DE4234885A1 - Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivatives - Google Patents
Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivativesInfo
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- DE4234885A1 DE4234885A1 DE19924234885 DE4234885A DE4234885A1 DE 4234885 A1 DE4234885 A1 DE 4234885A1 DE 19924234885 DE19924234885 DE 19924234885 DE 4234885 A DE4234885 A DE 4234885A DE 4234885 A1 DE4234885 A1 DE 4234885A1
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- Prior art keywords
- nitropyrazole
- bromo
- hydroxyethyl
- amino
- benzyl
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- 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
-
- 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
-
- 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
-
- 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
Abstract
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten der allgemeinen Formel (I)The present invention relates to a method for the preparation of 4,5-diaminopyrazole derivatives of general formula (I)
in der R1 und R2 unabhängig voneinander Wasserstoff, einen C1- bis C6-Alkylrest oder einen C2- bis C4-Hydro xyalkylrest bedeuten, sowie neue Pyrazol-Derivate, unter anderem 4,5-Diaminopyrazol-Derivate, die als Farbstoff vorstufen, zum Beispiel für Haarfarbstoffe, verwendet werden können.in which R 1 and R 2 independently of one another are hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4 -hydroxyalkyl radical, and also new pyrazole derivatives, including 4,5-diaminopyrazole derivatives, which precursors can be used as a dye, for example for hair dyes.
Es sind in der Literatur bereits mehrere Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten der Formel (I) bekannt. Diese Verfahren sind jedoch in vielerlei Hinsicht unbefriedigend.There are already several methods available in the literature Preparation of 4,5-diaminopyrazole derivatives of the formula (I) known. However, these procedures are in many ways Unsatisfactory.
So wird beispielsweise nach H. Dorn et al., Chem. Ber. 98, S. 3368 (1965), ausgehend von Ethoxymethylen-cyan essigsäureethylester und Methylhydrazin die 5-Amino-1- methylpyrazol-4-carbonsäure erhalten, aus der durch Decarboxylierung, in einer Gesamtausbeute von 40 Pro zent, das 5-Amino-1-methylpyrazol entsteht.For example, according to H. Dorn et al., Chem. Ber. 98, p. 3368 (1965), starting from ethoxymethylene-cyan ethyl acetate and methyl hydrazine the 5-amino-1- Get methylpyrazole-4-carboxylic acid from the by Decarboxylation, in a total yield of 40 Pro Cent, the 5-amino-1-methylpyrazole arises.
In der DE-OS 21 41 700 ist ein Einstufenverfahren be schrieben, nach dem aus N,N-Dimethylaminoacrylnitril und Methylhydrazin das 5-Amino-1-methylpyrazol in einer Aus beute von 71 Prozent erhalten werden kann.In DE-OS 21 41 700 is a one-step process wrote after from N, N-dimethylaminoacrylonitrile and Methylhydrazine the 5-amino-1-methylpyrazole in one go loot of 71 percent can be obtained.
Nach M.A. Khan et al., Can. J. Chem. 49, S. 3566 (1971), läßt sich das nach den beschriebenen Verfahren erhaltene 5-Amino-1-methylpyrazol mit einer Ausbeute von 23 Pro zent zum 5-Amino-1-methyl-4-nitropyrazol umsetzen. Kata lytische Reduktion dieses Produktes liefert nach V.P. Perevalov et al., Khim. Geterotsicl. Soedin. 8, S. 1090 (1985), 1-Methyl-4,5-diaminopyrazol-dihydrachlorid in einer Ausbeute von ca. 79 Prozent. Die Gesamtausbeute über die genannten Stufen beträgt 7 bis 13 Prozent.According to M.A. Khan et al., Can. J. Chem. 49, p. 3566 (1971), can be obtained by the methods described 5-amino-1-methylpyrazole with a yield of 23 Pro convert to 5-amino-1-methyl-4-nitropyrazole. Kata lytic reduction of this product provides according to V.P. Perevalov et al., Khim. Geterotsicl. Soedin. 8, p. 1090 (1985), 1-methyl-4,5-diaminopyrazole dihydrachloride in a yield of approximately 79 percent. The total yield over the above levels is 7 to 13 percent.
Gesamtausbeuten von bis zu 46 Prozent werden erhalten, wenn man das 5-Amino-1-methylpyrazol nach H. Dorn et al., Liebigs Ann. Chem. 717, S. 118 (1968), mit Isoamyl nitrit zum 5-Amino-1-methyl-4-nitropyrazol umsetzt und mit Zinn(II)chlorid zum 4,5-Diamino-1-methylpyrazol reduziert.Total yields of up to 46 percent are obtained if the 5-amino-1-methylpyrazole according to H. Dorn et al., Liebigs Ann. Chem. 717, p. 118 (1968), with isoamyl converts nitrite to 5-amino-1-methyl-4-nitropyrazole and with tin (II) chloride to give 4,5-diamino-1-methylpyrazole reduced.
Aus der DE-OS 38 43 892 ist ein Verfahren zur Herstel lung von 4,5-Diamino-1-methylpyrazol bekannt, in dem 2-Chloracrylnitril mit Hydrazin (G. Ege, Angew. Chem, 86, S. 237 (1974)) cyclisiert wird. Nach Acetylierung der Aminogruppe, Nitrierung und Abspaltung der Schutz gruppe erhält man die tautomeren Verbindungen 3-Amino-4- nitropyrazol und 5-Amino-4-nitropyrazol in einer Gesamt ausbeute von ca. 41 Prozent. Alkyliert man das Tautome rengemisch mit Dimethylsulfat, so erhält man in 70 pro zentiger Ausbeute ein Isomerengemisch, das sich chroma tographisch in die isomeren Verbindungen 5-Amino-1-me thyl-4-nitropyrazol (25 Prozent) und 3-Amino-1-methyl- 4-nitropyrazol (45 Prozent) auftrennen läßt. Durch Re duktion können die entsprechenden Diamino-Verbindungen erhalten werden. Die Gesamtausbeute von 1-Methyl-4,5- diaminopyrazol beträgt weniger als 10 Prozent.From DE-OS 38 43 892 is a process for the manufacture development of 4,5-diamino-1-methylpyrazole in which 2-chloroacrylonitrile with hydrazine (G. Ege, Angew. Chem, 86, p. 237 (1974)). After acetylation the amino group, nitration and elimination of protection the tautomeric compounds 3-amino-4- nitropyrazole and 5-amino-4-nitropyrazole in one total yield of approx. 41 percent. Alkylate the tautome ren mixture with dimethyl sulfate, so you get in 70 per zentiger yield an isomer mixture, the chroma topographically into the isomeric compounds 5-amino-1-me thyl-4-nitropyrazole (25 percent) and 3-amino-1-methyl 4-nitropyrazole (45 percent) can be separated. By Re the corresponding diamino compounds be preserved. The overall yield of 1-methyl-4,5- diaminopyrazole is less than 10 percent.
Aus der DE-OS 34 32 983 ist ein Verfahren zur Her stellung von 5-Amino-1-(2′-hydroxyethyl)-4-nitropyrazol bekannt. Ausgehend von 5-Amino-1-(2′-hydroxyethyl)pyra zol-4-carbonsäure wird die Verbindung durch Decarboxy lierung, anschließender Nitrosierung und Hydrierung, in einer Ausbeute von 59 Prozent erhalten.From DE-OS 34 32 983 is a method for Her position of 5-amino-1- (2'-hydroxyethyl) -4-nitropyrazole known. Starting from 5-amino-1- (2'-hydroxyethyl) pyra zol-4-carboxylic acid becomes the compound through decarboxy lation, subsequent nitrosation and hydrogenation, in obtained a yield of 59 percent.
Neben den zum Teil geringen Ausbeuten haben die beschriebenen Verfahren weitere Nachteile. So sind viele Ausgangsverbindungen, wie zum Beispiel Ethoxymethylcyan essigsäureethylester oder N,N-Dimethylaminoacrylnitril, nicht käuflich erhältlich oder nur durch zum Teil aufwendige Synthesen herstellbar. Darüberhinaus werden Hydrazinderivate als giftig und zum Teil krebserregend eingestuft.In addition to the sometimes low yields, the described methods further disadvantages. So are many Starting compounds such as ethoxymethylcyan ethyl acetate or N, N-dimethylaminoacrylonitrile, not available for sale or only partially complex syntheses can be produced. Beyond that Hydrazine derivatives as toxic and in part carcinogenic classified.
Die Herstellung von 4,5-Diaminopyrazol-Derivaten, die am Stickstoffatom der Aminogruppe in 5-Position substitu iert sind, ist nicht beschrieben.The preparation of 4,5-diaminopyrazole derivatives, which on Nitrogen atom of the amino group substituted in the 5-position are not described.
Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur isomerenreinen Herstellung von unter schiedlich substituierten 4,5-Diaminopyrazol-Derivaten zur Verfügung zu stellen.The object of the present invention was therefore a Process for the isomerically pure preparation of under differently substituted 4,5-diaminopyrazole derivatives to provide.
Es wurde nunmehr gefunden, daß sich die gestellte Aufgabe durch ein Verfahren zur Herstellung von 4,5-Di aminopyrazol-Derivaten der allgemeinen Formel (I)It has now been found that the posed Task through a process for the preparation of 4,5-Di aminopyrazole derivatives of the general formula (I)
in der R1 und R2 unabhängig voneinander Wasserstoff, einen C1- bis C6-Alkylrest oder einen C2- bis C4-Hydro xyalkylrest bedeuten, dadurch gekennzeichnet, daß manin which R 1 and R 2 independently of one another are hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4 -hydro xyalkyl radical, characterized in that
- (A) 3,5-Dibrom-4-nitropyrazol mit einem C1- bis C6-Al kyl-, C2- bis C4-Hydroxyalkyl- oder Benzylhalogenid oder einem C1- bis C6-Alkyl, C2- bis C4-Hydroxy alkyl- oder Benzylsulfat zu Verbindungen der allge meinen Formel (II) in der R3 einen C1- bis C6-Alkylrest, einen C2- bis C4-Hydroxyalkylrest oder einen Benzylrest bedeutet, umsetzt, (A) 3,5-dibromo-4-nitropyrazole with a C 1 to C 6 alkyl, C 2 to C 4 hydroxyalkyl or benzyl halide or a C 1 to C 6 alkyl, C 2 to C 4 -hydroxy alkyl or benzyl sulfate to compounds of general formula (II) in which R 3 denotes a C 1 to C 6 alkyl radical, a C 2 to C 4 hydroxyalkyl radical or a benzyl radical,
- (B) die Verbindungen der allgemeinen Formel (II) mit C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzyl amin zu Verbindungen der allgemeinen Formel (III) in der R3 und R4 unabhängig voneinander einen C1- bis C6-Alkylrest, einen C2- bis C4-Hydroxyalkylrest oder einen Benzylrest bedeuten, in 5-Position substituiert und sodann(B) the compounds of the general formula (II) with C 1 - to C 6 -alkyl-, C 2 - to C 4 -hydroxyalkyl- or benzyl amine to give compounds of the general formula (III) in which R 3 and R 4 independently of one another denote a C 1 to C 6 alkyl radical, a C 2 to C 4 hydroxyalkyl radical or a benzyl radical, substituted in the 5-position and then
- (C) die Verbindungen der allgemeinen Formel (III) durch katalytische Hydrierung zu den Verbindungen der allgemeinen Formel (I) reduziert,(C) the compounds of the general formula (III) catalytic hydrogenation to the compounds of the general formula (I) reduced,
hervorragend lösen läßt. Das vorstehend aufgeführte Ver fahren ist daher ein Gegenstand der Erfindung.can be solved excellently. The above Ver Driving is therefore an object of the invention.
Das allgemeine Reaktionsschema ist nachstehend angege ben.The general reaction scheme is given below ben.
