U.S. patent application number 09/978764 was filed with the patent office on 2002-05-02 for composition for dyeing keratin fibers which contain at least one diaminopyrazole, dyeing process, novel diaminopyrazoles and process for their preparation.
This patent application is currently assigned to L'Oreal. Invention is credited to Burande, Agnes, Hocquaux, Michel, Malle, Gerard, Vidal, Laurent.
Application Number | 20020050013 09/978764 |
Document ID | / |
Family ID | 9478759 |
Filed Date | 2002-05-02 |
United States Patent
Application |
20020050013 |
Kind Code |
A1 |
Vidal, Laurent ; et
al. |
May 2, 2002 |
Composition for dyeing keratin fibers which contain at least one
diaminopyrazole, dyeing process, novel diaminopyrazoles and process
for their preparation
Abstract
The invention relates to novel compositions for the oxidation
dyeing of keratin fibers, comprising at least one specific
diaminopyrazole derivative, to the dyeing process using this
composition, to novel diaminopyrazole derivatives and to a process
for their preparation.
Inventors: |
Vidal, Laurent; (Paris,
FR) ; Burande, Agnes; (Villeparisis, FR) ;
Malle, Gerard; (Meaux, FR) ; Hocquaux, Michel;
(Paris, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT &
DUNNER LLP
1300 I STREET, NW
WASHINGTON
DC
20005
US
|
Assignee: |
L'Oreal
|
Family ID: |
9478759 |
Appl. No.: |
09/978764 |
Filed: |
October 18, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09978764 |
Oct 18, 2001 |
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09494762 |
Jan 31, 2000 |
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09494762 |
Jan 31, 2000 |
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08642622 |
May 3, 1996 |
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6099592 |
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Current U.S.
Class: |
8/405 ; 8/406;
8/415 |
Current CPC
Class: |
A61K 8/494 20130101;
C07D 231/38 20130101; A61Q 5/10 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/415 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
May 5, 1995 |
FR |
95-05422 |
Claims
What is claimed is:
1. 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 a 3-substituted 4,5-diaminopyrazole of
the following formula (I) and an acid-addition salt thereof: 18in
which: R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 which may be
identical or different, represent a hydrogen atom; a linear or
branched C.sub.1-C.sub.6 alkyl radical; a C.sub.2-C.sub.4
hydroxyalkyl radical; a C.sub.2-C.sub.4 aminoalkyl radical; a
phenyl radical; a phenyl radical substituted with a halogen atom or
a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, nitro,
trifluoromethyl, amino or C.sub.1-C.sub.4 alkylamino radical; a
benzyl radical; a benzyl radical substituted with a halogen atom or
with a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy,
methylenedioxy or amino radical; or a radical 19in which m and n
are integers, which may be identical or different, from 1 to 3
inclusive, X represents an oxygen atom or the 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.sub.2 represents
a hydrogen atom, R.sub.2 may then also represent an amino or
C.sub.1-C.sub.4 alkylamino radical, R.sub.6 represents a linear or
branched C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.4
hydroxyalkyl radical; a C.sub.1-C.sub.4 aminoalkyl radical; a
C.sub.1-C.sub.4 dialkylamino (C.sub.1-C.sub.4) alkyl radical; a
C.sub.1-C.sub.4 alkylamino (C.sub.1-C.sub.4) alkyl radical; a
C.sub.1-C.sub.4 hydroxyalkylamino (C.sub.1-C.sub.4) alkyl radical;
a C.sub.1-C.sub.4 alkoxymethyl radical; a phenyl radical; a phenyl
radical substituted with a halogen atom or with a C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, nitro, trifluoromethyl, amino or
C.sub.1-C.sub.4 alkylamino radical; a benzyl radical; a benzyl
radical substituted with a halogen atom or with a C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, nitro, trifluoromethyl, amino or
C.sub.1-C.sub.4 alkylamino radical; a heterocycle selected from
thiophene, furan and pyridine, or alternatively a radical
--(CH.sub.2).sub.p--O--(CH.sub.2).sub.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, in the above formula (I): at least one of
the radicals R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represents a
hydrogen atom, when R.sub.2, or respectively R.sub.4, represents a
substituted or unsubstituted phenyl radical or a benzyl radical or
a radical 20 R.sub.3, or respectively R.sub.5, cannot then
represent any of these three radicals, when R.sub.4 and R.sub.5
simultaneously represent a hydrogen atom, R.sub.1 can then form,
with R.sub.2 and R.sub.3, a hexahydropyrimidine or
tetrahydroimidazole heterocycle optionally substituted with a
C.sub.1-C.sub.4 alkyl or 1,2,4-tetrazole radical, when R.sub.2,
R.sub.3, R.sub.4 and R.sub.5 represent a hydrogen atom or a
C.sub.1-C.sub.6 alkyl radical, R.sub.1 or R.sub.5 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.
2. A composition according to claim 1, wherein said 3-substituted
4,5-diamino-pyrazole of formula (I) is:
1-benzyl-4,5-diamino-3-methylpyra- zole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methoxyphenyl)-pyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methylphenyl)-pyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(3'-methylphenyl)-pyrazole,
4, 5-diamino-3-methyl-1-isopropylpyrazole,
4,5-diamino-3-(4'-methoxyphenyl)-- 1-isopropyl-pyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-3-hydroxyme- thyl-1-methylpyrazole,
4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-hydroxymet- hyl-1-tert-butylpyrazole,
4,5-diamino-3-hydroxymethyl-1-phenylpyrazole,
4,5-diamino-3-hydroxymethyl-1-(2'-methoxyphenyl)-pyrazole,
4,5-diamino-3-hydroxymethyl-1-(3'-methoxyphenyl)-pyrazloe,
4,5-diamino-3-hydroxymethyl-1-(4'-methoxyphenyl)-pyrazole,
1-benzyl-4,5-diamino-3-hydroxymethylpyrazole,
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-e- thylpyrazole,
3-aminomethyl-4,5-diamino-1-isopropylpyrazole,
3-aminomethyl-4,5-diamino-1-tert-butylpyrazole,
4,5-diamino-3-dimethylami- nomethyl-1-methylpyrazole,
4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazo- le,
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-ethylamino- methyl-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-methylami- nomethyl-1-isopropylpyrazole,
4,5-diamino-1-ethyl-3-methylaminomethylpyraz- ole,
1-tert-butyl-4,5-diamino-3-methylaminomethyl-pyrazole,
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-methyl-pyrazole,
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-isopropylpyrazole,
4,5-diamino-1-ethyl-3-[(.beta.-hydroxyethyl)aminomethyl]-pyrazole,
1-tert-butyl-4,5-diamino-3-[(.beta.-hydroxyethyl)amino-methyl]pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1,3-dimethylpyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-isopropyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-ethyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-phenyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(2-methoxyphenyl)-3-methylpyrazole-
,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(3-methoxyphenyl)-3-methylpyrazol-
e,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(4-methoxyphenyl)-3-methylpyrazo-
le,
4-amino-5-(.beta.-hydroxyethyl)amino-1-benzyl-3-methyl-pyrazole,
4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
4-amino-1-tert-butyl-3-me- thyl-5-methylaminopyrazole,
4,5-diamino-1,3-dimethylpyrazole,
4,5-diamino-3-tert-butyl-1-methylpyrazole,
4,5-diamino-1-tert-butyl-3-met- hylpyrazole,
4,5-diamino-1-methyl-3-phenylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-phenylpyrazole,
4,5-diamino-1-methyl-3-(2'-chlorophenyl)pyrazole,
4,5-diamino-1-methyl-3-- (4'-chlorophenyl)pyrazole,
4,5-diamino-1-methyl-3-(3'-trifluoromethylpheny- l)-pyrazole,
4,5-diamino-1,3-diphenylpyrazole, 4,5-diamino-3-methyl-1-phen-
ylpyrazole, 4-amino-1,3-dimethyl-5-phenylaminopyrazole,
4-amino-1-ethyl-3-methyl-5-phenylaminopyrazole,
4-amino-1,3-dimethyl-5-me- thylaminopyrazole,
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-methylamin- o-1-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole,
5-amino-3-methyl-4-methylamino-1-phenylpyrazole,
5-amino-1-methyl-4-(N-me-
thyl-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)aminopyrazo- le,
5-amino4-(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-phenylpyra- zole,
4-amino-5-ethylamino-3-(4'-methylphenyl)pyrazole,
4-amino-3-phenyl-5-propylaminopyrazole,
4-amino-5-butylamino-3-phenylpyra- zole,
4-amino-3-phenyl-5-phenylaminopyrazole,
4-amino-5-butylamino-3-pheny- lpyrazole,
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,
4,5-diamino-3-hydroxyme- thyl-1-isopropylpyrazole,
4-amino-1-ethyl-3-methyl-5-methylaminopyrazole, or
4-amino-5-(2'-aminoethyl)amino-1,3-dimethyl-pyrazole.
3. A composition according to claim 2, wherein said 3-substituted
4,5-diamino-pyrazole of formula (I) is:
4,5-diamino-1,3-dimethylpyrazole,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyraz- ole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole,
1-benzyl-4,5-diamino-3-meth- ylpyrazole,
4,5-diamino-3-tert-butyl-1-methylpyrazole,
4,5-diamino-1-tert-butyl-3-methylpyrazole,
4-5-diamino-1-(.beta.-hydroxye- thyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-1-ethyl-3-h- ydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-methyl-1-i- sopropylpyrazole, or
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole.
4. 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.
5. A composition according to claim 4, wherein said at least one
oxidation base represents from 0.005 to 6% by weight relative to
the total weight of the dye composition.
6. 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.sub.1-C.sub.4 lower alkanol, glycerol, a glycol, a glycol ether,
or an aromatic alcohol.
7. A composition according to claim 1, wherein said composition has
a pH from 3 to 12.
8. 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.
9. A composition according to claim 8, 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.
10. 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.
11. A composition according to claim 10, 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.
12. A composition according to claim 10, wherein said at least one
coupler represents from 0.0001 to 10% by weight relative to the
total weight of the dye composition.
13. 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.
14. A composition according to claim 1, wherein said keratin fibers
are human keratin fibers.
15. A composition according to claim 14, wherein said human keratin
fibers are hair.
16. 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.
17. A process according to claim 16, wherein said coloration is
developed merely by contact with atmospheric oxygen.
18. A process according to claim 17, wherein said coloration is
developed merely by contact with atmospheric oxygen, in the
presence of oxidation catalysts.
19. A process according to claim 18, wherein said oxidation
catalysts are metal salts.
20. A process according to claim 16, 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 composition is applied
to said fibers or (ii) sequentially with the dye composition.
21. A process according to claim 20, wherein said oxidizing agent
is hydrogen peroxide, urea peroxide, an alkali metal bromate or a
persalt.
22. A process according to claim 21, wherein said persalt is a
perborate or a persulphate.
23. A process according to claim 16, wherein said keratin fibers
are human keratin fibers.
24. A process according to claim 23, wherein said human keratin
fibers are hair.
25. A multi-compartment device or multi-compartment dyeing kit, a
first compartment of which contains a dye composition as defined in
claim 1, and a second compartment of which contains an oxidizing
composition.
