WO1994008969A1 - Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives - Google Patents

Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives Download PDF

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Publication number
WO1994008969A1
WO1994008969A1 PCT/EP1993/002644 EP9302644W WO9408969A1 WO 1994008969 A1 WO1994008969 A1 WO 1994008969A1 EP 9302644 W EP9302644 W EP 9302644W WO 9408969 A1 WO9408969 A1 WO 9408969A1
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Prior art keywords
nitropyrazole
bromo
amino
hydroxyethyl
benzyl
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PCT/EP1993/002644
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German (de)
French (fr)
Inventor
Hans Neunhoeffer
Stefan Gerstung
Thomas Clausen
Wolfgang R. Balzer
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Wella Aktiengesellschaft
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Priority to DEP4234885.4 priority
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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

description

A process for preparing 4,5-diaminopyrazole deriva- vaten whose Veirwendung for dyeing hair as well as new pyrazole derivatives

The present invention is a process for preparing 4,5-diaminopyrazole derivatives of the general formula (I)

Figure imgf000003_0001

Ri

in which R and R2 are independently hydrogen, mean a Ci to Cs-alkyl group or a C2 to C4-hydro- xyalkylrest, as well as new pyrazole derivatives, including 4,5-diaminopyrazole derivatives useful as dye precursors for example, for hair dyes can be used.

There are already known in the literature several processes for the preparation of 4,5-diaminopyrazole derivatives of formula (I). However, these methods are unsatisfactory in many respects.

For example, according to H. Dorn et al. Chem. Ber. 98, p 3368 (1965), starting from ethoxymethylene-cyano-acetic acid ethyl ester and methylhydrazine, the 5-amino-l- methylpyrazole-4-carboxylic acid from which by decarboxylation, centered in a total yield of 40 Pro¬, the 5-amino -l-methylpyrazole arises.

In DE-OS 2,141,700 a one step is attributed be¬ that can 5-amino-l-methylpyrazole in a Aus¬ yield of 71 percent after from N, N-dimethylaminoacrylonitrile and methylhydrazine be obtained.

MA Khan et al. Can. J. Chem. .49., P 3566 (1971), can be obtained after the described methods 5-amino-l-methylpyrazole at a yield of 23 Pro¬ center for the 5-amino-l-methyl-4-nitropyrazole realize. Kata- lytic reduction of this product delivers to VP Perevalov et al., Khim. Geterotsicl. Soedin. 8__, p 1090 (1985), l-methyl-4,5-diaminopyrazole dihydrochloride in a yield of about 79 percent. The overall yield over the said stages is 7 to 13 percent.

Overall yields of up to 46 percent are obtained when the 5-amino-l-methylpyrazole by H. Dorn et al., Liebigs Ann. Chem. 717, p 118 (1968), with isoamyl nitrite to 5-amino-l-methyl-4-nitropyrazole and reacted with tin (II) chloride to the 4,5-diamino-l-methylpyrazole reduced.

From DE-OS 38 43 892 a process for the production development of 4,5-diamino-l-methylpyrazole is known in which 2-chloroacrylonitrile with hydrazine (G. Ege, Angew. Chem, 86, p 237 (1974 )) is cyclized. After acetylation of the amino group, and elimination of the nitration Schutz¬ group the tautomeric compounds are obtained nitropyrazole 3-amino-4- and 5-amino-4-nitropyrazole in a Gesamt¬ yield of about 41 percent. Alkylated to the tautomerism renge ish with Dimethylsulfa, is obtained in 70 pro- zentiger yield an isomer mixture which is chroma¬ tographisch in the isomeric compounds 5-amino-l-me- thyl-4-nitropyrazole (25 percent) and 3 -amino-l-methyl-4-nitropyrazole (45 percent) can be separate. By Re¬ production the corresponding diamino compounds can be obtained. The total yield of l-methyl-4,5-diaminopyrazole is less than 10 percent.

From DE-OS 3,432,983 a process for the production position of 5-amino-l- (2'-hydroxyethyl) -4-nitropyrazole known. Starting from 5-amino-l- (2'-hydroxyethyl) pyrazole,-4-carboxylic acid to obtain the compound by decarboxylation, followed by nitrosation and hydrogenation, in a yield of 59 percent.

In addition to the low yields in some cases, the methods described have other drawbacks. Thus, many starting compounds, such as Ethoxymethylcyan- acetate or N, N-dimethylaminoacrylonitrile, not available commercially or by complex syntheses partly manufactured. In addition, hydrazine derivatives are classified as carcinogenic toxic and in part.

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.

It is an object of the present invention to provide a process for the production of isomerically pure unter¬ differently substituted 4,5-diaminopyrazole derivatives available.

It has now been found that the stated object by a method for the preparation of 4,5-di- aminopyrazole derivatives of the general formula (I)

Figure imgf000006_0001

I

Ri

Characterized in Ri and R2 are independently hydrogen, Ci to mean a CSS alkyl group or a C2 to C4-hydro- xyalkylrest in that

(A) 3,5-dibromo-4-nitropyrazole with a C] _- to Cδ-Al-alkyl-, C2 to C4 hydroxyalkyl or benzyl halide or a Ci to Cδ alkyl, C2 to C4 hydroxy - alkyl-or Benzylsulfat to compounds of the general formula (II)

Figure imgf000006_0002

wherein R3 represents a Ci to Cδ-alkyl group, a C2 to C4 hydroxyalkyl radical or a benzyl radical, is reacted, (B) the compounds of general formula (II) with Ci to Cδ alkyl, C2 to C4 hydroxyalkyl, or benzyl amine to form compounds of general formula (III)

Figure imgf000007_0001

I

R 3

wherein R3 and R4 are independently a Ci to C6 alkyl group, a C2 to C4 hydroxyalkyl radical or a benzyl radical substituted in the 5-position and then

the compounds of general formula (III) by catalytic hydrogenation to the compounds of general formula (I) is reduced (C),

can solve outstanding. Drive the Ver¬ listed above is therefore an object of the invention.

