DE4234885A1 - A process for preparing 4,5-diaminopyrazole derivatives, the use thereof for dyeing hair as well as new pyrazole derivatives - Google Patents

A process for preparing 4,5-diaminopyrazole derivatives, the use thereof for dyeing hair as well as new pyrazole derivatives

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Publication number
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
amino
hydroxyethyl
ml
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DE19924234885
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German (de)
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Hans Prof Dr Neunhoeffer
Stefan Gerstung
Thomas Dr Clausen
Wolfgang Dr Balzer
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Procter and Gamble Deutschland GmbH
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Procter and Gamble Deutschland GmbH
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Priority to DE19924234885 priority Critical patent/DE4234885A1/en
Publication of DE4234885A1 publication Critical patent/DE4234885A1/en
Priority claimed from US08/650,819 external-priority patent/US5663366A/en
Application status is Withdrawn legal-status Critical

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic 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
    • C07D231/14Heterocyclic 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
    • C07D231/38Nitrogen atoms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic 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
    • C07D231/14Heterocyclic 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
    • C07D231/16Halogen atoms or nitro radicals

Abstract

The present invention relates to a process for producing 4,5-diamino pyrazole derivatives of general formula (I) in which R1 and R2 are mutually independently hydrogen, a C1 to C6 alkyl residue or a C2 to C4 hydroxy alkyl residue, which may be used as colorant pre-products, e.g. for hair colorants, and novel pyrzole derivatives. The use of the process of the invention makes it possible to obtain 4,5-diamino pyrazole derivatives of general formula (I) without isomers and with good yields.

Description

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten der allgemeinen Formel (I) The present invention is a process for preparing 4,5-diaminopyrazole derivatives of the general formula (I)

in der R 1 und R 2 unabhängig voneinander Wasserstoff, einen C 1 - bis C 6 -Alkylrest oder einen C 2 - bis C 4 -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 are independently hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4-hydro xyalkylrest mean, as well as new pyrazole derivatives, including 4,5-diaminopyrazole derivatives precursors as a colorant, can be, for example, for hair dyes can be used.

Es sind in der Literatur bereits mehrere Verfahren zur Herstellung von 4,5-Diaminopyrazol-Derivaten der Formel (I) bekannt. There are already known in the literature several processes for the preparation of 4,5-diaminopyrazole derivatives of formula (I). Diese Verfahren sind jedoch in vielerlei Hinsicht unbefriedigend. However, these methods are unsatisfactory in many respects.

So wird beispielsweise nach H. Dorn et al., Chem. Ber. So Chem. Ber example, according to H. Dorn et al.,. 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. 98, p 3368 (1965), starting from ethoxymethylene-cyano acetic acid ethyl ester and methylhydrazine, the 5-amino-1- receive methylpyrazole-4-carboxylic acid, centered from the by decarboxylation, with a total yield of 40 Pro, 5-amino-1 -methylpyrazol 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, a single-stage process be written is capable of 5-amino-1-methylpyrazole at a yield of 71 percent from after from N, N-dimethylaminoacrylonitrile and methylhydrazine be obtained.

Nach MA Khan et al., Can. MA 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. J. Chem. 49, p 3566 (1971), can be obtained after the process described central 5-amino-1-methylpyrazole at a yield of 23 Pro implement for 5-amino-1-methyl-4-nitropyrazole. Kata lytische Reduktion dieses Produktes liefert nach VP Perevalov et al., Khim. Kata lytic reduction of this product delivers to VP Perevalov et al., Khim. Geterotsicl. Geterotsicl. Soedin. Soedin. 8, S. 1090 (1985), 1-Methyl-4,5-diaminopyrazol-dihydrachlorid in einer Ausbeute von ca. 79 Prozent. 8, p 1090 (1985), 1-methyl-4,5-diaminopyrazole-dihydrachlorid in a yield of about 79 percent. Die Gesamtausbeute über die genannten Stufen beträgt 7 bis 13 Prozent. The overall yield over the said stages 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. Overall yields of up to 46 percent are obtained when the 5-amino-1-methylpyrazole by 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. Chem. 717, p 118 (1968), with isoamyl nitrite is reacted to 5-amino-1-methyl-4-nitropyrazole and tin (II) chloride to the 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. From DE-OS 38 43 892 a process for the manufacture 1974 Lung known from 4,5-diamino-1-methylpyrazole in which 2-chloroacrylonitrile with hydrazine (G. Ege, Angew. Chem, 86, p 237 () ) is cyclized. 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. After acetylation of the amino group, nitration and deprotection of the tautomeric compounds are obtained nitropyrazole 3-amino-4- and 5-amino-4-nitropyrazole in an overall yield of about 41 percent. 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. Alkylated to the Tautome rengemisch with dimethyl sulfate, is obtained in 70 per zentiger yield an isomer mixture which is chroma tographisch in the isomeric compounds 5-amino-1-me thyl-4-nitropyrazole (25 percent) and 3-amino-1- methyl-4-nitropyrazole (45 percent) can be separate. Durch Re duktion können die entsprechenden Diamino-Verbindungen erhalten werden. production by re the corresponding diamino compounds can be obtained. Die Gesamtausbeute von 1-Methyl-4,5- diaminopyrazol beträgt weniger als 10 Prozent. The total 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. From DE-OS 34 32 983 a process for the preparation position of 5-amino-1- (2'-hydroxyethyl) -4-nitropyrazole known. 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. Starting from 5-amino-1- (2'-hydroxyethyl) pyra zol-4-carboxylic acid compound by the decarboxy-regulation, followed by nitrosation and hydrogenation, in a yield of 59 percent is obtained.

Neben den zum Teil geringen Ausbeuten haben die beschriebenen Verfahren weitere Nachteile. In addition to the low yields in some cases, the methods described have other drawbacks. So sind viele Ausgangsverbindungen, wie zum Beispiel Ethoxymethylcyan essigsäureethylester oder N,N-Dimethylaminoacrylnitril, nicht käuflich erhältlich oder nur durch zum Teil aufwendige Synthesen herstellbar. So many starting compounds, such as Ethoxymethylcyan acetate or N, N-dimethylaminoacrylonitrile available not commercially available or only by expensive part syntheses can be produced. Darüberhinaus werden Hydrazinderivate als giftig und zum Teil krebserregend eingestuft. In addition, hydrazine derivatives are classified as carcinogenic toxic and in part.

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 are substitu ated in the 5-position on the nitrogen atom of the amino group is not disclosed.

Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur isomerenreinen Herstellung von unter schiedlich substituierten 4,5-Diaminopyrazol-Derivaten zur Verfügung zu stellen. It is an object of the present invention to provide a process for the production of isomerically pure among differently substituted 4,5-diaminopyrazole derivatives available.

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 stated object by a method for the preparation of 4,5-di-aminopyrazole derivatives of general formula (I)

in der R 1 und R 2 unabhängig voneinander Wasserstoff, einen C 1 - bis C 6 -Alkylrest oder einen C 2 - bis C 4 -Hydro xyalkylrest bedeuten, dadurch gekennzeichnet, daß man xyalkylrest to C 4-hydro, characterized in that - in the R 1 and R 2 are independently hydrogen, a C 1 - to C 6 -alkyl radical or a C 2

  • (A) 3,5-Dibrom-4-nitropyrazol mit einem C 1 - bis C 6 -Al kyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylhalogenid oder einem C 1 - bis C 6 -Alkyl, C 2 - bis C 4 -Hydroxy alkyl- oder Benzylsulfat zu Verbindungen der allge meinen Formel (II) in der R 3 einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeutet, umsetzt, (A) 3,5-dibromo-4-nitropyrazole by a C 1 - 6 alkyl--Al-C, C 2 - to C 4 hydroxyalkyl or benzyl halide or a C 1 - to C 6 -alkyl, C 2 - alkyl to C 4 hydroxy or Benzylsulfat to compounds of the general mean formula (II) in which R 3 is a C 1 - to C 6 -alkyl radical, a C 2 - C 4 hydroxyalkyl means until or a benzyl radical, is reacted,
  • (B) die Verbindungen der allgemeinen Formel (II) mit C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzyl amin zu Verbindungen der allgemeinen Formel (III) in der R 3 und R 4 unabhängig voneinander einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeuten, in 5-Position substituiert und sodann (B) the compounds of general formula (II) with C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or benzyl amine to form compounds of general formula (III) in which R 3 and R 4 independently represent a C 1 - to C 6 -alkyl radical, a C 2 - to C 4 -hydroxyalkyl radical or a benzyl radical mean 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, the compounds of general formula (III) by catalytic hydrogenation to the compounds of general formula (I) is reduced (C),

hervorragend lösen läßt. can solve outstanding. Das vorstehend aufgeführte Ver fahren ist daher ein Gegenstand der Erfindung. Drive the Ver listed above is therefore an object of the invention.