26. At least one compound, said compound being a 3-substituted
4,5-diaminopyrazole or an acid-addition salt thereof, and having
the formula: 21in which R'.sub.1, R'.sub.2, R'.sub.3, R'.sub.4,
R'.sub.5 and R'.sub.6 have the same meanings as those indicated in
claim 1 for the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5 and R.sub.6 in the formula (I), with the following
provisos: (i) when R'.sub.1 represents a methyl radical, and when
R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, and when R'.sub.3 represents a hydrogen atom or a methyl
radical, R'.sub.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'.sub.1, represents an unsubstituted phenyl
radical and when R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5
simultaneously represent a hydrogen atom, R'.sub.6 is then other
than an unsubstituted phenyl radical; (iii) when R'.sub.1
represents an unsubstituted phenyl radical, and when R'.sub.6
represents a methyl radical, and when R'.sub.2, R'.sub.4 and
R'.sub.5 simultaneously represent a hydrogen atom, R'.sub.3 is then
other than a hydrogen atom, a methyl radical or an unsubstituted
phenyl radical; (iv) when R'.sub.1 represents an unsubstituted
phenyl radical, and when R'.sub.6 represents a methyl radical, and
when R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, and when R'.sub.2 represents a methyl or ethyl radical,
R'.sub.3 is then other than an unsubstituted phenyl radical; (v)
when R'.sub.1 represents an unsubstituted phenyl radical, and when
R'.sub.6 represents a methyl radical, and R'.sub.2, R'.sub.3 and
R'.sub.5 simultaneously represent a hydrogen atom, R'.sub.4 is then
other than a methyl radical; (vi) when R'.sub.2, R'.sub.3, R'.sub.4
and R'.sub.5 simultaneously represent a hydrogen atom, and when
R'.sub.6 represents a methyl radical, R'.sup.1 is then other than a
phenyl radical substituted with a chlorine atom or with a
trifluoroethyl, nitro or pyridyl radical; (vii) when R'.sub.1
represents a hydrogen atom, and when R'.sub.6 represents a phenyl
radical or a phenyl radical substituted with a chlorine atom or
with a methyl or methoxy radical, and when R'.sub.2, R'.sub.4 and
R'.sub.5 simultaneously represent a hydrogen atom, R'.sub.3 is then
other than a hydrogen atom or a C.sub.1-C.sub.4 alkyl or
unsubstituted phenyl radical; (viii) when R'.sub.1, R'.sub.2,
R'.sub.3, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, R'6 is then other than a methyl radical; (ix) when R'.sub.1
represents a .beta.-hydroxyethyl radical, and when R'.sub.2,
R'.sub.3, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, R'.sub.6 is then other than a methyl or unsubstituted phenyl
radical; (x) when R'.sub.4 represents a methyl radical, and when
R'.sub.5 represents an unsubstituted phenyl radical, and when
R'.sub.2 and R'.sub.3 simultaneously represent a hydrogen atom, and
when R'.sub.1 represents a hydrogen atom or a methyl radical,
R'.sub.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; (xi) when R'.sub.1 represents a tert-butyl
radical, and when R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5
simultaneously represent a hydrogen atom, R'.sub.6 is then other
than a methyl radical; (xii) when R'.sub.1 represents a pyridyl
radical, and when R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously
represent a hydrogen atom, and when R'.sub.3 represents a hydrogen
atom or a methyl radical, R'.sub.6 is then other than a methyl or
unsubstituted phenyl radical; (xiii) when R'.sub.1 represents a
methyl, ethyl or 4-aminophenyl radical, and when R'.sub.2, R'.sub.4
and R'.sub.5 simultaneously represent a hydrogen atom, and when
R'.sub.3 represents a hydrogen atom or an unsubstituted phenyl
radical, R'.sub.6 is then other than a methyl radical; (xiv) when
R'.sup.1 represents an isopropyl radical, and when R'.sub.2,
R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen atom, at
least one of the radicals R'.sub.3 and R'.sub.6 is then other than
a methyl radical; (xv) when R'.sub.1, represents a hydrogen atom or
an unsubstituted phenyl radical, and when R'.sub.2, R'.sub.4 and
R'.sub.5 simultaneously represent a hydrogen atom, and when
R'.sub.3 represents a benzyl radical or a phenyl radical
substituted with a methyl radical or with a chlorine atom, R'.sub.6
is then other than a methyl or unsubstituted phenyl radical.
27. A 3-substituted 4,5-diaminopyrazole compound according to claim
26, wherein said 3-substituted 4,5-diaminopyrazole is: 1
-benzyl-4,5-diamino-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-
-3-(4'-methoxyphenyl)-pyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-- methylphenyl)-pyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(3'-methylph- enyl)-pyrazole,
4,5-diamino-3-methyl-1-isopropylpyrazole,
4,5-diamino-3-(4'-methoxyphenyl)-1-isopropyl-pyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyph- enyl)pyrazole,
4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-- 1-isopropylpyrazole,
4,5-diamino-3-hydroxymethyl-1-tert-butylpyrazole,
4,5-diamino-3-hydroxymethyl-1-phenylpyrazole,
4,5-diamino-3-hydroxymethyl- -1-(2'-methoxyphenyl)-pyrazole,
4,5-diamino-3-hydroxymethyl-1-(3'-methoxyp- henyl)-pyrazole,
4,5-diamino-3-hydroxymethyl-1-(4'-methoxyphenyl)-pyrazole- ,
1-benzyl-4,5-diamino-3-hydroxymethylpyrazole,
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-e- thylpyrazole,
3-aminomethyl-4,5-diamino-1-isopropylpyrazole,
3-aminomethyl-4,5-diamino-1-tert-butylpyrazole,
4,5-diamino-3-dimethylami- nomethyl-1-methylpyrazole,
4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazo- le,
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-ethylamino- methyl-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-methylami- nomethyl-1-isopropylpyrazole,
4,5-diamino-1-ethyl-3-methylaminomethylpyraz- ole,
1-tert-butyl-4,5-diamino-3-methylaminomethyl-pyrazole,
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-methyl-pyrazole,
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-isopropylpyrazole,
4,5-diamino-1-ethyl-3-[(.beta.-hydroxyethyl)aminomethyl]-pyrazole,
1-tert-buty-4,5-diamino-3-[(.beta.-hydroxyethyl)amino-methyl]pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1,3-dimethylpyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-isopropyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-ethyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-phenyl-3-methyl-pyrazole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(2'-methoxyphenyl)-3-methylpyrazol-
e,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(3'-methoxyphenyl)-3-methylpyraz-
ole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-(4'-methoxyphenyl)-3-methylpyr-
azole,
4-amino-5-(.beta.-hydroxyethyl)amino-1-benzyl-3-methyl-pyrazole,
4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
4-amino-1-tert-butyl-3-me- thyl-5-methylaminopyrazole,
1-(4'-chlorobenzyl)-4,5-diamino-3-methylpyrazo- le,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4-amino-1-ethyl-3-methyl-5-methylaminopyrazole, or
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole.
28. A 3-substituted 4,5-diaminopyrazole according to claim 27,
wherein said 3-substituted 4,5-diaminopyrazole is:
1-benzyl-4,5-diamino-3-methylp- yrazole,
4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-m-
ethoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
4,5-diamino-3-hydroxymethyl- -1-isopropylpyrazole,
4,5-diamino-3-methyl-1-isopropylpyrazole, or
4-amino-5-(2'-aminoethyl)amino-1,3-dimethyl-pyrazole.
29. A process for the preparation of a compound of formula (I')
according to claim 26, in which R'.sub.6 represents a methyl
radical and R'.sub.1 is other than a hydrogen atom, said process
comprising: (a) reacting a 3-aminocrotononitrile with a
monosubstituted hydrazine, at a temperature of above 90.degree. 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-diaminopyrazoles of
formula (I') in which R'6 represents a methyl radical and R'.sub.1
is other than a hydrogen atom.
30. A process for the preparation of a compound of formula (I')
according to claim 26, in which R'.sub.5 is other than a methyl
radical and R'.sub.1 is other than a hydrogen atom, said process
comprising: (a) reacting a .beta.-keto acetonitrile with a
monosubstituted hydrazine, at a temperature of from 20 and
150.degree. 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') in which R'.sub.6 is other than
a methyl radical and R'.sub.1 is other than a hydrogen atom.
31. A process for the preparation of a compound of formula (I')
according to claim 26, in which R'.sub.6 represents a radical of
high steric bulk, comprising: (a) reacting a .beta.-keto
acetonitrile with a monosubstituted hydrazine in order 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') in which R'.sub.6 represents a radical of high steric
bulk.
32. A process for the preparation of a compound of formula (I')
according to claim 26, in which one of the radicals R'.sub.2 or
R'.sub.3 is other than a hydrogen atom, comprising: (a) reacting
.beta.-keto ester with a hydrazine, in order 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.sub.2N--R'.sub.3, to a 5-amino4-nitropyrazole; and (e)
hydrogenating, by catalytic hydrogenation, said
5-amino-4-nitropyrazole to obtain a 4,5-diaminopyrazole of formula
(I') in which one of the radicals R'.sub.2 or R'.sub.3 is other
than a hydrogen atom.
Description
[0001] The invention relates to novel compositions for the
oxidation dyeing of keratin fibers, which compositions comprise at
least one 3-substituted 4,5-diaminopyrazole as oxidation base, to
the dyeing process using this composition, to novel 3-substituted
4,5-diaminopyrazoles and to a process for their preparation.
[0002] It is known to dye keratin fibers, and in particular human
hair, with dye compositions containing oxidation dye precursors, in
particular ortho- or para-phenylenediamines, ortho- or
para-aminophenols and heterocyclic compounds such as
diaminopyrazole derivatives, which are generally referred to as
oxidation bases. The oxidation dye precursors, or oxidation bases,
are colorless or weakly colored compounds which, when combined with
oxidizing products, may give rise to colored compounds and dyes by
a process of oxidative condensation.
[0003] It is also known that the shades obtained with these
oxidation bases may be varied by combining them with couplers or
coloration modifiers, the latter being chosen in particular from
aromatic meta-diamines, meta-aminophenols, meta-diphenols and
certain heterocyclic compounds.
[0004] The variety of molecules used as oxidation bases and
couplers makes it possible to obtain a wide range of colors.
[0005] The so-called "permanent" coloration obtained by means of
these oxidation dyes must moreover satisfy a certain number of
requirements. Thus, it must have no toxicological drawbacks and it
must allow shades of the desired strength to be obtained and have
good resistance to external agents (light, inclement weather,
washing, permanent-waving, perspiration and friction).
[0006] The dyes must also allow white hairs to be covered and,
lastly, they must be as unselective as possible, i.e., they must
allow the smallest possible differences in coloration to be
produced over the entire length of the same keratin fiber, which
may indeed be differently sensitized (i.e. damaged) between its tip
and its root.
[0007] In order to obtain red shades, para-aminophenol is usually
used, alone or as a mixture with other bases, and in combination
with suitable couplers, and in order to obtain blue shades,
para-phenylenediamines are generally used.
[0008] European Patent Application EP-A-375,977 in particular has
already proposed to use certain diaminopyrazole derivatives,
namely, more precisely, 3,4- or 4,5-diaminopyrazoles, for the
oxidation dyeing of keratin fibers in red shades. However, the use
of the diaminopyrazoles described in EP-A-375,977 do not make it
possible to obtain a wide range of colors and, furthermore, the
process for the preparation of these compounds is long and
expensive.
[0009] Now, the inventors have discovered, entirely unexpectedly
and surprisingly, that the use of certain 3-substituted
4,5-diaminopyrazoles of formula (I) defined below for the part
which is novel per se, is not only suitable for use as oxidation
dye precursors but also make it possible to obtain dye compositions
leading to strong colorations, in shades ranging from red to blue.
Lastly, these compounds prove to be readily synthesizable.
[0010] These discoveries form the basis of the present
invention.