The general reaction scheme is ben angege¬ below.

Figure imgf000008_0001

Figure imgf000008_0002
i

Ri

(I)

As a starting compound for the synthesis of 4,5-diamino pyrazole derivatives (I), the known 3,5-dibromo-4- serves nitropyrazole (IV), which can be in the following manner provides darge:

According to R. Hüttel et al. Chem. Ber. .88./ P 1577 (1955), man.durch Nitration of pyrazole with a sulfuric ric acid-nitric acid mixture, the 4-nitropyrazole, the adhesive according to HJ et al. , Synthesis 1973, p 294 under milder conditions by nitration of the pyrazole N-nitropyrazole and subsequent rearrangement, with the aid of sulfuric acid (R. Hüttel et al., Chem. Ber. .8J3, p. 1586 (1955)), can be obtained. Subsequent bromination according Juffermanns JPH et al. , J. Org. Chem. 51, p 4656 (1986), provides the 3,5-dibromo-4-nitropyra- zol (IV). According to the inventive method, the 3,5-dibromo-4-nitropyrazole (IV) is first, by reaction with Ci to CSS alkyl, C2 to C4 hydroxyalkyl or Benzylhalo- halides in dimethylformamide (DMF) (Method I) or alkylated by reaction with Ci to C6 alkyl, C2 to C4-hydro- xyalkyl- or Benzylsulfat and brine (method II) in 1-position.

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. After completion of the evolution of gas is added dropwise an equimolar amount of Ci- to CSS alkyl, C2 to C4 hydroxyalkyl or benzyl halide, preferably chloride or bromide, dissolved in DMF to the reaction mixture and heated for three hours at 80 ° C , Subsequently, the solvent is vacuum lines abdestil¬ and the residue from methylene chloride umkristal¬ lisiert.

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 Ci-bis Cδ alkyl, C2 to C4-hydroxyalkyl zylsulfat staggered or Ben¬ -. 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.

In both processes, is obtained isomerically pure N-substitutable,-substituted 3,5-dibromo-4-nitropyrazoles of the formula (II) in good yields. In a subsequent step by heating the N-sub- stituted 3,5-dibromo-4-nitropyrazoles of the formula (II) in an aqueous, alcoholic or wä߬ rig-alcoholic solution of Ci- to Cδ alkyl, C2 ~ to C4 hydroxyalkyl or benzylamine or in the ent speaking amine itself, as a solvent, at a temperature of 60 to 80 ° C. As alcohols, methanol and / or ethanol are preferably used. 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. Then washed with water (10 to 20 ml) and dried in vacuo. Obtained isomerically pure 5-amino-3-bromo-4-nitro-pyrazole derivatives of the general formula (III) in good yields.

The compounds of general formula (III) are on closing, hydrogenated using a palladium-activated carbon catalyst having a palladium content of 10 percent by weight, with hydrogen. According to the invention ste¬ hen to two methods. 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. At 50 bar hydrogen atmosphere is 1 to 6 hours at room temperature, preferably 2 to 4 hours, stirred. aus¬ as a salt like Subsequently, the catalyst is filtered off over a glass filter crucible and acid, the product, with an equimolar amount of sulfuric translated to einge¬ pyrazole compound or zweifachmolaren amount of hydrochloric acid. According to method (2) of the aqueous solution of a compound of the general formula (III) 2 Spatel¬ tops of the catalyst described above and an equimolar amount to the starting compound sulfuric acid added and the mixture in a hydrogenation flask at room temperature (under pressure shaken Wasserstoffatomospäre 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.

Is obtained according to two methods isomerically pure 4,5-diaminopyrazole derivatives of the general formula (I) in good yields.

The compounds of general formula (I) in which Ri is hydrogen, are as Tauto ere before. The positions 3 and 5 in the pyrazole are not unter¬ distinguishable.

In the reduction of the compounds corresponding to general formula (III) in which R3 or R4 is a benzyl or benzyl zyl- a mean tert-butyl radical, the N-benzyl and N-tert be-butyl radicals reductively eliminated, so that compounds of general formula (I) are obtained in which R or R2 is hydrogen instead of benzyl or tert-butyl.

The present patent application are also new 3,5-dibromo-4-nitropyrazole derivatives of the general formula (II)

Figure imgf000011_0001

I

R in which R 3 represents a Ci to C6 alkyl group, a C2 to C4 hydroxyalkyl radical or a benzyl radical. Bei¬ games for compounds of formula (II) are 3,5-dibromo-l-methyl-4-nitropyrazole, 3,5-dibromo-l-ethyl-4-nitropyrazole, 3,5-dibromo-l isopropyl-4-nitropyrazol, 3,5-dibromo-l- (2'-hydroxyethyl) -4-nitropyrazole and 1-benzyl-3,5-dibromo-4-nitropyrazole.

