Composition for dyeing keratin fibers which contain at least one diaminopyrazole, dyeing process, novel diaminopyrazoles and process for their preparation

Claim 2

A composition for the oxidation dyeing of keratin fibers, comprising, in a medium which is suitable for dyeing, at least one oxidation base selected from: 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-phenylpyrazole, 4,5-diamino-3-hydroxymethyl-1-(2′-methoxyphenyl)-pyrazole, 4,5-diamino-3-hydroxymethyl-1-(3′-methoxyphenyl)-pyrazole, 4,5-diamino-3-hydroxymethyl-1-(4′-methoxyphenyl)-pyrazole, 4,5-diamino-3-methyl-1-(2′-methoxyphenyl)pyrazole, 4,5-diamino-3-methyl-1-(3′-methoxyphenyl)pyrazole, 4,5-diamino-3-methyl-1-(4′-methoxyphenyl)pyrazole, 3-aminomethyl-4,5-diamino-1-methylpyrazole, 3-aminomethyl-4,5-diamino-1-ethylpyrazole, 3-aminomethyl-4,5-diamino-1-isopropylpyrazole, 3-aminomethyl-4,5-diamino-1-tert-butyl-pyrazole, 4,5-diamino-3-dimethylaminomethyl-1-methylpyrazole, 4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazole, 4,5-diamino-3-dimethylaminomethyl-1-isopropyl-pyrazole, 4,5-diamino-3-dimethylaminomethyl-1-tert-butyl-pyrazole, 4,5-diamino-3-ethylaminomethyl-1-methylpyrazole, 4,5-diamino-3-ethylaminomethyl-1-ethylpyrazole, 4,5-diamino-3-ethylaminomethyl-1-isopropylpyrazole, 4,5-diamino-3-ethylaminomethyl-1-tert-butylpyrazole, 4,5-diamino-3-methylaminomethyl-1-methylpyrazole, 4,5-diamino-3-methylaminomethyl-1-isopropylpyrazole, 4,5-diamino-1-ethyl-3-methylaminomethylpyrazole, 1-tert-butyl-4,5-diamino-3-methylaminomethyl-pyrazole, 4,5-diamino-3-((-hydroxyethyl)aminomethyl)-1-methyl-pyrazole, 4,5-diamino-3-(.(-hydroxyethyl)aminomethyl)-1-isopropylpyrazole, 4,5-diamino-1-ethyl-3-(.(-hydroxyethyl)aminomethyl)-pyrazole, 1-tert-butyl-4,5-diamino-3-((-hydroxyethyl)aminomethyl)-pyrazole, 4-amino-5-(-hydroxyethyl)amino-1,3-dimethylpyrazole, 4-amino-5-(-hydroxyethyl)amino-1-isopropyl-3-methyl-pyrazole, 4-amino-5-(-hydroxyethyl)amino-1-ethyl-3-methyl-pyrazole, 4-amino-5-(-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole, 4-amino-5-(-hydroxyethyl)amino-1-phenyl-3-methyl-pyrazole, 4-amino-5-(-hydroxyethyl)amino-1-(2-methoxyphenyl)-3-methylpyrazole, 4-amino-5-(-hydroxyethyl)amino-1-(3-methoxyphenyl)-3-methylpyrazole, 4-amino-5-(-hydroxyethyl)amino-1-(4-methoxyphenyl)-3-methylpyrazole, 4-amino-5-(-hydroxyethyl)amino-1-benzyl-3-methyl-pyrazole, 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole, 4-amino-1-tert-butyl-3-methyl-5-methylaminopyrazole, 4,5-diamino-1,3-diphenylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4-amino-1,3-dimethyl-5-phenylaminopyrazole, 4-amino-1-ethyl-3-methyl-5-phenylaminopyrazole, 4-amino-1,3-dimethyl-5-methylaminopyrazole, 4-amino-3-methyl-1-isopropyl-5-methylaminopyrazole, 4-amino-3-isobutoxymethyl-1-methyl-5-methylamino-pyrazole, 4-amino-3-methoxyethoxymethyl-1-methyl-5-methylamino-pyrazole, 4-amino-3-hydroxymethyl-1-methyl-5-methylamino-pyrazole, 4-amino-1,3-diphenyl-5-phenylaminopyrazole, 4-amino-3-methyl-5-methylamino-1-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 5-amino-3-methyl-4-methylamino-1-phenylpyrazole, 5-amino-1-methyl-4-(N-methyl-N-phenyl)amino-3-(4′-chlorophenyl)pyrazole, 5-amino-3-ethyl-1-methyl-4-(N-methyl-N-phenyl)amino-pyrazole, 5-amino-1-methyl-4-(N-methyl-N-phenyl)amino-3-phenyl-pyrazole, 5-amino-3-ethyl-4-(N-methyl-N-phenyl)aminopyrazole, 5-amino-4-(N-methyl-N-phenyl)amino-3-phenylpyrazole, 5-amino-4-(N-methyl-N-phenyl)amino-3-(4′-methylphenyl)pyrazole, 5-amino-3-(4′-chlorophenyl)-4-(N-methyl-N-phenyl)aminopyrazole, 5-amino-3-(4′-methoxyphenyl)-4-(N-methyl-N-phenyl)aminopyrazole, 4-amino-5-methylamino-3-phenylpyrazole, 4-amino-5-ethylamino-3-phenylpyrazole, 4-amino-5-ethylamino-3-(4′-methylphenyl)pyrazole, 4-amino-3-phenyl-5-propylaminopyrazole, 4-amino-5-butylamino-3-phenylpyrazole, 4-amino-3-phenyl-5-phenylaminopyrazole, 4-amino-5-butylamino-3-phenylpyrazole, 4-amino-5-(4′-chlorophenyl)amino-3-phenylpyrazole, 4-amino-3-(4′-chlorophenyl)-5-phenylaminopyrazole, 4-amino-3-(4′-methoxyphenyl)-5-phenylaminopyrazole, 1-(4′-chlorobenzyl)-4,5-diamino-3-methylpyrazole, 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole; and any acid-addition salts thereof.