[0011] A first subject of the invention is thus a composition for
the oxidation dyeing of keratin fibers, and in particular human
keratin fibers such as the hair, characterized in that it
comprises, in a medium which is suitable for dyeing, at least one
3-substituted 4,5-diaminopyrazole of formula (I) below as oxidation
base and/or at least one of the addition salts thereof with an
acid: 1
[0012] in which:
[0013] R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 which may be
identical or different, represent a hydrogen atom; a linear or
branched C.sub.1-C.sub.6 alkyl radical; a C.sub.2-C.sub.4
hydroxyalkyl radical; a C.sub.2-C.sub.4 aminoalkyl radical; a
phenyl radical; a phenyl radical substituted with a halogen atom or
a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, nitro,
trifluoromethyl, amino or C.sub.1-C.sub.4 alkylamino radical; a
benzyl radical; a benzyl radical substituted with a halogen atom or
with a C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy,
methylenedioxy or amino radical; or a radical: 2
[0014] in which m and n are integers, which may be identical or
different, from 1 to 3 inclusive, X represents an oxygen atom or
the 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.sub.2 represents a hydrogen atom, R.sub.3 may then also represent
an amino or C.sub.1-C.sub.4 alkylamino radical,
[0015] R.sub.6 represents a linear or branched C.sub.1-C.sub.6
alkyl radical; a C.sub.1-C.sub.4 hydroxyalkyl radical; a
C.sub.1-C.sub.4 aminoalkyl radical; a C.sub.1-C.sub.4 dialkylamino
(C.sub.1-C.sub.4) alkyl radical; a C.sub.1-C.sub.4 alkylamino
(C.sub.1-C.sub.4) alkyl radical; a C.sub.1-C.sub.4
hydroxyalkylamino (C.sub.1-C.sub.4) alkyl radical; a
C.sub.1-C.sub.4 alkoxymethyl radical; a phenyl radical; a phenyl
radical substituted with a halogen atom or with a C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, nitro, trifluoromethyl, amino or
C.sub.1-C.sub.4 alkylamino radical; a benzyl radical; a benzyl
radical substituted with a halogen atom or with a C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, nitro, trifluoromethyl, amino or
C.sub.1-C.sub.4 alkylamino radical; a heterocycle chosen from
thiophene, furan and pyridine, or alternatively a radical
--(CH.sub.2).sub.p--O--(CH.sub.2).su- b.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, in the above formula (I):
[0016] at least one of the radicals R.sub.2, R.sub.3, R.sub.4 and
R.sub.5represents a hydrogen atom,
[0017] when R.sub.2, or respectively R.sub.4, represents a
substituted or unsubstituted phenyl radical or a benzyl radical or
a radical 3
[0018] R.sub.3, or respectively R.sub.5, cannot then represent any
of these three radicals,
[0019] when R.sub.4 and R.sub.5 simultaneously represent a hydrogen
atom, R.sub.1 can then form, with R.sub.2 and R.sub.3, a
hexahydropyrimidine or tetrahydroimidazole heterocycle optionally
substituted with a C.sub.1-C.sub.4 alkyl or 1,2,4-tetrazole
radical,
[0020] when R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent a
hydrogen atom or a C.sub.1-C.sub.6 alkyl radical, R.sub.1 or
R.sub.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.
[0021] As indicated above, the colorations obtained with the
oxidation dye composition in accordance with the invention are
strong and make it possible to achieve shades ranging from red to
blue. One of the essential characteristics of the oxidation bases
in accordance with the invention, in particular relative to those
described in the abovementioned document EP-A 375,977, lies in the
presence of a substituent radical R.sub.6 on the pyrazole ring.
[0022] In general, the addition salts with an acid which can be
used in the context of the dye compositions of the invention
(oxidation bases and couplers) are chosen in particular from the
hydrochlorides, hydrobromides, sulphates, tartrates, lactates and
acetates.
[0023] Among the 3-substituted 4,5-diaminopyrazoles of formula (I)
which can be used as oxidation base in the compositions in
accordance with the invention, mention may be made, in particular,
of:
[0024] 1-benzyl-4,5-diamino-3-methylpyrazole,
[0025]
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methoxyphenyl)-pyrazole,
[0026]
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methylphenyl)-pyrazole,
[0027]
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(3'-methylphenyl)-pyrazole,
[0028] 4,5-diamino-3-methyl-1-isopropylpyrazole,
[0029] 4,5-diamino-3-(4'-methoxyphenyl)-1-isopropyl-pyrazole,
[0030] 4,5-diamino-1-ethyl-3-methylpyrazole,
[0031] 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
[0032] 4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
[0033] 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
[0034] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0035] 4,5-diamino-3-hydroxymethyl-1-tert-butylpyrazole,
[0036] 4,5-diamino-3-hydroxymethyl-1-phenylpyrazole,
[0037]
4,5-diamino-3-hydroxymethyl-1-(2'-methoxyphenyl)-pyrazole,
[0038]
4,5-diamino-3-hydroxymethyl-1-(3'-methoxyphenyl)-pyrazole,
[0039]
4,5-diamino-3-hydroxymethyl-1-(4'-methoxyphenyl)-pyrazole,
[0040] 1-benzyl-4,5-diamino-3-hydroxymethylpyrazole,
[0041] 4,5-diamino-3-methyl-1-(2'-methoxyphenyl)pyrazole,
[0042] 4,5-diamino-3-methyl-1-(3'- methoxyphenyl)pyrazole,
[0043] 4,5-diamino-3-methyl-1-(4'-methoxyphenyl)pyrazole,
[0044] 3-aminomethyl-4,5-diamino-1-methylpyrazole,
[0045] 3-aminomethyl-4,5-diamino-1-ethylpyrazole,
[0046] 3-aminomethyl-4,5-diamino-1-isopropylpyrazole,
[0047] 3-aminomethyl-4,5-diamino-1-tert-butylpyrazole,
[0048] 4,5-diamino-3-dimethylaminomethyl-1-methylpyrazole,
[0049] 4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazole,
[0050] 4,5-diamino-3-dimethylaminomethyl-1-isopropyl-pyrazole,
[0051] 4,5-diamino-3-dimethylaminomethyl-1-tert-butyl-pyrazole,
[0052] 4,5-diamino-3-ethylaminomethyl-1-methylpyrazole,
[0053] 4,5-diamino-3-ethylaminomethyl-1-ethylpyrazole,
[0054] 4,5-diamino-3-ethylaminomethyl-1-isopropylpyrazole,
[0055] 4,5-diamino-3-ethylaminomethyl-1-tert-butylpyrazole,
[0056] 4,5-diamino-3-methylaminomethyl-1-methylpyrazole,
[0057] 4,5-diamino-3-methylaminomethyl-1-isopropylpyrazole,
[0058] 4,5-diamino-1-ethyl-3-methylaminomethylpyrazole,
[0059] 1-tert-butyl-4,5-diamino-3-methylaminomethyl-pyrazole,
[0060]
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-methyl-pyrazole,
[0061]
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-isopropylpyrazol-
e,
[0062]
4,5-diamino-1-ethyl-3-[(.beta.-hydroxyethyl)aminomethyl]-pyrazole,
[0063]
1-tert-butyl-4,5-diamino-3-[(.beta.-hydroxyethyl)amino-methyl]pyraz-
ole,
[0064]
4-amino-5-(.beta.-hydroxyethyl)amino-1,3-dimethylpyrazole,
[0065]
4-amino-5-(.beta.-hydroxyethyl)amino-1-isopropyl-3-methyl-pyrazole,
[0066]
4-amino-5-(.beta.-hydroxyethyl)amino-1-ethyl-3-methyl-pyrazole,
[0067]
4-amino-5-(.beta.-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole,
[0068]
4-amino-5-(.beta.-hydroxyethyl)amino-1-phenyl-3-methyl-pyrazole,
[0069]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(2-methoxyphenyl)-3-methylpy-
razole,
[0070]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(3-methoxyphenyl)-3-methylpy-
razole,
[0071]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(4-methoxyphenyl)-3-methylpy-
razole,
[0072]
4-amino-5-(.beta.-hydroxyethyl)amino-1-benzyl-3-methyl-pyrazole,
[0073] 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
[0074] 4-amino-1-tert-butyl-3-methyl-5-methylaminopyrazole,
[0075] 4,5-diamino-1,3-dimethylpyrazole,
[0076] 4,5-diamino-3-tert-butyl-1-methylpyrazole,
[0077] 4,5-diamino-1-tert-butyl-3-methylpyrazole,
[0078] 4,5-diamino-1-methyl-3-phenylpyrazole,
[0079] 4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
[0080] 4,5-diamino-1-(.beta.-hydroxyethyl)-3-phenylpyrazole,
[0081] 4,5-diamino-1-methyl-3-(2'-chlorophenyl)pyrazole,
[0082] 4,5-diamino-1-methyl-3-(4'-chlorophenyl)pyrazole,
[0083]
4,5-diamino-1-methyl-3-(3'-trifluoromethylphenyl)-pyrazole,
[0084] 4,5-diamino-1,3-diphenylpyrazole,
[0085] 4,5-diamino-3-methyl-1-phenylpyrazole,
[0086] 4-amino-1,3-dimethyl-5-phenylaminopyrazole,
[0087] 4-amino-1-ethyl-3-methyl-5-phenylaminopyrazole,
[0088] 4-amino-1,3-dimethyl-5-methylaminopyrazole,
[0089] 4-amino-3-methyl-1-isopropyl-5-methylaminopyrazole,
[0090]
4-amino-3-isobutoxymethyl-1-methyl-5-methylamino-pyrazole,
[0091]
4-amino-3-methoxyethoxymethyl-1-methyl-5-methylamino-pyrazole,
[0092] 4-amino-3-hydroxymethyl-1-methyl-5-methylamino-pyrazole,
[0093] 4-amino-1,3-diphenyl-5-phenylaminopyrazole,
[0094] 4-amino-3-methyl-5-methylamino-.beta.-phenylpyrazole,
[0095] 4-amino-1,3-dimethyl-5-hydrazinopyrazole,
[0096] 5-amino-3-methyl-4-methylamino-1-phenylpyrazole,
[0097]
5-amino-1-methyl-4-(N-methyl-N-phenyl)amino-3-(4'-chlorophenyl)pyra-
zole,
[0098]
5-amino-3-ethyl-1-methyl-4-(N-methyl-N-phenyl)amino-pyrazole,
[0099]
5-amino-1-methyl-4-(N-methyl-N-phenyl)amino-3-phenyl-pyrazole,
[0100] 5-amino-3-ethyl-4-(N-methyl-N-phenyl)aminopyrazole,
[0101] 5-amino-4-(N-methyl-N-phenyl)amino-3-phenylpyrazole,
[0102]
5-amino-4-(N-methyl-N-phenyl)amino-3-(4'-methylphenyl)pyrazole,
[0103]
5-amino-3-(4'-chlorophenyl)-4-(N-methyl-N-phenyl)aminopyrazole,
[0104]
5-amino-3-(4'-methoxyphenyl)-4-(N-methyl-N-phenyl)aminopyrazole,
[0105] 4-amino-5-methylamino-3-phenylpyrazole,
[0106] 4-amino-5-ethylamino-3-phenylpyrazole,
[0107] 4-amino-5-ethylamino-3-(4'-methylphenyl)pyrazole,
[0108] 4-amino-3-phenyl-5-propylaminopyrazole,
[0109] 4-amino-5-butylamino-3-phenylpyrazole,
[0110] 4-amino-3-phenyl-5-phenylaminopyrazole,
[0111] 4-amino-5-butylamino-3-phenylpyrazole,
[0112] 4-amino-5-(4'-chlorophenyl)amino-3-phenylpyrazole,
[0113] 4-amino-3-(4'-chlorophenyl)-5-phenylaminopyrazole,
[0114] 4-amino-3-(4'-methoxyphenyl)-5-phenylaminopyrazole,
[0115] 1-(4'-chlorobenzyl)-4,5-diamino-3-methylpyrazole,
[0116] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0117] 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
[0118] 4-amino-5-(2'-aminoethyl)amino-1,3-dimethyl-pyrazole, and
the addition salts thereof with an acid.