Als Ausgangsverbindung für die Synthese von 4,5-Diamino pyrazol-Derivaten (I) dient das bekannte 3,5-Dibrom-4- nitropyrazol (IV), welches auf folgende Weise darge stellt werden kann:As a starting compound for the synthesis of 4,5-diamino pyrazole derivatives (I) is the well-known 3,5-dibromo-4- nitropyrazole (IV), which is shown in the following manner can be put:
Nach R. Hüttel et al., Chem. Ber. 88, S. 1577 (1955), erhält man durch Nitrierung von Pyrazol mit einem Schwe felsäure-Salpetersäure-Gemisch das 4-Nitropyrazol, das nach H.J. Klebe et al., Synthesis 1973, S. 294 unter milderen Bedingungen durch Nitrierung von Pyrazol zum N-Nitropyrazol und anschließender Umlagerung, mit Hilfe von Schwefelsäure (R. Hüttel et al., Chem. Ber. 88, S. 1586 (1955)), erhalten werden kann. Anschließende Bromierung nach J.P.H. Juffermanns et al., J. Org. Chem. 51, S. 4656 (1986), liefert das 3,5-Dibrom-4-nitropyra zol (IV). According to R. Hüttel et al., Chem. Ber. 88, p. 1577 (1955), is obtained by nitrating pyrazole with a weld rock acid-nitric acid mixture the 4-nitropyrazole, the after H.J. Klebe et al., Synthesis 1973, p. 294 under milder conditions by nitration of pyrazole to N-nitropyrazole and subsequent rearrangement, with the help of sulfuric acid (R. Hüttel et al., Chem. Ber. 88, S. 1586 (1955)). Subsequent Bromination according to J.P.H. Juffermanns et al., J. Org. Chem. 51, p. 4656 (1986) provides 3,5-dibromo-4-nitropyra zol (IV).
Nach dem erfindungsgemäßen Verfahren wird zunächst das 3,5-Dibrom-4-nitropyrazol (IV) durch Umsetzung mit C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzylhalo geniden in Dimethylformamid (DMF) (Verfahren I) oder durch Umsetzung mit C1- bis C6-Alkyl-, C2- bis C4-Hydro xyalkyl- oder Benzylsulfat und Lauge (Verfahren II) in 1-Position alkyliert.According to the process of the invention, the 3,5-dibromo-4-nitropyrazole (IV) is first genidened by reaction with C 1 -C 6 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl halo in dimethylformamide (DMF) ( Process I) or by reaction with C 1 - to C 6 -alkyl-, C 2 - to C 4 -hydro xyalkyl- or benzyl sulfate and alkali (process II) alkylated in the 1-position.
Nach Verfahren I wird zu einer Vorlage von Natriumhydrid in absolutem DMF, unter Rühren bei Raumtemperatur, eine äquimolare Menge von 3,5-Dibrom-4-nitropyrazol, gelöst in absolutem DMF, über einem Zeitraum von einer Stunde zugetropft. Nach Beendigung der Gasentwicklung tropft man eine äquimolare Menge C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzylhalogenid, bevorzugt -chlorid oder -bromid, gelöst in DMF, zu und erhitzt das Reaktionsgemisch drei Stunden lang auf 80 °C. Anschließend wird das Lösungsmittel im Vakuum abdestil liert und der Rückstand aus Methylenchlorid umkristal lisiert.According to method I, an equimolar amount of 3,5-dibromo-4-nitropyrazole, dissolved in absolute DMF, is added dropwise over a period of one hour to an initial charge of sodium hydride in absolute DMF, with stirring at room temperature. After the evolution of gas has ceased, an equimolar amount of C 1 -C 6 -alkyl, C 2 - to C 4 -hydroxyalkyl or benzyl halide, preferably chloride or bromide, dissolved in DMF, is added dropwise and the reaction mixture is heated for three hours to 80 ° C. The solvent is then distilled off in vacuo and the residue is recrystallized from methylene chloride.
Nach Verfahren II wird das 3,5-Dibrom-4-nitropyrazol in wäßriger Lauge, vorzugsweise 2N Natron- oder Kalilauge, gelöst und mit einer zwei- bis fünffachen molaren Menge an C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Ben zylsulfat versetzt. Unter kräftigem Rühren läßt man 15 Stunden lang bei Raumtemperatur reagieren, filtriert an schließend das ausgefallene Produkt ab, wäscht mit Wasser bis die Waschlösung pH-neutral reagiert und trocknet im Vakuum.According to method II, the 3,5-dibromo-4-nitropyrazole in aqueous alkali, preferably 2N sodium or potassium hydroxide, and treated with a two- to five-fold molar amount of C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or ben zyl sulfate added. With vigorous stirring, the mixture is left to react at room temperature for 15 hours, the precipitated product is then filtered off, washed with water until the wash solution is pH-neutral and dried in vacuo.
Nach beiden Verfahren erhält man isomerenreine N-substi tuierte 3,5-Dibrom-4-nitropyrazole der allgemeinen Formel (II) in guten Ausbeuten. Both methods give isomerically pure N-substi did 3,5-dibromo-4-nitropyrazoles of the general Formula (II) in good yields.
In einem anschließenden Schritt erhitzt man die N-sub stituierten 3,5-Dibrom-4-nitropyrazole der allgemeinen Formel (II) in einer wäßrigen, alkoholischen oder wäß rig-alkoholischen Lösung von C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzylamin oder in dem ent sprechenden Amin selbst, als Lösungsmittel, auf eine Temperatur von 60 bis 80 °C. Als Alkohole werden bevorzugt Methanol und/oder Ethanol verwendet. Nach einer Reaktionszeit von 1 bis 20 Stunden, gießt man das abgekühlte Reaktionsgemisch auf 20 bis 150 ml Wasser und filtriert das abgeschiedene Produkt ab. Anschließend wäscht man mit Wasser (10 bis 20 ml) und trocknet im Vakuum. Man erhält isomerenreine 5-Amino-3-brom-4-nitro pyrazol-Derivate der allgemeinen Formel (III) in guten Ausbeuten.In a subsequent step, the N-substituted 3,5-dibromo-4-nitropyrazoles of the general formula (II) are heated in an aqueous, alcoholic or aqueous rig-alcoholic solution of C 1 -C 6 -alkyl-, C 2 - To C 4 -hydroxyalkyl or benzylamine or in the corresponding amine itself, as a solvent, to a temperature of 60 to 80 ° C. Methanol and / or ethanol are preferably used as alcohols. After a reaction time of 1 to 20 hours, the cooled reaction mixture is poured into 20 to 150 ml of water and the separated product is filtered off. Then it is washed with water (10 to 20 ml) and dried in vacuo. Isomerically pure 5-amino-3-bromo-4-nitro pyrazole derivatives of the general formula (III) are obtained in good yields.
Die Verbindungen der allgemeinen Formel (III) werden an schließend, unter Verwendung eines Palladium-Aktivkohle- Katalysators mit einem Palladiumanteil von 10 Gewichts prozent, mit Wasserstoff hydriert. Erfindungsgemäß ste hen dazu zwei Verfahren zur Verfügung. Nach Verfahren (1) wird der alkoholischen, bevorzugt ethanolischen, Lö sung einer Verbindung der allgemeinen Formel (III) zwei Spatelspitzen, ca. 100 mg, des Katalysators zugefügt und der Ansatz in einen Autoklaven überführt. Bei 50 bar Wasserstoffatmosphäre wird bei Raumtemperatur 1 bis 6 Stunden lang, bevorzugt 2 bis 4 Stunden, gerührt. Anschließend wird der Katalysator über einen Glasfilter tiegel abfiltriert und das Produkt, mit einer zur einge setzten Pyrazolverbindung äquimolaren Menge Schwefel säure oder zweifachmolaren Menge Salzsäure als Salz aus gefällt. Nach Verfahren (2) werden der wäßrigen Lösung einer Verbindung der allgemeinen Formel (III) 2 Spatel spitzen des vorstehend beschriebenen Katalysators und eine zur Ausgangsverbindung äquimolare Menge Schwefel säure zugegeben und der Ansatz in einem Hydrierkolben bei Raumtemperatur unter Wasserstoffatmosphäre (Normal druck geschüttelt. Sobald die dünnschichtchromatogra phische Untersuchung der Reaktionsmischung keinen Hinweis mehr auf noch vorliegendes Edukt gibt, wird über das Reaktionsgemisch einen Glasfiltertiegel abfiltriert, das Filtrat eingeengt und das Produkt durch Zugabe von Ethanol auskristallisiert.The compounds of general formula (III) are closing, using a palladium-activated carbon Catalyst with a palladium content of 10 weight percent, hydrogenated with hydrogen. According to the ste Two methods are available for this. According to procedure (1) the alcoholic, preferably ethanolic, Lö solution of a compound of general formula (III) two Spatula tips, approx. 100 mg, of the catalyst and the batch transferred to an autoclave. At 50 bar Hydrogen atmosphere becomes 1 to 6 at room temperature Stirred for hours, preferably 2 to 4 hours. Then the catalyst is placed over a glass filter crucible filtered off and the product, with one to the put pyrazole compound equimolar amount of sulfur acid or double molar amount of hydrochloric acid as salt like. According to method (2), the aqueous solution a compound of general formula (III) 2 spatulas tips of the catalyst described above and an amount of sulfur equimolar to the starting compound acid added and the approach in a hydrogenation flask at room temperature under a hydrogen atmosphere (normal pressure shaken. Once the thin layer chromatograph no physical examination of the reaction mixture There is more information about the educt still present the reaction mixture is filtered through a glass filter crucible, the filtrate was concentrated and the product by adding Ethanol crystallized out.
Man erhält nach beiden Verfahren isomerenreine 4,5- Diaminopyrazol-Derivate der allgemeinen Formel (I) in guten Ausbeuten.Isomerically pure 4.5- Diaminopyrazole derivatives of the general formula (I) in good yields.
Die Verbindungen der allgemeinen Formel (I), in denen R1 Wasserstoff bedeutet, liegen als Tautomere vor. Die Positionen 3 und 5 im Pyrazolring sind nicht unter scheidbar.The compounds of the general formula (I) in which R 1 is hydrogen are present as tautomers. Positions 3 and 5 in the pyrazole ring cannot be distinguished.
Bei der Reduktion von Verbindungen der allgemeinen For mel (III), in der R3 einen Benzylrest oder R4 einen Ben zyl- oder tert-Butylrest bedeuten, werden die N-Benzyl- und N-tert-Butylreste reduktiv abgespalten, so daß man Verbindungen der allgemeinen Formel (I) erhält, in der R1 bzw. R2 Wasserstoff statt Benzyl oder tert-Butyl bedeutet.In the reduction of compounds of the general formula (III) in which R 3 is a benzyl radical or R 4 is a benzyl or tert-butyl radical, the N-benzyl and N-tert-butyl radicals are cleaved reductively, so that Compounds of the general formula (I) is obtained in which R 1 or R 2 is hydrogen instead of benzyl or tert-butyl.
Gegenstand der vorliegenden Patentanmeldung sind ferner neue 3,5-Dibrom-4-nitropyrazol-Derivate der allgemeinen Formel (II)The subject of the present patent application are also new 3,5-dibromo-4-nitropyrazole derivatives of the general Formula (II)
in der R3 einen C1- bis C6-Alkylrest, einen C2- bis C4- Hydroxyalkylrest oder einen Benzylrest bedeutet. Bei spiele für Verbindungen der Formel (II) sind 3,5-Di brom-1-methyl-4-nitropyrazol, 3,5-Dibrom-1-ethyl-4-ni tropyrazol, 3,5-Dibrom-1-isopropyl-4-nitropyrazol, 3,5- Dibrom-1-(2′-hydroxyethyl)-4-nitropyrazol und 1-Benzyl- 3,5-dibrom-4-nitropyrazol.in which R 3 is a C 1 to C 6 alkyl radical, a C 2 to C 4 hydroxyalkyl radical or a benzyl radical. Examples of compounds of the formula (II) are 3,5-dibromo-1-methyl-4-nitropyrazole, 3,5-dibromo-1-ethyl-4-ni tropyrazole, 3,5-dibromo-1-isopropyl 4-nitropyrazole, 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitropyrazole and 1-benzyl-3,5-dibromo-4-nitropyrazole.
Ein weiterer Erfindungsgegenstand sind 3-Brom-5-amino- 4-nitropyrazol-Derivate der allgemeinen Formel (III)Another subject of the invention are 3-bromo-5-amino 4-nitropyrazole derivatives of the general formula (III)
in der R3 und R4 unabhängig voneinander einen C1- bis C6-Alkylrest, C2- bis C4-Hydroxyalkylrest oder einen Benzylrest bedeuten.in which R 3 and R 4 independently of one another denote a C 1 to C 6 alkyl radical, C 2 to C 4 hydroxyalkyl radical or a benzyl radical.