A further subject of the invention are 3-bromo-5-amino-4-nitropyrazole derivatives of the general formula (III)

Figure imgf000012_0001

to C4-hydroxyalkyl group or a benzyl group in R3 and R4 mean, independently, a Ci to C6 alkyl, C2.

are examples of compounds of formula (III)

3-bromo-l-methyl-5-methylamino-4-nitropyrazole,

3-Bromo-5- (2'-hydroxyethyl) amino-l-methyl-4-nitropyrazole,

3-bromo-5-tertiarybutylamino-l-methyl-4-nitropyrazole,

5-benzylamino-3-bromo-l-methyl-4-nitropyrazole,

5-benzylamino-3-bromo-l-ethyl-4-nitropyrazole,

5-benzylamino-3-bromo-l-isopropyl-4-nitropyrazol,

3-bromo-1- (2'-hydroxyethyl) -5- (2 '-hydroxyethyl) amino-4-nitropyrazole, 3-bromo-l- (2'-hydroxyethyl) -5-methylamino-4-nitropyrazole, 5 benzylamino-3-bromo-l- (2'-hydroxyethyl) -4-nitropyrazole l-benzyl-3-bromo-5-methylamino-4-nitropyrazole, l-benzyl-3-bromo-5-ethylamino-4-nitropyrazole, l-benzyl-3-bromo-5- (2'-hydroxyethyl) amino-4-nitropyrazole and l-benzyl-5-benzylamino-3-bromo-4-nitropyrazol are nen¬ NEN.

The present invention furthermore relates to novel 4,5-diaminopyrazole derivatives of the general formula (V)

Figure imgf000013_0001
I Ra

in which R is a hydrogen and R, represents a Ci to CSS alkyl group or a C2 to C4 hydroxyalkyl radical, with the proviso that when R is hydrogen, R a is not material Wasser¬, methyl or 2-hydroxyethyl.

As examples of compounds of formula (I) are

4-Amino-l-methyl-5-methylaminopyrazole,

4-amino-5- (2'-hydroxyethyl) amino-1-methylpyrazole,

4,5-Diamino-l-ethylpyrazole,

4,5-Diamino-l-isopropylpyrazol,

4-amino-l- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) amino-pyrazole, 4-amino-l- (2'-hydroxyethyl) -5-methylaminopyrazole, 4-amino- (3) 5 -methylaminopyrazol, 4-amino- (3) 5-ethylaminopyrazol and 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole,

called.

The compounds of formula (V) can be used as Farbstoffvor¬ step in oxidation for dyeing hair (see Example of Use).

Examples

A) Preparation of N-substituted 3, 5-dibromo-4-nitro-pyrazoles of the general formula (II)

a) General rule, procedure I:

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. After completion of gas evolution, 70 mmol Ci to C6 alkyl, C2 added dropwise to C4 hydroxyalkyl or benzyl halide in 30 ml of DMF and heated at 80 ° C for 3 hours. Subsequently, the solvent is distilled off in vacuo and the residue is crystallized from methylene chloride to.

b) General procedure, method II:

To a solution of 5 g (18.5 mmol) of 3,5-dibromo-4-nitropyrazole in 50 ml of 2N sodium hydroxide solution are 92.5 mmol one Ci to C6 alkyl, C2 to C4 hydroxy alkyl or Benzylsulfat, allowed to stir for 15 hours vigorously at room temperature and finally the precipitated product filtered off, washed with water until the wash solution pH-neutral reaction and dried in vacuo.

Preparation Example 1: 3,5-Dibromo-l-methyl-4-nitro-pyrazole

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

iH-NMR (60 MHz, DMSO-dδ): = 3.90 ppm (s; 3H; -CH3).

For this and all subsequent H-NMR spectra applies:

Details of the chemical shift takes place in delta

(Ppm), which occurs (J) of the coupling constant in Hertz

Standard: tetramethylsilane 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 +).

Preparation Example 2: 3,5-dibromo-l-ethyl-4-nitro-pyrazole

According to method II 3.59 g (65 percent of theory) of 3,5-dibromo-l-ethyl-4-nitropyrazole obtained using ethylsulfate, in the form of white crystals having a melting point 119-121 ° C.

iH-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 +).

Production Example 3: 3,5-Dibromo-l-isopropyl-4-nitro-pyrazole

According to method I are obtained, using 2-bromopropane, 13.14 g (60 percent of theory) of 3,5-dibromo-l-isopropyl-4-nitropyrazole in the form of yellow brown crystals having a melting point of 72 ° to 73 ° C. iH-NMR (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 +).

Production Example 4: 3,5-Dibromo-l- (2 'hydroxyethyl) -

4-nitropyrazole

According to method I are obtained using l-bromo-2-hydroxyethane, 14.77 g (67 percent of theory) of 3,5-dibromo-l- (2 '-hydroxyethyl) -4-nitropyrazole in the form of pale yellow crystals of a melting point of 103 to 105 ° C.

iH-NMR (60 MHz, DMSO-d6): = 4.90 (s; broad; 1H; -OH; with D2O exchangeable), 4.31 (m; 2H; -CH2-) and 4.08 to 3, 82 ppm (m; 2H; -CH2-; D2θ to exchange: t; 2H; J = 5 Hz).

MS (70 eV): m / e = 317 (M +).

