U.S. patent application number 09/925010 was filed with the patent office on 2003-01-30 for novel cationic 4-hydroxyindoles, their use for the oxidation dyeing of keratinous fibers, dyeing compositions, and methods of dyeing.
This patent application is currently assigned to L'OREAL. Invention is credited to Fadli, Aziz, LaGrange, Alain, Terranova, Eric.
Application Number | 20030019050 09/925010 |
Document ID | / |
Family ID | 9530653 |
Filed Date | 2003-01-30 |
United States Patent
Application |
20030019050 |
Kind Code |
A9 |
Terranova, Eric ; et
al. |
January 30, 2003 |
Novel cationic 4-hydroxyindoles, their use for the oxidation dyeing
of keratinous fibers, dyeing compositions, and methods of
dyeing
Abstract
The invention relates to novel 4-hydroxyindole derivatives
comprising at least one cationic group Z, Z being selected from
quaternized aliphatic chains, aliphatic chains containing at least
one quaternized saturated ring, and aliphatic chains containing at
least one quaternized unsaturated ring, to their use as a coupler
for the oxidation dyeing of keratinous fibers, to the dyeing
compositions comprising them, and to the methods of oxidation
dyeing which employ them.
Inventors: |
Terranova, Eric; (Bois
Colombes, FR) ; Fadli, Aziz; (Chelles, FR) ;
LaGrange, Alain; (Coupvray, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT &
DUNNER LLP
1300 I STREET, NW
WASHINGTON
DC
20006
US
|
Assignee: |
L'OREAL
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 0032937 A1 |
March 21, 2002 |
|
|
Family ID: |
9530653 |
Appl. No.: |
09/925010 |
Filed: |
August 9, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09925010 |
Aug 9, 2001 |
|
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09400818 |
Sep 21, 1999 |
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6306181 |
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Current U.S.
Class: |
8/405 ; 8/406;
8/408; 8/421 |
Current CPC
Class: |
C07D 209/14 20130101;
C07D 233/56 20130101; C07D 401/14 20130101; C07D 401/06 20130101;
C07D 231/12 20130101; C07D 249/08 20130101; A61K 8/492 20130101;
A61Q 5/10 20130101; C07D 209/42 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/408; 8/421 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 21, 1998 |
FR |
98 11751 |
Claims
What is claimed is:
1. A composition for dyeing keratinous fibers, comprising at least
one coupler chosen from compounds of formula (I) below and addition
salts thereof with an acid: 5in which: R.sub.1 is chosen from a
hydrogen atom; a group Z; a C.sub.1-C.sub.4 alkyl radical; a
C.sub.1-C.sub.4 monohydroxyalkyl radical; a C.sub.2-C.sub.4
polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a hydroxy(C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 aminoalkyl
radical; a C.sub.1-C.sub.4 aminoalkyl radical whose amine is mono-
or disubstituted by a C.sub.1-C.sub.4 alkyl radical, by an acetyl
radical, by a C.sub.1-C.sub.4 monohydroxyalkyl radical or by a
C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkyl)-C.sub.1-C.sub.4 thioalkyl radical, a
monohydroxy(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 thioalkyl
radical; a polyhydroxy(C.sub.2-C.sub.4 alkyl)-C.sub.1-C.sub.4
thioalkyl radical; a C.sub.1-C.sub.4 carboxyalkyl radical; a
(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 carbonylalkyl radical; a
C.sub.1-C.sub.4 acetylaminoalkyl radical; a C.sub.1-C.sub.4
cyanoalkyl radical; a C.sub.1-C.sub.4 trifluoroalkyl radical; a
C.sub.1-C.sub.4 haloalkyl radical; a C.sub.1-C.sub.4 phosphoalkyl
radical, and a C.sub.1-C.sub.4 sulphoalkyl radical; R.sub.2 and
R.sub.3, which may be identical or different, are chosen from a
hydrogen or halogen atom; a group Z; a group --NH--Z; a
C.sub.1-C.sub.4 alkyl radical; a carboxyl radical; a
(C.sub.1-C.sub.4 alkoxy)carbonyl radical or a formyl radical;
R.sub.4 and R.sub.5, which may be identical or different, are
chosen from a hydrogen or halogen atom; a group Z; a group --NH--Z;
a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 alkoxy radical;
an acetylamino radical; a C.sub.1-C.sub.5 monohydroxyalkyl radical;
a C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a thiophene radical; a furan
radical; a phenyl radical; an aralkyl radical in which the alkyl
moiety is C.sub.1-C.sub.4; a phenyl radical or aralkyl radical in
which the alkyl moiety is C.sub.1-C.sub.4, each substituted by a
halogen atom, by a C.sub.1-C.sub.4 alkyl radical, by a
trifluoromethyl radical, by a C.sub.1-C.sub.4 alkoxy radical, by an
amino radical or by an amino radical which is mono- or
disubstituted by a C.sub.1-C.sub.4 alkyl radical; a
(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical and a