Das allgemeine Reaktionsschema ist nachstehend angege ben. The general reaction scheme is angege 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 used, the known 3,5-dibromo-4-nitropyrazole (IV), which provides the following manner Darge can be:

Nach R. Hüttel et al., Chem. Ber. According to 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 HJ 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. 88, p 1577 (1955), is obtained by nitration of the pyrazole with a pivot ric acid-nitric acid mixture, the 4-nitropyrazole, the adhesive according to HJ et al., Synthesis 1973, p 294 for under milder conditions by nitration of pyrazole (() Hüttel R. et al., Chem. Ber. 88, pp 1586 1955) can be obtained N-nitropyrazole and subsequent rearrangement, with the aid of sulfuric acid. Anschließende Bromierung nach JPH Juffermanns et al., J. Org. Chem. 51, S. 4656 (1986), liefert das 3,5-Dibrom-4-nitropyra zol (IV). Subsequent bromination according Juffermanns JPH et al., J. Org. Chem. 51, p 4656 (1986), provides the 3,5-dibromo-4-nitropyra zol (IV).

Nach dem erfindungsgemäßen Verfahren wird zunächst das 3,5-Dibrom-4-nitropyrazol (IV) durch Umsetzung mit C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylhalo geniden in Dimethylformamid (DMF) (Verfahren I) oder durch Umsetzung mit C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydro xyalkyl- oder Benzylsulfat und Lauge (Verfahren II) in 1-Position alkyliert. According to the inventive method, the 3,5-dibromo-4-nitropyrazole (IV) is first, by reaction with C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or Benzylhalo halides in dimethylformamide (DMF) ( method I) or by reaction with C 1 - to C 6 -alkyl, C 2 - (4-hydro -C xyalkyl- or Benzylsulfat liquor and method II) is 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. According to method I is added dropwise to an initial charge of sodium hydride in absolute DMF, under stirring at room temperature, an equimolar amount of 3,5-dibromo-4-nitropyrazole, dissolved in absolute DMF, over a period of one hour. Nach Beendigung der Gasentwicklung tropft man eine äquimolare Menge C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylhalogenid, bevorzugt -chlorid oder -bromid, gelöst in DMF, zu und erhitzt das Reaktionsgemisch drei Stunden lang auf 80 °C. After completion of the evolution of gas is added dropwise an equimolar amount of C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or benzyl halide, preferably chloride or bromide, dissolved in DMF to the reaction mixture and heated for three hours to 80 ° C. Anschließend wird das Lösungsmittel im Vakuum abdestil liert und der Rückstand aus Methylenchlorid umkristal lisiert. Then the solvent in vacuo abdestil lines and the residue from methylene chloride lisiert umkristal.

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 C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Ben zylsulfat versetzt. According to method II, the 3,5-dibromo-4-nitropyrazole in aqueous alkali, preferably 2N sodium or potassium hydroxide is dissolved, and a two- to five-fold molar amount of C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or Ben zylsulfat added. 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. With vigorous stirring, is allowed to react for 15 hours at room temperature, filtered on closing the precipitated product filtered off, washed reacts with water until the wash solution 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. In both processes, is obtained isomerically pure N-substi-substituted 3,5-dibromo-4-nitropyrazoles of the 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 C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylamin oder in dem ent sprechenden Amin selbst, als Lösungsmittel, auf eine Temperatur von 60 bis 80 °C. In a subsequent step by heating the N-sub-substituted 3,5-dibromo-4-nitropyrazoles of the formula (II) in an aqueous, alcoholic or alcoholic solution of aq rig-C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or benzylamine or in the ent speaking amine itself, as a solvent, at a temperature of 60 to 80 ° C. Als Alkohole werden bevorzugt Methanol und/oder Ethanol verwendet. As alcohols, methanol and / or ethanol are preferably used. 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. After a reaction time of 1 to 20 hours, pouring the cooled reaction mixture to 20 to 150 ml of water and filtered from the precipitated product. Anschließend wäscht man mit Wasser (10 bis 20 ml) und trocknet im Vakuum. Then washed with water (10 to 20 ml) and dried in vacuo. Man erhält isomerenreine 5-Amino-3-brom-4-nitro pyrazol-Derivate der allgemeinen Formel (III) in guten Ausbeuten. Obtained isomerically pure 5-amino-3-bromo-4-nitro-pyrazole derivatives of general formula (III) 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. The compounds of general formula (III) are hydrogenated to closing, using a palladium-activated carbon catalyst having a palladium content of 10 weight percent, with hydrogen. Erfindungsgemäß ste hen dazu zwei Verfahren zur Verfügung. According to the invention ste hen to two methods. 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. According to method (1), the alcoholic, preferably ethanolic, Lö added solution of a compound of general formula (III) two spatula, about 100 mg, of the catalyst and the batch was transferred to an autoclave. Bei 50 bar Wasserstoffatmosphäre wird bei Raumtemperatur 1 bis 6 Stunden lang, bevorzugt 2 bis 4 Stunden, gerührt. At 50 bar hydrogen atmosphere is 1 to 6 hours at room temperature, preferably 2 to 4 hours, stirred. 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. Then the catalyst is filtered off through a glass filter crucible and the product, with an equimolar amount added to the pyrazole compound is sulfuric acid or hydrochloric acid as salt from zweifachmolaren amount like. 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. According to method (2) are added to the aqueous solution of a compound of general formula (III) 2 spatula tips of the catalyst described above and an equimolar to the starting compound amount of sulfuric acid and the mixture in a hydrogenation flask at room temperature pressure shaken under hydrogen atmosphere (normal. Once the dünnschichtchromatogra phical study of the reaction mixture is no longer any indication of starting material still present, is filtered off a glass filter over the reaction mixture, the filtrate was concentrated and the product crystallized by adding ethanol.

Man erhält nach beiden Verfahren isomerenreine 4,5- Diaminopyrazol-Derivate der allgemeinen Formel (I) in guten Ausbeuten. Is obtained according to two methods isomerically pure 4,5-diaminopyrazole derivatives of the general formula (I) in good yields.

Die Verbindungen der allgemeinen Formel (I), in denen R 1 Wasserstoff bedeutet, liegen als Tautomere vor. The compounds of general formula (I) in which R 1 is hydrogen, exist as tautomers. Die Positionen 3 und 5 im Pyrazolring sind nicht unter scheidbar. The positions 3 and 5 in the pyrazole are not distinguishable.

Bei der Reduktion von Verbindungen der allgemeinen For mel (III), in der R 3 einen Benzylrest oder R 4 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 R 1 bzw. R 2 Wasserstoff statt Benzyl oder tert-Butyl bedeutet. In the reduction of compounds of the general For mel (III), 3 is a benzyl radical or R 4 represent a tert-butyl radical Ben zyl- or in which R, which are N-benzyl- and N-tert-butyl radicals reductively eliminated, so that compounds of general formula (I) are obtained in which R 1 and 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 present patent application are also new 3,5-dibromo-4-nitropyrazole derivatives of the general formula (II)

in der R 3 einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 - Hydroxyalkylrest oder einen Benzylrest bedeutet. in which R 3 is a C 1 - hydroxyalkyl group or a benzyl group means - to C 6 -alkyl radical, a C 2 - through C 4. 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 games for compounds of formula (II) are 3,5-di- bromo-1-methyl-4-nitropyrazole, 3,5-dibromo-1-ethyl-4-ni tropyrazol, 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) A further subject of the invention are 3-bromo-5-amino-4-nitropyrazole derivatives of the general formula (III)

in der R 3 und R 4 unabhängig voneinander einen C 1 - bis C 6 -Alkylrest, C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeuten. in which R 3 and R 4 independently represent a C 1 - to C 4 -hydroxyalkyl radical or a benzyl radical, - to C 6 alkyl, C 2nd

Beispiele für Verbindungen der Formel (III) sind are examples of compounds of formula (III)

3-Brom-1-methyl-5-methylamino-4-nitropyrazol, 3-bromo-1-methyl-5-methylamino-4-nitropyrazole,
3-Brom-5-(2′-hydroxyethyl)amino-1-methyl-4-nitropyrazol, 3-Bromo-5- (2'-hydroxyethyl) amino-1-methyl-4-nitropyrazole,
3-Brom-5-tertiärbutylamino-1-methyl-4-nitropyrazol, 3-bromo-5-tertiarybutylamino-1-methyl-4-nitropyrazole,
5-Benzylamino-3-brom-1-methyl-4-nitropyrazol, 5-benzylamino-3-bromo-1-methyl-4-nitropyrazole,
5-Benzylamino-3-brom-1-ethyl-4-nitropyrazol, 5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole,
5-Benzylamino-3-brom-1-isopropyl-4-nitropyrazol, 5-benzylamino-3-bromo-1-isopropyl-4-nitropyrazol,
3-Brom-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl)amino-4- nitropyrazol, 3-bromo-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino-4-nitropyrazole,
3-Brom-1-(2′-hydroxyethyl)-5-methylamino-4-nitropyrazol, 3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole,
5-Benzylamino-3-brom-1-(2′-hydroxyethyl)-4-nitropyrazol, 5-benzylamino-3-bromo-1- (2'-hydroxyethyl) -4-nitropyrazole,
1-Benzyl-3-brom-5-methylamino-4-nitropyrazol, 1-Benzyl-3-bromo-5-methylamino-4-nitropyrazole,
1-Benzyl-3-brom-5-ethylamino-4-nitropyrazol, 1-Benzyl-3-bromo-5-ethylamino-4-nitropyrazole,
1-Benzyl-3-brom-5-(2′-hydroxyethyl) amino-4-nitropyrazol 1-Benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole
und 1-Benzyl-5-benzylamino-3-brom-4-nitropyrazol zu nen nen sind. and 1-benzyl-5-benzylamino-3-bromo-4-nitropyrazol are NEN NEN.