Beispiele für Verbindungen der Formel (III) sindExamples of compounds of the formula (III) are
3-Brom-1-methyl-5-methylamino-4-nitropyrazol,
3-Brom-5-(2′-hydroxyethyl)amino-1-methyl-4-nitropyrazol,
3-Brom-5-tertiärbutylamino-1-methyl-4-nitropyrazol,
5-Benzylamino-3-brom-1-methyl-4-nitropyrazol,
5-Benzylamino-3-brom-1-ethyl-4-nitropyrazol,
5-Benzylamino-3-brom-1-isopropyl-4-nitropyrazol,
3-Brom-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl)amino-4-
nitropyrazol,
3-Brom-1-(2′-hydroxyethyl)-5-methylamino-4-nitropyrazol,
5-Benzylamino-3-brom-1-(2′-hydroxyethyl)-4-nitropyrazol,
1-Benzyl-3-brom-5-methylamino-4-nitropyrazol,
1-Benzyl-3-brom-5-ethylamino-4-nitropyrazol,
1-Benzyl-3-brom-5-(2′-hydroxyethyl) amino-4-nitropyrazol
und 1-Benzyl-5-benzylamino-3-brom-4-nitropyrazol zu nen
nen sind.3-bromo-1-methyl-5-methylamino-4-nitropyrazole,
3-bromo-5- (2'-hydroxyethyl) amino-1-methyl-4-nitropyrazole,
3-bromo-5-tert-butylamino-1-methyl-4-nitropyrazole,
5-benzylamino-3-bromo-1-methyl-4-nitropyrazole,
5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole,
5-benzylamino-3-bromo-1-isopropyl-4-nitropyrazole,
3-bromo-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino-4-nitropyrazole,
3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole,
5-benzylamino-3-bromo-1- (2'-hydroxyethyl) -4-nitropyrazole,
1-benzyl-3-bromo-5-methylamino-4-nitropyrazole,
1-benzyl-3-bromo-5-ethylamino-4-nitropyrazole,
1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole
and 1-benzyl-5-benzylamino-3-bromo-4-nitropyrazole.
Gegenstand der vorliegenden Erfindung sind ferner neue 4,5-Diaminopyrazol-Derivate der allgemeinen Formel (V)The present invention also relates to new ones 4,5-diaminopyrazole derivatives of the general formula (V)
in der Ra und Rb Wasserstoff, einen C1- bis C6-Alkylrest oder einen C2- bis C4-Hydroxyalkylrest bedeuten, mit der Maßgabe, daß, wenn Rb Wasserstoff ist, Ra nicht Wasser stoff, Methyl oder 2-Hydroxyethyl ist.in which R a and R b are hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4 -hydroxyalkyl radical, with the proviso that when R b is hydrogen, R a is not hydrogen, methyl or Is 2-hydroxyethyl.
Als Beispiele für Verbindungen der Formel (I) werdenAs examples of compounds of formula (I)
4-Amino-1-methyl-5-methylaminopyrazol,
4-Amino-5-(2′-hydroxyethyl)amino-1-methylpyrazol,
4,5-Diamino-1-ethylpyrazol,
4,5-Diamino-1-isopropylpyrazol,
4-Amino-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl)amino
pyrazol,
4-Amino-1-(2′-hydroxyethyl)-5-methylaminopyrazol,
4-Amino-(3)5-methylaminopyrazol,
4-Amino-(3)5-ethylaminopyrazol und
4-Amino-(3)5-(2′-hydroxyethyl)aminopyrazol,4-amino-1-methyl-5-methylaminopyrazole,
4-amino-5- (2'-hydroxyethyl) amino-1-methylpyrazole,
4,5-diamino-1-ethylpyrazole,
4,5-diamino-1-isopropylpyrazole,
4-amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino pyrazole,
4-amino-1- (2'-hydroxyethyl) -5-methylaminopyrazole,
4-amino- (3) 5-methylaminopyrazole,
4-amino- (3) 5-ethylaminopyrazole and
4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole,
genannt.called.
Die Verbindungen der Formel (V) können als Farbstoffvor stufen in Oxidationshaarfärbemitteln zur Färbung von Haaren verwendet werden (siehe Verwendungsbeispiel).The compounds of formula (V) can be pre-dyed stages in oxidation hair dyes for coloring Hair can be used (see usage example).
Zu 1,75 g (70 mmol) Natriumhydrid in 150 ml absolutem DMF (Dimethylformamid) tropft man über einen Zeitraum von 1 Stunde 19,0 g (70 mmol) 3,5-Dibrom-4-nitropyrazol, gelöst in 90 ml absolutem DMF, zu. Nach Beendigung der Gasentwicklung werden 70 mmol C1 bis C6-Alkyl-, C2 bis C4-Hydroxyalkyl- oder Benzylhalogenid in 30 ml DMF zugetropft und 3 Stunden lang auf 80 °C erhitzt. Anschließend destilliert man das Lösungsmittel im Vakuum ab und kristallisiert den Rückstand aus Methylenchlorid um.19.0 g (70 mmol) of 3,5-dibromo-4-nitropyrazole, dissolved in 90 ml of absolute DMF, are added dropwise to 1.75 g (70 mmol) of sodium hydride in 150 ml of absolute DMF (dimethylformamide) over a period of 1 hour , too. After the evolution of gas has ended, 70 mmol of C 1 to C 6 alkyl, C 2 to C 4 hydroxyalkyl or benzyl halide in 30 ml of DMF are added dropwise and the mixture is heated to 80 ° C. for 3 hours. The solvent is then distilled off in vacuo and the residue is recrystallized from methylene chloride.
Zu einer Lösung von 5 g (18,5 mmol) 3,5-Dibrom-4- nitropyrazol in 50 ml 2N Natronlauge gibt man 92,5 mmol C1 bis C6-Alkyl-, C2 bis C4-Hydroxy alkyl- oder Benzylsulfat, läßt 15 Stunden lang bei Raumtemperatur kräftig rühren und filtriert schließlich das ausgefallene Produkt ab, wäscht mit Wasser bis die Waschlösung pH-neutral reagiert und trocknet im Vakuum.92.5 mmol of C 1 to C 6 -alkyl-, C 2 to C 4 -hydroxyalkyl- are added to a solution of 5 g (18.5 mmol) of 3,5-dibromo-4-nitropyrazole in 50 ml of 2N sodium hydroxide solution. or benzyl sulfate, allowed to stir vigorously at room temperature for 15 hours and finally filtered off the precipitated product, washed with water until the washing solution reacted pH-neutral and dried in vacuo.
Nach Verfahren II erhält man, unter Verwendung von Methylsulfat, 5,06 g (96 Prozent der Theorie) 3,5-Di brom-1-methyl-4-nitropyrazol in Form weißer Kristalle mit einem Schmelzpunkt von 154 °C.Method II gives, using Methyl sulfate, 5.06 g (96 percent of theory) 3,5-di bromo-1-methyl-4-nitropyrazole in the form of white crystals with a melting point of 154 ° C.
1H-NMR (60 MHz, DMSO-d6): = 3,90 ppm (s; 3H;-CH₃). 1 H-NMR (60 MHz, DMSO-d 6 ): = 3.90 ppm (s; 3H; -CH₃).
Für diese und alle folgenden 1H-NMR-Spektren gilt: Die
Angaben der chemischen Verschiebung erfolgt in delta
(ppm), die der Kopplungskonstanten (J) erfolgt in Hertz.
Standard: Tetramethylsilan
s = Singulett, d = Dublett, t = Triplett, q = Quartett,
m = Multiplett, Ph = Phenyl, Ring-H = Proton am Pyrazol
ring
MS (70 eV): m/e=287 (M⁺).The following applies to this and all the following 1 H-NMR spectra: The chemical shift is given in delta (ppm), that of the coupling constant (J) in Hertz. Standard: tetramethylsilane
s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, Ph = phenyl, ring H = proton on pyrazole ring
MS (70 eV): m / e = 287 (M⁺).
Nach Verfahren II erhält man, unter Verwendung von Ethylsulfat, 3,59 g (65 Prozent der Theorie) 3,5-Dibrom- 1-ethyl-4-nitropyrazol in Form weißer Kristalle mit einem Schmelzpunkt von 119 bis 121°C.Method II gives, using Ethyl sulfate, 3.59 g (65 percent of theory) 3,5-dibromo 1-ethyl-4-nitropyrazole in the form of white crystals a melting point of 119 to 121 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 4,26 (q; J=7,0 Hz; 2H;
-CH₂-CH₃) und 1,36 ppm
(t; J=7,0 Hz; 3H; -CH₂-CH₃).
MS (70 eV): m/e=297 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 4.26 (q; J = 7.0 Hz; 2H; - CH₂ -CH₃) and 1.36 ppm (t; J = 7.0 Hz; 3H; -CH₂- CH₃ ).
MS (70 eV): m / e = 297 (M⁺).
Nach Verfahren I erhält man, unter Verwendung von 2-Brompropan, 13,14 g (60 Prozent der Theorie) 3,5- Dibrom-1-isopropyl-4-nitropyrazol in Form braungelber Kristalle mit einem Schmelzpunkt von 72 bis 73 °C.Method I gives, using 2-bromopropane, 13.14 g (60 percent of theory) 3.5- Dibromo-1-isopropyl-4-nitropyrazole in the form of brown-yellow Crystals with a melting point of 72 to 73 ° C.
¹H-NM₆ (60 MHz, DMSO-d₆): = 4,84 (dq; J=6,5 Hz; 1H;
CH) und 1,42 ppm
(d; J=6 Hz; 6H; -CH(CH₃)₂).
MS (70 eV): m/e=311 (M⁺).¹H-NM₆ (60 MHz, DMSO-d₆): = 4.84 (dq; J = 6.5 Hz; 1H; CH) and 1.42 ppm (d; J = 6 Hz; 6H; -CH ( CH₃ ) ₂).
MS (70 eV): m / e = 311 (M⁺).
Nach Verfahren I erhält man, unter Verwendung von 1-Brom-2-hydroxyethan, 14,77 g (67 Prozent der Theorie) 3,5-Dibrom-1-(2′-hydroxyethyl)-4-nitropyrazol in Form blaßgelber Kristalle mit einem Schmelzpunkt von 103 bis 105 °C.Method I gives, using 1-bromo-2-hydroxyethane, 14.77 g (67 percent of theory) 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitropyrazole in the form pale yellow crystals with a melting point of 103 to 105 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 4,90 (s; breit; 1H; -OH;
mit D₂O austauschbar),
4,31 (m; 2H; -CH₂-) und
4,08-3,82 ppm (m; 2H;
-CH₂-; nach D₂O-Austausch:
t; 2H; J=5 Hz).
MS (70 eV): m/e=317 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 4.90 (s; broad; 1H; -OH; exchangeable with D₂O), 4.31 (m; 2H; -CH₂-) and 4.08-3, 82 ppm (m; 2H; -CH₂-; after D₂O exchange: t; 2H; J = 5 Hz).
MS (70 eV): m / e = 317 (M⁺).
Nach Verfahren I erhält man, unter Verwendung von Benzylchlorid, 17,94 g (71 Prozent der Theorie) 1-Benzyl-3,5-dibrom-4-nitrobenzol in Form blaßgelber Kristalle mit einem Schmelzpunkt von 128 °C.Method I gives, using Benzyl chloride, 17.94 g (71 percent of theory) 1-Benzyl-3,5-dibromo-4-nitrobenzene in the form of a pale yellow Crystals with a melting point of 128 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 7,26-7,41 (m; 5H; Ph-H) und
5,51 ppm (s; 2H; -CH₂-).
MS (70 eV): m/e = 363 (⁺).
1 H-NMR (60 MHz, DMSO-d₆): = 7.26-7.41 (m; 5H; Ph-H) and 5.51 ppm (s; 2H; -CH₂-).
MS (70 eV): m / e = 363 (⁺).