di(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical; Z is
chosen from the unsaturated cationic groups of formulae (II) and
(III) below and the saturated cationic groups of formula (IV)
below: 6in which: D is a linker which is an alkyl chain which is
linear or branched and can be interrupted by at least one
heteroatom and can be substituted by at least one hydroxyl or
C.sub.1-C.sub.6 alkoxy radical and carry at least one ketone
functional group; the ring members E, G, J, L and M, which may be
identical or different, are chosen from carbon, oxygen, sulphur and
nitrogen atoms; n is an integer ranging from between 0 and 4
inclusive; m is an integer ranging from between 0 and 5 inclusive;
the radicals R, which may be identical or different, are chosen
from a group Z, a halogen atom, a hydroxyl radical, a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro
radical, a cyano radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
C.sub.1-C.sub.6 alkoxy radical, a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, an amido radical, an
aldehydo radical, a carboxyl radical, a C.sub.1-C.sub.6
alkylcarbonyl radical, a thio radical, a C.sub.1-C.sub.6 thioalkyl
radical, a (C.sub.1-C.sub.6 alkyl)thio radical, an amino radical,
an amino radical protected by a (C.sub.1-C.sub.6 alkyl)carbonyl,
carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a group NHR"
or NR"R'" in which R" and R'", which may be identical or different,
are chosen from a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6
monohydroxyalkyl radical and a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; R.sub.6 is chosen from a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 carbamylalkyl radical, a (C.sub.1-C.sub.6
alkyl)-C.sub.1-C.sub.6 carboxyalkyl radical, a benzyl radical and a
group Z of formula (II), (III) or (IV); R.sub.7, R.sub.8 and
R.sub.9, which may be identical or different, are chosen from a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, an aryl radical, a benzyl
radical, a C.sub.1-C.sub.6 amidoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical or a
C.sub.1-C.sub.6 aminoalkyl radical whose amine is protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; where two of the radicals R.sub.7, R.sub.8
and R.sub.9 may also form, together with the nitrogen atom to which
they are attached, a 5- or 6-membered saturated ring containing
carbon or containing at least one additional heteroatom, it being
possible for the said ring to be unsubstituted or substituted by a
halogen atom, a hydroxyl radical, a C.sub.1-C.sub.6 alkyl radical,
a C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a nitro radical, a cyano radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, a C.sub.1-C.sub.6 alkoxy
radical, a tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl
radical, an amido radical, an aldehydo radical, a carboxyl radical,
a C.sub.1-C.sub.6 ketoalkyl radical, a thio radical, a
C.sub.1-C.sub.6 thioalkyl radical, a (C.sub.1-C.sub.6 alkyl)thio
radical, an amino radical, or an amino radical protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; one of the radicals R.sub.7, R.sub.8 and
R.sub.9 may also be chosen from a second group Z which may be
identical to or different from the first said group Z; R.sub.10 is
chosen from a C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
monohydroxyalkyl radical; a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; an aryl radical; a benzyl radical; a C.sub.1-C.sub.6
aminoalkyl radical or a C.sub.1-C.sub.6 aminoalkyl radical whose
amine is protected by a (C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl
or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a C.sub.1-C.sub.6
carboxyalkyl radical; a C.sub.1-C.sub.6 cyanoalkyl radical; a
C.sub.1-C.sub.6 carbamylalkyl radical; a C.sub.1-C.sub.6
trifluoroalkyl radical; a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
sulphonamidoalkyl radical; a
(C.sub.1-C.sub.6-alkyl)carboxy-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphinyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphonyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)keto-C.sub.1-C.sub.6 alkyl radical; an
N--(C.sub.1-C.sub.6 alkyl)carbamyl-C.sub.1-C.sub.6 alkyl radical;
or an N--(C.sub.1-C.sub.6 alkyl)sulphonamido-C.sub.1-C.sub.6 alkyl
radical; x and y are integers equal to 0 or 1; with the following
conditions: in the unsaturated cationic groups of formula (II):
when x is 0, the linker D is attached to the nitrogen atom, when x
is 1, the linker D is attached to one of the ring members E, G, J
or L, y can adopt the value 1 only: 1) when the ring members E, G,
J and L are simultaneously a carbon atom and when the radical