Preparation Example 5: l-Benzyl-3,5-dibromo-4-nitro-pyrazole

According to method I are obtained, using benzyl chloride, 17.94 g (71 percent of theory) of l-benzyl-3,5-dibromo-4-nitrobenzene in the form of pale yellow crystals having a melting point of 128 ° C.

lH-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 (M +). B) Preparation of 5-Amino-3-bromo-4-nitropyrazol- derivatives of general formula (III)

Preparation Example 6: 3-Bromo-l-methyl-5-methylamino-4-nitropyrazole

2 g (7.02 mmol) of 3,5-dibromo-l-methyl-4-nitropyrazole wer¬ the heated in 50 ml of a 40 percent solution of methylamine in ethanol for 4 hours to boiling temperature. After cooling, to the reaction mixture 100 ml of water, filtered off and the precipitated product washed with a little water (20 ml). After drying in vacuo gives 1.45 g (88 percent of theory) of 3-bromo-l-methyl-5-methylamino-4-nitropyrazole in the form of yellow crystals having a melting point of 185 ° C.

iH-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 +).

Preparation Example 7: 3-Bromo-5- (2'-hydroxyethylamino) - l-methyl-4-nitropyrazole

3 g (10.5 mmol) of 3,5-dibromo-l-methyl-4-nitropyrazole wer¬ the heated in a solution of 30 ml of ethanolamine in 30 ml Etha¬ nol 15 hours to boiling temperature. 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. emerged from the FIL crystallized from another product in the cold (5 ° C). 2.25 g is obtained (81 percent of theory) of 3-bromo-5- (2 'hydroxyethyl) amino-l-methyl-4-nitropyrazole moulder in the form of crystals having a melting point of 150 ° C.

iH-NMR (60 MHz, DMS0-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 +)

Preparation Example 8: 3-bromo-5-tert-butylamino-l- methyl-4-nitropyrazole

1.5 g (5.26 mmol) of 3,5-dibromo-l-methyl-4-nitropyrazole in a solution of 20 ml of tert-butylamine in 30 ml of ethanol at boiling temperature for 20 hours erhitzt.Nach cooling, the mixture is poured reaction mixture to 150 ml of water, the deposited product filtered off and washed with 100 ml of water. After drying in vacuo gives 1.14 g (78 percent of theory) of 3-bromo-5-tert-butylamino-l-methyl-4-nitropyrazole in the form of a pale yellow leaflets having a melting point of 75 to 77 ° C.

lH-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 (CH 3) 3).

MS (70 eV): m / e = 277 (M +). Preparation Example 9: 5-benzylamino-3-bromo-l-methyl-

4-nitropyrazole

2 g (7.02 mmol) of 3,5-dibromo-l-methyl-4-nitropyrazole get too hot in a solution of 11 g (0.1 mol) of benzylamine in 50 ml of ethanol for 10 hours to boiling temperature er¬. After cooling, the reaction mixture is poured onto 100 ml of water, filtered from the separated product and washed with water (20 ml). After drying in vacuo gives 1.76 g (81 percent of theory) of 5-benzyl zylamino-3-bromo-l-methyl-4-nitropyrazole in the form of yellow needles having a melting point of 133 ° C.

iH-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-, after D2θ exchange s) and 3.68 ppm (s; 3H; N-CH3).

MS (70 eV): m / e = 312 (M +).

Preparation Example 10: 5-benzylamino-3-bromo-l-ethyl-

4-nitropyrazole

6.3 g (21 mmol) of 3,5-dibromo-l-ethyl-4-nitropyrazol are heated in 10 ml of benzyl amine for 1 hour at 80 ° C. 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¬ domestic product crystallizes out. After one Umkristalli¬ Sieren from methanol to obtain 5.2 g (76 percent of theory) of 5-benzylamino-3-bromo-l-ethyl-4-nitropyrazole in the form of light yellow needles having a melting point of 92 C C. iH-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 (d; J = 6.7 Hz, 2H; CH-NH -;? D2θ to 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 +)

Preparation Example 11: 5-benzylamino-3-bromo-l-isopropyl-4-nitropyrazol

3.13 g (10 mmol) of 3,5-dibromo-l-isopropyl-4-nitropyrazol get too hot in 10 ml of benzyl amine for 1 hour er¬ to 80 ° C. Then poured the reaction mixture '50 ml of water and filtered from the precipitated product. After one recrystallization from a toluene / petroleum ether mixture (1: 1) gives 2.3 g (68 percent of theory) of 5-benzylamino-3-bromo-l-isopropyl-4-nitro-pyrazole in the form of light yellow crystals of melting point of 120 and 122 ° C.

iH-NMR (300 MHz, DMSO-d6): = 7.78 (t; J = 6.6 Hz; 1H; -NH; after D2θ exchange s), 7.25-7.39 (m; 5H; Ph -H); 4.66 (after exchange D2θ s d; J = 6.6Hz, 2H, NH- CH2); 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 +) Preparation Example 12: 3-bromo-l- (2 '-hydroxyethyl) -5-

(2 '-hydroxyethyl) amino-4-nitro-pyrazole

1.5 g (4.8 mmol) of 3,5-dibromo-l- (2 '-hydroxyethyl) -4-nitro-pyrazole in a solution of 0.58 g (9.6 mmol) of ethanolamine in 30 ml of ethanol heated for 15 hours at 80 ° C. After cooling, to the reaction mixture 50 ml of water and extracted three times with 70 ml ethyl acetate. Priority traction solutions 200 ml of n-hexane to the combined expression rate and distilled the solvent mixture in vacuo to one third of ur¬ sprünglichen amount. Are then added again to n-hexane until turbidity of the solution. Then filtered off and the crystallized product is washed with n-hexane (10 to 20 ml). This gives 1.04 g (74 percent of theory) of 3-bromo-, l- (2 '-hydroxyethyl) -5- (2' -hy¬ droxyethyl) amino-4-nitropyrazole in the form of pale yellow crystals having a melting point of 132 to 134 ° C.

iH-NMR (60 MHz, DMSO-DSS): = 7.42 (s; broad; 1H; -NH; with D2O exchangeable), 5.23 to 5.02 (m; 2H; -OH; with D2O exchangeable) (6H, -CH2-), 4.18 (m, 2H N-CH2) and 3,93- 3,45 ppm.