[0119] Among these 3-substituted 4,5-diaminopyrazoles, the
following are more particularly preferred:
[0120] 4,5-diamino-1,3-dimethylpyrazole,
[0121] 4,5-diamino-3-methyl-1-phenylpyrazole,
[0122] 4,5-diamino-1-methyl-3-phenylpyrazole,
[0123] 4-amino-1,3-dimethyl-5-hydrazinopyrazole,
[0124] 1-benzyl-4,5-diamino-3-methylpyrazole,
[0125] 4,5-diamino-3-tert-butyl-1-methylpyrazole,
[0126] 4,5-diamino-1-tert-butyl-3-methylpyrazole,
[0127] 4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
[0128] 4,5-diamino-1-ethyl-3-methylpyrazole,
[0129] 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
[0130] 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
[0131] 4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
[0132] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0133] 4,5-diamino-3-methyl-1-isopropylpyrazole,
[0134] 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, and the
addition salts thereof with an acid.
[0135] The 3-substituted 4,5-diaminopyrazole(s) of formula (I)
above preferably represent from 0.0005 to 12% by weight
approximately relative to the total weight of the dye composition,
and even more preferably from 0.005 to 6% by weight approximately
relative to this weight.
[0136] The appropriate medium for the dyeing (or the support)
generally comprises water or a mixture of water and at least one
organic solvent to solubilize the compounds which would not be
sufficiently soluble in water. Organic solvents which may be
mentioned, for example, are C.sub.1-C.sub.4 lower alkanols such as
ethanol and isopropanol; glycerol; glycols and glycol ethers such
as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl
ether, diethylene glycol monomethyl ether and monoethyl ether, as
well as aromatic alcohols such as benzyl alcohol or phenoxyethanol,
similar products and mixtures thereof.
[0137] The solvents may be present in proportions preferably of
approximately from 1 to 40% by weight relative to the total weight
of the dye composition, and even more preferably of approximately
from 5 to 30% by weight.
[0138] The pH of the dye composition in accordance with the
invention is generally from 3 to 12 and preferably is approximately
from 5 to 11. It may be adjusted to the desired value using
acidifying or basifying agents usually used in the dyeing of
keratin fibers.
[0139] Among the acidifying agents which may be mentioned, by way
of example, are inorganic or organic acids such as hydrochloric
acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as
acetic acid, tartaric acid, citric acid and lactic acid, and
sulphonic acids.
[0140] Among the basifying agents which may be mentioned, by way of
example, are aqueous ammonia, alkaline carbonates, alkanolamines
such as mono-, di- and triethanolamines and derivatives thereof,
sodium hydroxide, potassium hydroxide and the compounds of
following formula (II): 4
[0141] in which W is a propylene residue optionally substituted
with a hydroxyl group or a C.sub.1-C.sub.4 alkyl radical; R.sub.8,
R.sub.9, R.sub.10 and R.sub.11, which may be identical or
different, represent a hydrogen atom or a C.sub.1-C.sub.4 alkyl or
C.sub.1-C.sub.4 hydroxyalkyl radical.
[0142] In addition to the dyes defined above, the dye composition
in accordance with the invention may also contain at least one
additional oxidation base which may be chosen from the oxidation
bases conventionally used in oxidation dyeing and from which
mention may be made, in particular, of para-phenylenediamines,
bis(phenylalkylenediamine- s), para-aminophenols,
ortho-aminophenols and heterocyclic bases other than the
3-substituted 4,5-diaminopyrazoles used in accordance with the
invention.
[0143] Among the para-phenylenediamines which may be mentioned more
particularly as examples are para-phenylenediamine,
para-toluylenediamine, 2,6-dimethyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-n-propyl-para-phenylenedia- mine,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-phe- nylenediamine,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-amino-N-(.beta.-methoxyethyl)aniline, the para-phenylenediamines
described in French patent application FR 2,630,438, the disclosure
of which is hereby incorporated by reference, and the addition
salts thereof with an acid.
[0144] Among the bis(phenylalkylenediamines) which may be mentioned
more particularly as examples are
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-am-
inophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'--
aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)-tetramethylenediamine- ,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediami-
ne, N,N'-bis(4-methylaminophenyl)tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylene-diamine,
and the addition salts thereof with an acid.
[0145] Among the para-aminophenols which may be mentioned more
particularly as examples are para-aminophenol,
4-amino-3-methylphenol, 4-amino-3-fluorophenol,
4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,
4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,
4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol, and the addition
salts thereof with an acid.
[0146] Among the ortho-aminophenols which may be mentioned more
particularly as examples are 2-aminophenol, 2-amino-5-methylphenol,
2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and the addition
salts thereof with an acid.
[0147] Among the heterocyclic bases which may be mentioned more
particularly as examples are pyridine derivatives, pyrimidine
derivatives, pyrazole derivatives other than the 3-substituted
4,5-diaminopyrazoles used in accordance with the invention, and the
addition salts thereof with an acid.
[0148] When they are used, these additional oxidation bases
preferably represent from 0.0005 to 12% by weight approximately
relative to the total weight of the dye composition, and even more
preferably from 0.005 to 6% by weight approximately relative to
this weight.
[0149] The oxidation dye compositions in accordance with the
invention may also contain at least one coupler and/or at least one
direct dye, in particular to modify the shades or enrich them with
glints.
[0150] The couplers which can be used in the oxidation dye
compositions in accordance with the invention may be chosen from
the couplers used conventionally in oxidation dyeing and among
which mention may be made in particular of meta-phenylenediamines,
meta-aminophenols, meta-diphenols and heterocyclic couplers such
as, for example, indole derivatives, indoline derivatives, pyridine
derivatives and pyrazolones, and the addition salts thereof with an
acid.
[0151] These couplers are chosen more particularly from
2-methyl-5-aminophenol, 5-N-(O-hydroxyethyl)amino-2-methylphenol,
3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethyloxy)- benzene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol
a-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridine, 1-H-3-methyl-5-pyrazolone,
1-phenyl-3-methyl-5-pyrazolone, and the addition salts thereof with
an acid.
[0152] When they are present, these couplers preferably represent
from 0.0001 to 10% by weight approximately relative to the total
weight of the dye composition, and even more preferably from 0.005
to 5% by weight approximately relative to this weight.
[0153] The dye composition according to the invention may also
contain various adjuvants used conventionally in compositions for
dyeing the hair, such as anionic, cationic, nonionic, amphoteric or
zwitterionic surfactants or mixtures thereof, anionic, cationic,
nonionic, amphoteric or zwitterionic polymers or mixtures thereof,
inorganic or organic thickeners, antioxidants, penetration agents,
sequestering agents, fragrances, buffers, dispersing agents,
conditioners such as, for example, silicones, film-forming agents,
preserving agents and opacifying agents.
[0154] Obviously, a person skilled in the art will take care to
select this or these optional complementary compounds such that the
advantageous properties intrinsically attached to the oxidation dye
composition in accordance with the invention are not, or are
substantially not, damaged by the additions envisaged.
[0155] The dye composition according to the invention may be in
various forms, such as in the form of liquids, creams or gels or
any other form which is suitable for dyeing keratin fibers, and in
particular human hair.
[0156] The subject of the invention is also a process for dyeing
keratin fibers, and in particular human keratin fibers such as the
hair, which uses the dye composition as defined above.
[0157] According to this process, at least one dye composition as
defined above is applied to the fibers, for a period which is
sufficient to develop the desired coloration, either in air or with
the aid of an oxidizing agent.
[0158] According to a first embodiment of the process of the
invention, the fibers may be dyed without addition of an oxidizing
agent, merely by contact with atmospheric oxygen. In this case, the
dye composition may then optionally contain oxidation catalysts, so
as to accelerate the oxidation process.
[0159] Oxidation catalysts which may be mentioned more particularly
are metal salts such as manganese, cobalt, copper, iron, silver and
zinc salts.
[0160] Such compounds are, for example, manganese diacetate
tetrahydrate, manganese dichloride and its hydrates, manganese
dihydrogen carbonate, manganese acetylacetonate, manganese
triacetate and its hydrates, manganese trichloride, zinc
dichloride, zinc diacetate dihydrate, zinc carbonate, zinc
dinitrate, zinc sulphate, iron dichloride, iron sulphate, iron
diacetate, cobalt diacetate tetrahydrate, cobalt carbonate, cobalt
dichloride, cobalt dinitrate, cobalt sulphate heptahydrate, cupric
chloride and ammoniacal silver nitrate.
[0161] The manganese salts are particularly preferred.
[0162] When they are used, these metal salts are generally used in
proportions ranging from 0.001 to 4% by weight of metal equivalent
relative to the total weight of the dye composition, and preferably
from 0.005 to 2% by weight of metal equivalent relative to the
total weight of the dye composition.
[0163] According to a second embodiment of the process of the
invention, at least one dye composition as defined above is applied
to the fibers, the colour being developed at acidic, neutral or
alkaline pH using an oxidizing agent which is added, only at the
time of use, to the dye composition or which is present in an
oxidizing composition that is applied simultaneously or
sequentially in a separate manner.
[0164] According to this second embodiment of the dyeing process of
the invention, the dye composition described above is preferably
mixed, at the time of use, with an oxidizing composition
containing, in a medium which is suitable for dyeing, at least one
oxidizing agent present in an amount which is sufficient to develop
a coloration. The mixture obtained is then applied to the keratin
fibers and is generally left in place for 3 to 50 minutes
approximately, preferably for 5 to 30 minutes approximately, after
which the fibers are rinsed, washed with shampoo, rinsed again and
dried.
[0165] The oxidizing agent present in the oxidizing composition as
defined above may be chosen from the oxidizing agents
conventionally used for the is oxidation dyeing of keratin fibers,
and among which mention may be made of hydrogen peroxide, urea
peroxide, alkali metal bromates and persalts such as perborates and
persulphates. Hydrogen peroxide is particularly preferred.
[0166] The pH of the oxidizing composition containing the oxidizing
agent as defined above is such that, after mixing with the dye
composition, the pH of the resulting composition applied to the
keratin fibers preferably ranges from 3 to 12 approximately, and
even more preferably from 5 to 11. It is adjusted to the desired
value using acidifying or basifying agents usually used in the
dyeing of keratin fibers and as defined above.
[0167] The oxidizing composition as defined above may also contain
various adjuvants conventionally used in compositions for dyeing
the hair and as defined above.
[0168] The composition which is finally applied to the keratin
fibers may be in various forms, such as in the form of liquids,
creams or gels or in any other form which is suitable for dyeing
keratin fibers, and in particular human hair.
[0169] Another subject of the invention is a multi-compartment
device or dyeing kit or any other multi-compartment packaging
system, a first compartment of which contains the dye composition
as defined above and a second compartment of which contains the
oxidizing composition as defined above. These devices may be
equipped with a means which makes it possible to deliver the
desired mixture onto the hair, such as the devices described in
French patent FR-2,586,913 in the name of the present assignee, the
disclosure of which is hereby incorporated by reference.
[0170] Certain compounds of formula (I), used as oxidation base in
the context of the present invention, are novel and, in this
respect, constitute another subject of the invention.