R.sub.6 is carried by the nitrogen atom of the unsaturated ring; or
2) when at least one of the ring members E, G, J and L is a
nitrogen atom to which the radical R.sub.6 is attached; in the
unsaturated cationic groups of formula (III): when x is 0, the
linker D is attached to the nitrogen atom, when x is 1, the linker
D is attached to one of the ring members E, G, J, L or M, y can
adopt the value 1 only when at least one of the ring members E, G,
J, L and M represents a divalent atom and when the radical R.sub.6
is carried by the nitrogen atom of the unsaturated ring; in the
cationic groups of formula (IV): when x is 0, the linker is
attached to the nitrogen atom which carries the radicals R.sub.7 to
R.sub.9, when x is 1, two of the radicals R.sub.7 to R.sub.9 form,
conjointly with the nitrogen atom to which they are attached, a 5-
or 6-membered saturated ring as defined above, and the linker D is
carried by a carbon atom of the said saturated ring; X.sup.- is
chosen from a monovalent or divalent anion; with the proviso that:
the number of cationic groups Z of formula (II), (III) or (IV) is
at least 1.
2. The composition according to claim 1, wherein said keratinous
fibers are human keratinous fibers.
3. The composition according to claim 2, wherein said human
keratinous fibers are hair.
4. The composition according to claim 1, wherein said linker D of
said group Z is an alkyl chain that comprises 1 to 14 carbon
atoms.
5. The composition according to claim 1, wherein said alkyl and
alkoxy radicals of said formula (I) are linear or branched.
6. The composition according to claim 1, wherein said at least one
heteroatom of said unsaturated cationic groups of formulae (II),
(III) and (IV) is chosen from oxygen, sulphur and nitrogen
atoms.
7. The composition according to claim 1, wherein said 5- or
6-membered saturated ring containing carbon or containing at least
one additional heteroatom formed by two of said radicals R.sub.7,
R.sub.8, and R.sub.9 and nitrogen is chosen from a pyrrolidine
ring, a piperidine ring, a piperazine ring and a morpholine
ring.
8. The composition according to claim 1, wherein said unsaturated
groups Z of formula (II) are chosen from pyrrole, imidazole,
pyrazole, oxazole, thiazole and triazole rings.
9. The composition according to claim 1, wherein said rings of said
unsaturated groups Z of formula (III) are chosen from pyridine,
pyrimidine, pyrazine, oxazine and triazine rings.
10. The composition according to claim 1, wherein said X.sup.- is
chosen from a halogen atom, a hydroxide, a hydrogen sulphate and a
C.sub.1-C.sub.6 alkyl sulphate.
11. The composition according to claim 1, wherein said at least one
coupler is chosen from:
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-meth- ylpyridinium
methosulphate; 4-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-m-
ethylpyridinium methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)-4-yl-
methylindol-1-yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
4-(4-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-ylmethyl)-1-methylpyridinium
methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)-5-ylmethyl-indol-1--
yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
3-[4-hydroxy-5-(1-methy-
lpyridinium)-3-ylmethyl-indol-1-ylmethyl]-1-methylpyridinium
dimethosulphate;
3-[3-(5-benzyl-4-hydroxyindol-1-yl)propyl]-1-methyl-3H-i-
midazol-1-ium methosulphate;
[2-(4-hydroxy-1H-indol-3-yl)ethyl]trimethyl-a- mmonium
methosulphate; [2-(4-hydroxy-1-methyl-1H-indol-3-yl)ethyl]-trimeth-
ylammonium methosulphate;
(4-hydroxy-1-methyl-1H-indol-3-ylmethyl)-trimeth- ylammonium
methosulphate; (4-hydroxy-1H-indol-3-ylmethyl)trimethylammonium
methosulphate;
{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]propyl}-trimethy-
lammonium methosulphate;
{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-ami-
no]propyl}trimethylammonium methosulphate;
{3-[(4-hydroxy-5-methyl-1H-indo-
le-2-carbonyl)-amino]propyl}trimethylammonium methosulphate;
{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}trimethylam-
monium methosulphate;
3-{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]-propyl}-
-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1-methyl-1H-in-
dole-2-carbonyl)-amino]propyl}-1-methyl-3H-imidazol-1-ium
methosulphate;
3-{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-methyl-3H-
-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-c-
arbonyl)amino]propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
{3-[(4-hydroxy-1H-indole-6-carbonyl)amino]propyl}-trimethylammonium
monochloride;
{3-[(4-hydroxy-1-methyl-1H-indole-6-carbonyl)-amino]propyl}-
trimethylammonium monochloride; and addition salts thereof with an
acid.