2 g (7,02 mmol) 3,5-Dibrom-1-methyl-4-nitropyrazol wer den in 50 ml einer 40 prozentigen Lösung von Methylamin in Ethanol 4 Stunden lang auf Siedetemperatur erhitzt. Nach dem Abkühlen fügt man dem Reaktionsgemisch 100 ml Wasser zu, filtriert das abgeschiedene Produkt ab und wäscht mit wenig Wasser (20 ml). Nach dem Trocknen im Vakuum erhält man 1,45 g (88 Prozent der Theorie) 3-Brom-1-methyl-5-methylamino-4-nitropyrazol in Form gelber Kristalle mit einem Schmelzpunkt von 185 °C.2 g (7.02 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole that in 50 ml of a 40 percent solution of methylamine heated to boiling temperature in ethanol for 4 hours. After cooling, 100 ml are added to the reaction mixture Water, the separated product is filtered off and washes with a little water (20 ml). After drying in Vacuum gives 1.45 g (88 percent of theory) 3-bromo-1-methyl-5-methylamino-4-nitropyrazole in the form yellow crystals with a melting point of 185 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 7,50 (s; breit; 1H; -NH;
mit D₂O austauschbar),
3,88 (s; 3H; N-CH₃) und
3,16 ppm (d; 3H; J=6 Hz;
-NH-CH₃; nach D₂O Austausch
s).
MS (70 eV): m/e=236 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 7.50 (s; broad; 1H; -NH; exchangeable with D₂O), 3.88 (s; 3H; N-CH₃) and 3.16 ppm (d ; 3H; J = 6 Hz; -NH- CH₃ ; after D₂O exchange s).
MS (70 eV): m / e = 236 (M⁺).
3 g (10,5 mmol) 3,5-Dibrom-1-methyl-4-nitropyrazol wer den in einer Lösung von 30 ml Ethanolamin in 30 ml Etha nol 15 Stunden lang auf Siedetemperatur erhitzt. An schließend gießt man das Reaktionsgemisch auf 200 ml Wasser, filtriert das abgeschiedene Produkt ab, wäscht mit Wasser (20 ml) und trocknet im Vakuum. Aus dem Fil trat kristallisiert in der Kälte (5 °C) weiteres Produkt aus. 3 g (10.5 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole that in a solution of 30 ml ethanolamine in 30 ml etha nol heated to boiling temperature for 15 hours. On finally the reaction mixture is poured onto 200 ml Water, filters the separated product, washes with water (20 ml) and dries in vacuo. From the fil crystallized in the cold (5 ° C) another product out.
Man erhält 2,25 g (81 Prozent der Theorie) 3-Brom-5-(2′- hydroxyethyl)amino-1-methyl-4-nitropyrazol in Form gelber Kristalle mit einem Schmelzpunkt von 150 °C.2.25 g (81 percent of theory) of 3-bromo-5- (2'- hydroxyethyl) amino-1-methyl-4-nitropyrazole in the form yellow crystals with a melting point of 150 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 7,38 (s; breit; 1H; -NH;
mit D₂O austauschbar),
4,98 (s; breit; 1H; -OH;
mit D₂O austauschbar),
3,82 (s; 3H; N-CH₃) und
3,60 ppm (m; 4H;
-NH-CH₂-CH₂).
MS (70 eV): m/e=266 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 7.38 (s; broad; 1H; -NH; exchangeable with D₂O), 4.98 (s; broad; 1H; -OH; exchangeable with D₂O), 3 , 82 (s; 3H; N-CH₃) and 3.60 ppm (m; 4H; -NH- CH₂-CH₂ ).
MS (70 eV): m / e = 266 (M⁺).
1,5 g (5,26 mmol) 3,5-Dibrom-1-methyl-4-nitropyrazol werden in einer Lösung von 20 ml tert-Butylamin in 30 ml Ethanol 20 Stunden lang auf Siedetemperatur erhitzt. Nach dem Abkühlen gießt man das Reaktionsgemisch auf 150 ml Wasser, filtriert das abgeschiedene Produkt ab und wäscht mit 100 ml Wasser. Nach dem Trocknen im Vakuum erhält man 1,14 g (78 Prozent der Theorie) 3-Brom-5-tert-butylamino-1-methyl-4-nitropyrazol in Form blaßgelber Blättchen mit einem Schmelzpunkt von 75 bis 77 °C.1.5 g (5.26 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole are in a solution of 20 ml of tert-butylamine in 30 ml Ethanol heated to boiling temperature for 20 hours. To after cooling, the reaction mixture is poured onto 150 ml Water, the separated product is filtered off and washes with 100 ml of water. After drying in a vacuum you get 1.14 g (78 percent of theory) 3-bromo-5-tert-butylamino-1-methyl-4-nitropyrazole in the form pale yellow leaves with a melting point of 75 to 77 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 5,35 (s; 1H; -NH; tauscht
mit D₂O aus), 3,75 (s; 3H;
N-CH₃) und 1,20 ppm (s; 9H;
-C(CH₃)₃).
MS (70 eV): m/e=277 (M⁺).
1 H-NMR (60 MHz, DMSO-d₆): = 5.35 (s; 1H; -NH; exchanges with D₂O), 3.75 (s; 3H; N-CH₃) and 1.20 ppm (s; 9H; -C (CH₃) ₃).
MS (70 eV): m / e = 277 (M⁺).
2 g (7,02 mmol) 3,5-Dibrom-1-methyl-4-nitropyrazol werden in einer Lösung von 11 g (0,1 ml) Benzylamin in 50 ml Ethanol 10 Stunden lang auf Siedetemperatur er hitzt. Nach dem Abkühlen gießt man das Reaktionsgemisch auf 100 ml Wasser, filtriert das abgeschiedene Produkt ab und wäscht mit Wasser (20 ml). Nach dem Trocknen im Vakuum erhält man 1,76 g (81 Prozent der Theorie) 5-Ben zylamino-3-brom-1-methyl-4-nitropyrazol in Form gelber Nadeln mit einem Schmelzpunkt von 133 °C.2 g (7.02 mmol) 3,5-dibromo-1-methyl-4-nitropyrazole are in a solution of 11 g (0.1 ml) of benzylamine in 50 ml of ethanol at boiling temperature for 10 hours is heating. After cooling, the reaction mixture is poured on 100 ml of water, the separated product is filtered and wash with water (20 ml). After drying in Vacuum gives 1.76 g (81 percent of theory) of 5-ben zylamino-3-bromo-1-methyl-4-nitropyrazole in the form of yellow Needles with a melting point of 133 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 7,88 (t; 1H; J=6 Hz; -NH;
mit D₂O austauschbar),
7,32 (m; 5H; Ph-H), 4,73
(d; 2H; J=6 Hz; -NH-CH₂-;
nach D₂O-Austausch s) und
3,68 ppm (s; 3H; N-CH₃).
MS (70 eV): m/e=312 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 7.88 (t; 1H; J = 6 Hz; -NH; exchangeable with D₂O), 7.32 (m; 5H; Ph-H), 4.73 (d; 2H; J = 6 Hz; -NH-CH₂-; after D₂O exchange s) and 3.68 ppm (s; 3H; N-CH₃).
MS (70 eV): m / e = 312 (M⁺).
6,3 g (21 mmol) 3,5-Dibrom-1-ethyl-4-nitropyrazol werden in 10 ml Benzylamin 1 Stunde lang auf 80 °C erhitzt. An schließend gießt man das Reaktionsgemisch auf 50 ml Wasser und trennt das abgeschiedene Öl ab, aus dem, nach Zugabe von 20 bis 30 ml Essigsäureethylester, das Pro dukt auskristallisiert. Nach einmaligem Umkristalli sieren aus Methanol erhält man 5,2 g (76 Prozent der Theorie) 5-Benzylamino-3-brom-1-ethyl-4-nitropyrazol in Form hellgelber Nadeln mit einem Schmelzpunkt von 92 °C.6.3 g (21 mmol) of 3,5-dibromo-1-ethyl-4-nitropyrazole heated in 10 ml of benzylamine at 80 ° C for 1 hour. On finally the reaction mixture is poured onto 50 ml Water and separates the separated oil from which, after Add 20 to 30 ml of ethyl acetate, the Pro product crystallized. After a single recrystallization 5.2 g (76 percent of Theory) 5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole in Shape of light yellow needles with a melting point of 92 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,90 (t; J=6,7 Hz; 1H; -NH;
tauscht mit D₂O aus), 7,26-
7,40 (m; 5H; Ph-H), 4,68
(J=6,7 Hz, 2H; NH-CH₂-;
nach D₂O-Austausch s), 4,00
(q; J=7,3 Hz; 2H;
-CH₂-CH₃), und 1,18 ppm
(t; J=7,2 Hz; 3H;
-CH₂-CH₃).
MS (70 eV): m/e=324 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.90 (t; J = 6.7 Hz; 1H; -NH; exchanges with D₂O), 7.26-7.40 (m; 5H; Ph -H), 4.68 (J = 6.7 Hz, 2H; NH- CH₂ -; after D₂O exchange s), 4.00 (q; J = 7.3 Hz; 2H; - CH₂ -CH₃), and 1.18 ppm (t; J = 7.2 Hz; 3H; -CH₂- CH₃ ).
MS (70 eV): m / e = 324 (M⁺).
3,13 g (10 mmol) 3,5-Dibrom-1-isopropyl-4-nitropyrazol werden in 10 ml Benzylamin 1 Stunde lang auf 80 °C er hitzt. Anschließend gießt man das Reaktionsgemisch auf 50 ml Wasser und filtriert das abgeschiedene Produkt ab. Nach einmaligem Umkristallisieren aus einem Toluol/ Petrolether-Gemisch (1 : 1) erhält man 2,3 g (68 Prozent der Theorie) 5-Benzylamino-3-brom-1-isopropyl-4-nitro pyrazol in Form hellgelber Kristalle mit einem Schmelzpunkt von 120 und 122 °C.3.13 g (10 mmol) of 3,5-dibromo-1-isopropyl-4-nitropyrazole are in 10 ml of benzylamine for 1 hour at 80 ° C is heating. The reaction mixture is then poured on 50 ml of water and the separated product is filtered off. After recrystallization from a toluene / Petroleum ether mixture (1: 1) gives 2.3 g (68 percent of theory) 5-benzylamino-3-bromo-1-isopropyl-4-nitro pyrazole in the form of light yellow crystals with a Melting point of 120 and 122 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,78 (t; J=6,6 Hz; 1H; -NH;
nach D₂O-Austausch s),
7,25-7,39 (m; 5H; Ph-H);
4,66 (d; J=6,6 Hz; 2H, -NH-
CH₂-; nach D₂O-Austausch
s); 4,57 (dq; J=6,4 Hz;
1H; -CH(CH₃)₂) und 1,19 ppm
(d; J=6,4 Hz; 6 H;
-CH(CH₃)₂).
MS (70 eV): m/e=338 (M⁺).
1 H-NMR (300 MHz, DMSO-d₆): = 7.78 (t; J = 6.6 Hz; 1H; -NH; after D₂O exchange s), 7.25-7.39 (m; 5H; Ph-H); 4.66 (d; J = 6.6 Hz; 2H, -NH- CH₂ -; after D₂O exchange s); 4.57 (dq; J = 6.4 Hz; 1H; - CH (CH₃) ₂) and 1.19 ppm (d; J = 6.4 Hz; 6 H; -CH ( CH₃ ) ₂).
MS (70 eV): m / e = 338 (M⁺).