MS (70 eV): m / e = 296 (M +)

Preparation Example 13: 3-bromo-l- (2 '-hydroxyethyl) -5-methylamino-4-nitropyrazole

3.15 g (10 mmol) of 3,5-dibromo-l- (2 '-hydroxyethyl) -4-nitro-pyrazole are dissolved in 70 ml of a 30 percent solution of methylamine in water is heated for 1 hour at 60 ° C. After cooling, the product precipitates as light yellow crystals having a melting point of 158 to 160 ° C, from. This gives 2.4 g (91 percent of theory) of 3-bromo-l- (2 'hydroxyethyl) -5-methylamino-4-nitropyrazole.

iH-NMR (300 MHz DMSO-d6): = 7.67 (s; 1H; -NH; exchanges with D2O O); 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 D2θ exchange s).

MS (70 eV): m / e = 266 (M +).

Preparation 14: 5-benzylamino-3-bromo-l- (2 '-hy¬ droxyethyl) -4-nitropyrazole

6.3 g (20 mmol) was heated 3,5-dibromo-l- (2 '-hydroxyethyl) -4-pyrazol be nitrated in 20 ml of benzylamine for 2 hours at 60 ° C. 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. To give 4 g (59 percent of theory) of 5-benzylamino-3-bromo-l- (2 '-hydroxyethyl) -4-nitropyrazole in the form of yellow crystals having a melting point 133-135 ° C. iH-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; -0H; exchanges with D2O off), 4.77 (d, J = 6.6Hz, 2H; -NH-CH2-; after D2O exchange OFF s), 3.99 ( t; J = 4.9H; 2H; -CH2-) and 3.96 ppm (t; J = 5Hz, 2H; -CH2 ~).

MS (70 eV): m / e = 340 (M +)

Preparation Example 15: l-Benzyl-3-bromo-5-methylaπtino-

4-nitropyrazole

3.61 g (10 mmol) l-benzyl-3,5-dibromo-4-nitropyrazole in 100 ml of a solution of 35prozentigen Metyl- amine in water for 4 hours heated to 60 ° C. After cooling, it is filtered off secluded Nieder¬ impact and crystallized once from ethanol. 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.

iH-NMR (300 MHz, DMSO-DSS): = 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;

-CH 3). MS (70 eV): m / e = 312 (M +). Preparation Example 16: l-Benzyl-3-bromo-5-ethylamino

4-nitropyrazole

3.61 (10 mmol) l-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. After cooling, the product precipitates in form of colorless crystals having a melting point of 122 ° C. 2.88 g is obtained nitropyrazole 89 percent of theory) of l-benzyl-3-bromo-5-ethylamino-4.

iH-NMR (300 MHz, DMS0-d6): = 7.15 to 7.41 (m; 6H; -NH and

Ph-H; 1H exchanges with D2O off), 5.37 (s; 1H; -CH 2), 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 +)

Preparation Example 17: l-Benzyl-3-bromo-5- (2'-hydroxycarboxylic ethyl) amino-4-nitropyrazole

3.61 g (10 mmol) l-benzyl-3,5-dibromo-4-nitropyrazole are heated in 15 ml of ethanolamine for 2 hours at 80 ° C. After cooling, pour the Reaktionsge¬ mixed into 30 ml of water and filtered from the precipitate separated. A single recrystallization from toluene, 2.5 g (74 percent of theory) of l-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. iH-NMR (300 MHz, DMSO-d6): = 7.54 (t; 1H; -NH; exchanges with D20 off), 7.15-7.40 (m; 5H; Ph-H), 5.44 (s; 2H; -CH2-Ph), 5.05 (t; 1H; -0H; exchanges with D2O off) and 3.32 to 3.53 ppm (m; 4H; -CH2 ~ CH2 -).

MS (70 eV): m / e = 342 (M +).

Preparation Example 18: l-benzyl-5-benzylamino-3-bromo-

4-nitropyrazole

3.61 g (10 mmol) l-benzyl-3,5-dibromo-4-nitropyrazole wer¬ the heated in a solution of 3.6 g of benzylamine for 2 hours at 60 ° C. After cooling, the mixture is poured Reaktions¬ to 20 ml of water and the deposited precipitate was filtered off. After one Umkristalli¬ Sieren of a naphtha / toluene mixture (1: 1) gives 2.6 g (68 percent of theory) of l-benzyl-5-benzyl-amino-3-bromo-4-nitropyrazole in the form of pale yellow crystals having a melting point of 103 ° C.

iH-NMR (300 MHz, DMSO-DSS): = 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 = 6.1Hz, 2H; -NH- CH2-Ph; after D2θ exchange s).