12. The composition according to claim 1, wherein said addition
salts with an acid are chosen from hydrochlorides, hydrobromides,
sulphates, citrates, succinates, tartrates, lactates and
acetates.
13. The composition according to claim 1, wherein said at least one
coupler is present in an amount ranging from 0.0005 to 12% by
weight of the total weight of said dyeing composition.
14. The composition according to claim 1, wherein said at least one
coupler is present in an amount ranging from 0.005 to 6% by weight
of the total weight of said dyeing composition.
15. The composition according to claim 1, wherein said composition
further comprises at least one oxidation base chosen from
para-phenylenediamines, bisphenylalkylenediamines,
para-aminophenols, ortho-aminophenols and heterocyclic bases.
16. The composition according to claim 15, wherein said
para-phenylenediamines are chosen from para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N-ethyl-N-(.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine and the addition
salts thereof with an acid.
17. The composition according to claim 15, wherein said
para-phenylenediamines are chosen from para-phenylenediamine,
para-tolylenediamine, 2-isopropyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-par- a-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)-paraphenylenediamine,
2-chloro-para-phenylenediamine,
2-.beta.-acetylaminoethyloxy-para-phenyle- nediamine, and the
addition salts thereof with an acid.
18. The composition according to claim 15, wherein said
bisphenylalkylenediamines are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N-
,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-
-N,N'-bis(4'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetrameth- ylenediamine,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)-tetram-
ethylenediamine,
N,N'-bis(4-methylaminophenyl)-tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts
thereof with an acid.
19. The composition according to claim 15, wherein said
para-aminophenols are chosen from 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.-hydroxyethylamino-methyl)phenol,
4-amino-2-fluorophenol, and the addition salts thereof with an
acid.
20. The composition according to claim 15, wherein said
ortho-aminophenols are chosen from 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetamido-2-aminophenol, and the addition salts thereof with an
acid.
21. The composition according to claim 15, wherein said
heterocyclic bases are chosen from pyridine derivatives, pyrimidine
derivatives and pyrazole derivatives.
22. The composition according to claim 21, wherein said pyridine
derivatives are chosen from 2,5-diaminopyridine,
2-(4-methoxyphenyl)amino- -3-aminopyridine,
2,3-diamino-6-methoxypyridine, 2-(.beta.-methoxyethyl)am-
ino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and the
addition salts thereof with an acid.
23. The composition according to claim 21, wherein said pyrimidine
derivatives are chosen from 2,4,5,6-tetraaminopyrimidine,
4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and
pyrazolo-pyrimidine derivatives.
24. The composition according to claim 23, wherein said
pyrazolo-pyrimidine derivatives are chosen from
pyrazolo[1,5-a]pyrimidine- -3,7-diamine;
2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
pyrazolo[1,5-a]pyrimidine-3-5-diamine;
2,7-dimethylpyrazolo[1,5-a]pyrimid- ine-3,5-diamine;
3-aminopyrazolo[1,5-a]pyrimidin-7-ol;
3-aminopyrazolo[1,5-a]pyrimidin-5-ol;
2-(7-aminopyrazolo[1,5-a]pyrimidin-- 3-ylamino)ethanol,
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyeth-
yl)amino]ethanol,
2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethy-
l)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, the
addition salts thereof with an acid, and the tautomeric forms
thereof when a tautomeric equilibrium exists, and the addition
salts thereof with an acid.
25. The composition according to claim 21, wherein said pyrazole
derivatives are chosen from 4,5-diamino-1-methylpyrazole,
3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopy- razole,
1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1--
methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyph- enyl)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,
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylaminopyrazole,
3,5-diamino-4-(.beta.-hydroxy- ethyl)amino-1-methylpyrazole, and
the addition salts thereof with an acid.
26. The composition according to claim 15, wherein said at least
one oxidation base is present in an amount ranging from 0.0005 to
12% by weight of the total weight of said dyeing composition.
