad Celsius.4.00 g (10.0 mmol) of 3,5-dibromo-l- (4 '-methoxybenzyl) -4-nitropyrazole are mixed in 30 ml of ethanol with 0.61 g (10.0 mmol) of ethanolamine and at 70 degrees Celsius stirred overnight. A thin layer chromatogram shows that an approximately 50 percent conversion has taken place. A further 0.60 g (10.0 mmol) of ethanolamine are added and the mixture is stirred at 70 degrees Celsius for 2 hours. Now, in the thin layer chromatogram (running agent: methylene chloride), along with a small amount of starting material, a single reaction product can be found. The reaction mixture is poured onto water, a yellow substance crystallizing which is filtered off with suction. Yield: 3.39 g (91 percent of theory) of 3-bromo-5- (2-hydroxyethylamino) -1- (4-methoxybenzyl) -4-nitropyrazole with a melting point of 112 degrees Celsius.
iH-NMR (60 MHz, DMSO-d6):cT= 7,50 (s; breit; 1H; -NH; mit D2O austauschbar), 7,05 (m; 4H; Ph-H), 5,34 (s: 2H; CH2-Ph-OCH3) , 5,00 (s; breit; 1H; -OH; mit D2O austauschbar), 3,75 (s; 3H; -OCH3) und 3,45 ppm (m; 4H; -CH2-CH2-)iH-NMR (60 MHz, DMSO-d6): cT = 7.50 (s; broad; 1H; -NH; exchangeable with D2O), 7.05 (m; 4H; Ph-H), 5.34 (s : 2H; CH2-Ph-OCH3), 5.00 (s; broad; 1H; -OH; exchangeable with D2O), 3.75 (s; 3H; -OCH3) and 3.45 ppm (m; 4H; - CH2-CH2-)
MS (70 eV) :m/e= 372 (M+)MS (70 eV): m / e = 372 (M + )
III. Synthese von 3-Brom-5-tert-butylamino-l-(4 '- methoxybenzyl)-4'-nitropyrazolIII. Synthesis of 3-bromo-5-tert-butylamino-l- (4 '- methoxybenzyl) -4'-nitropyrazole
0,50 g (1,28 mmol) 3,5-Dibrom-l-(4'-methoxybenzyl)-4- nitropyrazol werden in einer Lösung von 10 g tert- Butylamin in 40 ml Ethanol 20 Stunden unter Rückfluß erhitzt. Nach dem Abkühlen der Reaktionsmischung gießt man in 100 ml Wasser und extrahiert dreimal mit je 50 ml Essigester. Nach dem Trocknen über Magnesiumsulfat wird einrotiert und der Rückstand an Kieselgel mit Dichlor- methan adsorptiv filtriert. Ausbeute: 490 mg (99 Prozent der Theorie) 3-Brom-5-tert- butylamino-1-(4'-methoxybenzyl)-4-nitropyrazol als blaßgelbe Kristalle mit einem Schmelzpunkt von 72 Grad Celsius.0.50 g (1.28 mmol) of 3,5-dibromo-1- (4'-methoxybenzyl) -4-nitropyrazole are refluxed in a solution of 10 g of tert-butylamine in 40 ml of ethanol for 20 hours. After the reaction mixture has cooled, it is poured into 100 ml of water and extracted three times with 50 ml of ethyl acetate each time. After drying over magnesium sulfate, the mixture is evaporated in a rotary evaporator and the residue is filtered adsorptively on silica gel with dichloromethane. Yield: 490 mg (99 percent of theory) of 3-bromo-5-tert-butylamino-1- (4'-methoxybenzyl) -4-nitropyrazole as pale yellow crystals with a melting point of 72 degrees Celsius.
iH-NMR (60 MHz, DMSO-d6): = 7,00 ppm (m; 4H; Ph-H), 5,32 (s; 1H; N-H; mit D2O austauschbar), 5,22 (s; 2H; IN-CH2-), 3,70 (s; 3H; OCH3) und 1,18 ppm (s; 9H; -C(CH3)3)iH-NMR (60 MHz, DMSO-d6): = 7.00 ppm (m; 4H; Ph-H), 5.32 (s; 1H; NH; exchangeable with D2O), 5.22 (s; 2H; IN-CH2-), 3.70 (s; 3H; OCH3) and 1.18 ppm (s; 9H; -C (CH3) 3 )
MS (70 eV) :m/e= 394 (M+)MS (70 eV): m / e = 394 (M +)
IV. Synthese von 5-Benzylamino-3-brom-l-<.4 '-methoxy¬ benzyl .-4-nitropyrazolIV. Synthesis of 5-benzylamino-3-bromo-1 - <. 4 '-methoxy-benzyl.-4-nitropyrazole
4,00 g (10,0 mmol) 3,5-Dibrom-l-(4'-methoxybenzyl)-4- nitropyrazol werden in 30 ml Ethanol mit 11,0 g (100 mmol) Benzylamin versetzt. Man erhitzt 3,5 Stunden zum Sieden. Man gießt die Reaktionsmischung auf 100 ml Wasser und extrahiert zweimal mit je 100 ml Essigester. Nach Trocknung mit Magnesiumsulfat filtriert man den öligen Rückstand adsorptiv an Kieselgel mit Hexan/ Chloroform (1:2) .4.00 g (10.0 mmol) of 3,5-dibromo-1- (4'-methoxybenzyl) -4-nitropyrazole are mixed with 11.0 g (100 mmol) of benzylamine in 30 ml of ethanol. The mixture is heated to boiling for 3.5 hours. The reaction mixture is poured onto 100 ml of water and extracted twice with 100 ml of ethyl acetate each time. After drying with magnesium sulfate, the oily residue is filtered adsorptively on silica gel with hexane / chloroform (1: 2).