1,5 g (4,8 mmol) 3,5-Dibrom-1-(2′-hydroxyethyl)-4-nitro pyrazol werden in einer Lösung von 0,58 g (9,6 mmol) Ethanolamin in 30 ml Ethanol 15 Stunden lang auf 80 °C erhitzt. Nach dem Abkühlen fügt man dem Reaktionsgemisch 50 ml Wasser zu und extrahiert drei mal mit je 70 ml Essigsäureethylester. Man gibt zu den vereinigten Ex traktionslösungen 200 ml n-Hexan und destilliert das Lösungsmittelgemisch im Vakuum auf ein Drittel der ur sprünglichen Menge ab. Danach fügt man erneut n-Hexan bis zur Trübung der Lösung zu. Anschließend filtriert man das auskristallisierte Produkt ab und wäscht mit n-Hexan (10 bis 20 ml). Man erhält 1,04 g (74 Prozent der Theorie) 3-Brom-1-(2′-hydroxyethyl)-5-(2′-hy droxyethyl)amino-4-nitropyrazol in Form hellgelber Kristalle mit einem Schmelzpunkt von 132 bis 134 °C.1.5 g (4.8 mmol) of 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitro pyrazole in a solution of 0.58 g (9.6 mmol) Ethanolamine in 30 ml of ethanol at 80 ° C for 15 hours heated. After cooling, the reaction mixture is added 50 ml of water and extracted three times with 70 ml each Ethyl acetate. One gives to the united ex traction solutions 200 ml n-hexane and distilled the Solvent mixture in a vacuum on a third of the original amount. Then add n-hexane again until the solution becomes cloudy. Then filtered the crystallized product is washed off and washed with n-hexane (10 to 20 ml). 1.04 g (74 percent of theory) 3-bromo-1- (2'-hydroxyethyl) -5- (2'-hy droxyethyl) amino-4-nitropyrazole in the form of light yellow Crystals with a melting point of 132 to 134 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 7,42 (s; breit; 1H; -NH;
mit D₂O austauschbar),
5,23-5,02 (m; 2H; -OH; mit
D₂O austauschbar), 4,18
(m; 2H; N-CH₂-) und 3,93-
3,45 ppm (m; 6H; -CH₂-).
MS (70 eV): m/e=296 (M⁺).
1 H-NMR (60 MHz, DMSO-d₆): = 7.42 (s; broad; 1H; -NH; exchangeable with D₂O), 5.23-5.02 (m; 2H; -OH; exchangeable with D₂O) , 4.18 (m; 2H; N-CH₂-) and 3.93-3.45 ppm (m; 6H; -CH₂-).
MS (70 eV): m / e = 296 (M⁺).
3,15 g (10 mmol) 3,5-Dibrom-1-(2′-hydroxyethyl)-4-nitro pyrazol werden in 70 ml einer 30prozentigen Lösung von Methylamin in Wasser 1 Stunde lang auf 60 °C erwärmt. Nach dem Abkühlen fällt das Produkt in Form hellgelber Kristalle, mit einem Schmelzpunkt von 158 bis 160 °C, aus. Man erhält 2,4 g (91 Prozent der Theorie) 3-Brom-1-(2′-hydroxyethyl)-5-methylamino-4-nitropyrazol.3.15 g (10 mmol) of 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitro pyrazole are in 70 ml of a 30 percent solution of Warm methylamine in water at 60 ° C for 1 hour. After cooling, the product falls in the form of a light yellow Crystals with a melting point of 158 to 160 ° C, out. 2.4 g (91 percent of theory) are obtained. 3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole.
¹H-NMR (300 MHz, DMSO-d₆): = 7,67 (s; 1H; -NH; tauscht
mit D₂O aus); 5,06 (s; 1H;
-OH; tauscht mit D₂O aus),
4,18 (t; 2H; N-CH₂-), 3,68
(t; 2H; -CH₂-OH) und 3,15
ppm (d; J=4,5 Hz; 3H; -NH-
CH₃; nach D₂O-Austausch s).
MS (70 eV): m/e=266 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.67 (s; 1H; -NH; exchanges with D₂O); 5.06 (s; 1H; -OH; exchanges with D₂O), 4.18 (t; 2H; N-CH₂-), 3.68 (t; 2H; - CH₂ -OH) and 3.15 ppm ( d; J = 4.5 Hz; 3H; -NH- CH₃ ; after D₂O exchange s).
MS (70 eV): m / e = 266 (M⁺).
6,3 g (20 mmol) 3,5-Dibrom-1-(2′-hydroxyethyl)-4-nitro pyrazol werden in 20 ml Benzylamin 2 Stunden lang auf 60 °C erhitzt. Nach dem Abkühlen gießt man auf 50 ml Wasser, filtriert das abgeschiedene Produkt ab und kristallisiert einmal aus Toluol/Ligroin (1 : 1) um. Man erhält 4 g (59 Prozent der Theorie) 5-Benzylamino-3- brom-1-(2′-hydroxyethyl)-4-nitropyrazol in Form gelber Kristalle mit einem Schmelzpunkt von 133 bis 135 °C.6.3 g (20 mmol) of 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitro pyrazole are soaked in 20 ml of benzylamine for 2 hours Heated to 60 ° C. After cooling, pour on 50 ml Water, the separated product is filtered off and once recrystallized from toluene / ligroin (1: 1). Man receives 4 g (59 percent of theory) of 5-benzylamino-3- brom-1- (2'-hydroxyethyl) -4-nitropyrazole in the form of yellow Crystals with a melting point of 133 to 135 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,89 (t; J=6,6 Hz; 1H; -NH;
tauscht mit D₂O aus), 7,22-
7,44 (m; 5H; Ph-H); 5,15
(s; 1H; -OH; tauscht mit D₂O
aus), 4,77 (d; J=6,6 Hz;
2H; -NH-CH₂-; nach D₂O-Aus
tausch s), 3,99 (t; J=
4,9H; 2H; -CH₂-) und 3,96
ppm (t; J=5 Hz; 2H; -CH₂-).
MS (70 eV): m/e=340 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.89 (t; J = 6.6 Hz; 1H; -NH; exchanges with D₂O), 7.22- 7.44 (m; 5H; Ph -H); 5.15 (s; 1H; -OH; exchanges with D₂O), 4.77 (d; J = 6.6 Hz; 2H; -NH- CH₂ -; after D₂O exchange s), 3.99 ( t; J = 4.9H; 2H; - CH₂ -) and 3.96 ppm (t; J = 5 Hz; 2H; -CH₂-).
MS (70 eV): m / e = 340 (M⁺).
3,61 g (10 mmol) 1-Benzyl-3,5-dibrom-4-nitropyrazol werden in 100 ml einer 35prozentigen Lösung von Metyl amin in Wasser 4 Stunden lang auf 60 °C erhitzt. Nach dem Abkühlen filtriert man den abgeschiedenen Nieder schlag ab und kristallisiert einmal aus Ethanal um. Man erhält 2,7 g (87 Prozent der Theorie) 1-Benzyl- 3-brom-5-methylamino-4-nitropyrazol in Form farbloser Kristalle mit einem Schmelzpunkt von 116 °C.3.61 g (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole are in 100 ml of a 35 percent solution of Metyl amine in water heated to 60 ° C for 4 hours. To after cooling, the deposited precipitate is filtered tee off and crystallize once from ethanal. Man receives 2.7 g (87 percent of theory) of 1-benzyl 3-bromo-5-methylamino-4-nitropyrazole in the form of colorless Crystals with a melting point of 116 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,71 (s; 1H; -NH; tauscht
mit D₂O aus), 7,15-7,40 (m;
5H, Ph-H), 5,45 (s; 2H;
-CH₂-) und 3,02 ppm (s; 3H;
-CH₃).
MS (70 eV): m/e=312 (M⁺).
1 H-NMR (300 MHz, DMSO-d₆): = 7.71 (s; 1H; -NH; exchanges with D₂O), 7.15-7.40 (m; 5H, Ph-H), 5.45 (s; 2H; -CH₂-) and 3.02 ppm (s; 3H; -CH₃).
MS (70 eV): m / e = 312 (M⁺).
3,61 (10 mmol) 1-Benzyl-3,5-dibrom-4-nitropyrazol werden in 120 ml einer 30prozentigen wäßrigen Ethylaminlösung 1 Stunde lang auf 60 °C erhitzt. Nach dem Abkühlen scheidet sich das Produkt in Form farbloser Kristalle mit einem Schmelzpunkt von 122 °C ab. Man erhält 2,88 g 89 Prozent der Theorie) 1-Benzyl-3-brom-5-ethylamino-4- nitropyrazol.3.61 (10 mmol) 1-benzyl-3,5-dibromo-4-nitropyrazole in 120 ml of a 30 percent aqueous ethylamine solution Heated to 60 ° C for 1 hour. After cooling the product separates in the form of colorless crystals with a melting point of 122 ° C. 2.88 g are obtained 89 percent of theory) 1-Benzyl-3-bromo-5-ethylamino-4- nitropyrazole.
¹H-NMR (300 MHz, DMSO-d₆): = 7,15-7,41 (m; 6H; -NH und
Ph-H; 1H tauscht mit D₂O
aus), 5,37 (s; 1H; -CH₂-),
3,32-3,39 (m; 2H; -CH₂-CH₃)
und 1,07-1,12 ppm (t; 3H;
-CH₂-CH₃).
MS (70 eV): m/e=326 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.15-7.41 (m; 6H; -NH and Ph-H; 1H exchanges with D₂O), 5.37 (s; 1H; -CH₂- ), 3.32-3.39 (m; 2H; - CH₂- CH₃ ) and 1.07-1.12 ppm (t; 3H; -CH₂- CH₃ ).
MS (70 eV): m / e = 326 (M⁺).
3,61 g (10 mmol) 1-Benzyl-3,5-dibrom-4-nitropyrazol werden in 15 ml Ethanolamin 2 Stunden lang auf 80 °c erhitzt. Nach dem Abkühlen gießt man das Reaktionsge misch auf 30 ml Wasser und filtriert den abgeschiedenen Niederschlag ab. Nach einmaligem Umkristallisieren aus Toluol erhält man 2,5 g (74 Prozent der Theorie) 1-Benzyl-3-brom-5-(2′-hydroxyethyl)amino-4-nitropyrazol in Form blaßgelber Kristalle mit einem Schmelzpunkt von 110 bis 112 °C.3.61 g (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole are in 15 ml of ethanolamine at 80 ° C for 2 hours heated. After cooling, the reaction mixture is poured mix to 30 ml of water and filter the separated Precipitation. After recrystallization once Toluene gives 2.5 g (74 percent of theory) 1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole in the form of pale yellow crystals with a melting point of 110 to 112 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,54 (t; 1H; -NH; tauscht
mit D₂O aus), 7,15-7,40
(m; 5H; Ph-H), 5,44 (s; 2H;
-CH₂-Ph), 5,05 (t; 1H; -OH;
tauscht mit D₂O aus) und
3,32-3,53 ppm (m; 4H; -CH₂-CH₂-).
MS (70 eV): m/e=342 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.54 (t; 1H; -NH; exchanges with D₂O), 7.15-7.40 (m; 5H; Ph-H), 5.44 (s; 2H; - CH₂- Ph), 5.05 (t; 1H; -OH; exchanges with D₂O) and 3.32-3.53 ppm (m; 4H; - CH₂-CH₂ -).
MS (70 eV): m / e = 342 (M⁺).
3,61 g (10 mmol) 1-Benzyl-3,5-dibrom-4-nitropyrazol wer den in einer Lösung von 3,6 g Benzylamin 2 Stunden lang auf 60 °C erhitzt. Nach dem Abkühlen wird das Reaktions gemisch auf 20 ml Wasser gegossen und der abgeschiedene Niederschlag abfiltriert. Nach einmaligem Umkristalli sieren aus einem Ligroin/Toluol-Gemisch (1 : 1) erhält man 2,6 g (68 Prozent der Theorie) 1-Benzyl-5-benzyl amino-3-brom-4-nitropyrazol in Form blaßgelber Kristalle mit einem Schmelzpunkt von 103 °C.3.61 g (10 mmol) 1-benzyl-3,5-dibromo-4-nitropyrazole in a solution of 3.6 g benzylamine for 2 hours heated to 60 ° C. After cooling, the reaction poured into 20 ml of water and the separated Filtered precipitate. After a single recrystallization sieren from a ligroin / toluene mixture (1: 1) is obtained 2.6 g (68 percent of theory) 1-benzyl-5-benzyl amino-3-bromo-4-nitropyrazole in the form of pale yellow crystals with a melting point of 103 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 8,04 (t; J=6,1 Hz; 1H; -NH;
tauscht mit D₂O aus), 7,08-
7,47 (m; 10H; Ph-H), 5,24
(s; 2H; -CH₂-Ph) und 4,55
ppm (d; J=6,1 Hz; 2H; -NH-
CH₂-Ph; nach D₂O-Austausch
s).