[0171] These novel 3-substituted 4,5-diamino-pyrazoles and the
addition salts thereof with an acid correspond to the following
formula (I'): 5
[0172] in which R'.sub.1, R'.sub.2, R'.sub.3, R'.sub.4, R'.sub.5
and R'.sub.6 have the same meanings as those indicated above for
the radicals R.sub.1,R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6
in the formula (I), with, however, the following provisos:
[0173] (i) when R'.sub.1 represents a methyl radical, and when
R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, and when R'.sub.3 represents a hydrogen atom or a methyl
radical, R'.sub.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;
[0174] (ii) when R'.sub.1 represents an unsubstituted phenyl
radical and when R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5
simultaneously represent a hydrogen atom, R'.sub.6 is then other
than an unsubstituted phenyl radical;
[0175] (iii) when R'.sub.1 represents an unsubstituted phenyl
radical, and when R'6 represents a methyl radical, and when
R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, R'.sub.3 is then other than a hydrogen atom, a methyl radical
or an unsubstituted phenyl radical;
[0176] (iv) when R'.sub.1 represents an unsubstituted phenyl
radical, and when R'.sub.6 represents a methyl radical, and when
R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen atom, and
when R'.sub.2 represents a methyl or ethyl radical, R'.sub.3 is
then other than an unsubstituted phenyl radical;
[0177] (v) when R'.sub.1 represents an unsubstituted phenyl
radical, and when R'.sub.6 represents a methyl radical, and
R'.sub.2, R'.sub.3 and R'.sub.5 simultaneously represent a hydrogen
atom, R'.sub.4 is then other than a methyl radical;
[0178] (vi) when R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5
simultaneously represent a hydrogen atom, and when R'.sub.6
represents a methyl radical, R'.sub.1 is then other than a phenyl
radical substituted with a chlorine atom or with a trifluoroethyl,
nitro or pyridyl radical;
[0179] (vii) when R'.sub.1 represents a hydrogen atom, and when
R'.sub.6 represents a phenyl radical or a phenyl radical
substituted with a chlorine atom or with a methyl or methoxy
radical, and when R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously
represent a hydrogen atom, R'.sub.3 is then other than a hydrogen
atom or a C.sub.1-C.sub.4 alkyl or unsubstituted phenyl
radical;
[0180] (viii) when R'.sub.1, R'.sub.2, R'.sub.3, R'.sub.4 and
R'.sub.5 simultaneously represent a hydrogen atom, R'.sub.6 is then
other than a methyl radical;
[0181] (ix) when R'.sub.1 represents a .beta.-hydroxyethyl radical,
and when R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5 simultaneously
represent a hydrogen atom, R'.sub.6 is then other than a methyl or
unsubstituted phenyl radical;
[0182] (x) when R'.sub.4 represents a methyl radical, and when
R'.sub.5 represents an unsubstituted phenyl radical, and when
R'.sub.2 and R'.sub.3 simultaneously represent a hydrogen atom, and
when R'.sub.1 represents a hydrogen atom or a methyl radical,
R'.sub.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;
[0183] (xi) when R'.sub.1 represents a tert-butyl radical, and when
R'.sub.2, R'.sub.3, R'.sub.4 and R'.sub.5 simultaneously represent
a hydrogen atom, R'.sub.6 is then other than a methyl radical;
[0184] (xii) when R'.sub.1 represents a pyridyl radical, and when
R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously represent a hydrogen
atom, and when R'.sub.3 represents a hydrogen atom or a methyl
radical, R'.sub.6 is then other than a methyl or unsubstituted
phenyl radical;
[0185] (xiii) when R'.sub.1 represents a methyl, ethyl or
4-aminophenyl radical, and when R'.sub.2, R'.sub.4 and R'.sub.5
simultaneously represent a hydrogen atom, and when R'.sub.3
represents a hydrogen atom or an unsubstituted phenyl radical,
R'.sub.6 is then other than a methyl radical;
[0186] (xiv) when R'.sub.1 represents an isopropyl radical, and
when R'.sub.2, R'.sub.4 and R'.sub.5 simultaneously represent a
hydrogen atom, at least one of the radicals R'.sub.3 and R'.sub.6
is then other than a methyl radical;
[0187] (xv) when R'.sub.1 represents a hydrogen atom or an
unsubstituted phenyl radical, and when R'.sub.2, R'.sub.4 and
R'.sub.5 simultaneously represent a hydrogen atom, and when
R'.sub.3 represents a benzyl radical or a phenyl radical
substituted with a methyl radical or with a chlorine atom, R'.sub.6
is then other than a methyl or unsubstituted phenyl radical.
[0188] Among the novel compounds of formula (I') which may be
mentioned in particular are:
[0189] 1-benzyl-4,5-diamino-3-methylpyrazole,
[0190]
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methoxyphenyl)-pyrazole,
[0191]
4,5-diamino-1-(.beta.-hydroxyethyl)-3-(4'-methylphenyl)-pyrazole,
[0192] 4,5-diamino-1
-(.beta.-hydroxyethyl)-3-(3'-methylphenyl)-pyrazole,
[0193] 4,5-diamino-3-methyl-1-isopropylpyrazole,
[0194] 4,5-diamino-3-(4'-methoxyphenyl)-1-isopropyl-pyrazole,
[0195] 4,5-diamino-1-ethyl-3-methylpyrazole,
[0196] 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
[0197] 4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
[0198] 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
[0199] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0200] 4,5-diamino-3-hydroxymethyl-1-tert-butylpyrazole,
[0201] 4,5-diamino-3-hydroxymethyl-1-phenylpyrazole,
[0202]
4,5-diamino-3-hydroxymethyl-1-(2-methoxyphenyl)-pyrazole,
[0203]
4,5-diamino-3-hydroxymethyl-1-(3'-methoxyphenyl)-pyrazole,
[0204]
4,5-diamino-3-hydroxymethyl-1-(4'-methoxyphenyl)-pyrazole,
[0205] 1-benzyl-4,5-diamino-3-hydroxymethylpyrazole,
[0206] 4,5-diamino-3-methyl-1-(2'-methoxyphenyl)pyrazole,
[0207] 4,5-diamino-3-methyl-1-(3'-methoxyphenyl)pyrazole,
[0208] 4,5-diamino-3-methyl-1-(4'-methoxyphenyl)pyrazole,
[0209] 3-aminomethyl-4,5-diamino -1-methylpyrazole,
[0210] 3-aminomethyl-4,5-diamino-1-ethylpyrazole,
[0211] 3-aminomethyl-4,5-diamino-1-isopropylpyrazole,
[0212] 3-aminomethyl-4,5-diamino-1-tert-butylpyrazole,
[0213] 4,5-diamino-3-dimethylaminomethyl-1-methylpyrazole,
[0214] 4,5-diamino-3-dimethylaminomethyl-1-ethylpyrazole,
[0215] 4,5-diamino-3-dimethylaminomethyl-1-isopropyl-pyrazole,
[0216] 4,5-diamino-3-dimethylaminomethyl-1-tert-butyl-pyrazole,
[0217] 4,5-diamino-3-ethylaminomethyl-1-methylpyrazole,
[0218] 4,5-diamino-3-ethylaminomethyl-1-ethylpyrazole,
[0219] 4,5-diamino-3-ethylaminomethyl-1-isopropylpyrazole,
[0220] 4,5-diamino-3-ethylaminomethyl-1-tert-butylpyrazole,
[0221] 4,5-diamino-3-methylaminomethyl-1-methylpyrazole,
[0222] 4,5-diamino-3-methylaminomethyl-1-isopropylpyrazole,
[0223] 4,5-diamino-1-ethyl-3-methylaminomethylpyrazole,
[0224] 1-tert-butyl-4,5-diamino-3-methylaminomethyl-pyrazole,
[0225]
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-methyl-pyrazole,
[0226]
4,5-diamino-3-[(.beta.-hydroxyethyl)aminomethyl]-1-isopropylpyrazol-
e,
[0227]
4,5-diamino-1-ethyl-3-[(.beta.-hydroxyethyl)aminomethyl]-pyrazole,
[0228]
1-tert-butyl-4,5-diamino-3-[(.beta.-hydroxyethyl)amino-methyl]pyraz-
ole,
[0229]
4-amino-5-(.beta.-hydroxyethyl)amino-1,3-dimethylpyrazole,
[0230]
4-amino-5-(.beta.-hydroxyethyl)amino-1-isopropyl-3-methyl-pyrazole,
[0231]
4-amino-5-(.beta.-hydroxyethyl)amino-1-ethyl-3-methyl-pyrazole,
[0232]
4-amino-5-(.beta.-hydroxyethyl)amino-1-tert-butyl-3-methylpyrazole,
[0233]
4-amino-5-(.beta.-hydroxyethyl)amino-1-phenyl-3-methyl-pyrazole,
[0234]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(2'-methoxyphenyl)-3-methylp-
yrazole,
[0235]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(3'-methoxyphenyl)-3-methylp-
yrazole,
[0236]
4-amino-5-(.beta.-hydroxyethyl)amino-1-(4'-methoxyphenyl)-3-methylp-
yrazole,
[0237]
4-amino-5-(.beta.-hydroxyethyl)amino-1-benzyl-3-methyl-pyrazole,
[0238] 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
[0239] 4-amino-1-tert-butyl-3-methyl-5-methylaminopyrazole,
[0240] 1-(4'-chlorobenzyl)-4,5-diamino-3-methylpyrazole,
[0241] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0242] 4-amino-1-ethyl-3-methyl-5-methylaminopyrazole,
[0243] 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, and the
addition salts thereof with an acid.
[0244] Among the novel compounds of formula (I') which are more
particularly preferred are:
[0245] 1-benzyl-4,5-diamino-3-methylpyrazole,
[0246] 4,5-diamino-1-ethyl-3-methylpyrazole,
[0247] 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
[0248] 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
[0249] 4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
[0250] 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
[0251] 4,5-diamino-3-methyl-1-isopropylpyrazole,
[0252] 4-amino-5-(2'-aminoethyl)amino-1,3-dimethyl-pyrazole, and
the addition salts thereof with an acid.
[0253] The subject of the invention is also processes for the
preparation of the novel compounds of formula (I').
[0254] When R'.sub.6 represents a methyl radical, and when R'.sub.1
is other than a hydrogen atom, (compounds of formula (I'A) below),
process A corresponding to the following synthetic scheme: 6
[0255] is preferably used, this reaction scheme comprising
reacting, in a first step, a 3-aminocrotononitrile (1) with a
monosubstituted hydrazine (2), at a temperature generally above
90.degree. C., and preferably from 95 to 150.degree. C., in an
alcoholic solvent, followed, in a second step, in nitrosing the
5-aminopyrazole (3) in the 4-position, by reaction with an
inorganic or organic nitrite, in order to give the 5-amino
4-nitrosopyrazole (4) which leads, in a third step, by catalytic
hydrogenation to the 4,5-diaminopyrazoles of formula (I'A).
[0256] In order to have good control over the temperature during
the first step, it is generally preferred to work at the reflux
temperature of the solvent used. Among the alcohols used as
reaction solvent which may be mentioned more particularly are
n-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol,
3-methyl-1-butanol, 2-methyl-1-propanol, n-pentanol, 2-pentanol,
3-methyl-3-pentanol, 4-methyl-2-pentanol or 2-ethyl-1-butanol.
[0257] Among the inorganic nitrites which may be used, for example,
are sodium nitrite or potassium nitrite, in aqueous acetic acid
medium, at a temperature preferably from 0 to 5.degree. C.
[0258] Among the organic nitrites which may be used, for example,
is isoamyl nitrite, the reaction being carried out at room
temperature, in a lower alcohol in the presence of an acid such as
hydrochloric acid or acetic acid.
[0259] The catalytic hydrogenation of the compounds (4) is
preferably carried out in a lower alcohol, in the presence of a
catalyst such as palladium-on-charcoal, at a temperature generally
of from 20 to 100.degree. C.
[0260] When R'.sub.6 is other than a methyl radical, and when
R'.sub.1 is other than a hydrogen atom (compounds of formula (I'B)
below), process B corresponding to the following synthetic scheme:
7
[0261] is preferably used, this synthetic scheme comprising
reacting, in a first step, a .beta.-keto acetonitrile (5) with a
monosubstituted hydrazine (2), at a temperature generally of from
20 to 150.degree. C., in an alcoholic solvent, in order to obtain
the 5-aminopyrazole (6), which is then nitrosated in the
4-position, in a second step, to give a 4-nitro-5-aminopyrazole
(7), which is itself then hydrogenated, in a third step, to lead to
the 4,5-diaminopyrazoles of formula
[0262] The solvents used according to this process B are the same
as those mentioned for the process A described above.