Gegenstand der vorliegenden Erfindung sind ferner neue 4,5-Diaminopyrazol-Derivate der allgemeinen Formel (V) The present invention furthermore relates to novel 4,5-diaminopyrazole derivatives of the general formula (V)

in der R a und R b Wasserstoff, einen C 1 - bis C 6 -Alkylrest oder einen C 2 - bis C 4 -Hydroxyalkylrest bedeuten, mit der Maßgabe, daß, wenn R b Wasserstoff ist, R a nicht Wasser stoff, Methyl oder 2-Hydroxyethyl ist. b in which R a and R is hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4 -hydroxyalkyl mean, with the proviso that when R b is hydrogen, R a non-substance water, methylene or 2-hydroxyethyl.

Als Beispiele für Verbindungen der Formel (I) werden As examples of compounds of formula (I) are

4-Amino-1-methyl-5-methylaminopyrazol, 4-amino-1-methyl-5-methylaminopyrazole,
4-Amino-5-(2′-hydroxyethyl)amino-1-methylpyrazol, 4-amino-5- (2'-hydroxyethyl) amino-1-methylpyrazole,
4,5-Diamino-1-ethylpyrazol, 4,5-Diamino-1-ethylpyrazole,
4,5-Diamino-1-isopropylpyrazol, 4,5-Diamino-1-isopropylpyrazol,
4-Amino-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl)amino pyrazol, 4-amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino pyrazole,
4-Amino-1-(2′-hydroxyethyl)-5-methylaminopyrazol, 4-amino-1- (2'-hydroxyethyl) -5-methylaminopyrazole,
4-Amino-(3)5-methylaminopyrazol, 4-amino- (3) 5-methylaminopyrazole,
4-Amino-(3)5-ethylaminopyrazol und 4-amino- (3) 5-ethylaminopyrazol and
4-Amino-(3)5-(2′-hydroxyethyl)aminopyrazol, 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 used as Farbstoffvor step in oxidation for dyeing hair (see Example of Use).

Beispiele Examples A) Herstellung von N-substituierten 3,5-Dibrom-4-nitro pyrazolen der allgemeinen Formel (II) A) Preparation of N-substituted 3,5-dibromo-4-nitro pyrazoles of the general formula (II) a) Allgemeine Vorschrift, Verfahren I a) General procedure, Procedure I

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. To 1.75 g (70 mmol) of sodium hydride in 150 ml of absolute DMF (dimethylformamide) is added dropwise over a period of 1 hour 19.0 g (70 mmol) of 3,5-dibromo-4-nitropyrazole, dissolved in 90 ml of absolute DMF to. Nach Beendigung der Gasentwicklung werden 70 mmol C 1 bis C 6 -Alkyl-, C 2 bis C 4 -Hydroxyalkyl- oder Benzylhalogenid in 30 ml DMF zugetropft und 3 Stunden lang auf 80 °C erhitzt. After completion of gas evolution, 70 mmol C 1 to C 6 alkyl, C 2 are added dropwise to C 4 hydroxyalkyl or benzyl halide in 30 ml of DMF and heated at 80 ° C for 3 hours. Anschließend destilliert man das Lösungsmittel im Vakuum ab und kristallisiert den Rückstand aus Methylenchlorid um. Subsequently, the solvent is distilled off in vacuo and the residue is crystallized from methylene chloride to.

b) Allgemeine Vorschrift, Verfahren II b) General procedure, method II

Zu einer Lösung von 5 g (18,5 mmol) 3,5-Dibrom-4- nitropyrazol in 50 ml 2N Natronlauge gibt man 92,5 mmol C 1 bis C 6 -Alkyl-, C 2 bis C 4 -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. To a solution of 5 g (18.5 mmol) of 3,5-dibromo-4-nitropyrazole in 50 ml of 2N sodium hydroxide solution are added 92.5 mmol C 1 to C 6 alkyl, C 2 to C 4 hydroxy alkyl or Benzylsulfat allowed to stir for 15 hours at room temperature vigorously and then filtered from the precipitated product, washing with water until the wash solution pH-neutral reaction and dried in vacuo.

Herstellungsbeispiel 1 Preparation Example 1 3,5-Dibrom-1-methyl-4-nitro pyrazol 3,5-Dibromo-1-methyl-4-nitro-pyrazole

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. According to method II 5.06 g (96 percent of theory) are obtained using methyl sulfate, 3,5-di- bromo-1-methyl-4-nitropyrazole in the form of white crystals having a melting point of 154 ° C.

1 H-NMR (60 MHz, DMSO-d 6 ): = 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 1 H-NMR-Spektren gilt: Die Angaben der chemischen Verschiebung erfolgt in delta (ppm), die der Kopplungskonstanten (J) erfolgt in Hertz. For this and all the following 1 H NMR spectra of the following applies: The information of the chemical shift occurs in delta (ppm), the (J) is carried out of the coupling constant in Hertz. Standard: Tetramethylsilan Standard: tetramethylsilane
s = Singulett, d = Dublett, t = Triplett, q = Quartett, m = Multiplett, Ph = Phenyl, Ring-H = Proton am Pyrazol ring s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, Ph = phenyl, ring-H = proton on the pyrazole ring
MS (70 eV): m/e=287 (M⁺). MS (70 eV): m / e = 287 (M⁺).

Herstellungsbeispiel 2 Preparation Example 2 3,5-Dibrom-1-ethyl-4-nitro pyrazol 3,5-dibromo-1-ethyl-4-nitro-pyrazole

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. According to method II are obtained, using ethyl sulfate, 3.59 g (65 percent of theory) of 3,5-dibromo-1-ethyl-4-nitropyrazole in the form of white crystals having a melting point 119-121 ° 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 ). ¹H-NMR (60 MHz, DMSO-d₆): = 4.26 (q, J = 7.0 Hz, 2H, - CH₂ -CH₃); J = 7.0 Hz; 3H; and 1.36 ppm (t -CH₂- CH₃).
MS (70 eV): m/e=297 (M⁺). MS (70 eV): m / e = 297 (M⁺).

Herstellungsbeispiel 3 Preparation Example 3 3,5-Dibrom-1-isopropyl-4-nitro pyrazol 3,5-Dibromo-1-isopropyl-4-nitro-pyrazole

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. According to method I 13,14 g (60 percent of theory) are obtained using 2-bromopropane, 3,5-dibromo-1-isopropyl-4-nitropyrazole in the form of yellow brown crystals having 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). 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⁺). MS (70 eV): m / e = 311 (M⁺).

Herstellungsbeispiel 4 Preparation Example 4 3,5-Dibrom-1-(2′-hydroxyethyl)- 4-nitropyrazol 3,5-dibromo-1- (2'-hydroxyethyl) - 4-nitropyrazole

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. According to method I 14,77 g (67 percent of theory) of 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitropyrazole in the form of pale yellow crystals are obtained, by using 1-bromo-2-hydroxyethane, 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). ¹H-NMR (60 MHz, DMSO-d₆): = 4.90 (s; broad; 1H; -OH; with D₂O exchangeable), 4.31 (m; 2H; -CH₂-), and from 4.08 to 3, 82 ppm (m; 2H; -CH₂-, after D₂O exchange: t; 2H; J = 5 Hz).
MS (70 eV): m/e=317 (M⁺). MS (70 eV): m / e = 317 (M⁺).

Herstellungsbeispiel 5 Preparation Example 5 1-Benzyl-3,5-dibrom-4-nitro pyrazol 1-benzyl-3,5-dibromo-4-nitro-pyrazole

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. According to method I are obtained, using benzyl chloride, 17.94 g (71 percent of theory) of 1-benzyl-3,5-dibromo-4-nitrobenzene in the form of pale yellow crystals having 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-). ¹H-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 (⁺). MS (70 eV): m / e = 363 (⁺).