MS (70 eV): m/e=388 (M⁺).
1 H-NMR (300 MHz, DMSO-d₆): = 8.04 (t; J = 6.1 Hz; 1H; -NH; exchanges with D₂O), 7.08-7.47 (m; 10H; Ph -H), 5.24 (s; 2H; - CH₂- Ph) and 4.55 ppm (d; J = 6.1 Hz; 2H; -NH- CH₂- Ph; after D₂O exchange s).
MS (70 eV): m / e = 388 (M⁺).
Eine in den folgenden Herstellungsbeispielen angege bene Menge einer Verbindung der allgemeinen Formel (II) wird in 130 ml Ethanol gelöst und in einen Au toklaven (250 ml) überführt. Nach der Zugabe von 2 Spatelspitzen (ca. 100 mg) eines Palladium/Aktiv kohle-Katalysators, mit einem Palladiumanteil von 10 Gewichtsprozent, wird über den in den nachfolgenden Herstellungsbeispielen angegebenen Zeitraum, bei 50 bar Wasserstoffatmosphäre, bei Raumtemperatur ge rührt. Anschließend wird die Reaktionsmischung mit tels einer Wasserstrahlpumpe in einen Glaskolben überführt und der Katalysator sofort über einen Glasfiltertiegel abfiltriert. Danach fügt man dem Filtrat eine zur Ausgangsverbindung äquimolare Menge Schwefelsäure (97prozentig) oder die zweifachmolare Menge Salzsäure (36prozentig) zu.One given in the following manufacturing examples bene amount of a compound of the general formula (II) is dissolved in 130 ml of ethanol and in an Au transferred to toclaves (250 ml). After adding 2 Spatula tips (approx. 100 mg) of a palladium / active carbon catalyst, with a palladium content of 10 Weight percent, is above that in the following Production examples given period, at 50 bar hydrogen atmosphere, at room temperature stirs. Then the reaction mixture with a water jet pump into a glass bulb transferred and the catalyst immediately over one Filtered glass filter crucible. Then you add that Filtrate an amount equimolar to the starting compound Sulfuric acid (97 percent) or the double molar Amount of hydrochloric acid (36 percent).
Eine in den folgenden Herstellungsbeispielen angege bene Menge einer Verbindung der allgemeinen Formel (III) wird in einem Hydrierkolben mit einer äquimo laren Menge 97prozentiger Schwefelsäure, 2 Spatel spitzen Palladium/Aktivkohle-Katalysator (10 Ge wichtsprozent Palladium) und der jeweils angegebenen Menge Wasser bei Raumtemperatur unter Wasserstoff atmosphäre (Normaldruck) über den in den nachfol genden Herstellungsbeispielen angegebenen Zeitraum geschüttelt. Der Reaktionsverlauf wird mittels Dünnschichtchromatographie kontrolliert. Nach vollständiger Umsetzung des Eduktes wird das Reak tionsgemisch über einen Glasfiltertiegel abfiltriert. Nach dem Abdestillieren des Lösungsmittels wird das Produkt aus Ethanol kristallisiert.One given in the following manufacturing examples bene amount of a compound of the general formula (III) is in a hydrogenation flask with an equimo laren amount of 97 percent sulfuric acid, 2 spatulas pointed palladium / activated carbon catalyst (10 Ge percent by weight palladium) and the specified Amount of water at room temperature under hydrogen atmosphere (normal pressure) above in the following given manufacturing examples specified period shaken. The course of the reaction is by means of Controlled thin layer chromatography. To the reaction becomes complete implementation of the react tion mixture filtered through a glass filter crucible. After the solvent has been distilled off, this becomes Product crystallized from ethanol.
0,5 g (2,13 mmol) 3-Brom-1-methyl-5-methylamino-4-nitro pyrazol werden in einer Lösung von 220 mg (2,13 mmol) Schwefelsäure in 20 ml Wasser, nach Zugabe des Katalysa tors, 14 Stunden lang, wie in Verfahren (2) beschrieben, hydriert. Nach dem Abfiltrieren des Katalysators engt man das Filtrat bis zur Trockene ein und kristallisiert den Rückstand aus Ethanol um. Man erhält 370 mg (78 Prozent der Theorie) 4-Amino-1-methyl-5-methylaminopy razol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 185 bis 188 °C.0.5 g (2.13 mmol) 3-bromo-1-methyl-5-methylamino-4-nitro pyrazole in a solution of 220 mg (2.13 mmol) Sulfuric acid in 20 ml of water, after adding the catalyst tors for 14 hours as described in method (2) hydrated. After filtering off the catalyst tight the filtrate is dried to dryness and crystallized the residue from ethanol. 370 mg (78 Percent of theory) 4-Amino-1-methyl-5-methylaminopy razole hydrosulfate in the form of colorless crystals with a Melting point from 185 to 188 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 8,53 (s; breit, 5H, -NH₂;
-NH; H₂SO₄; mit D₂O aus
tauschbar), 7,30 (s; 1H;
Ring-H 3,58 (s; 3H; N-CH₃)
und 2,80 ppm (s; 3H;
-NH-CH₃).
MS (70 eV): m/e=126 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 8.53 (s; broad, 5H, -NH₂; -NH; H₂SO₄; exchangeable with D₂O), 7.30 (s; 1H; ring H 3, 58 (s; 3H; N-CH₃) and 2.80 ppm (s; 3H; -NH- CH₃ ).
MS (70 eV): m / e = 126 (M⁺).
1 g (3,77 mmol) 3-Brom-5-(2′-hydroxyethyl)amino-1-me thyl-4-nitropyrazol werden in einer Lösung von 380 mg (3,77 mmol) Schwefelsäure in 50 ml Wasser 2 Stunden lang nach Verfahren (2) hydriert. Man erhält 720 mg (75 Pro zent der Theorie) 4-Amino-5-(2′-hydroxyethyl)amino-1-me thylpyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 94 bis 97 °C.1 g (3.77 mmol) of 3-bromo-5- (2'-hydroxyethyl) amino-1-me thyl-4-nitropyrazole are in a solution of 380 mg (3.77 mmol) sulfuric acid in 50 ml water for 2 hours hydrogenated according to process (2). 720 mg (75 per Cent of theory) 4-amino-5- (2'-hydroxyethyl) amino-1-me thylpyrazole hydrosulfate in the form of colorless crystals a melting point of 94 to 97 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 8,00 (s; breit; 6H; -NH₂;
-NH, -OH, H₂SO₄. tauscht mit
D₂O aus), 7,45 (s; 1H;
Ring-H), 3,60 (s; 3H;
-CH₃) und 3,50-3,10 (m; 4H;
-CH₂-CH₂-).
MS (70eV): m/e=156 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 8.00 (s; broad; 6H; -NH₂; -NH, -OH, H₂SO₄. Exchanges with D₂O), 7.45 (s; 1H; ring- H), 3.60 (s; 3H; -CH₃) and 3.50-3.10 (m; 4H; - CH₂ - CH₂ -).
MS (70 eV): m / e = 156 (M⁺).
a) 0,5 g (1,81 mmol) 3-Brom-5-tert-butylamino-1-me thyl-4-nitropyrazol werden in einer Lösung von 1,84 mg (1,81 mmol) Schwefelsäure in 20 ml Wasser, nach Zugabe des Katalysators, 48 Stunden lang nach Ver fahren (2) hydriert. Man erhält, nach Abdestillieren des Lösungsmittels auf die Hälfte der ursprünglichen Menge und Zugabe einer äquivalenten Menge Ethanol, 360 mg (87 Prozent der Theorie) 4,5-Diamino-1-me thylpyrazol-hydrosulfat-hydrat in Form von weißen Kristallen mit einem Schmelzpunkt von 200 bis 201 °C.a) 0.5 g (1.81 mmol) of 3-bromo-5-tert-butylamino-1-me thyl-4-nitropyrazole are in a solution of 1.84 mg (1.81 mmol) sulfuric acid in 20 ml water, after Add the catalyst for 48 hours after ver drive (2) hydrogenated. It is obtained after distillation of the solvent to half of the original Amount and addition of an equivalent amount of ethanol, 360 mg (87 percent of theory) 4,5-diamino-1-me thylpyrazole hydrosulfate hydrate in the form of white Crystals with a melting point of 200 to 201 ° C.
b) 0,5 g (1,61 mmol) 5-Benzylamino-3-brom-1-methyl-4-ni tropyrazol werden in einer Lösung von 165 mg (161 mmol) Schwefelsäure in 20 ml Wasser, nach Zugabe des Katalysators, 48 Stunden lang, wie im Verfahren (2) beschrieben, hydriert. Anschließend filtriert man den Katalysator ab und engt das Filtrat auf ca. 2 ml ein. Nach Zugabe von wenig Ethanol (ca. 2 ml) schei det sich das Produkt in Form weißer Kristalle ab. Man erhält 330 mg (90 Prozent der Theorie) 4,5-Dia mino-1-methylpyrazol-hydrosulfat-hydrat in Form von weißen Kristallen mit einem Schmelzpunkt von 200 bis 201 °C.b) 0.5 g (1.61 mmol) of 5-benzylamino-3-bromo-1-methyl-4-ni tropyrazole are dissolved in a solution of 165 mg (161 mmol) sulfuric acid in 20 ml water, after adding the Catalyst for 48 hours as in process (2) described, hydrogenated. Then filter the catalyst and the filtrate is concentrated to about 2 ml a. Add a little ethanol (approx. 2 ml) the product is in the form of white crystals. 330 mg (90 percent of theory) of 4,5-dia are obtained mino-1-methylpyrazole hydrosulfate hydrate in the form of white crystals with a melting point of 200 to 201 ° C.
1,62 g (5,6 mmol) 3-Benzylamino-3-brom-1-ethyl-4-nitro pyrazol werden über einen Zeitraum von 2 Stunden nach Vorschrift (1) hydriert. Nach Abfiltrieren des Katalysa tors fällt man durch Zugabe von 1 ml (11,6 mmol) konzen trierter Salzsäure (36prozentig) das Produkt als Dihy drochlorid aus. Man erhält 0,8 g (72 Prozent der Theo rie) 4,5-Diamino-1-ethylpyrazol-dihydrochlorid in Form farbloser Kristalle mit einem Schmelzpunkt von 184 bis 186 °C.1.62 g (5.6 mmol) of 3-benzylamino-3-bromo-1-ethyl-4-nitro pyrazole are used over a period of 2 hours Regulation (1) is hydrogenated. After filtering off the catalyst tors are concentrated by adding 1 ml (11.6 mmol) trated hydrochloric acid (36 percent) the product as dihy drochloride. 0.8 g (72 percent of Theo rie) 4,5-diamino-1-ethylpyrazole dihydrochloride in the form colorless crystals with a melting point of 184 to 186 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 8,01 (s; breit; 6H; -NH₂;
HCl; tauscht mit D₂O aus),
7,63 (s; 1H; Ring-H; 4,03
(q; J=6,4 Hz; 2H; -CH₂-
CH₃) und 1,25 ppm (t; J=
6,5 Hz; 3H; -CH₂-CH₃).
MS (70eV): m/e=126 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 8.01 (s; broad; 6H; -NH₂; HCl; exchanges with D₂O), 7.63 (s; 1H; Ring-H; 4.03 ( q; J = 6.4 Hz; 2H; - CH₂ - CH₃) and 1.25 ppm (t; J = 6.5 Hz; 3H; -CH₂- CH₃ ).
MS (70 eV): m / e = 126 (M⁺).
0,5 g (1,6 mmol) 1-Benzylamino-3-brom-1-isopropyl-4-ni tropyrazol werden 2 Stunden lang nach Vorschrift (1) hydriert. Nach Abfiltrieren des Katalysators wird das Produkt mit 0,3 ml (3,5 mmol) konzentrierter Salzsäure als Dihydrochlorid ausgefällt. Man erhält 0,25 g (73 Prozent der Theorie) 4,5-Diamino-1-isopropylpyrazol dihydrochlorid in Form farbloser Kristalle mit einem Schmelzpunkt von 164 °C.0.5 g (1.6 mmol) of 1-benzylamino-3-bromo-1-isopropyl-4-ni tropyrazole for 2 hours according to regulation (1) hydrated. After filtering off the catalyst Product with 0.3 ml (3.5 mmol) concentrated hydrochloric acid precipitated as dihydrochloride. 0.25 g (73 Percent of theory) 4,5-Diamino-1-isopropylpyrazole dihydrochloride in the form of colorless crystals with a Melting point of 164 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 7,90 (s; breit; 6H; -NH₂;
HCl; tauscht mit D₂O aus),
7,51 (s; 1H; Ring-H), 4,54
(m; 1H; -CH (CH₃)₂) und
1,30 ppm (d; 6H-CH(CH₃)₂).