[0263] The nitrosation and hydrogenation reactions are performed
according to the conditions described for process A described
above.
[0264] When R'.sub.6 represents a radical which is of high steric
bulk (compounds of formula (I'C) below), process C corresponding to
the following synthetic scheme: 8
[0265] is preferably used, this synthetic scheme comprising
reacting, in a first step, a .beta.-keto acetonitrile (5) with a
monosubstituted hydrazine (2) in order to obtain a 5-amino-pyrazole
(6) according to the operating conditions mentioned for process B
described above. The 5-amino-pyrazole (6) is then acetylated in the
5-position, in a second step, to lead to a 5-acetylaminopyrazole
(8), which is itself then nitrated in the 4-position and
deacetylated in the 5-position, in a third step, to give a
5-amino-4-5 nitropyrazole (9), preferably by fuming nitric acid in
concentrated sulphuric medium, at a temperature preferably of from
0 to 5.degree. C. The 5-amino-4-nitropyrazole (9) is then
hydrogenated, in a fourth step, according to the operating
conditions mentioned in process A above, to lead to the
4,5-diaminopyrazoles of formula (I'C).
[0266] When one of the radicals R'.sub.2 or R'.sub.3 is other than
a hydrogen atom (compounds of formula (I'D) below), process D
corresponding to the following synthetic scheme: 9
[0267] is preferably used, this synthetic scheme comprising
reacting, in a first step, a .beta.-keto ester (10) with a
hydrazine (2) in order to obtain a 5-hydroxypyrazole (11), which is
in equilibrium with its 5-pyrazolone tautomeric form, as described,
for example, in Org. Synth., Edward C. Taylor (1976), 55, 73-7. The
5-hydroxypyrazole (11) is then nitrated in the 4-position, in a
second step, and then chlorinated in the 5-position, in a third
step, according to the method as described, for example, in U.S.
Pat. No. 4,025,530. The 5-chloro-4-nitropyrazole (13) then leads,
in a fourth step, in the presence of a primary amine
H.sub.2N--R'.sub.3, to a 5-amino-4-nitropyrazole (14) and then, in
a fifth step, by catalytic hydrogenation according to the method
described above for process A, to the 4,5-diaminopyrazoles of
formula (I'D).
[0268] The examples which follow are intended to illustrate the
invention without, however, limiting the scope thereof.
PREPARATION EXAMPLE
Preparation Example 1
Synthesis of 4,5-diamino-1,3-dimethylpyrazole Dihydrochloride
[0269] 10
[0270] a) Preparation of 5-amino-1,3-dimethylpyrazole
[0271] To a solution of 16.5 g (0.2 mol) of 3-aminocrotononitrile
in 40 cm.sup.3 of n-pentanol were added 12.9 g (0.28 mol) of
methylhydrazine. The solution was maintained at reflux for 3 hours.
The pentanol and the excess methylhydrazine were subsequently
distilled off under reduced pressure. The beige precipitate
obtained was taken up in 150 cm.sup.3 of heptane, filtered on a
sinter funnel and then dried under vacuum at a temperature of
40.degree. C. 13.5 g of 5-amino-1,3-dimethylpyrazole were obtained
in the form of a beige solid, the melting point of which was from
80 to 81.degree. C.
[0272] b) Preparation of 5-amino-1,3-dimethyl-4-nitrosopyrazole
[0273] To a solution of 11.1 g (0.1 mol) of
5-amino-1,3-dimethylpyrazole, obtained in the above step, in 125
cm.sup.3 of absolute ethanol were added dropwise 1 cm.sup.3 of 12 N
hydrochloric acid and then 13.5 cm.sup.3 of isoamyl nitrite, at
0.degree. C. The solution was subsequently warmed to and left at
room temperature for 4 hours. The reaction medium was then filtered
on a sinter funnel and the precipitate obtained was washed with 100
cm.sup.3 of isopropyl ether. After drying under vacuum at room
temperature, 7.5 g of 5-amino-1,3-dimethyl-4-nitroso- -pyrazole
were obtained in the form of an orange-coloured solid, the melting
point of which was from 169 to 171.degree. C.
[0274] c) Preparation of 4,5-diamino-1 3-dimethylpyrazole
dihydrochloride
[0275] To a solution of 7 g (0.05 mol) of
5-amino-1,3-dimethylpyrazole, obtained in the above step, in 200
cm.sup.3 of ethanol were added 1.2 g of 5% by weight
palladium-on-charcoal containing 50% water. The suspension was
placed in a hydrogenator under a hydrogen pressure of 10 bar, at a
temperature of 75.degree. C. for 3 hours, with vigorous stirring.
The reaction medium was poured into a solution of 50 cm.sup.3 of
ethanol and 17 cm.sup.3 of 12 N hydrochloric acid cooled to
0.degree. C. This solution was subsequently clarified by filtration
on a sinter funnel and then evaporated to dryness under reduced
pressure. The brown solid obtained was taken up, at reflux, in 45
cm.sup.3 of 5 N hydrochloric ethanol and 13 cm.sup.3 of water, and
then cooled to room temperature. The white precipitate obtained was
filtered on a sinter funnel and then dried under vacuum at room
temperature. 5.7 g of 4,5-diamino-1,3-dimethylpyrazole
dihydrochloride were obtained in the form of white crystals, the
decomposition temperature of which was from 210 to 212.degree. C.
The elemental analysis calculated for C.sub.5H.sub.10N.sub.4. 2HCI
was:
1 % C H N Cl Calculated 30.17 6.08 28.14 35.62 Found 30.15 6.08
28.07 35.77
Preparation Example 2
Synthesis of 4,5-diamino-3-methyl-1-phenylpyrazole
dihydrochloride
[0276] 11
[0277] a) Preparation of
5-amino-3-methyl-4-nitroso-1-phenylpyrazole
[0278] To a solution of 17.3 g (0.1 mol) of
5-amino-3-methyl-1-phenylpyraz- ole in 200 cm.sup.3 of absolute
ethanol were added dropwise 0.5 cm.sup.3 of 12 N hydrochloric acid
and then 13.5 m.sup.3 of isoamyl nitrite, at 0.degree. C. The
solution was then warmed to and left at room temperature for 4
hours. An orange-coloured solid crystallized out. This solid was
filtered off on a sinter funnel and washed with 100 cm.sup.3 of
isopropyl ether. After drying under vacuum at room temperature, 17
g of 5-amino-3-methyl-4-nitroso-1-phenylpyrazole were obtained in
the form of an orange-coloured solid, the melting point of which
was from 202 to 204.degree. C.
[0279] b) Preparation of 4,5-diamino-3-methyl-1-phenylpyrazole
dihydrochloride
[0280] To a solution of 10 g (0.05 mol) of
5-amino-3-methyl-4-nitroso-1-ph- enylpyrazole, obtained in the
above step, in 80 cm.sup.3 of absolute ethanol and 20 cm.sup.3 of 2
N hydrochloric acid were added 1.2 g of 5% by weight
palladium-on-charcoal containing 50% water. The suspension was
placed in a hydrogenator under a hydrogen pressure of 10 bar, at a
temperature of 75.degree. C. for 3 hours, with vigorous stirring.
The contents of the hydrogenator were subsequently recovered and
filtered on a sinter funnel. The filtrate was poured into a
solution, at 0.degree. C., of 70 cm.sup.3 of absolute ethanol and
30 cm.sup.3 of 12 N hydrochloric acid and then evaporated to
dryness. The residue was taken up in 100 cm.sup.3 of isopropyl
ether: a beige solid crystallized out. This solid was filtered on a
sinter funnel and then washed with 100 cm.sup.3 of isopropyl ether
and purified by recrystallization from a mixture of 100 cm.sup.3 of
water and 50 cm.sup.3 of 3.5 M ethanolic hydrochloric acid
solution. The crystallized solid was filtered off on a sinter
funnel, washed with 100 cm.sup.3 of isopropyl ether and dried under
vacuum at room temperature. 8 g of
4,5-diamino-3-methyl-1-phenylpyr- azole dihydrochloride were
obtained in the form of a white solid, the melting point of which
was from 208 to 210.degree. C. The elemental analysis calculated
for C.sub.10H.sub.17N.sub.4. 2HCl was:
2 % C H N Cl Calculated 45.99 5.40 21.45 27.15 Found 46.17 5.40
21.32 27.10
Preparation Example 3
Synthesis of 4,5-diamino-1-methyl-3-phenylpyrazole
Dihydrochloride
[0281] 12
[0282] a) Preparation of 5-amino-1-methyl-3-phenylpyrazole
[0283] To a solution of 29 g (0.2 mol) of benzoylacetonitrile in
100 cm.sup.3 of n-pentanol were added 14.7 cm.sup.3 (0.28 mol) of
methylhydrazine and the mixture was heated at reflux for 2 hours.
The n-pentanol and the excess methylhydrazine were subsequently
distilled off under reduced pressure. A beige solid was obtained,
which was taken up in 100 cm.sup.3 of heptane at room temperature
and filtered off on a sinter funnel. After drying under vacuum at a
temperature of 40.degree. C., 27 g of
5-amino-1-methyl-3-phenylpyrazole were obtained in the form of a
beige solid, the melting point of which was from 104 to 106.degree.
C.
[0284] b) Preparation of
5-amino-1-methyl-4-nitroso-3-phenylpyrazole
[0285] To a solution of 17.3 g (0.1 mol) of
5-amino-1-methyl-3-phenylpyraz- ole, obtained in the above step, in
200 cm.sup.3 of absolute ethanol were added dropwise 0.5 cm.sup.3
of 12 N hydrochloric acid and then 13.5 cm.sup.3 of isoamyl
nitrite, at 0.degree. C. The solution was subsequently warmed to
and left at room temperature for 4 hours. An orange-coloured solid
crystallized out. This was filtered off on a sinter funnel and
washed with 100 cm.sup.3 of isopropyl ether. After drying under
vacuum at room temperature, 17 g of
5-amino-1-methyl-4-nitroso-3-ph- enylpyrazole were obtained in the
form of an orange-coloured solid, the melting point of which was
from 224 to 226.degree. C.
[0286] c) Preparation of 4,5-diamino-1-methyl-3-phenylpyrazole
dihydrochloride
[0287] To a solution of 10 g (0.05 mol) of
5-amino-1-methyl-4-nitroso-3-ph- enylpyrazole, obtained in the
above step, in 80 cm.sup.3 of absolute ethanol and 20 cm.sup.3 of 2
N hydrochloric acid solution were added 1.2 g of 5% by weight
palladium-on-charcoal containing 50% water. The suspension was
placed in a hydrogenator under a hydrogen pressure of 10 bar, at a
temperature of 75.degree. C. for 3 hours, with vigorous stirring.