Ausbeute: 4,13 g (99 Prozent der Theorie) 5-Benzyl- amino-3-brom-l-(4'-methoxybenzyl)-4-nitropyrazol mit einem Schmelzpunkt von 125 bis 127 Grad Celsius (Hexan/ Chloroform 1:2) iH-NMR (60 MHz, DMSO-d6) :cT= 7,93 (t; 1H; J=6Hz; -NH; mit D2θ aus¬ tauschbar) 7,40-6,80 (m; 9H; Ph-H), 5,15 (s; 2H; CH3O-PI1-CH2 ) , 4,58 (d; 2H; J=6Hz; -NH-CH2-; nach D2O- Austausch s) und 3,73 ppm (s; 3Hz; -OCH3)Yield: 4.13 g (99 percent of theory) of 5-benzylamino-3-bromo-1- (4'-methoxybenzyl) -4-nitropyrazole with a melting point of 125 to 127 degrees Celsius (hexane / chloroform 1: 2 ) iH-NMR (60 MHz, DMSO-d6): cT = 7.93 (t; 1H; J = 6Hz; -NH; exchangeable with D2θ) 7.40-6.80 (m; 9H; Ph-H ), 5.15 (s; 2H; CH3O-PI1-CH2), 4.58 (d; 2H; J = 6Hz; -NH-CH2-; after D2O exchange s) and 3.73 ppm (s; 3Hz ; -OCH3)
MS (70 eV) :m/e= 418 (M+)MS (70 eV): m / e = 418 (M + )
V. Synthese von 5-Benzylamino-3-brom-l-.4 '-methyl¬ benzyl . -4-nitropyrazolV. Synthesis of 5-benzylamino-3-bromo-l-.4 '-methyl¬ benzyl. -4-nitropyrazole
15 g (40 mmol) 3,5-Dibrom-l-(4 '-methylbenzyl)-4-nitro- pyrazol werden in 120 ml Ethanol mit 15 ml Benzylamin versetzt. Nach 1 Stunde Erwärmen wird auf Eis gegossen, abgesaugt und aus Ethanol umkristallisiert.15 g (40 mmol) of 3,5-dibromo-1- (4'-methylbenzyl) -4-nitrophyrazole are mixed with 120 ml of ethanol with 15 ml of benzylamine. After heating for 1 hour, it is poured onto ice, suction filtered and recrystallized from ethanol.
Ausbeute: 10,0 g (62 Prozent der Theorie) 5-Benzylamino- 3-brom-l-(4 '-methylbenzyl)-4-nitro-pyrazol mit einem Schmelzpunkt von 108 Grad Celsius.Yield: 10.0 g (62 percent of theory) of 5-benzylamino-3-bromo-1- (4'-methylbenzyl) -4-nitro-pyrazole with a melting point of 108 degrees Celsius.
iH-NMR (300 MHz, DMS0-d6 ) : = 2,29 (s; 3H; -CH3) ; 4,54 (d; J=6,4Hz; 2H; NH-CH2-; nach D2O- Austausch s); 5,51 (s; 2H; 1-CH2); 7,15-7,35 (m; 9H; Ph-H) und 8,00 ppm (t, J=6,4 Hz; 1H; NH; tauscht mit D2θ aus)iH-NMR (300 MHz, DMS0-d6): = 2.29 (s; 3H; -CH3); 4.54 (d; J = 6.4Hz; 2H; NH-CH2-; after D2O exchange s); 5.51 (s; 2H; 1-CH2); 7.15-7.35 (m; 9H; Ph-H) and 8.00 ppm (t, J = 6.4 Hz; 1H; NH; exchanges with D2θ)
MS (70 eV) :m/e= 400 (M+)MS (70 eV): m / e = 400 (M + )
VI. Synthese von 5-Benzylamino-3-brom-l-(4 '-chlor¬ benzyl . -4-nitropyrazolVI. Synthesis of 5-benzylamino-3-bromo-1- (4'-chlorobenzyl. -4-nitropyrazole
9,88 g (25 mmol) 3,5-Dibrom-l-(4 '-chlorbenzyl)-4-nitro- pyrazol werden in 50 ml Ethanol mit 15 ml Benzylamin 1 Stunde erwärmt. Man gießt auf Eis, saugt ab und kristallisiert aus Ethanol um.9.88 g (25 mmol) of 3,5-dibromo-1- (4'-chlorobenzyl) -4-nitrophyrazole are heated in 50 ml of ethanol with 15 ml of benzylamine for 1 hour. It is poured onto ice, suction filtered and recrystallized from ethanol.