MS (70 eV): m/e=140 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 7.90 (s; broad; 6H; -NH₂; HCl; exchanges with D₂O), 7.51 (s; 1H; Ring-H), 4.54 (m; 1H; - CH (CH₃) ₂) and 1.30 ppm (d; 6H-CH ( CH₃ ) ₂).
MS (70 eV): m / e = 140 (M⁺).
0,8 g (2,7 mmol) 3-Brom-1-(2′-hydroxyethyl)-5-(2′-hydro xyethyl)amino-4-nitropyrazol werden nach Vorschrift (1) 4 Stunden lang hydriert. Nach Abfiltrieren des Kataly sators fügt man 0,27 g (2,7 mmol) Schwefelsäure (97pro zentig) zu. Nach Abkühlen auf -30 °C erhält man 630 mg (82 Prozent der Theorie) 4-Amino-1-(2′-hydroxyethyl)-5- (2′-hydroxyethyl)aminopyrazol-hydrosulfat in Form farb loser Kristalle mit einem Schmelzpunkt von 140 bis 142°C.0.8 g (2.7 mmol) 3-bromo-1- (2'-hydroxyethyl) -5- (2'-hydro xyethyl) amino-4-nitropyrazole according to regulation (1) Hydrogenated for 4 hours. After filtering off the Kataly 0.27 g (2.7 mmol) of sulfuric acid (97pro cent) to. After cooling to -30 ° C, 630 mg are obtained (82 percent of theory) 4-amino-1- (2′-hydroxyethyl) -5- (2'-hydroxyethyl) aminopyrazole hydrosulfate in the color form loose crystals with a melting point of 140 to 142 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 10,18 (s; breit; 7H; -NH;
-NH₂; -OH; H₂SO₄; mit D₂O
austauschbar), 7,37 (s; 1H;
Ring-H), 4,00 (m; 2H;
-CH₂-), 3,53
(m; breit; 4H; -CH₂-) und
3,13 ppm (m; 2H; -CH₂-).
MS (70 eV): m/e=186 (M⁺).
1 H-NMR (60 MHz, DMSO-d₆): = 10.18 (s; broad; 7H; -NH; -NH₂; -OH; H₂SO₄; exchangeable with D₂O), 7.37 (s; 1H; Ring-H ), 4.00 (m; 2H; -CH₂-), 3.53 (m; broad; 4H; -CH₂-) and 3.13 ppm (m; 2H; -CH₂-).
MS (70 eV): m / e = 186 (M⁺).
2,65 g (10 mmol) 3-Brom-1-(2′-hydroxyethyl)-5-methylami no-4-nitropyrazol werden 4 Stunden lang nach Vorschrift (1) hydriert. Nach Zugabe von 1 g (10 mmol) Schwefel säure und 10 ml Isopropanol scheidet sich das Produkt ab. Man erhält 1 g (40 Prozent der Theorie) 4-Amino-1- (2′-hydroxyethyl)-5-methylaminopyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 138 bis 140 °C.2.65 g (10 mmol) 3-bromo-1- (2'-hydroxyethyl) -5-methylami No-4-nitropyrazole are used for 4 hours as directed (1) hydrogenated. After adding 1 g (10 mmol) of sulfur acid and 10 ml of isopropanol separate the product from. 1 g (40 percent of theory) of 4-amino-1- (2'-Hydroxyethyl) -5-methylaminopyrazole hydrosulfate in Form of colorless crystals with a melting point of 138 up to 140 ° C.
¹H-NMR (300 MHz, DMSO-d₆): = 9,6 (s; 2H; -NH₂, tauscht
mit D₂O aus), 7,38 (s; 1H;
Ring-H), 6,35 (s; 2H; -NH
und -OH; tauscht mit D₂O
aus), 3,96 (t; J=5,8 Hz;
2H; -CH₂-CH₂), 3,65 (t; J=
5,7 Hz; 2H; -CH₂-CH₂-) und
2,80 ppm (s; 3H; -NH-CH₃).
MS (70 eV): m/e=156 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 9.6 (s; 2H; -NH₂, exchanges with D₂O), 7.38 (s; 1H; Ring-H), 6.35 (s; 2H ; -NH and -OH; exchanges with D₂O), 3.96 (t; J = 5.8 Hz; 2H; -C H₂ -CH₂), 3.65 (t; J = 5.7 Hz; 2H; -CH₂-C H₂ -) and 2.80 ppm (s; 3H; -NH-C H₃ ).
MS (70 eV): m / e = 156 (M⁺).
1,7 g (5 mmol) 5-Benzylamino-3-brom-1-(2′-hydroxyethyl)- 4-nitropyrazol werden 4 Stunden lang nach Vorschrift (1) hydriert. Nach Zugabe von 0,5 g (5 mmol) Schwefelsäure erhält man 0,8 g (62 Prozent der Theorie) 4,5-Diamino-1- (2′-hydroxyethyl)pyrazol-hydrosulfat-hydrat in Form farbloser Kristalle mit einem Schmelzpunkt von 158 bis 160 °C. 1.7 g (5 mmol) 5-benzylamino-3-bromo-1- (2'-hydroxyethyl) - 4-nitropyrazole for 4 hours according to regulation (1) hydrated. After adding 0.5 g (5 mmol) of sulfuric acid 0.8 g (62 percent of theory) of 4,5-diamino-1- are obtained (2'-hydroxyethyl) pyrazole hydrosulfate hydrate in the form colorless crystals with a melting point of 158 to 160 ° C.
1 g (2,9 mmol) 1-Benzyl-3-brom-5-methylamino-4-nitro pyrazol werden in einer Lösung von 0,29 g (2,9 mmol) Schwefelsäure in 50 ml Wasser gemäß Vorschrift (2) über einen Zeitraum von 8 Stunden hydriert. Nach Abfiltrieren des Katalysators und Zugabe von 50 ml Ethanol wird das Filtrat auf 30 ml eingeengt und auf -30 °C abgekühlt. Man erhält 244 mg (40% der Theorie) 4-Amino-(3)5-me thylaminopyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 182 °C.1 g (2.9 mmol) of 1-benzyl-3-bromo-5-methylamino-4-nitro pyrazole in a solution of 0.29 g (2.9 mmol) Sulfuric acid in 50 ml of water according to regulation (2) hydrogenated for a period of 8 hours. After filtering of the catalyst and the addition of 50 ml of ethanol The filtrate was concentrated to 30 ml and cooled to -30 ° C. 244 mg (40% of theory) of 4-amino- (3) 5-me are obtained thylaminopyrazole hydrosulfate in the form of colorless crystals with a melting point of 182 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 10,10-9,20 (m; 6H; NH; -NH₂;
H₂SO₄; mit D₂O austausch
bar); 7,95 (s; 1H; Ring-H)
und
2,85 ppm (s; 3H; -CH₃).
MS (70 eV): m/e=112 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 10.10-9.20 (m; 6H; NH; -NH₂; H₂SO₄; exchangeable with D₂O); 7.95 (s; 1H; Ring-H) and 2.85 ppm (s; 3H; -CH₃).
MS (70 eV): m / e = 112 (M⁺).
0,5 g (1,31 mmol) 1-Benzyl-3-Brom-5-ethylamino-4-nitro pyrazol werden in einer Lösung von 130 mg (1,31 mmol) Schwefelsäure in 50 ml Wasser gemäß Vorschrift (2) über einen Zeitraum von 8 Stunden hydriert. Nach Abfiltrieren des Katalysators wird das Filtrat auf 10 ml eingeengt. Anschließend gibt man 10 ml Ethanol hinzu, woraufhin das Produkt in Form farbloser Kristalle, mit einem Schmelz punkt von 188 °C, auskristallisiert. Man erhält 0,1 g (34 Prozent der Theorie) 4-Amino-(3)5-ethylaminopyra zol-hydrosulfat.0.5 g (1.31 mmol) of 1-benzyl-3-bromo-5-ethylamino-4-nitro pyrazole in a solution of 130 mg (1.31 mmol) Sulfuric acid in 50 ml of water according to regulation (2) hydrogenated for a period of 8 hours. After filtering of the catalyst, the filtrate is concentrated to 10 ml. Then add 10 ml of ethanol, whereupon the Product in the form of colorless crystals with an enamel point of 188 ° C, crystallized. 0.1 g is obtained (34 percent of theory) 4-Amino- (3) 5-ethylaminopyra zol hydrosulfate.
¹H-NMR (300 MHz, DMSO-d₆): = 8,53 (s; breit; 6H; -NH;
-NH₂; H₂SO₄; tauscht mit
D₂O aus), 7,78 (s; 1H;
Ring-H); 3,21 (q; J=7,1
Hz; 2H; -CH₂-CH₃) und 1,18
ppm (t; J=7,1 Hz; 3H;
-CH₂-CH₃).
MS (70 eV): m/e=126 (M⁺).1 H-NMR (300 MHz, DMSO-d₆): = 8.53 (s; broad; 6H; -NH; -NH₂; H₂SO₄; exchanges with D₂O), 7.78 (s; 1H; Ring-H); 3.21 (q; J = 7.1 Hz; 2H; - CH₂- CH₃ ) and 1.18 ppm (t; J = 7.1 Hz; 3H; -CH₂- CH₃ ).
MS (70 eV): m / e = 126 (M⁺).
1 g (2,9 mmol) 1-Benzyl-3-brom-5-(2′-hydroxyethyl)amino- 4-nitropyrazol werden in einer Lösung von 0,29 g (2,9 mmol) Schwefelsäure und 50 ml Wasser über einen Zeitraum von 3 Stunden gemäß Vorschrift (2) hydriert. Nach Abfil trieren des Katalysators wird das Lösungsmittel im Vaku um abdestilliert. Das dabei auskristallisierte Produkt wird mit wenig (20 ml) Ethanol gewaschen und anschlie ßend getrocknet. Man erhält 240 mg (35 Prozent der Theorie) 4-Amino-(3)5-(2′-hydroxyethyl)aminopyrazol hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 185 °C.1 g (2.9 mmol) of 1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino 4-nitropyrazole are dissolved in a solution of 0.29 g (2.9 mmol) sulfuric acid and 50 ml water over a period of time hydrogenated for 3 hours according to regulation (2). After Abfil trieren of the catalyst, the solvent is in a vacuum to distill off. The product that crystallized out is washed with a little (20 ml) ethanol and then eats dried. 240 mg (35 percent of the Theory) 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole hydrosulfate in the form of colorless crystals with a Melting point of 185 ° C.
¹H-NMR (60 MHz, DMSO-d₆): = 8,35 (s; breit; 6H; -NH;
-NH₂; -OH; H₂SO₄, mit D₂O
austauschbar), 7,58 (s;
1H; Ring-H); 3,55 (m; 2H; -CH₂-OH) und 3,15 ppm (m;
2H; -NH-CH₂-).
MS (70 eV): m/e=142 (M⁺).1 H-NMR (60 MHz, DMSO-d₆): = 8.35 (s; broad; 6H; -NH; -NH₂; -OH; H₂SO₄, exchangeable with D₂O), 7.58 (s; 1H; Ring-H ); 3.55 (m; 2H; - CH₂ -OH) and 3.15 ppm (m; 2H; -NH- CH₂ -).
MS (70 eV): m / e = 142 (M⁺).