MS (70 eV): m / e = 388 (M +) C) Preparation of 4,5-diaminopyrazole derivatives of the general formula (I)

a) General procedure, Process (1):

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 a Au¬ toklaven (250 ml) was transferred. After the addition of 2 spatula tips (about 100 mg) of a palladium / active carbon catalyst, with a Polladiumanteil of 10 percent by weight, is indicated in the following Preparation Examples period at 50 bar hydrogen atmosphere ge at room temperature the mixture is stirred. Subsequently, the reaction mixture is mit¬ means of a water jet pump in a glass flask and transferred to the catalyst is filtered immediately through a glass filter crucible. Are then added an equimolar amount of sulfuric acid to Ausgangsverbingung (97prozentig) or zweifachmolare amount of hydrochloric acid (36prozentig) to the filtrate.

b) General procedure, Process (2):

A angege¬ in the following Production Examples bene amount of a compound of the general formula

(III) in a hydrogenation flask with an equimolar amount 97prozentiger sulfuric acid, 2 Spatel¬ acute palladium / charcoal catalyst (10 Ge weight percent palladium) and the amount of water indicated in each case at room temperature under Wasserstoff¬ atmosphere (normal pressure) via the in given the nachfol¬ constricting Preparation examples period shaken. The reaction course is monitored by thin layer chromatography. After complete conversion of the starting material, the reaction mixture is filtered tion through a filter crucible. After distilling off the solvent, the product from ethanol is crystallized.

Preparation 19: 4-Amino-l-methyl-5-methylamino pyrazol

0.5 g (2.13 mmol) of 3-bromo-l-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 described for 14 hours, as in method (2), hydrogenated. After filtering off the catalyst the filtrate is concentrated to dryness and the residue is recrystallized from ethanol. This gives 370 mg (78 percent of theory) of 4-amino-l-methyl-5-methylaminopy- razol hydrosulfate in the form of colorless crystals having a melting point 185-188 ° C.

iH-NMR (60 MHz, DMSO-d6): = 8.53 (s; broad; 5H, -NH 2;

-NH; H2SO4; ((Ring-H 3.58 s; s; 1H 3H; N-CH3) exchangeable with D2O aus¬), 7.30 and 2.80 ppm (s; 3H; NH-CH3).

MS (70 eV): m / e = 126 (M +).

Production Example 20: 4-amino-5- (2'-hydroxyethyl) amino-1-methylpyrazole no

1 g (3.77 mmol) (2 '-hydroxyethyl), 3-bromo-5-amino-1-me- thyl-4-nitropyrazole in a solution of 380 mg (3.77 mmol) of sulfuric acid in 50 ml of water 2 hours according to method (2) hydrogenated. This gives 720 mg (75 Pro¬ cent of theory) of 4-amino-5- (2 '-hydroxyethyl) amino-l-me- thylpyrazol hydrosulfate in the form of colorless crystals having a melting point of 94-97 ° C.

iH-NMR (60 MHz, DMS0-d6): = 8.00 (s; broad; 6H; -NH2;

-NH, -0H, H2SO4, exchanges with

D2O off), 7.45 (s; 1H;

Ring-H), 3.60 (s; 3H;

-CH3), and 3.50 to 3.10 (m; 4H;

-CH2-CH2-) • MS (70 eV): m / e = 156 (M +).

Preparation 21: 4,5-Diamino-l-methylpyrazole

a) 0.5 g (1.81 mmol) of 3-bromo-5-tert-butylamino-l-me- thyl-4-nitropyrazol be (in a solution of 1.84 mg 1.81 mmol) of sulfuric acid in 20 ml water for 48 hours to go to addition of the catalyst according to Ver¬ (2) hydrogenated. 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-l-me- thylpyrazol hydrosulfate hydrate in the form of white crystals with a melting point of 200 to

201 ° C.

b) 0.5 g (1.61 mmol) of 5-benzylamino-3-bromo-l-methyl-4-ni- tropyrazol (in a solution of 165 mg 161 mmol) of sulfuric acid in 20 ml of water, after addition of the catalyst, 48 described hours, as in the method (2), hydrogenated. Then filtered off the catalyst and the filtrate was concentrated to about 2 ml a. After addition of small amount of ethanol (about 2 mL) schei¬ det the product as white crystals from. 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.

Preparation 22: 4,5-Diamino-l-ethylpyrazole

1.62 g (5.6 mmol) is hydrogenated over a period of 2 hours after the procedure (1) 3-benzylamino-3-bromo-l-ethyl-4-nitro-pyrazole. After filtering off the Katalysa¬ tors is precipitated by addition of 1 ml (11.6 mmol) konzen¬ trated hydrochloric acid (36prozentig) the product as a hydrochloride of dihydroxyacetone. This gives 0.8 g (72 percent of the RIE Theo¬) 4,5-Diamino-l-ethylpyrazole dihydrochloride in the form of colorless crystals having a melting point 184-186 ° C.

iH-NMR (300 MHz, DMSO-d6): = 8.01 (s; broad; 6H; -NH2;

HC1; exchanged with D2O off), 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 +)

Preparation 23: 4,5-Diamino-l-isopropylpyrazol

0.5 g (1.6 mmol) l-benzylamino-3-bromo-l-isopropyl-4-ni- tropyrazol 2 hours according to the instructions (1) hydrogenated. After filtering off the catalyst, the product with 0.3 ml (3.5 mmol) of concentrated hydrochloric acid is precipitated as dihydrochloride. 0.25 g is obtained (73 percent of theory) of 4,5-diamino-l-isopropylpyrazol- dihydrochloride in the form of colorless crystals having a melting point of 164 ° C. iH-NMR (300 MHz, DMSO-d6): = 7.90 (s; broad; 6H; -NH2;