Ausbeute: 8 g (76 Prozent der Theorie) 5-Benzyl- amino-3-brom-l-(4 '-chlorbenzyl)-4-nitro-pyrazol mit einem Schmelzpunkt von 139 bis 141 Grad Celsius.Yield: 8 g (76 percent of theory) of 5-benzylamino-3-bromo-1- (4'-chlorobenzyl) -4-nitro-pyrazole with a melting point of 139 to 141 degrees Celsius.
iH-NMR (300 MHz, DMSO-d6):cf= 4,54 (d; J=5,4Hz; 2H; NH-CH2-; nach D2O- Austausch s), 5,23 (s; 2H; 1-CH2-); 7,10-7,38 (m; 9H; Ph-H) und 8,00 (t; 1H; -NH; tauscht mit D2O aus)iH-NMR (300 MHz, DMSO-d6): cf = 4.54 (d; J = 5.4Hz; 2H; NH-CH2-; after D2O exchange s), 5.23 (s; 2H; 1- CH2-); 7.10-7.38 (m; 9H; Ph-H) and 8.00 (t; 1H; -NH; exchanges with D2O)
MS (70 eV) :m/e= 421 (M+) VII. Synthese von 5-Benzylamino-3-brom-l-(3'-methoxy¬ benzyl )-4-nitro-pyrazolMS (70 eV): m / e = 421 (M + ) VII. Synthesis of 5-benzylamino-3-bromo-1- (3'-methoxy-benzyl) -4-nitro-pyrazole
7,8 g (20 mmol) 3,5-Dibrom-l-(3 '-methoxybenzyl)-4-nitro- pyrazol werden 1 Stunde mit 15 ml Benzylamin auf 80 Grad Celsius erwärmt. Man gießt auf Eis, saugt ab und kristallisiert aus Ethanol um.7.8 g (20 mmol) of 3,5-dibromo-l- (3 '-methoxybenzyl) -4-nitrophyrazole are heated to 80 degrees Celsius with 15 ml of benzylamine for 1 hour. It is poured onto ice, suction filtered and recrystallized from ethanol.
Ausbeute: 5,8 g (70 Prozent der Theorie) 5-Benzylamino-3- brom-1-(3'-methoxybenzyl)-4-nitro-pyrazol mit einem Schmelzpunkt von 98 Grad Celsius.Yield: 5.8 g (70 percent of theory) of 5-benzylamino-3-bromo-1- (3'-methoxybenzyl) -4-nitro-pyrazole with a melting point of 98 degrees Celsius.
iH-NMR (300 MHz, DMSO-d6) :</= 4,54 (d; J=6,0 Hz; 2H; NH-CH2- nach D2O- Austausch s); 5,19 (s; 2H; I-CH2-); 6,00-7,33 (m; 9H; Ph-H) und 8,02 (t; J=6,0Hz; 1H, NH; tauscht mit D2O aus)iH-NMR (300 MHz, DMSO-d6): </ = 4.54 (d; J = 6.0 Hz; 2H; NH-CH2 after D2O exchange s); 5.19 (s; 2H; I-CH2-); 6.00-7.33 (m; 9H; Ph-H) and 8.02 (t; J = 6.0Hz; 1H, NH; exchanges with D2O)
MS (70 eV) :m/e= 417 (M+)MS (70 eV): m / e = 417 (M + )
Beispiel 3: Synthese von l-Benzyl-4,5-diamino-pyrazolen der allgemeinen Formel (I)Example 3: Synthesis of l-benzyl-4,5-diamino-pyrazoles of the general formula (I)
Hydrierung von 5-Alkylamino-l-benzyl-3-brom-4-nitro- pyrazolen der allgemeinen Formel (IV). Allgemeine Vorschrift A:Hydrogenation of 5-alkylamino-1-benzyl-3-bromo-4-nitro-pyrazoles of the general formula (IV). General regulation A:
Das l-Alkyl-5-aminoalkyl-3-brom-4-nitropyrazol wird mitThe l-alkyl-5-aminoalkyl-3-bromo-4-nitropyrazole is with
130 ml Ethanol und 2 Spatelspitzen eines Palladium/130 ml ethanol and 2 spatula tips of a palladium /
Aktivkohle-Katalysators (10 %) in den AutoklavenActivated carbon catalyst (10%) in the autoclave
(250 ml) überführt und während des angegebenen Zeitraumes bei 50 bar Wasserstoffatmosphäre und Raumtemperatur (20 bis 30 Grad Celsius) gerührt. Nach Reaktionsende saugt man mit einer Wasserstrahlpumpe die Reaktionsmischung in einen Glaskolben und filtriert sofort über eine(250 ml) transferred and stirred during the specified period at 50 bar hydrogen atmosphere and room temperature (20 to 30 degrees Celsius). After the end of the reaction, the reaction mixture is sucked into a glass flask with a water jet pump and immediately filtered through a
Glasfritte. Das Filtrat wird mit einer äquimolaren Menge konzentrierter Schwefelsäure (97 %) versetzt.Glass frit. An equimolar amount of concentrated sulfuric acid (97%) is added to the filtrate.
I • Synthese von 4-Amino-l- (4 '-methoxybenzyl , -5-methyl- aminopyrazolI • Synthesis of 4-amino-1- (4'-methoxybenzyl, -5-methylaminopyrazole
1,04 g (3,00 mmol) 3-Brom-l-(4 '-methoxybenzyl)-5-methyl- amino-4-nitro-pyrazol werden 2 Stunden analog Vorschrift A hydriert. Man versetzt mit 0,30 g (2,80 mmol) konzen¬ trierter Schwefelsäure (97 Prozent). Nach Einengen erhält man 0,86 g (87 Prozent der Theorie) 4-Amino-l-(4 '- methoxybenzyl)-5-methylamino-pyrazol-hydrosulfat in Form eines Öls.1.04 g (3.00 mmol) of 3-bromo-1- (4'-methoxybenzyl) -5-methylamino-4-nitro-pyrazole are hydrogenated for 2 hours as described in procedure A. 0.30 g (2.80 mmol) of concentrated sulfuric acid (97 percent) are added. After concentration, 0.86 g (87 percent of theory) of 4-amino-1- (4'-methoxybenzyl) -5-methylamino-pyrazole hydrosulfate is obtained in the form of an oil.