1 g (2,4 mmol) 1-Benzyl-5-benzylamino-3-brom-4-nitro pyrazol werden in einer Lösung von 0,25 g (2,4 mmol) Schwefelsäure und 50 ml Wasser über einen Zeitraum von 4 Stunden gemäß Vorschrift (2) hydriert. Nach Abfiltrieren des Katalysators fügt man dem Filtrat 50 ml Ethanol zu und kühlt auf -30 °C ab. Man erhält 184 mg (39 Prozent der Theorie) 4,(3)5-Diaminopyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 240 °C (Zersetzung).1 g (2.4 mmol) of 1-benzyl-5-benzylamino-3-bromo-4-nitro pyrazole in a solution of 0.25 g (2.4 mmol) Sulfuric acid and 50 ml water over a period of 4 Hours hydrogenated according to regulation (2). After filtering of the catalyst, 50 ml of ethanol are added to the filtrate and cools down to -30 ° C. 184 mg (39 percent of theory) 4, (3) 5-diaminopyrazole hydrosulfate in the form colorless crystals with a melting point of 240 ° C (Decomposition).
6,35 g 4-Amino-1-(2′-hydroxyethyl)-5-methylamino
pyrazol
2,73 g 3-Aminophenol
10,00 g Laurylalkohol-diglycolethersulfat-Natriumsalz
(28prozentige wäßrige Lösung)
10,00 g 6.35 g of 4-amino-1- (2'-hydroxyethyl) -5-methylamino pyrazole
2.73 g of 3-aminophenol
10.00 g of lauryl alcohol diglycol ether sulfate sodium salt (28 percent aqueous solution)
10.00 g
Ammoniak (22prozentige wäßrige Lösung)
100,00 gAmmonia (22% aqueous solution)
100.00 g
50 g des vorstehenden Haarfärbemittels werden unmittel bar vor Gebrauch mit 50 g Wasserstoffperoxidlösung (6- prozentig) gemischt. Das Gemisch wird anschließend auf blonde Naturhaare aufgetragen und 30 Minuten lang bei einer Temperatur von 40 °C einwirken gelassen. Das Haar wird anschließend mit Wasser gespült und getrocknet. Das Haar ist in einem modischen Purpurton gefärbt.50 g of the above hair dye are immediately bar before use with 50 g hydrogen peroxide solution (6- percent) mixed. The mixture is then on applied natural blonde hair and added for 30 minutes allowed to act at a temperature of 40 ° C. The hair is then rinsed with water and dried. The Hair is colored in a fashionable purple tone.
Claims (32)
- (A) 3,5-Dibrom-4-nitropyrazol mit einem C1- bis C6- Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzyl halogenid oder einem C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzylsulfat zu Verbin dungen der allgemeinen Formel (II) in der R3 einen C1- bis C6-Alkylrest, einen C2- bis C4-Hydroxyalkylrest oder einen Benzylrest bedeutet, umsetzt,
- (B) die Verbindungen der allgemeinen Formel (II) mit C1- bis C6-Alkyl-, C2- bis C4-Hydroxyalkyl- oder Benzylamin zu Verbindungen der allgemeinen Formel (III) in der R3 und R4 unabhängig voneinander einen C1- bis C6-Alkylrest, einen C2- bis C4-Hydroxy alkylrest oder einen Benzylrest bedeuten, in 5-Position substituiert und sodann
- (C) die Verbindungen der allgemeinen Formel (III) durch katalytische Hydrierung zu den Verbin dungen der allgemeinen Formel (I) reduziert.
- (A) 3,5-dibromo-4-nitropyrazole with a C 1 to C 6 alkyl, C 2 to C 4 hydroxyalkyl or benzyl halide or a C 1 to C 6 alkyl, C 2 - To C 4 hydroxyalkyl or benzyl sulfate to compounds of the general formula (II) in which R 3 denotes a C 1 to C 6 alkyl radical, a C 2 to C 4 hydroxyalkyl radical or a benzyl radical,
- (B) the compounds of the general formula (II) with C 1 - to C 6 -alkyl-, C 2 - to C 4 -hydroxyalkyl- or benzylamine to give compounds of the general formula (III) in which R 3 and R 4 independently of one another denote a C 1 -C 6 -alkyl radical, a C 2 -C 4 -hydroxyalkyl radical or a benzyl radical, substituted in the 5-position and then
- (C) the compounds of the general formula (III) are reduced by catalytic hydrogenation to the compounds of the general formula (I).
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924234885 DE4234885A1 (en) | 1992-10-16 | 1992-10-16 | Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivatives |
| BR9305675A BR9305675A (en) | 1992-10-16 | 1993-09-29 | Process for the preparation of 4,5-diaminopyrazole derivatives, their application to dye hair, as well as new pyrazole derivatives |
| EP93921874A EP0618902A1 (en) | 1992-10-16 | 1993-09-29 | Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives |
| JP6509556A JPH07502542A (en) | 1992-10-16 | 1993-09-29 | Process for producing 4,5-diaminopyrazole derivatives, their use for dyeing hair, and novel pyrazole derivatives |
| PCT/EP1993/002644 WO1994008969A1 (en) | 1992-10-16 | 1993-09-29 | Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives |
| ES93921874T ES2060574T1 (en) | 1992-10-16 | 1993-09-29 | PROCEDURE FOR THE PREPARATION OF DERIVATIVES OF 4,5-DIAMINOPYRAZOLE, ITS USE FOR THE COLORING OF HAIR AND NEW DERIVATIVES OF PYRAZOLE. |
| US08/650,819 US5663366A (en) | 1992-10-16 | 1996-05-20 | Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924234885 DE4234885A1 (en) | 1992-10-16 | 1992-10-16 | Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4234885A1 true DE4234885A1 (en) | 1994-04-21 |
Family
ID=6470605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19924234885 Withdrawn DE4234885A1 (en) | 1992-10-16 | 1992-10-16 | Process for the preparation of 4,5-diaminopyrazole derivatives, their use for dyeing hair and new pyrazole derivatives |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0618902A1 (en) |
| JP (1) | JPH07502542A (en) |
| BR (1) | BR9305675A (en) |
| DE (1) | DE4234885A1 (en) |
| ES (1) | ES2060574T1 (en) |
| WO (1) | WO1994008969A1 (en) |
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| GB8713769D0 (en) * | 1987-06-12 | 1987-07-15 | May & Baker Ltd | Compositions of matter |
| JP2897232B2 (en) * | 1988-12-23 | 1999-05-31 | ライオン株式会社 | 1H-pyrazolo [3,4-b] pyrazine derivatives and antitumor agents containing the compounds |
| DE3843892A1 (en) * | 1988-12-24 | 1990-06-28 | Wella Ag | OXIDATION HAIR AGENTS CONTAINING DIAMINOPYRAZOL DERIVATIVES AND NEW DIAMINOPYRAZOLE DERIVATIVES |
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1992
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- 1993-09-29 BR BR9305675A patent/BR9305675A/en not_active Application Discontinuation
- 1993-09-29 EP EP93921874A patent/EP0618902A1/en not_active Withdrawn
- 1993-09-29 WO PCT/EP1993/002644 patent/WO1994008969A1/en not_active Application Discontinuation
- 1993-09-29 JP JP6509556A patent/JPH07502542A/en not_active Ceased
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| EP0786244A1 (en) * | 1995-11-25 | 1997-07-30 | Wella Aktiengesellschaft | Oxidation hair-dye comprising 3,4,5 triaminopyrazole derivatives, and novel 3,4,5 triaminopyrazole derivatives |
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| WO1997042173A1 (en) * | 1996-05-03 | 1997-11-13 | L'oreal | New diamino pyrazols, their synthesis, keratin fibre dyeing compositions containing them, keratin fibre dyeing methods |
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| US6780203B1 (en) | 1997-09-01 | 2004-08-24 | L'ORéAL S.A. | Dyeing composition for keratin fibres |
| US6090162A (en) * | 1997-11-07 | 2000-07-18 | L'oreal S.A. | Composition for the oxidation dyeing of keratinous fibres comprising a 5-substituted 3,4-diaminopyrazole and a halogenated meta-aminophenol |
| WO2002009662A2 (en) * | 2000-08-02 | 2002-02-07 | Henkel Kommanditgesellschaft Auf Aktien | Agent for dyeing keratin containing fibers |
| WO2002009662A3 (en) * | 2000-08-02 | 2002-06-27 | Henkel Kgaa | Agent for dyeing keratin containing fibers |
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| EP1404288B1 (en) * | 2000-12-22 | 2008-10-29 | L'oreal | Composition for oxidation dyeing of keratinous fibres comprising a amino pyrazole and a cellulose compound |
| FR2821077A1 (en) * | 2001-02-21 | 2002-08-23 | Oreal | NOVEL DIAMINOPYRAZOLE COMPOUNDS AND THEIR USE IN KERATIN FIBER OXIDATION STAIN |
| WO2002070489A1 (en) * | 2001-02-21 | 2002-09-12 | L'oreal | Diaminopyrazole compounds and the use thereof in the oxidation dyeing of keratinous fibres |
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| US7018426B2 (en) | 2001-03-01 | 2006-03-28 | Wella Ag | Oxidation dye |
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| US7070629B2 (en) | 2001-09-28 | 2006-07-04 | L'oreal, S.A. | Dye composition comprising at least one diaminopyrazole oxidation base, at least one paraphenylenediamine oxidation base comprising a cyclic amino group, and at least one coupler |
| EP1764082A2 (en) | 2003-12-01 | 2007-03-21 | L'oreal | 4-5-diamino-N,N-dihydro-pyrazol-3-one derivatives for use in composition for dyeing keratin fibres |
| EP1728500A1 (en) | 2005-05-31 | 2006-12-06 | L'oreal | Composition for dyeing keratinic fibres comprising a diamino-N,N-dihydro-pyrazolon derivative and a cationic oxidation dye |
| EP1733713A1 (en) | 2005-05-31 | 2006-12-20 | L'oreal | Composition for dyeing keratinic fibres comprising a diamino-N,N-dihydro-pyrazolone dervative, a coupling agent and a selected surface-active agent |
| EP1733715A1 (en) | 2005-05-31 | 2006-12-20 | L'oreal | Composition for dyeing keratinic fibres comprising a diamino-N,N-dihydro-pyrazolone derivative, a coupling agent and a heterocyclic direct dye |
| EP1728499A1 (en) | 2005-05-31 | 2006-12-06 | L'oreal | Composition for dyeing keratinic fibres comprising a diamino-N,N-dihydro-pyrazolone derivative and a 2,3-diaminopyridine coupler |
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| EP1733716A1 (en) | 2005-05-31 | 2006-12-20 | L'oreal | Composition for dyeing keratin fibres comprising a diamino-N,N-dihydro-pyrazolone derivative, a coupling agent and an associative polyurethane polymer |
| US7485156B2 (en) | 2005-05-31 | 2009-02-03 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler and at least one associative polyurethane polymer |
| US7488356B2 (en) | 2005-05-31 | 2009-02-10 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one surfactant |
| US7488355B2 (en) | 2005-05-31 | 2009-02-10 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising a diamino-N,N-dihydropyrazolone compound, a coupler, and a polyol |
| US7582121B2 (en) | 2005-05-31 | 2009-09-01 | L'oreal S.A. | Composition for dyeing keratin fibers, comprising at least one diamino-N,N-dihydropyrazolone derivative, at least one coupler, and at least one heterocyclic direct dye |
| FR2945740A1 (en) * | 2009-05-19 | 2010-11-26 | Oreal | Composition, useful for dyeing keratin fibers, preferably human hair, comprises oxidation bases comprising 2-((2-(4-amino-phenylamino)-ethyl)-(2-hydroxy-ethyl)-amino)-ethanol and 4,5-diaminopyrazole compound in a medium |
| WO2014202150A1 (en) | 2013-06-21 | 2014-12-24 | Alfa Parf Group S.P.A. | New cationic dyes, kits and compositions thereof, and process for dyeing keratin fibers |
| WO2023152322A1 (en) | 2022-02-10 | 2023-08-17 | Wella Germany Gmbh | Hair coloring using oxidative dye precursors comprising pyrazole primaries and couplers, in combination with solubilized vat dyes, for improving color wash fastness |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07502542A (en) | 1995-03-16 |
| WO1994008969A1 (en) | 1994-04-28 |
| EP0618902A1 (en) | 1994-10-12 |
| ES2060574T1 (en) | 1994-12-01 |
| BR9305675A (en) | 1994-12-20 |
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