B) Herstellung von 5-Amino-3-brom-4-nitropyrazol- Derivaten der allgemeinen Formel (III) B) Preparation of 5-Amino-3-bromo-4-nitropyrazol- derivatives of general formula (III) Herstellungsbeispiel 6 Preparation Example 6 3-Brom-1-methyl-5-methylamino-4- nitropyrazol 3-bromo-1-methyl-5-methylamino-4-nitropyrazole

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. 2 g (7.02 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole who heated the in 50 ml of a 40 percent solution of methylamine in ethanol for 4 hours to boiling temperature. Nach dem Abkühlen fügt man dem Reaktionsgemisch 100 ml Wasser zu, filtriert das abgeschiedene Produkt ab und wäscht mit wenig Wasser (20 ml). After cooling, to the reaction mixture 100 ml of water, filtered off and the precipitated product washed with a little water (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. After drying in vacuo gives 1.45 g (88 percent of theory) of 3-bromo-1-methyl-5-methylamino-4-nitropyrazole in the form of yellow crystals having 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). ¹H-NMR (60 MHz, DMSO-d₆): = 7.50 (s; broad; 1H; -NH; with D₂O exchangeable), 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⁺). MS (70 eV): m / e = 236 (M⁺).

Herstellungsbeispiel 7 Preparation Example 7 3-Brom-5-(2′-hydroxyethylamino)- 1-methyl-4-nitropyrazol 3-Bromo-5- (2'-hydroxyethylamino) - 1-methyl-4-nitropyrazole

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. 3 g (10.5 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole who heated the in a solution of 30 ml of ethanolamine in 30 ml Etha nol 15 hours to boiling temperature. An schließend gießt man das Reaktionsgemisch auf 200 ml Wasser, filtriert das abgeschiedene Produkt ab, wäscht mit Wasser (20 ml) und trocknet im Vakuum. On closing pouring the reaction mixture into 200 ml of water, filtered off the precipitated product, washing with water (20 ml) and dried in vacuo. Aus dem Fil trat kristallisiert in der Kälte (5 °C) weiteres Produkt aus. emerged from the Fil crystallized from another product in the cold (5 ° C).

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. This gives 2.25 g (81 percent of theory) of 3-bromo-5- (2'-hydroxyethyl) amino-1-methyl-4-nitropyrazole in the form of yellow crystals having 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 ). ¹H-NMR (60 MHz, DMSO-d₆): = 7.38 (s; broad; 1H; -NH; with D₂O exchangeable), 4.98 (s; broad; 1H; -OH; with D₂O exchangeable), 3 , 82 (s; 3H; N-CH₃) and 3.60 ppm (m; 4H; -NH- CH₂-CH₂).
MS (70 eV): m/e=266 (M⁺). MS (70 eV): m / e = 266 (M⁺).

Herstellungsbeispiel 8 Preparation Example 8 3-Brom-5-tert-butylamino-1- methyl-4-nitropyrazol 3-bromo-5-tert-butylamino-1-methyl-4-nitropyrazole

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. 1.5 g (5.26 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole are heated in a solution of 20 ml of tert-butylamine in 30 ml of ethanol for 20 hours to boiling temperature. Nach dem Abkühlen gießt man das Reaktionsgemisch auf 150 ml Wasser, filtriert das abgeschiedene Produkt ab und wäscht mit 100 ml Wasser. After cooling, the reaction mixture is poured onto 150 ml of water, filtered from the separated product and washed with 100 ml of water. 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. After drying in vacuo gives 1.14 g (78 percent of theory) of 3-bromo-5-tert-butylamino-1-methyl-4-nitropyrazole in the form of a pale yellow leaflets having 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). ¹H-NMR (60 MHz, DMSO-d₆): = 5.35 (s; 1H; -NH; exchanges with D₂O off), 3.75 (s; 3H; N-CH₃) and 1.20 ppm (s; 9H; -C (CH₃) ₃).
MS (70 eV): m/e=277 (M⁺). MS (70 eV): m / e = 277 (M⁺).

Herstellungsbeispiel 9 Preparation Example 9 5-Benzylamino-3-brom-1-methyl- 4-nitropyrazol 5-benzylamino-3-bromo-1-methyl-4-nitropyrazole

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. 2 g (7.02 mmol) of 3,5-dibromo-1-methyl-4-nitropyrazole in a solution of 11 g (0.1 ml) of benzylamine in 50 ml of ethanol for 10 hours to boiling temperature it hitzt. Nach dem Abkühlen gießt man das Reaktionsgemisch auf 100 ml Wasser, filtriert das abgeschiedene Produkt ab und wäscht mit Wasser (20 ml). After cooling, the reaction mixture is poured onto 100 ml of water, filtered from the separated product and washed with water (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. After drying in vacuo gives 1.76 g (81 percent of theory) of 5-Ben zylamino-3-bromo-1-methyl-4-nitropyrazole in the form of yellow needles having 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). ¹H-NMR (60 MHz, DMSO-d₆): = 7.88 (t; 1H; J = 6Hz; -NH-; with D₂O exchangeable), 7.32 (m; 5H; Ph-H), 4.73 (d; 2H; J = 6 Hz, -NH-CH₂-; D₂O to interchange s) and 3.68 ppm (s; 3H; N-CH₃).
MS (70 eV): m/e=312 (M⁺). MS (70 eV): m / e = 312 (M⁺).

Herstellungsbeispiel 10 Preparation 10 5-Benzylamino-3-brom-1-ethyl- 4-nitropyrazol 5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole

6,3 g (21 mmol) 3,5-Dibrom-1-ethyl-4-nitropyrazol werden in 10 ml Benzylamin 1 Stunde lang auf 80 °C erhitzt. 6.3 g (21 mmol) of 3,5-dibromo-1-ethyl-4-nitropyrazol are heated in 10 ml of benzyl amine for 1 hour at 80 ° C. 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. On closing pouring the reaction mixture onto 50 ml water and separated off the separated oil from which, after addition of 20 ml to 30 ml of ethyl acetate, the pro duct crystallized. 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. After one Umkristalli Sieren from methanol to obtain 5.2 g (76 percent of theory) of 5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole in the form of light yellow needles having 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 ). H-NMR (300 MHz, DMSO-d₆): = 7.90 (t; J = 6.7 Hz; 1H; -NH; exchanges with D₂O off), 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⁺). MS (70 eV): m / e = 324 (M⁺).

Herstellungsbeispiel 11 Preparation 11 5-Benzylamino-3-brom-1-isopro pyl-4-nitropyrazol 5-benzylamino-3-bromo-1-propyl-4-nitropyrazol ISOPRO

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. 3.13 g (10 mmol) of 3,5-dibromo-1-isopropyl-4-nitropyrazole in 10 ml of benzyl amine for 1 hour at 80 ° C, it hitzt. Anschließend gießt man das Reaktionsgemisch auf 50 ml Wasser und filtriert das abgeschiedene Produkt ab. Then pouring the reaction mixture onto 50 ml of water and filtered from the precipitated product. 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. After one recrystallization from a toluene / petroleum ether mixture (1: 1) gives 2.3 g (68 percent of theory) of 5-benzylamino-3-bromo-1-isopropyl-4-nitro pyrazole in the form of pale yellow crystals having 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); H-NMR (300 MHz, DMSO-d₆): = 7.78 (t, after D₂O exchange s J = 6.6 Hz; 1H; -NH), 7.25-7.39 (m; 5H; ph-H); 4,66 (d; J=6,6 Hz; 2H, -NH- CH₂ -; nach D₂O-Austausch s); - 4.66 (s after D₂O exchange d; J = 6.6 Hz 2H, -NH- CH₂) 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). 4.57 (dq, J = 6.4 Hz; 1H; - CH (CH₃) ₂) and 1.19 ppm (d; J = 6.4 Hz; 6H; -CH (CH₃) ₂).
MS (70 eV): m/e=338 (M⁺). MS (70 eV): m / e = 338 (M⁺).

Herstellungsbeispiel 12 Preparation 12 3-Brom-1-(2′-hydroxyethyl)-5- (2′-hydroxyethyl)amino-4-nitro pyrazol 3-bromo-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino-4-nitro-pyrazole

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. 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) of ethanolamine in 30 ml ethanol 15 heated for hours at 80 ° C. Nach dem Abkühlen fügt man dem Reaktionsgemisch 50 ml Wasser zu und extrahiert drei mal mit je 70 ml Essigsäureethylester. After cooling, to the reaction mixture 50 ml of water and extracted three times with 70 ml ethyl acetate. 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. Are added to the combined solutions traction Ex 200 ml of n-hexane and distilling the solvent mixture in vacuo to one third of the amount for sprünglichen. Danach fügt man erneut n-Hexan bis zur Trübung der Lösung zu. Are then added again to n-hexane until turbidity of the solution. Anschließend filtriert man das auskristallisierte Produkt ab und wäscht mit n-Hexan (10 bis 20 ml). Then filtered off and the crystallized product is washed with n-hexane (10 to 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. This gives 1.04 g (74 percent of theory) of 3-bromo-1- (2'-hydroxyethyl) -5- (2'-hy droxyethyl) amino-4-nitropyrazole in the form of pale yellow crystals having a melting point 132-134 ° 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-). ¹H-NMR (60 MHz, DMSO-d₆): = 7.42 (s; broad; 1H; -NH; with D₂O exchangeable), 5.23 to 5.02 (m; 2H; -OH; with D₂O exchangeable) , 4.18 (m; 2H; N-CH₂-) and 3,93- 3,45 ppm (m; 6H; -CH₂-).
MS (70 eV): m/e=296 (M⁺). MS (70 eV): m / e = 296 (M⁺).