iH-NMR (60 MHz, 9,60-7,73 (s; breit; 7H; -NH; - H2; H2SO4; mit D2O austauschbar), 7,51 (s; 1H; 3-H) , 7,02 (m; 4H; Ph-H), 5,13 (s; 2H; -CH2-Ph- OCH3), 3,70 (s; 3H; -OCH3) und 2,80 ppm (s; 3H; CH3NH-)iH-NMR (60 MHz, 9.60-7.73 (s; broad; 7H; -NH; - H2; H2SO4; interchangeable with D2O), 7.51 (s; 1H; 3-H), 7.02 (m; 4H; Ph- H), 5.13 (s; 2H; -CH2-Ph- OCH3), 3.70 (s; 3H; -OCH3) and 2.80 ppm (s; 3H; CH3NH-)
MS (70 eV):m/e= 232 (M+) II. Synthese von 4-Amino-5-(2 '-hydroxyethylamino)-1- (4 '-methoxybenzyl)-pyrazolMS (70 eV): m / e = 232 (M + ) II. Synthesis of 4-amino-5- (2'-hydroxyethylamino) -1- (4'-methoxybenzyl) pyrazole
1,04 g (2,80 mmol) 3-Brom-5-(2 '-hydroxyethylamino)-1- (4 '-methoxybenzyl)-4-nitropyrazol werden 3 Stunden analog Arbeitsvorschrift A hydriert. Man erhält 0,81 g (80 Prozent der Theorie) 4-Amino-5-(2'-hydroxyethyl¬ amino)-l-(4'-methoxybenzyl)-pyrazol-hydrosulfat in Form eines Öls.1.04 g (2.80 mmol) of 3-bromo-5- (2'-hydroxyethylamino) -1- (4'-methoxybenzyl) -4-nitropyrazole are hydrogenated for 3 hours as described in procedure A. 0.81 g (80 percent of theory) of 4-amino-5- (2'-hydroxyethyl¬ amino) -l- (4'-methoxybenzyl) pyrazole hydrosulfate are obtained in the form of an oil.
iH-NMR (60 MHz, 8,66-3,83 (s; breit; 9H; -NH; -NH2-0H, H2SO4 mit D2O aus¬ tauschbar) , 7,37 (s; 1H; 3-H), 7,00 (m; 4H; Ph-H), 5,13 (s; 2H; CH3θ-Ph-CH2-) , 3,73 (s; 3H; -OCH3) und 3,67-3,32 ppm (m; 4H; -CH2-CH2-)iH-NMR (60 MHz, 8.66-3.83 (s; broad; 9H; -NH; -NH2-0H, H2SO4 exchangeable with D2O), 7.37 (s; 1H; 3-H), 7.00 (m; 4H ; Ph-H), 5.13 (s; 2H; CH3θ-Ph-CH2-), 3.73 (s; 3H; -OCH3) and 3.67-3.32 ppm (m; 4H; -CH2- CH2-)
MS (79 eV) :m/e= 262 (M+)MS (79 eV): m / e = 262 (M + )
III. Synthese von 4,5-Diamino-l-.4'-methoxybenzyl ,- pyrazolIII. Synthesis of 4,5-diamino-1-4'-methoxybenzyl, - pyrazole
a) 1,00 g (2,40 mmol) 5-Benzylamino-3-brom-l-(4'- methoxybenzyl)-4-nitropyrazol werden 3 Stunden lang analog Vorschrift A hydriert. Ausbeute: 590 mg (78 Prozent der Theorie) 4,5-Diamino- l-(4 '-methoxybenzyl )-pyrazolhydrosulfat mit einem Schmelzpunkt von 186 bis 187 Grad Celsius.a) 1.00 g (2.40 mmol) of 5-benzylamino-3-bromo-1- (4'-methoxybenzyl) -4-nitropyrazole are hydrogenated for 3 hours as described in procedure A. Yield: 590 mg (78 percent of theory) of 4,5-diamino-l- (4'-methoxybenzyl) pyrazole hydrosulfate with a melting point of 186 to 187 degrees Celsius.
iH-NMR (60 MHz, 9,10-5,51 (s; breit; 7H; 2 -NH2; H2SO4; mit D2O austauschbar), 7,30 (s; 1H; 3-H) , 7,05 (m; 4H; Ph-H), 5,12 (s; 2H; CH3O-PI.- CH2-) und 3,73 ppm (s; 3H; -OCH3)iH-NMR (60 MHz, 9.10-5.51 (s; broad; 7H; 2 -NH2; H2SO4; interchangeable with D2O), 7.30 (s; 1H; 3-H), 7.05 (m; 4H; Ph-H) , 5.12 (s; 2H; CH3O-PI.- CH2-) and 3.73 ppm (s; 3H; -OCH3)
MS (70 eV) :m/e= 218 (M+)MS (70 eV): m / e = 218 (M + )
b) 260 mg (0,68 mmol) 3-Brom-5-tert-butylamino-l-b) 260 mg (0.68 mmol) 3-bromo-5-tert-butylamino-l-
(4 '-methoxybenzyl)-4-nitropyrazol werden in 100 ml absolutem Ethanol mit 2 Spatelspitzen Palladium- Aktivkohle-Katalysator versetzt und 2 Stunden bei 50 bar und Raumtemperatur hydriert.(4'-Methoxybenzyl) -4-nitropyrazole are mixed in 100 ml of absolute ethanol with 2 spatula tips of palladium-activated carbon catalyst and hydrogenated for 2 hours at 50 bar and room temperature.