Claim 3

A composition according to claim 1 , wherein said at least one oxidation base represents from 0.0005 to 12% by weight relative to the total weight of the dye composition.

Claim 4

A composition according to claim 2 , wherein said at least one oxidation base represents from 0.005 to 6% by weight relative to the total weight of the dye composition.

Claim 5

A composition according to claim 1 , wherein said medium which is suitable for dyeing comprises water or a mixture of water and at least one organic solvent, said organic solvent being a C 1 -C 4 lower alkanol, glycerol, a glycol, a glycol ether, or an aromatic alcohol.

Claim 6

A composition according to claim 1 , wherein said composition has a pH from 3 to 12.

Claim 7

A composition according to claim 1 , wherein said composition contains at least one additional oxidation base, said additional oxidation base being a para-phenylenediamine, a bis(phenylalkylenediamine), a para-aminophenol, an ortho-aminophenol, a heterocyclic base other than the 3-substituted 4,5-diaminopyrazoles of formula (I), or an acid-addition salt of said additional oxidation base.

Claim 8

A composition according to claim 6 , wherein said at least one additional oxidation base represents from 0.0005 to 12% by weight relative to the total weight of the dye composition.

Claim 9

A composition according to claim 1 , wherein said composition contains at least one coupler; at least one direct dye; or at least one coupler and at least one direct dye.

Claim 10

A composition according to claim 8 , wherein said at least one coupler is a meta-phenylenediamine, a meta-aminophenol, a meta-diphenol, a heterocyclic coupler, or an acid-addition salt of said at least one coupler.

Claim 11

A composition according to claim 8 , wherein said at least one coupler represents from 0.0001 to 10% by weight relative to the total weight of the dye composition.

Claim 12

A composition according to claim 1 , wherein said acid-addition salt is a hydrochloride, a hydrobromide, a sulphate, a tartrate, a lactate or an acetate.

Claim 13

A composition according to claim 1 , wherein said keratin fibers are human keratin fibers.

Claim 14

A composition according to claim 12 , wherein said human keratin fibers are hair.

Claim 15

A process for the dyeing of keratin fibers comprising the step of applying to said fibers at least one dye composition as defined in claim 1 , for a period sufficient and in an amount effective to develop the desired coloration using air or with the aid of an oxidizing agent.

Claim 16

A process according to claim 14 , wherein said coloration is developed merely by contact with atmospheric oxygen.