Herstellungsbeispiel 13 Preparation 13 3-Brom-1-(2′-hydroxyethyl)-5- methylamino-4-nitropyrazol 3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole

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. 3.15 g (10 mmol) of 3,5-dibromo-1- (2'-hydroxyethyl) are heated in 70 ml of a 30 percent solution of methylamine in water for 1 hour at 60 ° C -4-nitro pyrazole. Nach dem Abkühlen fällt das Produkt in Form hellgelber Kristalle, mit einem Schmelzpunkt von 158 bis 160 °C, aus. After cooling, the product precipitates as light yellow crystals having a melting point of 158 to 160 ° C, from. Man erhält 2,4 g (91 Prozent der Theorie) 3-Brom-1-(2′-hydroxyethyl)-5-methylamino-4-nitropyrazol. This gives 2.4 g (91 percent of theory) of 3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole.

¹H-NMR (300 MHz, DMSO-d₆): = 7,67 (s; 1H; -NH; tauscht mit D₂O aus); H-NMR (300 MHz, DMSO-d₆): = 7.67 (s; 1H; -NH; exchanges with D₂O O); 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). 5.06 (s; 1H; -OH; exchanges with D₂O off), 4.18 (t; 2H; N-CH₂-), 3.68 (t, 2H, - CH₂-OH) and 3.15 ppm ( d, J = 4.5 Hz; 3H; CH₃ -NH-; after D₂O exchange s).
MS (70 eV): m/e=266 (M⁺). MS (70 eV): m / e = 266 (M⁺).

Herstellungsbeispiel 14 Preparation 14 5-Benzylamino-3-brom-1-(2′-hy droxyethyl)-4-nitropyrazol 5-benzylamino-3-bromo-1- (2'-hy droxyethyl) -4-nitropyrazole

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. 6.3 g (20 mmol) of 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitro are heated in 20 ml of benzylamine for 2 hours at 60 ° C pyrazole. Nach dem Abkühlen gießt man auf 50 ml Wasser, filtriert das abgeschiedene Produkt ab und kristallisiert einmal aus Toluol/Ligroin (1 : 1) um. After cooling it is poured onto 50 ml of water, filtered off and the deposited product was crystallized once from toluene / ligroin (1: 1) to. 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. To give 4 g (59 percent of theory) of 5-benzylamino-3-bromo-1- (2'-hydroxyethyl) -4-nitropyrazole in the form of yellow crystals having a melting point 133-135 ° 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); H-NMR (300 MHz, DMSO-d₆): = 7.89 (t; J = 6.6 Hz; 1H; -NH; exchanges with D₂O off), 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-). 5.15 (s; 1H; -OH; exchanges with D₂O off), 4.77 (d; J = 6.6 Hz, 2H; -NH- CH₂ -; after D₂O exchange-off s), 3.99 ( J = 5 Hz, 2H; -CH₂-) t; J = 4.9H, 2H, -) and 3.96 ppm (t - CH₂.
MS (70 eV): m/e=340 (M⁺). MS (70 eV): m / e = 340 (M⁺).

Herstellungsbeispiel 15 Preparation Example 15 1-Benzyl-3-brom-5-methylamino- 4-nitropyrazol 1-Benzyl-3-bromo-5-methylamino-4-nitropyrazole

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. 3.61 g (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole in 100 ml of a solution of 35prozentigen Metyl amine heated to 60 ° C for 4 hours in water. Nach dem Abkühlen filtriert man den abgeschiedenen Nieder schlag ab und kristallisiert einmal aus Ethanal um. After cooling, it is filtered off the precipitate separated and crystallized once around from acetaldehyde. 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. 2.7 g is obtained (87 percent of theory) of 1-benzyl-3-bromo-5-methylamino-4-nitropyrazole in the form of colorless crystals having 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). H-NMR (300 MHz, DMSO-d₆): = 7.71 (s; 1H; -NH; exchanges with D₂O off), 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⁺). MS (70 eV): m / e = 312 (M⁺).

Herstellungsbeispiel 16 Preparation 16 1-Benzyl-3-brom-5-ethylamino- 4-nitropyrazol 1-Benzyl-3-bromo-5-ethylamino-4-nitropyrazole

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. 3.61 (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole are heated in 120 ml of a 30 percent aqueous solution of ethylamine for 1 hour at 60 ° C. Nach dem Abkühlen scheidet sich das Produkt in Form farbloser Kristalle mit einem Schmelzpunkt von 122 °C ab. After cooling, the product precipitates in form of colorless crystals having a melting point of 122 ° C. Man erhält 2,88 g 89 Prozent der Theorie) 1-Benzyl-3-brom-5-ethylamino-4- nitropyrazol. 2.88 g is obtained nitropyrazole 89 percent of theory) of 1-benzyl-3-bromo-5-ethylamino-4.

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 ). H-NMR (300 MHz, DMSO-d₆): = 7.15 to 7.41 (m; 6H; -NH and Ph-H, 1H exchanges with D₂O off), 5.37 (s; 1H; -CH₂- ), 3.32 to 3.39 (m, 2H, - CH₂ -CH₃) and 1.07 to 1.12 ppm (t; 3H; -CH₂- CH₃).
MS (70 eV): m/e=326 (M⁺). MS (70 eV): m / e = 326 (M⁺).

Herstellungsbeispiel 17 Preparation 17 1-Benzyl-3-brom-5-(2′-hydroxy ethyl)amino-4-nitropyrazol 1-Benzyl-3-bromo-5- (2'-hydroxy ethyl) amino-4-nitropyrazole

3,61 g (10 mmol) 1-Benzyl-3,5-dibrom-4-nitropyrazol werden in 15 ml Ethanolamin 2 Stunden lang auf 80 °c erhitzt. 3.61 g (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole are heated in 15 ml of ethanolamine for 2 hours at 80 ° c. Nach dem Abkühlen gießt man das Reaktionsge misch auf 30 ml Wasser und filtriert den abgeschiedenen Niederschlag ab. After cooling, pour the Reaktionsge mixed into 30 ml of water and filtered from the precipitate separated. 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. A single recrystallization from toluene, 2.5 g (74 percent of theory) of 1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole in the form of pale yellow crystals having 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 -). H-NMR (300 MHz, DMSO-d₆): = 7.54 (t; 1H; -NH; exchanges with D₂O off), 7.15-7.40 (m; 5H; Ph-H), 5.44 (s, 2H, - CH₂-Ph), 5.05 (t; 1H; -OH; exchanges with D₂O off) and 3.32 to 3.53 ppm (m; 4H; - CH₂-CH₂ -).
MS (70 eV): m/e=342 (M⁺). MS (70 eV): m / e = 342 (M⁺).

Herstellungsbeispiel 18 Preparation 18 1-Benzyl-5-benzylamino-3-brom- 4-nitropyrazol 1-Benzyl-5-benzylamino-3-bromo-4-nitropyrazole

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. 3.61 g (10 mmol) of 1-benzyl-3,5-dibromo-4-nitropyrazole who heated the in a solution of 3.6 g of benzylamine for 2 hours at 60 ° C. Nach dem Abkühlen wird das Reaktions gemisch auf 20 ml Wasser gegossen und der abgeschiedene Niederschlag abfiltriert. After cooling, the reaction mixture is poured on 20 ml water and the deposited precipitate was filtered off. 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. After one Umkristalli Sieren of a naphtha / toluene mixture (1: 1) gives 2.6 g (68 percent of theory) of 1-benzyl-5-benzyl amino-3-bromo-4-nitropyrazole in the form of pale yellow crystals of 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). H-NMR (300 MHz, DMSO-d₆): = 8.04 (t; J = 6.1 Hz; 1H; -NH; exchanges with D₂O off), 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⁺). MS (70 eV): m / e = 388 (M⁺).