HC1; exchanged with D2O off),

7.51 (s; 1H; ring-H), 4.54 (1H; -CH (CH3) 2) and 1.30 ppm (d; 6H-CH (CH3) 2) •

MS (70 eV): m / e = 140 (M +)

Production Example 24: 4-amino-l- (2'-hydroxyethyl) -5-

aminopyrazole (2'-hydroxyethyl)

0.8 g (2.7 mmol) of 3-bromo-l- (2'-hydroxyethyl) -5- (2 '-hydro¬ xyethyl) amino-4-nitropyrazole after procedure (1) was hydrogenated for 4 hours. After filtering off the Kataly¬ crystallizer is added 0.27 g (2.7 mmol) of sulfuric acid (97pro- zentig) to. After cooling to - 30 C C to obtain 630 mg (82 percent of theory) of 4-amino-l- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) aminopyrazole hydrosulfate farb¬ in the form of a white crystal having a melting point 140-142 ° C.

iH-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 +). Production Example 25: 4-amino-l- (2 '-hydroxyethyl) -5-methylaminopyrazole

2.65 g (10 mmol) 3-bromo-l- (2 '-hydroxyethyl) -5-methylami- no-4-nitropyrazol 4 hours according to the instructions (1) hydrogenated. After addition of 1 g (10 mmol) sulfuric acid and 10 ml of isopropanol is deposited from the product. 1 g is obtained (40 percent of theory) of 4-amino-l- (2 '-hydroxyethyl) -5-methylaminopyrazole hydrosulfate in the form of colorless crystals having a melting point of 138 to 140 ° C.

iH-NMR (300 MHz, DMSO-d6): = 9.6 (s; 2H; -NH 2, exchanged with D2θ 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; -CH2-CH2), 3.65 (t; J = 5.7 Hz, 2H, - CH2-CH2) and

2.80 ppm (s; 3H; NH-CH3)

MS (70 eV): m / e = 156 (M⁺)

Preparation 26: 4,5-diamino-l- (2'-hydroxyethyl) pyrazole

1.7 g (5 mmol) of 5-benzylamino-3-bromo-l- (2 '-hydroxyethyl) - 4-nitropyrazole 4 hours according to the instructions (1) hydrogenated. After addition of 0.5 g (5 mmol) of sulfuric acid is obtained 0.8 g (62 percent of theory) of 4, 5-diamino-l- (2 '-hydroxyethyl) pyrazole hydrochloride sulfate hydrate in the form of colorless crystals having a melting point 158-160 ° C. Production Example 27: 4-amino- (3) 5-methylaminopyrazole

1 g (2.9 mmol) l-benzyl-3-bromo-5-methylamino-4-nitro-pyrazole are dissolved in a solution of 0.29 g (2.9 mmol) of sulfuric acid in 50 ml water according to rule (2) hydrogenated over a period of 8 hours. After filtering off the catalyst and addition of 50 ml of ethanol, the filtrate is concentrated to 30 ml and - cooled 30 ° 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.

iH-NMR (60 MHz, DMS0-d6): = 10.10 to 9.20 (m; 6H; NH; -NH2;

H2SO4; with D2θ-exchangeable bar); 7.95 (s; 1H; ring-H) and

2.85 ppm (s; 3H; -CH3). MS (70 eV): m / e = 112 (M +).

Production Example 28: 4-amino- (3) 5-ethylaminopyrazol

0.5 g (1.31 mmol) l-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 over a period of 8 hours. after filtering

the catalyst, the filtrate is concentrated to 10 ml. Are then added 10 ml of ethanol, whereupon the product in form of colorless crystals, with a Schmelz¬ of 188 ° C crystallized point. This gives 0.1 g (34 percent of theory) of 4-amino- (3) 5-ethylaminopyra- zol hydrosulfate.

iH-NMR (300 MHz, DMSO-d6): = 8.53 (s; broad; 6H; -NH;

-NH2; H2SO4; exchanged with D2O off), 7.78 (s; 1H; ring-H); (T; J = 7.1 Hz; 3H; -CH2-CH3) 3.21 (q; J = 7.1 Hz; 2H -CH2-CH3) and 1.18 ppm.

MS (70 eV): m / e = 126 (M +).

Production Example 29: 4-amino- (3) 5- (2'-hydroxyethyl) aminopyrazole

1 g (2.9 mmol) l-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). After Abfil¬ trate of the catalyst, the solvent is distilled off in order Vaku¬. The case crystallized product is washed with a small (20 ml) and ethanol anschlie¬ ßend dried. 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. iH-NMR (60 MHz, DMSO-d6): = 8.35 (s; broad; 6H; -NH;

-NH2; -OH; H2SO4 with D2O from exchangeable), 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 +)

Preparation 30: 4, (3) 5-diaminopyrazole

1 g (2.4 mmol) l-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 according to rule (2) hydrogenated. After filtering off the catalyst the filtrate is added 50 ml of ethanol and cooled to - 30 ° C from. 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).

Example of use:

6.35 g of 4-amino-l- (2 '-hydroxyethyl) -5-methylamino-pyrazole 2.73 g of 3-aminophenol 10.00 g lauryl alcohol diglycolethersufat sodium salt

(28 percent aqueous solution) 10.00 g of ammonia (22 percent aqueous solution)

100.00 g 50 g of the above hair colorant are mixed unmittel¬ bar before use with 50 g hydrogen peroxide solution (6 percent). The mixture is then applied to blonde natural hair and allowed to act for 30 minutes at a temperature of 40 ° C. The hair is then rinsed with water and dried. The hair is dyed in a fashionable purple color.