The contents of the hydrogenator were recovered and filtered on a
sinter funnel. The filtrate was poured into a solution of 70
cm.sup.3 of absolute ethanol and 30 cm.sup.3 of 12 N hydrochloric
acid cooled to 0.degree. C. A white solid precipitated out. This
precipitate was filtered off on a sinter funnel and then washed
with 100 cm.sup.3 of isopropyl ether. After drying under vacuum at
room temperature, 10 g of 4,5-diamino-1-methyl-3-phenylpyrazole
dihydrochloride were obtained, which product was then purified by
recrystallization from a mixture of 30 cm.sup.3 of water and 50
cm.sup.3 of 3.5 M ethanolic hydrochloric acid solution. The
recrystallized solid was filtered off on a sinter funnel, washed
with 100 cm.sup.3 of isopropyl ether and dried under vacuum at room
temperature. 8 g of 4,5-diamino-1-methyl-3-phenylpyrazole
dihydrochloride were obtained in the form of a white solid, the
melting point of which was from 218 to 220.degree. C. The elemental
analysis calculated for C.sub.10H.sub.12N.sub.4. 2HCI was:
3 % C H N Cl Calculated 45.99 5.40 21.45 27.15 Found 46.27 5.60
21.32 27.10
Preparation Example 4
Synthesis of 4-amino-1,3-dimethyl-5-hydrazinopyrazole
dihydrochloride
[0288] 13
[0289] A suspension of 8.6 g (0.05 mol) of
1,3-dimethyl-5-hydrazino-4-nitr- opyrazole and 1.5 g of 5% by
weight palladium-on-charcoal containing 50% water in 200 cm.sup.3
of ethanol was placed in a hydrogenator. After stirring under a
hydrogen pressure of 10 bar, at a temperature of 75.degree. C. for
3 hours, the reaction medium was poured into a solution of 60
cm.sup.3 of ethanol and 20 cm.sup.3 of 12 N hydrochloric acid
cooled to 0.degree. C. The solution was clarified by filtration on
a sinter funnel and then evaporated to dryness under reduced
pressure. The brown solid obtained was taken up, at reflux, in 50
cm.sup.3 of 5 N hydrochloric ethanol and 14 cm.sup.3 of water and
was then cooled to room temperature. The white precipitate obtained
was filtered off on a sinter funnel and then dried under vacuum at
room temperature. 9.5 g of 4-amino-1,3-dimethyl-5-hydrazinopyrazole
dihydrochloride were obtained in the form of white crystals, the
melting point of which was from 202 to 204.degree. C. The elemental
analysis calculated for C.sub.5H.sub.11N.sub.5. 2HCI was:
4 % C H N Cl Calculated 28.05 6.12 32.71 33.12 Found 28.52 6.20
32.96 32.88
Preparation Example 5
Synthesis of 1-benzyl-4,5-diamino-3-methylpyrazole
dihydrochloride
[0290] 14
[0291] a) Preparation of 5-amino-1-benzyl-3-methylpyrazole
[0292] To a solution of 16.4 g (0.2 mol) of 3-aminocrotononitrile
in 100 cm.sup.3 of n-pentanol were added 26.9 g (0.22 mol) of
benzylhydrazine and the mixture was then heated at reflux for 12
hours. The n-pentanol was subsequently distilled off under reduced
pressure and a thick oil was obtained, which was purified by
chromatography on silica gel. A pale yellow solid was obtained,
which was crystallized from isopropyl ether and was then filtered
on a sinter funnel. After drying under vacuum at 40.degree. C., 17
g of the expected product were obtained in the form of a pale
yellow solid, the melting point of which was from 76 to 78.degree.
C.
[0293] b) Preparation of
5-amino-1-benzyl-3-methyl-4-nitrosopyrazole
[0294] To a solution of 18.7 g (0.1 mol) of
5-amino-1-benzyl-3-methylpyraz- ole, obtained in the above step, in
200 cm.sup.3 of absolute ethanol were added dropwise 0.5 cm.sup.3
of 12 N hydrochloric acid and then 13.5 cm.sup.3 of isoamyl
nitrite, at 0.degree. C. The solution was subsequently warmed to
and left at room temperature for 4 hours. An orange-coloured solid
crystallized out. It was filtered off on a sinter funnel and washed
with 100 cm.sup.3 of ethanol and then with 100 cm.sup.3 of
isopropyl ether. After drying under vacuum at room temperature, 13
g of the expected product were obtained in the form of an
orange-coloured solid, the melting point of which was from 178 to
180.degree. C.
[0295] c) Preparation of 1-benzyl-4,5-diamino-3-methylpyrazole
dihydrochloride
[0296] To a solution of 5 g (0.02 mol) of
5-amino-1-benzyl-3-methyl-5-nitr- osopyrazole, obtained in the
above step, in 200 cm.sup.3 of methanol was added 0.9 g of 5% by
weight palladium-on-charcoal containing 50% water. The suspension
was placed in a hydrogenator under a pressure of 20 bar of
hydrogen, at room temperature for 3 hours, with vigorous stirring.
The contents of the hydrogenator were removed and filtered on a
sinter funnel. The filtrate was subsequently poured into 100
cm.sup.3 of 3.5 M hydrochloric ethanol solution. This solution was
concentrated under vacuum. A thick oil was obtained, which was
crystallized by addition of 50 cm.sup.3 of acetone. A solid was
obtained, which was filtered off on a sinter funnel. After drying
under vacuum at room temperature, 6 g of
1-benzyl-4,5-diamino-3-methylpyrazole dihydrochloride were obtained
in the form of a white solid, the melting point of which was from
190 to 192.degree. C. The elemental analysis calculated for
C.sub.11H.sub.14N.sub.4. 2HCI was:
5 % C H N Cl Calculated 48.01 5.86 20.36 25.77 Found 48.03 5.90
20.40 25.75
Preparation Example 6
Synthesis of 4,5-diamino-1-methyl-3-tert -butylpyrazole
dihydrochloride
[0297] 15
[0298] a) Preparation of 5-amino-1-methyl-3-tert-butylpyrazole
[0299] To a solution of 12.5 g (0.1 mol) of
4,4-dimethyl-3-oxopentanenitri- le in 50 cm.sup.3 of n-propanol
were added, at room temperature, 4.6 g (0.1 mol) of
methylhydrazine. The reaction medium was maintained at reflux for 1
hour and then cooled to room temperature. The white solid obtained
was filtered off on a sinter funnel and then washed with isopropyl
ether. After drying under vacuum at 40.degree. C., 10 g of the
expected product were obtained in the form of a beige solid, the
melting point of which was 157.degree. C.
[0300] b) Preparation of
5-acetamido-1-methyl-3-tert-butylpyrazole
[0301] To a solution of 10 g (0.065 mol) of
5-amino-1-methyl-3-tert-butylp- yrazole, obtained in the above
step, in 25 cm.sup.3 of acetic acid were added, at room
temperature, 13.5 cm.sup.3 (0.13 mol) of acetic anhydride. After
stirring for 1 hour, the reaction medium was poured onto 100
cm.sup.3 of ice. The solution was extracted three times with 100
cm.sup.3 of dichloromethane and the organic phase was dried over
sodium sulphate and then distilled under vacuum on a rotary
evaporator. The solid obtained was taken up in 100 cm.sup.3 of
isopropyl ether, filtered on a sinter funnel and then dried under
vacuum at 40.degree. C. 12 g of the expected product were obtained
in the form of a beige solid, which product was recrystallized from
30 cm.sup.3 of ethyl acetate in order to isolate 8.5 g of the
expected product in the form of white crystals, the melting point
of which was 138.degree. C.
[0302] c) Preparation of
5-amino-1-methyl4-nitro-3-tert-butylpyrazole
[0303] To 30 cm.sup.3 of concentrated sulphuric acid were added 8.5
g (0.044 mol) of 5-acetamido-1-methyl-3-tert-butylpyrazole, at
5.degree. C. with vigorous stirring, followed by 2.5 cm.sup.3
(0.066 mol) of fuming nitric acid. After stirring for 2 hours, the
reaction mixture was poured onto 100 g of ice and stirred for 30
minutes. The solid obtained was filtered off on a sinter funnel,
washed with 20 cm.sup.3 of water and then dried under vacuum at
40.degree. C. 8.5 g of the expected product were obtained in the
form of a yellow solid, the melting point of which was 124.degree.
C.
[0304] d) Preparation of 4,5-diamino-1-methyl-3-tert-butylpyrazole
dihydrochloride
[0305] A suspension of 8.5 g (0.035 mol) of
5-amino-1-methyl-4-nitro-3-ter- t-butylpyrazole and 1.5 g of 5% by
weight palladium-on-charcoal containing 50% water in 200 cm.sup.3
of ethanol was placed in a hydrogenator. After stirring for 3 hours
under a hydrogen pressure of 10 bar, at a temperature of 75.degree.
C., the reaction medium was poured into a solution, precooled to
0.degree. C., of 60 cm.sup.3 of ethanol and 20 cm.sup.3 of 12 N
hydrochloric acid. The solution was clarified by filtration on a
sinter funnel and then evaporated to dryness under reduced
pressure. The brown solid obtained was taken up, at reflux, in 35
cm.sup.3 of 5 N hydrochloric ethanol and 11 cm.sup.3 of water and
then cooled to room temperature. The white crystals obtained were
filtered off on a sinter funnel and then dried under vacuum at room
temperature. 4.9 g of the expected product were obtained in the
form of white crystals, the melting point of which was 260.degree.
C. The elemental analysis for C.sub.8H.sub.10N.sub.4. 2HCI was:
6 % C H N Cl Calculated 39.84 7.52 23.23 29.40 Found 39.73 7.63
23.16 29.20
Preparation Example 7
Synthesis of 4,5-diamino-3-methyl-1-tert-butylpyrazole
dihydrochloride
[0306] 16
[0307] a) Preparation of 5-amino-3-methyl-1-tert-butylpyrazole
[0308] To a solution of 16.4 g (0.2 mol) of 3-aminocrotononitrile
in 100 cm.sup.3 of n-pentanol were added 19.4 g (0.22 mol) of
tert-butylhydrazine. This solution was heated at reflux for 20
hours. The n-pentanol was subsequently distilled off under reduced
pressure. A pale yellow solid was obtained, which was taken up in
100 cm.sup.3 of isopropyl ether at room temperature and filtered on
a sinter funnel. After drying under vacuum at 40.degree. C., 18 g
of the expected product were obtained in the form of a pale yellow
solid, the melting point of which was from 172 to 175.degree.
C.
[0309] b) Preparation of
5-amino-3-methyl4-nitroso-1-tert-butylpyrazole
[0310] To a solution of 15.3 g (0.1 mol) of
5-amino-3-methyl-1-tert-butylp- yrazole, obtained in the above
step, in 200 cm.sup.3 of absolute ethanol were added dropwise 0.5
cm.sup.3 of 12 N hydrochloric acid and then 13.5 cm.sup.3 (0.1 mol)
of isoamyl nitrite, at 0.degree. C. The solution was subsequently
warmed to and left at room temperature for 4 hours.
[0311] The ethanol was evaporated off under a pressure of 175 mbar,
at 40.degree. C. An orange-coloured solid was crystallized from
heptane at 0.degree. C. and then filtered off on a sinter funnel.
After drying under vacuum at room temperature, 11 g of the expected
product were obtained in the form of an orange-coloured solid, the
melting point of which was 120.degree. C.
[0312] c) Preparation of 4,5-diamino-3-methyl-1-tert-butylpyrazole
dihydrochloride
[0313] To a solution of 9 g (0.05 mol) of
5-amino-3-methyl-4-nitroso-1-ter- t-butylpyrazole, obtained in the
above step, in 600 cm.sup.3 of absolute ethanol were added 2 g of
5% by weight palladium-on-charcoal containing 50% water. The
suspension was placed in a hydrogenator under a pressure of 20 bar
of hydrogen, at room temperature for 4 hours, with vigorous
stirring. The contents of the hydrogenator were removed and
filtered on a sinter funnel. The filtrate was subsequently poured
into 100 cm.sup.3 of 3.5 M hydrochloric ethanol solution. This
solution was concentrated under vacuum to the point at which
crystallization commenced. The crystals were subsequently washed
with 3.5 M hydrochloric ethanol solution and then filtered off on a
sinter funnel. A white solid was obtained, which was recrystallized
from a mixture of 40 cm.sup.3 of 3.5 M hydrochloric ethanol and 12
cm.sup.3 of distilled water. After drying under vacuum at room
temperature, 8 g of the expected product were obtained in the form
of white crystals, the melting point of which was from 252 to
255.degree. C. The elemental analysis for C.sub.8H.sub.16N.sub.4.