C) Herstellung von 4,5-Diaminopyrazol-Derivaten der allgemeinen Formel (I) C) Preparation of 4,5-diaminopyrazole derivatives of the general formula (I) a) Allgemeine Vorschrift, Verfahren (1) a) General procedure, method (1)

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. A angege in the following Production Examples bene amount of a compound of the general formula (II) is dissolved in 130 ml of ethanol and in an Au toklaven (250 ml) was transferred. 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. After the addition of 2 spatula tips (about 100 mg) of a palladium / activated carbon catalyst, with a palladium content of 10 percent by weight, is indicated in the following Preparation Examples period at 50 bar atmosphere of hydrogen, stirred ge at room temperature. Anschließend wird die Reaktionsmischung mit tels einer Wasserstrahlpumpe in einen Glaskolben überführt und der Katalysator sofort über einen Glasfiltertiegel abfiltriert. Subsequently, the reaction mixture is transferred by means of a water jet pump in a glass flask and the catalyst is filtered immediately through a glass filter crucible. Danach fügt man dem Filtrat eine zur Ausgangsverbindung äquimolare Menge Schwefelsäure (97prozentig) oder die zweifachmolare Menge Salzsäure (36prozentig) zu. Are then added an equimolar amount of sulfuric acid to the starting compound (97prozentig) or zweifachmolare amount of hydrochloric acid (36prozentig) to the filtrate.

b) Allgemeine Vorschrift, Verfahren (2) b) General procedure, Process (2)

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. A angege in the following Production Examples bene amount of a compound of the general formula (III) in a hydrogenation flask with a äquimo stellar amount 97prozentiger sulfuric acid, 2 spatula tips of palladium / charcoal catalyst (10 Ge weight percent palladium) and the respectively specified amount of water at room temperature under hydrogen atmosphere (normal pressure) shaken indicated in the preparation examples nachfol constricting period. Der Reaktionsverlauf wird mittels Dünnschichtchromatographie kontrolliert. The reaction course is monitored by thin layer chromatography. Nach vollständiger Umsetzung des Eduktes wird das Reak tionsgemisch über einen Glasfiltertiegel abfiltriert. After complete conversion of the starting material, the reac tion mixture is filtered through a filter crucible. Nach dem Abdestillieren des Lösungsmittels wird das Produkt aus Ethanol kristallisiert. After distilling off the solvent, the product from ethanol is crystallized.

Herstellungsbeispiel 19 Preparation 19 4-Amino-1-methyl-5-methylamino pyrazol 4-amino-1-methyl-5-methylamino pyrazol

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. 0.5 g (2.13 mmol) 3-bromo-1-methyl-5-methylamino-4-nitro pyrazol be in a solution of 220 mg (2.13 mmol) of sulfuric acid in 20 ml of water, after addition of the Katalysa tors , for 14 hours as described in method (2), hydrogenated. Nach dem Abfiltrieren des Katalysators engt man das Filtrat bis zur Trockene ein und kristallisiert den Rückstand aus Ethanol um. After filtering off the catalyst the filtrate is concentrated to dryness and the residue is recrystallized from ethanol. 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. This gives 370 mg (78 percent of theory) of 4-amino-1-methyl-5-methylaminopy razol hydrosulfate in the form of colorless crystals having a melting point 185-188 ° 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 ). ¹H-NMR (60 MHz, DMSO-d₆): = 8.53 (s, broad, 5H, -NH₂ -NH; H₂SO₄; with D₂O from exchangeable), 7.30 (s; 1H; H-3 ring, 58 (s; 3H; N-CH₃) and 2.80 ppm (s; 3H; CH₃ -NH-).
MS (70 eV): m/e=126 (M⁺). MS (70 eV): m / e = 126 (M⁺).

Herstellungsbeispiel 20 Preparation 20 4-Amino-5-(2′-hydroxyethyl)ami no-1-methylpyrazol 4-amino-5- (2'-hydroxyethyl) ami no-1-methylpyrazole

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. 1 g (3.77 mmol) of 3-bromo-5- (2'-hydroxyethyl) amino-1-me thyl-4-nitropyrazole in a solution of 380 mg (3.77 mmol) of sulfuric acid in 50 ml water for 2 hours long by method (2) hydrogenated. 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. This gives 720 mg (75 per cent of theory) of 4-amino-5- (2'-hydroxyethyl) amino-1-me thylpyrazol hydrosulfate in the form of colorless crystals having a melting point of 94-97 ° 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 -). ¹H-NMR (60 MHz, DMSO-d₆): = 8.00 (s; broad; 6H; -NH₂ -NH, -OH, exchanged with D₂O H₂SO₄ in.), 7.45 (s; 1H; ring H), 3.60 (s; 3H; -CH₃) and 3.50 to 3.10 (m; 4H; - CH₂ - CH₂ -).
MS (70eV): m/e=156 (M⁺). MS (70 eV): m / e = 156 (M⁺).

Herstellungsbeispiel 21 Preparation 21 4,5-Diamino-1-methylpyrazol 4,5-diamino-1-methylpyrazole

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. a) 0.5 g (1.81 mmol) of 3-bromo-5-tert-butylamino-1-me thyl-4-nitropyrazol be (in a solution of 1.84 mg 1.81 mmol) of sulfuric acid in 20 ml of water after addition of the catalyst, 48 hours after Ver drive (2) hydrogenated. 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. Obtained by distilling off the solvent to half of the initial volume and adding an equivalent amount of ethanol, 360 mg (87 percent of theory) of 4,5-diamino-1-me thylpyrazol hydrosulfate hydrate in the form of white crystals having a melting point 200-201 ° 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. b) 0.5 g (1.61 mmol) of 5-benzylamino-3-bromo-1-methyl-4-ni are tropyrazol (in a solution of 165 mg 161 mmol) of sulfuric acid in 20 ml of water, after addition of the catalyst, described for 48 hours, as in the method (2), hydrogenated. Anschließend filtriert man den Katalysator ab und engt das Filtrat auf ca. 2 ml ein. Then filtered off the catalyst and the filtrate was concentrated to about 2 ml a. Nach Zugabe von wenig Ethanol (ca. 2 ml) schei det sich das Produkt in Form weißer Kristalle ab. After addition of a little ethanol det the product as white crystals from (about 2 ml) failed. 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. 330 mg is obtained (90 percent of theory) of 4,5-Dia mino-1-methylpyrazole hydrochloride sulfate hydrate in the form of white crystals having a melting point 200-201 ° C.

Herstellungsbeispiel 22 Preparation 22 4,5-Diamino-1-ethylpyrazol 4,5-Diamino-1-ethylpyrazole

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. 1.62 g (5.6 mmol) of 3-benzylamino-3-bromo-1-ethyl-4-nitro pyrazol over a period of 2 hours after the procedure (1) are hydrogenated. 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. After filtering off the Katalysa tors is precipitated by addition of 1 ml (11.6 mmol) concentrated trated hydrochloric acid (36prozentig) the product as a hydrochloride of dihydroergotamine. 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. This gives 0.8 g (72 percent of the RIE Theo) of 4,5-diamino-1-ethylpyrazole dihydrochloride in the form of colorless crystals having a melting point 184-186 ° 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 ). H-NMR (300 MHz, DMSO-d₆): = 8.01 (s; broad; 6H; -NH₂; HCl; exchanges with D₂O off), 7.63 (s; 1H; ring-H; 4.03 ( J = 6.5 Hz; 3H; CH₃ -CH₂-) q; J = 6.4 Hz, 2H, - CH₃) and 1.25 ppm (t - CH₂.
MS (70eV): m/e=126 (M⁺). MS (70 eV): m / e = 126 (M⁺).

Herstellungsbeispiel 23 Preparation Example 23 4,5-Diamino-1-isopropylpyrazol 4,5-Diamino-1-isopropylpyrazol

0,5 g (1,6 mmol) 1-Benzylamino-3-brom-1-isopropyl-4-ni tropyrazol werden 2 Stunden lang nach Vorschrift (1) hydriert. 0.5 g (1.6 mmol) of 1-benzylamino-3-bromo-1-isopropyl-4-ni tropyrazol be hydrogenated for 2 hours according to the instructions (1). Nach Abfiltrieren des Katalysators wird das Produkt mit 0,3 ml (3,5 mmol) konzentrierter Salzsäure als Dihydrochlorid ausgefällt. After filtering off the catalyst, the product with 0.3 ml (3.5 mmol) of concentrated hydrochloric acid is precipitated as dihydrochloride. 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. 0.25 g is obtained (73 percent of theory) of 4,5-diamino-1-isopropylpyrazol dihydrochloride in the form of colorless crystals having 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). H-NMR (300 MHz, DMSO-d₆): = 7.90 (s; broad; 6H; -NH₂; HCl; exchanges with D₂O off), 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⁺). MS (70 eV): m / e = 140 (M⁺).

Herstellungsbeispiel 24 Preparation 24 4-Amino-1-(2′-hydroxyethyl)-5- (2′-hydroxyethyl)aminopyrazol aminopyrazole 4-amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl)

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. 0.8 g (2.7 mmol) (2'-hydroxyethyl) -5- (2'-hydro xyethyl) amino-4-nitropyrazole after procedure (1) hydrogenated for 3-bromo-1- 4 hours. Nach Abfiltrieren des Kataly sators fügt man 0,27 g (2,7 mmol) Schwefelsäure (97pro zentig) zu. After filtering off the Kataly crystallizer is added 0.27 g (2.7 mmol) of sulfuric acid (97pro zentig) to. 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. After cooling to -30 ° C are obtained 630 mg (82 percent of theory) of 4-amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) aminopyrazole hydrosulfate in the form of colorless crystals having 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-). ¹H-NMR (60 MHz, DMSO-d₆): = 10.18 (s; broad; 7H -NH; -NH₂; -OH; H₂SO₄; with D₂O exchangeable), 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⁺). MS (70 eV): m / e = 186 (M⁺).