Ausbeute: 170 mg (79 Prozent der Theorie) 4,5-Diamino- l-(4 '-methoxybenzyl)-pyrazol-hydrosulfat vom Schmelzpunkt 186 bis 187 Grad Celsius. Yield: 170 mg (79 percent of theory) of 4,5-diamino-l- (4'-methoxybenzyl) pyrazole hydrosulfate with a melting point of 186 to 187 degrees Celsius.
IV. Synthese von 4 ,5-Diamino-l-f3 '-methoxybenzyl) pyrazolIV. Synthesis of 4,5-diamino-l-f3'-methoxybenzyl) pyrazole
1,64 g (4 mmol) 5-Benzylamino-3-brom-l-( 3 '-methoxy¬ benzyl)-4-nitro-pyrazol werden 4 Stunden analog Vor¬ schrift A hydriert. Man erhält 1,0 g (82 Prozent der Theorie) 4,5-Diamino-l-(3 '-methoxybenzyl) -pyrazolhydro- sulfat mit einem Schmelzpunkt von 185 Grad Celsius (unter Zersetzung) .1.64 g (4 mmol) of 5-benzylamino-3-bromo-1- (3 '-methoxy-benzyl) -4-nitro-pyrazole are hydrogenated for 4 hours in accordance with regulation A. 1.0 g (82 percent of theory) of 4,5-diamino-l- (3'-methoxybenzyl) pyrazole hydrosulfate with a melting point of 185 degrees Celsius (with decomposition) are obtained.
1H. -NMR (300 MHz, DMSO-d6):<= 7,43 (s; 1H; 3-H) , 7,23 (dd; J=7,2Hz und 8,1 Hz; 1H; Ph-3H) ; 6,84 (d; J=8,3Hz; 1H; Ph-4H); 6,73 (s; 1H; Ph-IH); 6,71 (d; J=7Hz; 1H; Ph-2H); 6,5-5,5 (s; breit; 6H; NH?; H2SO4; tauscht mit D2O aus); 5,18 (s; 2H; -CH2-) und 3,70 ppm (s; 3H; -OCH3)1H. -NMR (300 MHz, DMSO-d6): <= 7.43 (s; 1H; 3-H), 7.23 (dd; J = 7.2Hz and 8.1 Hz; 1H; Ph-3H); 6.84 (d; J = 8.3Hz; 1H; Ph-4H); 6.73 (s; 1H; Ph-IH); 6.71 (d; J = 7Hz; 1H; Ph-2H); 6.5-5.5 (s; broad; 6H; NH ?; H2SO4; exchanges with D2O); 5.18 (s; 2H; -CH2-) and 3.70 ppm (s; 3H; -OCH3)
MS (70 eV):m/e= 218 (M+)MS (70 eV): m / e = 218 (M + )
Synthese von 4 ,5-Diamino-l-ι.4 • -methylbenzyl ,- pyrazolSynthesis of 4, 5-diamino-l-ι.4 • methylbenzyl, - pyrazole
3,0 g (7,5 mmol) 5-Benzylamino-3-brom-l-(4 ' -methyl¬ benzyl)-4-nitropyrazol werden 4 Stunden analog Vorschrift A hydriert. Man erhält 1,90 g (84 Prozent der Theorie) 4,5-Diamino-l-(4 '-methylbenzyl)-pyrazolhydrosulfat mit einem Schmelzpunkt von 163 bis 167 Grad Celsius (unter Zersetzung) . iH-NMR (300 MHz, DMSO-d6 ) 7,31 (s; 1H; 3-H), 7,21-7,05 ; 4H; Ph-H); 5,8-6,7 (s; 6H; NH2; H2SO4; tauscht mit D2O aus); 5,12 (s; 2H; -CH2-) und 2,26 ppm (s; 3H; -CH3)3.0 g (7.5 mmol) of 5-benzylamino-3-bromo-1- (4'-methylbenzyl) -4-nitropyrazole are hydrogenated for 4 hours as described in procedure A. 1.90 g (84 percent of theory) of 4,5-diamino-1- (4'-methylbenzyl) pyrazole hydrosulfate with a melting point of 163 to 167 degrees Celsius (with decomposition) are obtained. iH-NMR (300 MHz, DMSO-d6) 7.31 (s; 1H; 3-H), 7.21-7.05; 4H; Ph-H); 5.8-6.7 (s; 6H; NH2; H2SO4; exchanges with D2O); 5.12 (s; 2H; -CH2-) and 2.26 ppm (s; 3H; -CH3)
MS (70 eV) :m/e= 202 (M+)MS (70 eV): m / e = 202 (M + )
VI . Synthese von 4,5-Diamino-l-f4 '-chlorbenzyl . -pyrazolVI. Synthesis of 4,5-diamino-l-f4'-chlorobenzyl. -pyrazole
3,15 g (7,5 mmol) 5-Benzylamino-3-brom-l-(4 '-chlor¬ benzyl)-4-nitropyrazol werden 3 Stunden nach Vorschrift A hydriert. Man erhält 2 g (82 Prozent der Theorie) 4 ,5-Diamino-l-(4 '-chlorbenzyl)-pyrazolhydrosulfat mit einem Schmelzpunkt von 188 Grad Celsius (unter Zersetzung) .3.15 g (7.5 mmol) of 5-benzylamino-3-bromo-1- (4'-chlorobenzyl) -4-nitropyrazole are hydrogenated for 3 hours according to instruction A. 2 g (82 percent of theory) of 4,5-diamino-1- (4'-chlorobenzyl) pyrazole hydrosulfate with a melting point of 188 degrees Celsius (with decomposition) are obtained.