Claim 17

A process according to claim 15 , wherein said coloration is developed merely by contact with atmospheric oxygen, in the presence of oxidation catalysts.

Claim 18

A process according to claim 16 , wherein said oxidation catalysts are metal salts.

Claim 19

A process according to claim 14 , further comprising developing said coloration at acidic, neutral or alkaline pH using an effective amount of an oxidizing agent which is added to the dye composition only at the time of use or which is present in an oxidizing composition that is applied: (i) separately from the dye composition at the same time that said dye composiiton is applied to said fibers or (ii) sequentially with the dye composition.

Claim 20

A process according to claim 18 , wherein said oxidizing agent is hydrogen peroxide, urea peroxide, an alkali metal bromate or a persalt.

Claim 21

A process according to claim 19 , wherein said persalt is a perborate or a persulphate.

Claim 22

A process according to claim 14 , wherein said keratin fibers are human keratin fibers.

Claim 23

A process according to claim 21 , wherein said human keratin fibers are hair.

Claim 24

At least one compound, said compound being selected from 4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole and an acid-addition salt thereof.

Claim 25

At least one compound, said compound being selected from 4-amino-5-(2′-aminoethyl)amino-1,3-dimethyl-pyrazole and an acid-addition salt thereof.

Claim 26

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that R′ 1 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a methyl radical, it being understood that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (ii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and R′ 2 , R′ 3 and R′ 5 simultaneously represent a hydrogen atom, R′ 4 is then other than a methyl radical; (iv) when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 6 represents a methyl radical, R′ 1 is then other than a phenyl radical substituted with a chlorine atom or with a trifluoroethyl, nitro or pyridyl radical; (v) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a methyl radical; and (vi) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; said process comprising: (a) reacting a 3-aminocrotononitrile with a monosubstituted hydrazine at a temperature of above 90° C. in an alcoholic solvent, to obtain a 5-aminopyrazole; (b) nitrosing the 5-aminopyrazole in the 4-position, by reaction with an inorganic or organic nitrite to give a 5-amino-4-nitrosopyrazole; and (c) hydrogenating, by catalytic hydrogenation, said 5-amino-4-nitrosopyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 27

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that R′ 1 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a methyl radical, it being understood that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (ii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and R′ 2 , R′ 3 and R′ 5 simultaneously represent a hydrogen atom, R′ 4 is then other than a methyl radical; (iv) when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 6 represents a methyl radical, R′ 1 is then other than a phenyl radical substituted with a chlorine atom or with a trifluoroethyl, nitro or pyridyl radical; (v) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a methyl radical; and (vi) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; said process comprising: (a) reacting a 3-aminocrotononitrile with a monosubstituted hydrazine at a temperature of above 90° C. in an alcoholic solvent, to obtain a 5-aminopyrazole; (b) nitrosing the 5-aminopyrazole in the 4-position, by reaction with an inorganic or organic nitrite to give a 5-amino-4-nitrosopyrazole; and (c) hydrogenating, by catalytic hydrogenation, said 5-amino-4-nitrosopyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 28

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that R′ 1 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, it being understood that R′ 6 is other than a methyl radical, and that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical and when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iv) when R′ 4 represents a methyl radical, and when R′ 5 represents an unsubstituted phenyl radical, and when R′ 2 and R′ 3 simultaneously represent a hydrogen atom, and when R′ 1 represents a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical or a phenyl radical substituted with a methyl, ethyl, or methoxy radical or with a chlorine atom; (v) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical; (vi) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (vii) when R′ 1 represents methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (viii) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 2 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (ix) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; said process comprising: (a) reacting a β-keto acetonitrile with a monosubstituted hydrazine at a temperature of from 20 to 150° C. in an alcoholic solvent, to obtain a 5-aminopyrazole; (b) nitrosating the 5-aminopyrazole in the 4-position to obtain a 4-nitro-5-aminopyrazole; and (c) hydrogenating, said 4-nitro-5-aminopyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 29