Herstellungsbeispiel 25 Preparation 25 4-Amino-1-(2′-hydroxyethyl)-5- methylaminopyrazol 4-amino-1- (2'-hydroxyethyl) -5-methylaminopyrazole

2,65 g (10 mmol) 3-Brom-1-(2′-hydroxyethyl)-5-methylami no-4-nitropyrazol werden 4 Stunden lang nach Vorschrift (1) hydriert. 2.65 g (10 mmol) 3-bromo-1- (2'-hydroxyethyl) -5-methylami no-4-nitropyrazol 4 hours according to the instructions (1) hydrogenated. Nach Zugabe von 1 g (10 mmol) Schwefel säure und 10 ml Isopropanol scheidet sich das Produkt ab. After addition of 1 g (10 mmol) sulfuric acid and 10 ml of isopropanol is deposited from the product. 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. Is obtained 1 g (40 percent of theory) of 4-amino-1- (2'-hydroxyethyl) -5-methylaminopyrazole hydrosulfate in the form of colorless crystals having a melting point of 138 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; -C H₂ -CH₂), 3,65 (t; J= 5,7 Hz; 2H; -CH₂-C H₂ -) und 2,80 ppm (s; 3H; -NH-C H₃ ). H-NMR (300 MHz, DMSO-d₆): = 9.6 (s; 2H; -NH₂, exchanges with D₂O off), 7.38 (s; 1H; ring-H), 6.35 (s; 2H -NH and -OH; exchanges with D₂O off), 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⁺). MS (70 eV): m / e = 156 (M⁺).

Herstellungsbeispiel 26 Preparation 26 4,5-Diamino-1-(2′-hydroxyethyl) pyrazol 4,5-diamino-1- (2'-hydroxyethyl) pyrazole

1,7 g (5 mmol) 5-Benzylamino-3-brom-1-(2′-hydroxyethyl)- 4-nitropyrazol werden 4 Stunden lang nach Vorschrift (1) hydriert. 1.7 g (5 mmol) of 5-benzylamino-3-bromo-1- (2'-hydroxyethyl) - 4-nitropyrazole 4 hours according to the instructions (1) hydrogenated. 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. After addition of 0.5 g (5 mmol) of sulfuric acid is obtained 0.8 g (62 percent of theory) of 4,5-diamino-1- (2'-hydroxyethyl) pyrazole hydrochloride sulfate hydrate in the form of colorless crystals having a melting point 158-160 ° C.

Herstellungsbeispiel 27 Preparation 27 4-Amino-(3)5-methylaminopyrazol 4-amino- (3) 5-methylaminopyrazole

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. 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) of sulfuric acid in 50 ml water according to rule (2) hydrogenated a period of 8 hours. Nach Abfiltrieren des Katalysators und Zugabe von 50 ml Ethanol wird das Filtrat auf 30 ml eingeengt und auf -30 °C abgekühlt. After filtering off the catalyst and addition of 50 ml of ethanol, the filtrate is concentrated to 30 ml and cooled to -30 ° C. Man erhält 244 mg (40% der Theorie) 4-Amino-(3)5-me thylaminopyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 182 °C. This gives 244 mg (40% of theory) of 4-amino- (3) 5-me thylaminopyrazol hydrosulfate in the form of colorless crystals having 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); ¹H-NMR (60 MHz, DMSO-d₆): = 10.10 to 9.20 (m; 6H; NH; -NH₂; H₂SO₄, with D₂O exchange bar); 7,95 (s; 1H; Ring-H) und 2,85 ppm (s; 3H; -CH₃). 7.95 (s; 1H; ring-H) and 2.85 ppm (s; 3H; -CH₃).
MS (70 eV): m/e=112 (M⁺). MS (70 eV): m / e = 112 (M⁺).

Herstellungsbeispiel 28 Preparation 28 4-Amino-(3)5-ethylaminopyrazol 4-amino- (3) 5-ethylaminopyrazol

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. 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) of sulfuric acid in 50 ml water according to rule (2) hydrogenated a period of 8 hours. Nach Abfiltrieren des Katalysators wird das Filtrat auf 10 ml eingeengt. After filtering off the catalyst, the filtrate is concentrated to 10 ml. Anschließend gibt man 10 ml Ethanol hinzu, woraufhin das Produkt in Form farbloser Kristalle, mit einem Schmelz punkt von 188 °C, auskristallisiert. Are then added 10 ml of ethanol, whereupon the product point of 188 ° C crystallizes in the form of colorless crystals having a melting. Man erhält 0,1 g (34 Prozent der Theorie) 4-Amino-(3)5-ethylaminopyra zol-hydrosulfat. 0.1 g is obtained (34 percent of theory) of 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); H-NMR (300 MHz, DMSO-d₆): = 8.53 (s; broad; 6H; -NH; -NH₂; H₂SO₄; exchanges with D₂O off), 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 ). (J = 7.1 Hz; 3H; CH₃ -CH₂-t) - 3.21 (q; J = 7.1 Hz; 2H CH₂ -CH₃) and 1.18 ppm.
MS (70 eV): m/e=126 (M⁺). MS (70 eV): m / e = 126 (M⁺).

Herstellungsbeispiel 29 Preparation 29 4-Amino-(3)5-(2′-hydroxyethyl) aminopyrazol 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole

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. 1 g (2.9 mmol) of 1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole in a solution of 0.29 g (2.9 mmol) of sulfuric acid and 50 ml of water hydrogenated a period of 3 hours according to rule (2). Nach Abfil trieren des Katalysators wird das Lösungsmittel im Vaku um abdestilliert. After Abfil trate of the catalyst, the solvent is distilled off in the vacuum circuit. Das dabei auskristallisierte Produkt wird mit wenig (20 ml) Ethanol gewaschen und anschlie ßend getrocknet. The case crystallized product is washed with a small (20 ml) of ethanol and subsequently dried ßend. 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. This gives 240 mg (35 percent of theory) of 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole hydrosulfate in the form of colorless crystals having 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); ¹H-NMR (60 MHz, DMSO-d₆): = 8.35 (s; broad; 6H; -NH; -NH₂; -OH; H₂SO₄, with D₂O exchangeable), 7.58 (s; 1H; ring-H ); 3,55 (m; 2H; - CH₂ -OH) und 3,15 ppm (m; 2H; -NH- CH₂ -). 3.55 (m, 2H, - CH₂-OH) and 3.15 ppm (m; 2H; -NH- CH₂ -).
MS (70 eV): m/e=142 (M⁺). MS (70 eV): m / e = 142 (M⁺).

Herstellungsbeispiel 30 Preparation 30 4,(3)5-Diaminopyrazol 4, (3) 5-diaminopyrazole

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. 1 g (2.4 mmol) of 1-benzyl-5-benzylamino-3-bromo-4-nitro pyrazol be in a solution of 0.25 g (2.4 mmol) of sulfuric acid and 50 ml of water over a period of 4 hours hydrogenated in accordance with rule (2). Nach Abfiltrieren des Katalysators fügt man dem Filtrat 50 ml Ethanol zu und kühlt auf -30 °C ab. After filtering off the catalyst the filtrate is added 50 ml of ethanol and cooled to -30 ° C. Man erhält 184 mg (39 Prozent der Theorie) 4,(3)5-Diaminopyrazol-hydrosulfat in Form farbloser Kristalle mit einem Schmelzpunkt von 240 °C (Zersetzung). 184 mg is obtained (39 percent of theory) 4, (3) 5-diaminopyrazole hydrosulfate in the form of colorless crystals having a melting point of 240 ° C (decomposition).

Verwendungsbeispiel usage example

6,35 g 4-Amino-1-(2′-hydroxyethyl)-5-methylamino pyrazol 6.35 g of 4-amino-1- (2'-hydroxyethyl) -5-methylamino pyrazol
2,73 g 3-Aminophenol 2.73 g of 3-aminophenol
10,00 g Laurylalkohol-diglycolethersulfat-Natriumsalz (28prozentige wäßrige Lösung) 10.00 g of lauryl alcohol-diglycolethersulfat sodium salt (28 percent aqueous solution)
10,00 g 10.00 g

Ammoniak (22prozentige wäßrige Lösung) Ammonia (22 percent aqueous solution)
100,00 g 100.00 g

50 g des vorstehenden Haarfärbemittels werden unmittel bar vor Gebrauch mit 50 g Wasserstoffperoxidlösung (6- prozentig) gemischt. 50 g of the above hair colorant are mixed (6- percent) immediacy bar before use with 50 g of hydrogen peroxide solution. Das Gemisch wird anschließend auf blonde Naturhaare aufgetragen und 30 Minuten lang bei einer Temperatur von 40 °C einwirken gelassen. The mixture is then applied to blonde natural hair and allowed to act for 30 minutes at a temperature of 40 ° C. Das Haar wird anschließend mit Wasser gespült und getrocknet. The hair is then rinsed with water and dried. Das Haar ist in einem modischen Purpurton gefärbt. The hair is dyed in a fashionable purple color.