iH-NMR (300 MHz, DMSO-d6 ) :<f= 7,13-7,39 (m; 5H; 3-H und Ph-H) ; 6,0-6,8 (s; breit; 6H; H2; H2SO4, tauscht mit D2O aus) und 5,12 ppm (s; 2H; -CH2-)iH-NMR (300 MHz, DMSO-d6): <f = 7.13-7.39 (m; 5H; 3-H and Ph-H); 6.0-6.8 (s; broad; 6H; H2; H2SO4, exchanges with D2O) and 5.12 ppm (s; 2H; -CH 2 -)
MS (70 eV) :m/e= 222 (M+)MS (70 eV): m / e = 222 (M + )
Für sämtliche NMR-Spektren gilt:The following applies to all NMR spectra:
s = Singulett, d = Dublett, t = Triplett, q = Quartett, = Multiplett Haarfärbebeispieles = singlet, d = doublet, t = triplet, q = quartet, = multiplet Hair coloring examples
Beispiel 4: Haarfärbemittel in GelformExample 4: Hair dye in gel form
1,51 g 4,5-Diamino-l-(4 '-methoxybenzyl)-pyrazol- hydrosulfat 0,65 g 5-Amino-2-methylphenol 0,15 g Natriumsulfit 5,00 g Laurylalkohol-diglycolethersulfat-Natrium- salz (28-prozentige wäßrige Lösung) 1,00 g Hydroxyethylcellulose, hochviskos 10,00 g Ammoniak (22-prozentige wäßrige Lösung) 81,69 g Wasser 100,00 g1.51 g 4,5-diamino-l- (4'-methoxybenzyl) pyrazole hydrosulfate 0.65 g 5-amino-2-methylphenol 0.15 g sodium sulfite 5.00 g lauryl alcohol diglycol ether sulfate sodium salt ( 28% aqueous solution) 1.00 g hydroxyethyl cellulose, highly viscous 10.00 g ammonia (22% aqueous solution) 81.69 g water 100.00 g
50 g des vorstehenden Haarfärbemittels werden kurz vor dem Gebrauch mit 50 g Wasserstoffperoxidlösung (6-prozentig) vermischt und das Gemisch anschließend auf blonde Naturhaare aufgetragen. Nach einer Einwirkzeit; von 30 Minuten bei 40 Grad Celsius wird das Haar mit Wasser gespült und getrocknet. Das Haar hat eine intensive leuchtende rotorange Färbung erhalten.50 g of the above hair dye are mixed with 50 g of hydrogen peroxide solution (6 percent) shortly before use and the mixture is then applied to natural blonde hair. After an exposure time; from 30 minutes at 40 degrees Celsius, the hair is rinsed with water and dried. The hair has an intense bright red-orange color.
Beispiel 5: HaarfärbelösungExample 5: Hair dye solution
1,60 g 4,5-Diamino-l-( 3 '-methoxybenzyl )-pyrazol¬ hydrosulfat 0,45 g 3-Aminophenol1.60 g of 4,5-diamino-1- (3'-methoxybenzyl) pyrazole hydrosulfate 0.45 g of 3-aminophenol
0,30 g 2-Amino-4-(2 '-hydroxyethyl)amino-anisol- sulfat 10,00 g Laurylalkohol-diglycolethersulfat-Natriu - salz (28-prozentige wäßrige Lösung) 10,00 g Ammoniak (22-prozentige wäßrige Lösung) 77,65 q Wasser 100,00 g Man vermischt kurz vor dem Gebrauch 50 g des vorstehend beschriebenen Haarfärbemittels mit 50 g Wasserstoff¬ peroxidlösung (6-prozentig) und läßt die Mischung 30 Minuten bei 40 Grad Celsius auf blonde Naturhaare ein¬ wirken. Das Haar wird mit Wasser gespült und getrocknet. Das Haar ist in einem modischen Bordeauxton gefärbt.0.30 g of 2-amino-4- (2'-hydroxyethyl) amino anisole sulfate 10.00 g lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution) 10.00 g ammonia (22 percent aqueous solution ) 77.65 q water 100.00 g Shortly before use, 50 g of the hair dye described above are mixed with 50 g of hydrogen peroxide solution (6 percent) and the mixture is allowed to act on blonde natural hair for 30 minutes at 40 degrees Celsius. The hair is rinsed with water and dried. The hair is colored in a fashionable bordeaux shade.
Beispiele 6 bis 23: HaarfärbelösungenExamples 6 to 23: Hair dye solutions
Es werden Haarfärbelösungen folgender Zusammensetzung hergestellt:Hair dye solutions of the following composition are produced:
0,025 mol Entwickler nach Tabelle 1 0,025 mol Kuppler nach Tabelle 1 10,00 g Laurylalkohol-diglycolethersulfat-Natrium- salz (28-prozentige wäßrige Lösung) 10,00 g Ammoniak (22-prozentige wäßrige Lösung) ad 100.00 g Wasser 100,00 g0.025 mol developer according to Table 1 0.025 mol coupler according to Table 1 10.00 g lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution) 10.00 g ammonia (22 percent aqueous solution) ad 100.00 g water 100.00 g
Die Haarfärbelösungen werden gemäß Beispiel 5 zubereitet und auf zu 90 Prozent ergraute, menschliche Haare aufge¬ tragen. Die resultierenden Färbungen sind in Tabelle 1 dargestellt. The hair dye solutions are prepared according to Example 5 and applied to 90 percent gray human hair. The resulting colorations are shown in Table 1.