2HCI was:
7 % C H N Cl Calculated 39.84 7.52 23.23 29.40 Found 39.70 7.49
23.37 29.44
Preparation Example 8
Synthesis of 4,5-diamino-1-1-.beta.-hydroxyethyl-3-methylpyrazole
dihydrochloride
[0314] 17
[0315] a) Preparation of
5-amino-1-(.beta.-hydroxyethyl)-3-methylpyrazole
[0316] To a solution of 16.4 g (0.2 mol) of 3-aminocrotononitrile
in 100 cm.sup.3 of n-pentanol were added 16.7 g (0.22 mol) of
.beta.-hydroxyethylhydrazine and the mixture was then heated at
reflux for 12 hours. The n-pentanol was subsequently distilled off
under reduced pressure. A thick oil was obtained, which
crystallizes by addition of 150 cm.sup.3 of isopropyl ether. A
beige solid was obtained, which was filtered off on a sinter
funnel. After drying under vacuum at 40.degree. C., 18 g of the
expected product were obtained in the form of a beige solid, the
melting point of which was from 66 to 68.degree. C.
[0317] b) Preparation of
5-amino-1-(.beta.-hydroxyethyl)-3-methyl-4-nitros- opyrazole
[0318] To a solution of 14.1 g (0.1 mol) of
5-amino-1-(.beta.-hydroxyethyl- )-3-methylpyrazole, obtained in the
above step, in 200 cm.sup.3 of absolute ethanol were added dropwise
0.5 cm.sup.3 of 12 N hydrochloric acid and then 13.5 cm.sup.3 of
isoamyl nitrite, at 0.degree. C. The solution was subsequently
warmed to and left at room temperature for 4 hours. A red solid
crystallized out and was filtered off on a sinter funnel and then
washed with 100 cm.sup.3 of ethanol, and then with 100 cm.sup.3 of
isopropyl ether. After drying under vacuum at room temperature,
10.5 g of the expected product were obtained in the form of red
crystals, the melting point of which was from 170 to 175.degree.
C.
[0319] c) Preparation of
4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyraz- ole
dihydrochloride
[0320] To a solution of 8.5 g (0.05 mol) of the product obtained in
the above step, in 800 cm.sup.3 of methanol, were added 2 g of 5%
by weight palladium-on-charcoal containing 50% water. The
suspension was placed in a hydrogenator under a pressure of 20 bar
of hydrogen, at 30.degree. C. for 4 hours, with vigorous stirring.
The contents of the hydrogenator were subsequently removed and
filtered on a sinter funnel in 100 cm.sup.3 of 6 M hydrochloric
ethanol solution. This solution was concentrated under vacuum. A
thick oil was obtained, which crystallized by addition of 50
cm.sup.3 of isopropyl ether. A white solid was obtained, which was
recrystallized from a mixture of 45 cm.sup.3 of 6 M hydrochloric
ethanol and 3.5 cm.sup.3 of distilled water. After drying under
vacuum at room temperature, 7.5 g of the expected product were
obtained in the form of white crystals, the melting point of which
was from 190 to 193 .degree. C. The elemental analysis calculated
for C.sub.6H.sub.12N.sub.4O. 2HCI was:
8 % C H N O Cl Calculated 31.46 6.16 24.45 6.98 30.95 Found 31.44
6.21 24.10 7.07 30.98
Preparation Example 9
Synthesis of 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole
dihydrochloride
[0321] a) Preparation of
5-[(2'-aminoethyl)amino]-1,3-dimethyl-4-nitropyra- zole
hydrochloride
[0322] To a solution of 17.5 g (0.1 mol) of
5-chloro-1,3-dimethylpyrazole in 200 cm.sup.3 of n-propanol were
added 7.3 cm.sup.3 (0.11 mol) of ethylenediamine. This solution was
heated at reflux for 4 hours. The solution was subsequently cooled
to and left at room temperature for 15 hours. A bright yellow solid
crystallized out and was then filtered off on a sinter funnel.
After drying under vacuum at 40 .degree.C., 19 g of the expected
product were obtained in the form of a yellow solid, the melting
point of which was 235.degree. C.
[0323] b) Preparation of
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazo- le
dihydrochloride
[0324] To a solution of 10 g (0.04 mol) of
5-[(2'-aminoethyl)amino]-1,3-di- methyl-4-nitropyrazole
hydrochloride, obtained in the above step, in 20 cm.sup.3 of
methanol were added 2 g of 5% by weight palladium-on-charcoal
containing 50% water. The suspension was placed in a hydrogenator
under a pressure of 10 bar of hydrogen, at 40.degree. C. for 3
hours, with vigorous stirring. The contents of the hydrogenator
were removed and filtered on a sinter funnel in 100 cm.sup.3 of 3.5
M hydrochloric ethanol solution. This solution was concentrated
under vacuum. A thick oil was obtained, which crystallized by
addition of 50 cm.sup.3 of isopropyl ether. The solid formed was
filtered off on a sinter funnel and then washed with 20 cm.sup.3 of
isopropyl ether and purified by recrystallization from a mixture of
33 cm.sup.3 of absolute ethanol and 16 cm.sup.3 of 6 M hydrochloric
acid. The crystallized solid was filtered off on a sinter funnel,
washed with 50 cm.sup.3 of isopropyl ether and dried under vacuum
at room temperature. 5 g of 4-amino-5-(2'-aminoethyl)a-
mino-1,3-dimethylpyrazole dihydrochloride were obtained in the form
of a white solid, the melting point of which was from 238 to
240.degree. C.
[0325] The elemental analysis for C.sub.7H.sub.15N.sub.5. 2HCI
was:
9 % C H N Cl Calculated 34.72 7.08 28.92 29.28 Found 34.70 7.05
28.89 29.50
Application Examples
Examples 10 to 18 of Dyeing in Alkaline Medium
[0326] The following dye compositions, in accordance with the
invention, were prepared (contents in grams):
10 COMPOSITION 10 11 12 13 14 15 16 17 18
4,5-diamino-1,3-dimethylpyrazole 0.597 0.597 0.597 0.597
dihydrochloride 4-amino-1,3-dimethyl-5-hydrazinopyrazole 0.642
0.642 dihydrochloride 4,5-diamino-3-methyl-1-phenylpyrazole 0.783
dihydrochloride 4,5-diamino-3-methyl-1-tert-but- ylpyrazole 0.742
dihydrochloride 4,5-diamino-1-methyl-3-tert-butylpyrazole 0.724
dihydrochloride 3-aminophenol 0.327 0.501
5-N-(.beta.-hydroxyethyl)amino-2-methylphenol
2,4-diamino-1-.beta.-hydroxyethyloxybenzene 0.723 dihydrochloride
2,6-dihydroxy-4-methylpyridine 0.539 dihydrochloride monohydrate
2-methyl-5-aminophenol 0.369 6-hydroxyindoline hydrochloride 0.515
4-hydroxyindole 0.399 4-hydroxy-N-methylindole 0.442 Common dye
support (*) (*) (*) (*) (*) (*) (*) (*) (*) Demineralized water qs
100 g 100 g 100 g 100 g 100 g 100 g 100 g 100 g 100 g
[0327]
11 ( ) common dye support: Oleyl alcohol polyglycerolated with 2
mol 4.0 g of glycerol Oleyl alcohol polyglycerolated with 4 mol
5.69 g A.M. of glycerol, containing 78% active material (A.M.)
Oleic acid 3.0 g Oleylamine containing 2 mol of ethylene 7.0 g
oxide, sold under the trade name Ethomeen O12 by the company Akzo
Diethylaminopropyl laurylaminosuccin- 3.0 g A.M. amate, sodium
salt, containing 55% A.M. Oleyl alcohol 5.0 g Oleic acid
diethanolamide 12.0 g Propylene glycol 3.5 g Ethyl alcohol 7.0 g
Dipropylene glycol 0.5 g Propylene glycol monomethyl ether 9.0 g
Aqueous sodium metabisulphite solution 0.485 g A.M. containing 35%
A.M. Ammonium acetate 0.8 g Antioxidant, sequestering agent qs
Fragrance, preserving agent qs Aqueous ammonia containing 20% NH3
10 g
[0328] Each dye composition 10 to 18 was mixed, at the time of use,
with an equal amount by weight of an oxidizing composition
consisting of 20-volumes aqueous-peroxide solution (6% by
weight).
[0329] Each resulting composition was applied for 30 minutes to
locks of natural grey hair containing 90% white hairs. The locks of
hair were subsequently rinsed, washed with a standard shampoo and
then dried.
[0330] The locks of hair were dyed in the shades featured in the
table below:
12 SHADE ON NATURAL EXAMPLE pH OF THE MIXTURE HAIR 10 9.8
Iridescent 11 9.9 Coppery golden 12 9.9 Slightly iridescent blonde
13 9.9 Violet 14 10.0 Iridescent 15 9.8 Purplish blue 16 9.8 Dark
purple 17 9.7 Iridescent 18 9.9 Blue
Examples 19 and 20 of Dyeing in Acidic Medium
[0331] The following dye compositions, in accordance with the
invention, were prepared (contents in grams):
13 COMPOSITION 19 20 4,5-diamino-1,3-dimethy- lpyrazole 0.597 BASES
dihydrochloride COUPL 4-amino-1,3-dimethyl-5-hydrazinopyrazole
0.642 dihydrochloride 2,4-diamino-1-.beta.-hydroxyethyloxybenzene
0.723 dichlorohydride 2-methyl-5-aminophenol 0.369 Common dye
support (**) (**) Dimineralized water qs 100 g 100 g
[0332]
14 ( ) common dye support: Oleyl alcohol polyglycerolated with 2
mol 4.0 g of glycerol Oleyl alcohol polyglycerolated with 4 mol
5.69 g A.M. of glycerol, containing 78% active material (A.M.)
Oleic acid 3.0 g Oleylamine containing 2 mol of ethylene 7.0 g
oxide, sold under the trade name Ethomeen O12 by the company Akzo
Diethylaminopropyl laurylaminosuccin- 3.0 g A.M. amate, sodium
salt, containing 55% A.M. Oleyl alcohol 5.0 g Oleic acid
diethanolamide 12.0 g Propylene glycol 3.5 g Ethyl alcohol 7.0 g
Dipropylene glycol 0.5 g Propylene glycol monomethyl ether 9.0 g
Aqueous sodium metabisulphite solution 0.455 g A.M. containing 35%
A.M. Ammonium acetate 0.8 g Antioxidant, sequestering agent qs
Fragrance, preserving agent qs Monoethanolamine qs pH 9.8
[0333] Each dye composition was mixed, at the time of use, with an
equal amount by weight of an oxidizing composition consisting of
20-volumes aqueous-peroxide solution (6% by weight), and the pH of
which had been adjusted to between 1 and 1.5 with 2.5 g of
orthophosphoric acid per 100 g of aqueous hydrogen peroxide.
[0334] Each resulting composition was applied for 30 minutes to
locks of natural grey hair containing 90% white hairs. The locks of
hair were subsequently rinsed, washed with a standard shampoo and
then dried.
[0335] The locks of hair were dyed in the shades featured in the
table below:
15 SHADE ON NATURAL EXAMPLE pH OF THE MIXTURE HAIR 19 6.9 Purplish
blue 20 6.8 Iridescent
Example 21 of Dyeing in Air
[0336] The following dye composition, in accordance with the
invention, was prepared:
16 4,5-Diamino-1,3-dimethylpyrazole 0.398 g dihydrochloride
2,4-Diamino-1-.beta.-hydroxyethyloxy- 0.482 g benzene
dihydrochloride
* * * * *