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that R′ 1 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, it being understood that R′ 6 is other than a methyl radical, and that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical and when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iv) when R′ 4 represents a methyl radical, and when R′ 5 represents an unsubstituted phenyl radical, and when R′ 2 and R′ 3 simultaneously represent a hydrogen atom, and when R′ 1 represents a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical or a phenyl radical substituted with a methyl, ethyl, or methoxy radical or with a chlorine atom; (v) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical; (vi) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (vii) when R′ 1 represents methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (viii) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 2 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (ix) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; said process comprising: (a) reacting a β-keto acetonitrile with a monosubstituted hydrazine at a temperature of from 20 to 150° C. in an alcoholic solvent, to obtain a 5-aminopyrazole; (b) nitrosating the 5-aminopyrazole in the 4-position to obtain a 4-nitro-5-aminopyrazole; and (c) hydrogenating, said 4-nitro-5-aminopyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 30

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, it being understood that R′ 6 represents a radical of high steric bulk, and that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical and when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iv) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (v) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and R′ 2 , R′ 3 and R′ 5 simultaneously represent a hydrogen atom, R′ 4 is then other than a methyl radical; (vi) when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 6 represents a methyl radical, R′ 1 is then other than a phenyl radical substituted with a chlorine atom or with a trifluoroethyl, nitro or pyridyl radical; (vii) when R′ 1 represents a hydrogen atom, and when R′ 6 represents a phenyl radical or a phenyl radical substituted with a chlorine atom or with a methyl or methoxy radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom or a C 1 -C 4 alkyl or unsubstituted phenyl radical; (viii) when R′ 4 represents a methyl radical, and when R′ 5 represents an unsubstituted phenyl radical, and when R′ 2 and R′ 3 simultaneously represent a hydrogen atom, and when R′ 1 represents a hydrogen atom or a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical or a phenyl radical substituted with a methyl, ethyl or methoxy radical or with a chlorine atom; (ix) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (x) when R′ 1 represents a methyl, ethyl or 4-aminophenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or an unsubstituted phenyl radical, R′ 6 is then other than a methyl radical; (xi) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, at least one of the radicals R′ 3 and R′ 6 is then other than a methyl radical; (xii) when R′ 1 represents a hydrogen atom or an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (xiii) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (xiv) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (xv) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; and (xvi) when R′ 1 , R′ 2 , R′ 4 and R′ 5 silmultaneously represent a hydrogen atom and when R′ 3 represents a hydrogen atom, a hydroxybutyl radical, or a methyl radical, R′ 6 is then other than a cyclohexylisopropyl radical, said process comprising: (a) reacting a β-keto acetonitrile with a monosubstituted hydrazine to obtain a 5-aminopyrazole; (b) acetylating said 5-aminopyrazole in the 5-position to obtain a 5-acetylaminopyrazole; (c) nitrating said 5-acetylaminopyrazole in the 4-position and deacetylating said 5-acetylaminopyrazole in the 5-position to obtain a 5-amino-4-nitropyrazole; and (d) hydrogenating, said 5-amino-4-nitropyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 31

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, it being understood that R′ 6 represents a radical of high steric bulk, and that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical and when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is then other than an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iv) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (v) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and R′ 2 , R′ 3 and R′ 5 simultaneously represent a hydrogen atom, R′ 4 is then other than a methyl radical; (vi) when R′ 2 , R′ 3 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 6 represents a methyl radical, R′ 1 is then other than a phenyl radical substituted with a chlorine atom or with a trifluoroethyl, nitro or pyridyl radical; (vii) when R′ 1 represents a hydrogen atom, and when R′ 6 represents a phenyl radical or a phenyl radical substituted with a chlorine atom or with a methyl or methoxy radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom or a C 1 -C 4 alkyl or unsubstituted phenyl radical; (viii) when R′ 4 represents a methyl radical, and when R′ 5 represents an unsubstituted phenyl radical, and when R′ 2 and R′ 3 simultaneously represent a hydrogen atom, and when R′ 1 represents a hydrogen atom or a methyl radical, R′ 6 is then other than an unsubstituted phenyl radical or a phenyl radical substituted with a methyl, ethyl or methoxy radical or with a chlorine atom; (ix) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (x) when R′ 1 represents a methyl, ethyl or 4-aminophenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or an unsubstituted phenyl radical, R′ 6 is then other than a methyl radical; (xi) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, at least one of the radicals R′ 3 and R′ 6 is then other than a methyl radical; (xii) when R′ 1 represents a hydrogen atom or an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (xiii) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (xiv) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (xv) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; and (xvi) when R′ 1 , R′ 2 , R′ 4 and R′ 5 silmultaneously represent a hydrogen atom and when R′ 3 represents a hydrogen atom, a hydroxybutyl radical, or a methyl radical, R′ 6 is then other than a cyclohexylisopropyl radical, said process comprising: (a) reacting a β-keto acetonitrile with a monosubstituted hydrazine to obtain a 5-aminopyrazole; (b) acetylating said 5-aminopyrazole in the 5-position to obtain a 5-acetylaminopyrazole; (c) nitrating said 5-acetylaminopyrazole in the 4-position and deacetylating said 5-acetylaminopyrazole in the 5-position to obtain a 5-amino-4-nitropyrazole; and (d) hydrogenating, said 5-amino-4-nitropyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 32