Tabelle 1:Table 1:
Fortsetzung Tabelle 1: Continuation of table 1:

Claims

Patentansprüche Claims
1. Mittel zur oxidativen Färbung von Haaren auf der1. Agent for the oxidative coloring of hair on the
Basis einer Entwicklersubstanz-Kupplersubstanz-Kombi¬ nation, dadurch gekennzeichnet, daß es al.: Entwick¬ lersubstanz ein 4,5-Diaminopyrazol der allgemeinen Formel (I)Basis of a developer substance-coupler substance combination, characterized in that it al .: developer substance is a 4,5-diaminopyrazole of the general formula (I)
in der R Halogen, Alkyl mit 1 bis 4 Kohlenstoff- atomen oder Alkoxy mit 1 bis 4 Kohlenstoffatomen darstellt und R2 Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen bedeutet oder dessen physiologisch verträgliche, wasserlösliche Salze enthält.in which R represents halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R2 represents hydrogen, alkyl with 1 to 4 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms or contains its physiologically compatible, water-soluble salts.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Entwicklersubstanz der allgemeinen Formel (I) ausgewählt ist aus 4,5-Diamino-1-(4'-methoxybenzyl)- pyrazol, 4,5-Diamino-l-(4'-methylbenzyl)-pyrazol,2. Composition according to claim 1, characterized in that the developer substance of the general formula (I) is selected from 4,5-diamino-1- (4'-methoxybenzyl) pyrazole, 4,5-diamino-l- (4 ' methylbenzyl) pyrazole,
4,5-Diamino-l-(4'-chlorbenzyl)-pyrazol und 4,5-Diamino-l-(3'-methoxybenzyl)-pyrazol.4,5-diamino-1- (4'-chlorobenzyl) pyrazole and 4,5-diamino-1- (3'-methoxybenzyl) pyrazole.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeich¬ net, daß die Entwicklersubstanz der Formel (I) in einer Menge von 0,01 bis 3,0 Gewichtsprozent enthal¬ ten ist. 4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Kupplersubstanz ausgewählt ist aus o^-Naphthol, Resorcin, 4-Chlorresorcin, 4,6- Dichlorresorcin, 2-Methylresorcin, 2-Amino-4-(2'- hydroxyethyl)amino-anisol, 5-Amino-2-methylphenol, 3-Amino-2-methylphenol, 4-Hydroxy-l,2-methylendioxy- benzol, 4-Amino-l,2-methylendioxybenzol, 4-(2'-Hydro¬ xyethyl)amino-1,2-methylendioxybenzol, 2 ,4-Diamino- phenetol, 2,4-Diamino-5-methylphenetol, 2,4-Diamino- benzylalkohol, m-Phenylendiamin, 2,4-Diaminophenoxy- ethanol, 3. Composition according to claim 1 or 2, characterized gekennzeich¬ net that the developer substance of formula (I) is contained in an amount of 0.01 to 3.0 percent by weight. 4. Agent according to one of claims 1 to 3, characterized in that the coupler substance is selected from o ^ -naphthol, resorcinol, 4-chlororesorcinol, 4,6-dichlororesorcinol, 2-methylresorcinol, 2-amino-4- (2 ' - hydroxyethyl) amino-anisole, 5-amino-2-methylphenol, 3-amino-2-methylphenol, 4-hydroxy-l, 2-methylenedioxybenzene, 4-amino-l, 2-methylenedioxybenzene, 4- (2 ' -Hydro¬ xyethyl) amino-1,2-methylenedioxybenzene, 2,4-diaminophenetol, 2,4-diamino-5-methylphenetol, 2,4-diamino-benzyl alcohol, m-phenylenediamine, 2,4-diaminophenoxyethanol ,
4-Hydroxyindol, 3-Amino-5-hydroxy-2,6-di- methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin.4-hydroxyindole, 3-amino-5-hydroxy-2,6-dimethoxypyridine and 3,5-diamino-2,6-dimethoxypyridine.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Gesamtmenge der Entwickler¬ substanz-Kupplersubstanz-Kombination 0,1 bis 5,0 Gewichtsprozent beträgt.5. Composition according to one of claims 1 to 4, characterized in that the total amount of the developer-substance-coupler substance combination is 0.1 to 5.0 percent by weight.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es eine zusätzliche Farb¬ komponente enthält, die ausgewählt ist aus 6-Amino- 2-methylphenol, 2-Amino-5-methylphenol, Diamond Fuchsine (C.I. 42 510), Leather Ruby HF (C.I. 42 520), 2-Nitro-l,4-diaminobenzol, 2-Amino-4-nitro- phenol, 2-Amino-5-nitrophenol, 2-Amino-4,6-dinitro- phenol, 2-Amino-5-(2'-hydroxyethyl)amino-nitrobenzol, 2-Methylamino-5-bis-(2'-hydroxyethyl)amino-nitro¬ benzol, Acid Brown 4 (C.I. 14 805), 1,4-Diamino- anthrachinon und 1,4,5,8-Tetraaminoanthrachinon. 6. Composition according to one of claims 1 to 5, characterized in that it contains an additional Farb¬ component, which is selected from 6-amino-2-methylphenol, 2-amino-5-methylphenol, diamond fuchsine (CI 42 510) , Leather Ruby HF (CI 42 520), 2-nitro-l, 4-diaminobenzene, 2-amino-4-nitro-phenol, 2-amino-5-nitrophenol, 2-amino-4,6-dinitro-phenol, 2-amino-5- (2'-hydroxyethyl) amino-nitrobenzene, 2-methylamino-5-bis- (2'-hydroxyethyl) amino-nitro¬ benzene, Acid Brown 4 (CI 14 805), 1,4-diamino - anthraquinone and 1,4,5,8-tetraaminoanthraquinone.