Claims

claims
1) A process for preparing 4,5-Diaminopyrazol- derivatives with the general formula (I)
Figure imgf000037_0001
i
in which R and R2 are independently hydrogen, a Ci to C6 alkyl group or a C2 to C4 hybrid droxyalkylrest mean, characterized in that
(A) 3,5-dibromo-4-nitropyrazole with a Ci to CSS alkyl, C2 to C4 hydroxyalkyl or benzyl halide or a Cχ ~ to CSS alkyl, C2 to C4-hydroxyalkyl or Benzylsulfat Verbin¬ to compounds of the general formula (II)
Figure imgf000037_0002
in R3 a Ci to C6 alkyl group, a C2 to C4 hydroxyalkyl radical or a benzyl radical, is reacted,
(B) the compounds of general formula (II) with Ci to Coe-alkyl, C2 to C4 hydroxyalkyl or benzyl amine to form compounds of general formula (III)
Figure imgf000038_0001
I
R 3
wherein R3 and R4 are independently alkyl Ci to a CSS alkyl group, a C2 to C4 hydroxy or denote a benzyl radical substituted in the 5-position and then
(C) the compounds of general formula (III) by catalytic hydrogenation to the compounds reduced Verbin¬ of the general formula (I).
2) compounds of general formula (II)
Figure imgf000039_0001
wherein R3 represents a Ci to Cδ-alkyl group, a C2 to C4 hydroxyalkyl radical or a benzyl radical.
3) 3,5-dibromo-l-methyl-4-nitropyrazole.
4) 3,5-dibromo-l-ethyl-4-nitropyrazole.
5) 3,5-Dibromo-l-isopropyl-4-nitropyrazole.
6) 3,5-dibromo-l- (2 '-hydroxyethyl) -4-nitropyrazole.
7) l-benzyl-3,5-dibromo-4-nitropyrazole.
8) compounds of general formula (III)
Figure imgf000039_0002
I
R 3 to C 4 hydroxyalkyl group or a benzyl group in R3 and R4 mean, independently, a Ci to CSS-alkyl, C2.
) Of 3-bromo-l-methyl-5-methylamino-4-nitropyrazole.
3-bromo-5- (2 '-hydroxyethyl) amino-l-methyl-4-nitro-pyrazole.
1 3-bromo-5-tertiarybutylamino-l-methyl-4-nitropyrazole.
5-benzylamino-3-bromo-l-methyl-4-nitropyrazole.
5-benzylamino-3-bromo-l-ethyl-4-nitropyrazole.
5-benzylamino-3-bromo-l-isopropyl-4-nitropyrazole.
3-bromo-1- (2 '-hydroxyethyl) -5- (2' -hydroxyethyl) amino-4-nitropyrazole.
3-bromo-l- (2 '-hydroxyethyl) -5-methylamino-4-nitro-pyrazole.
5-benzylamino-3-bromo-l- (2 '-hydroxyethyl) -4-nitro-pyrazole
l-benzyl-3-bromo-5-methylamino-4-nitropyrazole.
l-benzyl-3-bromo-5-ethylamino-4-nitropyrazole.
l-benzyl-3-bromo-5- (2 '-hydroxyethyl) amino-4-nitro-pyrazole.
l-benzyl-5-benzylamino-3-bromo-4-nitropyrazole. 22) compounds of general formula (V)
Figure imgf000041_0001
kylrest or in which R a and R b is hydrogen, a Ci to C6-A1- mean a C2 to C4 hydroxyalkyl radical, with the proviso that when R b is hydrogen, R a is not hydrogen, methyl or 2-hydroxy- ethyl is.
23) 4-Amino-l-methyl-5-methylaminopyrazole.
24) 4-Amino-5- (2 '-hydroxyethyl) amino-1-methylpyrazole.
25) 4,5-Diamino-l-ethylpyrazole.
26) 4, 5-diamino-l-isopropylpyrazol.
27) 4-amino-1- (2'-hydroxyethyl) -5- (2'-hydroxyethyl) - aminopyrazole.
28) 4-Amino-l- (2'-hydroxyethyl) -5-methylaminopyrazole.
29) 4-amino- (3) 5-methylaminopyrazole. 30) 4-amino- (3) 5-ethylaminopyrazol.
31) 4-amino (3) 5- (2'-hydroxyethyl) aminopyrazole.
32) Use of a compound of the general formula (V) as the dye precursor in Oxidationshaarfärbe- means.
PCT/EP1993/002644 1992-10-16 1993-09-29 Process for producing 4,5-diamino pyrazole derivatives, their use for colouring hair and novel pyrazole derivatives WO1994008969A1 (en)

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US5769903A (en) * 1995-02-27 1998-06-23 L'oreal Composition for the oxidation dyeing of keratin fibers, comprising an oxidation base, an indole coupler and an additional heterocyclic coupler, and dyeing process
US5980585A (en) * 1997-12-16 1999-11-09 L'oreal Compositions for dyeing keratinous fibers comprising imidazopyridine derivatives and process
US6027538A (en) * 1997-08-25 2000-02-22 L'oreal S.A. Compositions for dyeing keratinous fibers comprising indazoleamine derivatives and dyeing process
US6063136A (en) * 1996-08-26 2000-05-16 L'oreal S.A. Compositions containing pyrrolo-oxazole couplers for dyeing keratin fibers and dyeing methods
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