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that one of the radicals R′ 2 or R′ 3 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, wherein said at least one oxidation base is present in an amount effective to dye said keratin fibers, it being understood that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (iv) when R′ 1 represents a hydrogen atom, and when R′ 6 represents a phenyl radical or a phenyl radical substituted with a chlorine atom or with a methyl or methoxy radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom or a C 1 -C 4 alkyl or unsubstituted phenyl radical; (v) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a methyl radical, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (vi) when R′ 1 represents a methyl, ethyl or 4-aminophenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents an unsubstituted phenyl radical, R′ 6 is then other than a methyl radical; (vii) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, at least one of the radicals R′ 3 and R′ 6 is then other than a methyl radical; (viii) when R′ 1 represents a hydrogen atom or an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (ix) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (x) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (xi) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; and (xii) when R′ 1 , R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom and when R′ 3 represents a hydroxybutyl radical, or a methyl radical, R′ 6 is then other than a cyclohexylisopropyl radical, said process comprising: (a) reacting a β-keto ester with a hydrazine to obtain a 5-hydroxypyrazole in equilibrium with its 5-pyrazolone tautomeric form; (b) nitrating said 5-hydroxypyrazole in the 4-position; (c) chlorinating said 5-hydroxypyrazole in the 5-position to obtain a 5-chloro-4-nitropyrazole; (d) converting said 5-chloro-4-nitropyrazole, in the presence of a primary amine H 2 N—R′ 3 , to a 5-amino-4-nitropyrazole; and (e) hydrogenating, by catalytic hydrogenation, said 5-amino-4-nitropyrazole to obtain a 4,5-diaminopyrazole of formula (I′).