Claims (32)

1. Verfahren zur Herstellung von 4,5-Diaminopyrazol- Derivaten der allgemeinen Formel (I) in der R 1 und R 2 unabhängig voneinander Wasserstoff, einen C 1 - bis C 6 -Alkylrest oder einen C 2 - bis C 4 -Hy droxyalkylrest bedeuten, dadurch gekennzeichnet, daß man 1. A process for the preparation of 4,5-Diaminopyrazol- derivatives of general formula (I) in which R 1 and R 2 are independently hydrogen, a C 1 - to C 6 -alkyl radical or a C 2 - to C 4 -Hy droxyalkylrest mean, characterized in that
  • (A) 3,5-Dibrom-4-nitropyrazol mit einem C 1 - bis C 6 - Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzyl halogenid oder einem C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylsulfat zu Verbin dungen der allgemeinen Formel (II) in der R 3 einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeutet, umsetzt, Halide to C 4 hydroxyalkyl or benzyl, or a C 1 - - (A) 3,5-dibromo-4-nitropyrazole by a C 1 - to C 6 - alkyl, C 2 to C 6 alkyl, C 2 - to C 4 hydroxyalkyl or Benzylsulfat Verbin to compounds of the general formula (II) 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, is reacted,
  • (B) die Verbindungen der allgemeinen Formel (II) mit C 1 - bis C 6 -Alkyl-, C 2 - bis C 4 -Hydroxyalkyl- oder Benzylamin zu Verbindungen der allgemeinen Formel (III) in der R 3 und R 4 unabhängig voneinander einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 -Hydroxy alkylrest oder einen Benzylrest bedeuten, in 5-Position substituiert und sodann (B) the compounds of general formula (II) with C 1 - to C 6 -alkyl, C 2 - to C 4 hydroxyalkyl or benzyl amine to form compounds of general formula (III) in which R 3 and R 4 are independently alkyl to C 4 hydroxy or denote a benzyl radical substituted in the 5-position, and then - a C 1 - to C 6 -alkyl radical, a C 2
  • (C) die Verbindungen der allgemeinen Formel (III) durch katalytische Hydrierung zu den Verbin dungen der allgemeinen Formel (I) reduziert. (C) the compounds of general formula (III) by catalytic hydrogenation to the compounds reduced Verbin of the general formula (I).
2. Verbindungen der allgemeinen Formel (II) in der R 3 einen C 1 - bis C 6 -Alkylrest, einen C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeutet. 2. Compounds of general formula (II) in which R 3 is a C 1 - C 4 hydroxyalkyl means until or a benzyl - to C 6 -alkyl radical, a C 2nd
3. 3,5-Dibrom-1-methyl-4-nitropyrazol. 3. 3,5-Dibromo-1-methyl-4-nitropyrazole.
4. 3,5-Dibrom-1-ethyl-4-nitropyrazol. 4. 3,5-Dibromo-1-ethyl-4-nitropyrazole.
5. 3,5-Dibrom-1-isopropyl-4-nitropyrazol. 5. 3,5-dibromo-1-isopropyl-4-nitropyrazole.
6. 3,5-Dibrom-1-(2′-hydroxyethyl)-4-nitropyrazol. 6. 3,5-dibromo-1- (2'-hydroxyethyl) -4-nitropyrazole.
7. 1-Benzyl-3,5-dibrom-4-nitropyrazol. 7. 1-benzyl-3,5-dibromo-4-nitropyrazole.
8. Verbindungen der allgemeinen Formel (III) in der R 3 und R 4 unabhängig voneinander einen C 1 - bis C 6 -Alkylrest, C 2 - bis C 4 -Hydroxyalkylrest oder einen Benzylrest bedeuten. 8. Compounds of general formula (III) a C 1 is independently in the R 3 and R 4 each other - to C 4 -hydroxyalkyl radical or a benzyl radical, - to C 6 alkyl, C 2nd
9. 3-Brom-1-methyl-5-methylamino-4-nitropyrazol. 9. 3-bromo-1-methyl-5-methylamino-4-nitropyrazole.
10. 3-Brom-5-(2′-hydroxyethyl)amino-1-methyl-4-nitro pyrazol. 10. 3-Bromo-5- (2'-hydroxyethyl) amino-1-methyl-4-nitro-pyrazole.
11. 3-Brom-5-tertiärbutylamino-1-methyl-4-nitropyrazol. 11. 3-Bromo-5-tertiarybutylamino-1-methyl-4-nitropyrazole.
12. 5-Benzylamino-3-brom-1-methyl-4-nitropyrazol. 12. 5-benzylamino-3-bromo-1-methyl-4-nitropyrazole.
13. 5-Benzylamino-3-brom-1-ethyl-4-nitropyrazol. 13. 5-benzylamino-3-bromo-1-ethyl-4-nitropyrazole.
14. 5-Benzylamino-3-brom-1-isopropyl-4-nitropyrazol. 14. 5-benzylamino-3-bromo-1-isopropyl-4-nitropyrazole.
15. 3-Brom-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl)amino- 4-nitropyrazol. 15. 3-Bromo-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino-4-nitropyrazole.
16. 3-Brom-1-(2′-hydroxyethyl)-5-methylamino-4-nitro pyrazol. 16 3-bromo-1- (2'-hydroxyethyl) -5-methylamino-4-nitro-pyrazole.
17. 5-Benzylamino-3-brom-1-(2′-hydroxyethyl)-4-nitro pyrazol. 17. 5-benzylamino-3-bromo-1- (2'-hydroxyethyl) -4-nitro pyrazole.
18. 1-Benzyl-3-brom-5-methylamino-4-nitropyrazol. 18. 1-benzyl-3-bromo-5-methylamino-4-nitropyrazole.
19. 1-Benzyl-3-brom-5-ethylamino-4-nitropyrazol. 19. 1-benzyl-3-bromo-5-ethylamino-4-nitropyrazole.
20. 1-Benzyl-3-brom-5-(2′-hydroxyethyl)amino-4-nitro pyrazol. 20. 1-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitro-pyrazole.
21. 1-Benzyl-5-benzylamino-3-brom-4-nitropyrazol. 21. 1-benzyl-5-benzylamino-3-bromo-4-nitropyrazole.
22. Verbindungen der allgemeinen Formel (V) in der R a und R b Wasserstoff, einen C 1 - bis C 6 -Al kylrest oder einen C 2 - bis C 4 -Hydroxyalkylrest bedeuten, mit der Maßgabe, daß, wenn R b Wasserstoff ist, R a nicht Wasserstoff, Methyl oder 2-Hydroxy ethyl ist. 22. Compounds of the general formula (V) b in which R a and R is hydrogen, a C 1 - to C 6 -alkyl kylrest 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 2-hydroxy ethyl.
23. 4-Amino-1-methyl-5-methylaminopyrazol. 23. 4-Amino-1-methyl-5-methylaminopyrazole.
24. 4-Amino-5-(2′-hydroxyethyl)amino-1-methylpyrazol. 24. 4-Amino-5- (2'-hydroxyethyl) amino-1-methylpyrazole.
25. 4,5-Diamino-1-ethylpyrazol. 25 4,5-Diamino-1-ethylpyrazole.
26. 4,5-Diamino-1-isopropylpyrazol. 26 4,5-Diamino-1-isopropylpyrazol.
27. 4-Amino-1-(2′-hydroxyethyl)-5-(2′-hydroxyethyl) aminopyrazol. aminopyrazole 27 4-Amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl).
28. 4-Amino-1-(2′-hydroxyethyl)-5-methylaminopyrazol. 28. 4-Amino-1- (2'-hydroxyethyl) -5-methylaminopyrazole.
29. 4-Amino-(3)5-methylaminopyrazol. 29 4-amino- (3) 5-methylaminopyrazole.
30. 4-Amino-(3)5-ethylaminopyrazol. 30, 4-amino- (3) 5-ethylaminopyrazol.
31. 4-Amino-(3)5-(2′-hydroxyethyl)aminopyrazol. 31 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole.
32. Verwendung einer Verbindung der allgemeinen Formel (V) als Farbstoffvorstufe in Oxidationshaarfärbe mitteln. 32. Use of a compound of the general formula (V) as the dye precursor in Oxidationshaarfärbe means.
DE19924234885 1992-10-16 1992-10-16 A process for preparing 4,5-diaminopyrazole derivatives, the use thereof for dyeing hair as well as new pyrazole derivatives Withdrawn DE4234885A1 (en)

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DE19924234885 DE4234885A1 (en) 1992-10-16 1992-10-16 A process for preparing 4,5-diaminopyrazole derivatives, the use thereof for dyeing hair as well as new pyrazole derivatives
EP19930921874 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
ES93921874T ES2060574T1 (en) 1992-10-16 1993-09-29 Process for the preparation of derivatives of 4,5-diaminopyrazole, its use for hair coloring 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
JP50955694A JPH07502542A (en) 1992-10-16 1993-09-29
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
US08/650,819 US5663366A (en) 1992-10-16 1996-05-20 Process for the synthesis of 4,5-diaminopyrazole derivatives useful for dyeing hair

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EP0618902A1 (en) 1994-10-12

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