7. 4,5-Diamino-pyrazole der allgemeinen Formel (I)7. 4,5-diamino-pyrazoles of the general formula (I)
in der Rl Halogen, Alkyl mit 1 bis 4 Kohlenstoff¬ atomen oder Alkoxy mit 1 bis 4 Kohlenstoffatomen darstellt und R2 Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen bedeutet.in which R 1 represents halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms and R 2 is hydrogen, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 2 to 4 carbon atoms.
8. 4,5-Diamino-l-(4'-methoxybenzyl)-pyrazol8. 4,5-diamino-1- (4'-methoxybenzyl) pyrazole
9. 4,5-Diamino-l-(4'-methylbenzyl)-pyrazol9. 4,5-diamino-1- (4'-methylbenzyl) pyrazole
10. 4,5-Diamino-l-(4'-chlorbenzyl)-pyrazol10. 4,5-diamino-1- (4'-chlorobenzyl) pyrazole
11. 4,5-Diamino-l-(3'-methoxybenzyl)-pyrazol11. 4,5-diamino-l- (3'-methoxybenzyl) pyrazole
12. 4-Amino-l-(4'-methoxybenzyl)-5-methylamino-pyrazol12. 4-amino-1- (4'-methoxybenzyl) -5-methylamino-pyrazole
13. 4-Amino-5-(2'-hydroxyethyl)amino-l-(4'-methoxy¬ benzyl)-pyrazol 13. 4-amino-5- (2'-hydroxyethyl) amino-1- (4'-methoxybenzyl) pyrazole
14. Verfahren zur Herstellung der Verbindungen gemäß An¬ spruch 7, dadurch gekennzeichnet, daß man 3,5-Dibrom- 4-nitropyrazol mit einem geeigneten Benzylhalogenid in Gegenwart von Natriumhydrid zur Reaktion bringt, anschließend das erhaltene l-Benzyl-3,5-dibrom-4-ni- tropyrazolderivat mit einem Amin umsetzt und das so erhaltene 5-Alkylamino-l-benzyl-3-brom-4-nitropy- razolderivat katalytisch reduziert. 14. A process for the preparation of the compounds according to claim 7, characterized in that 3,5-dibromo-4-nitropyrazole is reacted with a suitable benzyl halide in the presence of sodium hydride, then the l-benzyl-3,5- dibromo-4-nipropyrazole derivative is reacted with an amine and the resulting 5-alkylamino-1-benzyl-3-bromo-4-nitropyrazole derivative is catalytically reduced.
EP93921871A 1992-10-16 1993-09-29 Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production Withdrawn EP0618903A1 (en)

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DE4234887A DE4234887A1 (en) 1992-10-16 1992-10-16 Oxidation hair dye containing 4,5-diaminopyrazole derivatives as well as new 4,5-diaminopyrazole derivatives and process for their preparation
DE4234887 1992-10-16
PCT/EP1993/002641 WO1994008970A1 (en) 1992-10-16 1993-09-29 Oxidation hair dye containing 4,5-diaminopyrazole derivatives and novel 4,5-diaminopyrazole derivatives and process for their production

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FR3130575A1 (en) 2021-12-22 2023-06-23 L'oreal Cosmetic composition comprising propane-1,3-diol, one or more alkaline agents, one or more nonionic surfactants, one or more non-associative anionic acrylic polymers and one or more colorants
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FR3136976A1 (en) 2022-06-22 2023-12-29 L'oreal Composition for lightening keratin fibers and process for lightening keratin fibers using this composition
FR3136970A1 (en) 2022-06-22 2023-12-29 L'oreal Keratin fiber treatment process
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FR3136967A1 (en) 2022-06-22 2023-12-29 L'oreal Composition for lightening keratin fibers and process for lightening keratin fibers using this composition
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FR3136966A1 (en) 2022-06-22 2023-12-29 L'oreal Composition for lightening keratin fibers and process for lightening keratin fibers using this composition
FR3136974A1 (en) 2022-06-22 2023-12-29 L'oreal Process for treating keratin fibers comprising a pre-treatment or post-treatment step
FR3139719A1 (en) 2022-09-21 2024-03-22 L'oreal Compositions and methods for modifying hair color.
FR3139718A1 (en) 2022-09-19 2024-03-22 L'oreal Compositions and methods for modifying hair color.
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ES2061428T1 (en) 1994-12-16
WO1994008970A1 (en) 1994-04-28
DE4234887A1 (en) 1994-04-21
JP3538424B2 (en) 2004-06-14
US5534267A (en) 1996-07-09
JPH07502541A (en) 1995-03-16

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