Claim 33

The process for the preparation of a 3-substituted 4,5-diaminopyrazole or an acid-addition salt thereof, having the formula: wherein R′ 1 , R′ 2 , R′ 3 , R′ 4 , and R′ 5 , which may be identical or different, represent a hydrogen atom; a linear or branched C 1 -C 6 alkyl radical; a C 2 -C 4 hydroxyalkyl radical; a C 2 -C 4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, methylenedioxy or amino radical; or a radical wherein m and n are integers, which may be identical or different, from 1 to 3 inclusive, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl radical and Z represents a methyl radical, a group OR or NRR′ in which R and R′, which may be identical or different, denote a hydrogen atom, a methyl radical or an ethyl radical, it being understood that one of the radicals R′ 2 or R′ 3 is other than a hydrogen atom, and when R′ 2 represents a hydrogen atom, R′ 3 may then also represent an amino or C 1 -C 4 alkylamino radical, R′ 6 represents a linear or branched C 1 -C 6 alkyl radical; a C 1 -C 4 hydroxyalkyl radical; a C 1 -C 4 aminoalkyl radical; a C 1 -C 4 dialkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 hydroxyalkylamino (C 1 -C 4 ) alkyl radical; a C 1 -C 4 alkoxymethyl radical; a phenyl radical; a phenyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or C 1 -C 4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro, trifluoromethyl, amino or a C 1 -C 4 alkylamino radical; a heterocycle which is thiophene, furan or pyridine, or alternatively a radical —(CH 2 ) p —O—(CH 2 ) q —OR″, in which p and q are integers, which may be identical or different, from 1 to 3 inclusive and R″ represents a hydrogen atom or a methyl radical, wherein said at least one oxidation base is present in an amount effective to dye said keratin fibers, it being understood that in the above formula (I′): at least one of the radicals R′ 2 , R′ 3 , R′ 4 and R′ 5 represents a hydrogen atom, when R′ 2 , or respectively R′ 4 , represents a substituted or unsubstituted phenyl radical or a benzyl radical or a radical R′ 3 , or respectively R′ 5 , cannot then represent any of these three radicals, when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 1 can then form, with R′ 2 and R′ 3 , a hexahydropyrimidine or tetrahydroimidazole heterocycle optionally substituted with a C 1 -C 4 alkyl or 1,2,4-tetrazole radical, when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen, when R′ 2 , R′ 3 , R′ 4 and R′ 5 represent a hydrogen atom or a C 1 -C 6 alkyl radical, R′ 1 or R′ 6 may then also represent a 2-, 3-, or 4-pyridyl, 2- or 3-thienyl or 2- or 3-furyl heterocyclic residue optionally substituted with a methyl radical or alternatively a cyclohexyl radical, with the following provisos: (i) when R′ 1 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a hydrogen atom or a methyl radical, R′ 6 is then other than a hydroxymethyl, isobutyloxymethyl, methoxyethyloxymethyl, cyclohexyl, thiophene, pyridine or phenyl radical or phenyl radical substituted with a methyl radical or with a trifluoromethyl radical or with a chlorine atom; (ii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom, a methyl radical or an unsubstituted phenyl radical; (iii) when R′ 1 represents an unsubstituted phenyl radical, and when R′ 6 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 2 represents a methyl or ethyl radical, R′ 3 is then other than an unsubstituted phenyl radical; (iv) when R′ 1 represents a hydrogen atom, and when R′ 6 represents a phenyl radical or a phenyl radical substituted with a chlorine atom or with a methyl or methoxy radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 3 is then other than a hydrogen atom or a C 1 -C 4 alkyl or unsubstituted phenyl radical; (v) when R′ 1 represents a pyridyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a methyl radical, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (vi) when R′ 1 represents a methyl, ethyl or 4-aminophenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents an unsubstituted phenyl radical, R′ 6 is then other than a methyl radical; (vii) when R′ 1 represents an isopropyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, at least one of the radicals R′ 3 and R′ 6 is then other than a methyl radical; (viii) when R′ 1 represents a hydrogen atom or an unsubstituted phenyl radical, and when R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom, and when R′ 3 represents a benzyl radical or a phenyl radical substituted with a methyl radical or with a chlorine atom, R′ 6 is then other than a methyl or unsubstituted phenyl radical; (ix) when R′ 1 represents a methyl radical, and when R′ 4 and R′ 5 simultaneously represent a hydrogen atom, R′ 2 and R′ 3 are other than an ethyl radical; (x) when R′ 1 is hydrogen, a C 1 -C 6 alkyl radical, or a C 2 -C 4 hydroxyalkyl radical and when R′ 6 is a C 1 -C 6 alkyl radical, a C 1 -C 4 hydroxyalkyl radical, a phenyl radical, a substituted phenyl radical, a benzyl radical, or a substituted benzyl radical, then at least one of R′ 2 , R′ 3 , R′ 4 or R′ 5 is not hydrogen; (xi) when R′ 1 and R′ 2 represent a methyl radical, and when R′ 3 , R′ 4 , and R′ 5 simultaneously represent a hydrogen atom, R′ 6 is other then an isopropyl radical; and (xii) when R′ 1 , R′ 2 , R′ 4 and R′ 5 simultaneously represent a hydrogen atom and when R′ 3 represents a hydroxybutyl radical, or a methyl radical, R′ 6 is then other than a cyclohexylisopropyl radical, said process comprising: (a) reacting a β-keto ester with a hydrazine to obtain a 5-hydroxypyrazole in equilibrium with its 5-pyrazolone tautomeric form; (b) nitrating said 5-hydroxypyrazole in the 4-position; (c) chlorinating said 5-hydroxypyrazole in the 5-position to obtain a 5-chloro-4-nitropyrazole; (d) converting said 5-chloro-4-nitropyrazole, in the presence of a primary amine H 2 N—R′ 3 , to a 5-amino-4-nitropyrazole; and (e) hydrogenating, by catalytic hydrogenation, said 5-amino-4-nitropyrazole to obtain a 4,5-diaminopyrazole of formula (I′).