27. The composition according to claim 15, wherein said at least
one oxidation base is present in an amount ranging from 0.005 to 6%
by weight of the total weight of said dyeing composition.
28. The composition according to claim 1, wherein said composition
further comprises at least one additional coupler.
29. The composition according to claim 28, wherein said at least
one additional coupler is chosen from meta-phenylenediamines,
meta-aminophenols, meta-diphenols and heterocyclic couplers.
30. The composition according to claim 28, wherein said at least
one additional coupler is chosen from 2-methyl-5-aminophenol,
5-N-(.beta.-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)benz- ene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, and the addition salts thereof with
an acid.
31. The composition according to claim 29, wherein said
heterocyclic couplers are chosen from indole derivatives, indoline
derivatives, pyridine derivatives and pyrazolines, and the addition
salts thereof with an acid.
32. The composition according to claim 28, wherein said at least
one additional coupler is present in an amount ranging from 0.0001
to 10% by weight, approximately, of the total weight of said dyeing
composition.
33. The composition according to claim 28, wherein said at least
one additional coupler is present in an amount ranging from 0.005
to 5% by weight, approximately, of the total weight of said dyeing
composition.
34. The composition according to claim 28, wherein said addition
salts with an acid are chosen from hydrochlorides, hydrobromides,
sulphates, citrates, succinates, tartrates, lactates and
acetates.
35. The composition according to claim 1, wherein said composition
further comprises a medium, wherein said medium comprises water or
a mixture of water and at least one organic solvent.
36. The composition according to claim 35, wherein said at least
one organic solvent is chosen from C.sub.1-C.sub.4 lower alkanols;
glycerol; glycols and glycol ethers; aromatic alcohols, and
mixtures thereof.
37. The composition according to claim 36, wherein said
C.sub.1-C.sub.4 lower alkanols are chosen from ethanol and
isopropanol.
38. The composition according to claim 36, wherein said glycols and
glycol ethers are chosen from 2-butoxyethanol, propylene glycol,
propylene glycol monomethyl ether, diethylene glycol monoethyl
ether and monomethyl ether.
39. The composition according to claim 36, wherein said aromatic
alcohols are chosen from benzyl alcohol and phenoxyethanol.
40. The composition according to claim 36, wherein said at least
one organic solvent is present in an amount ranging from 1 to 40%
by weight relative to the total weight of said dyeing
composition.
41. The composition according to claim 36, wherein said at least
one organic solvent is present in an amount ranging from 5 to 30%
by weight relative to the total weight of said dyeing
composition.
42. The composition according to claim 1, wherein said composition
has a pH ranging from 3 to 12.
43. The composition according to claim 1, wherein said composition
has a pH ranging from 5 to 11.
44. The composition according to claim 15, wherein said composition
further comprises at least one direct dye.
45. The composition according to claim 15, wherein said composition
is present in an amount sufficient for oxidation dyeing.
46. The composition according to claim 15, wherein said composition
further comprises at least one oxidizing agent.
47. The composition according to claim 46, wherein said at least
one oxidizing agent is chosen from hydrogen peroxide, urea
peroxide, alkali metal bromates, persalts, and enzymes.
48. The composition according to claim 47, wherein said persalts
are chosen from perborates and persulphates.
49. The composition according to claim 47, wherein said enzymes are
chosen from peroxidases, laccases and oxidoreductases having 2
electrons.
50. The composition according to claim 46, wherein said at least
one oxidizing agent is a hydrogen peroxide.
51. The composition according to claim 1, wherein said composition
is in a form chosen from a liquid, a cream and a gel.
52. A process for dyeing keratin fibers, comprising applying a
dyeing composition for the oxidation dyeing of fibers to said
fibers and developing for a period of time sufficient to achieve
the desired coloration, wherein said dyeing composition comprises:
at least one coupler chosen from compounds of formula (I) below and
the addition salts thereof with an acid: 7in which: R.sub.1 is
chosen from a hydrogen atom; a group Z; a C.sub.1-C.sub.4 alkyl
radical; a C.sub.1-C.sub.4 monohydroxyalkyl radical; a
C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a hydroxy(C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 aminoalkyl
radical; a C.sub.1-C.sub.4 aminoalkyl radical whose amine is mono-
or disubstituted by a C.sub.1-C.sub.4 alkyl radical, by an acetyl
radical, by a C.sub.1-C.sub.4 monohydroxyalkyl radical or by a
C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkyl)-C.sub.1-C.sub.4 thioalkyl radical, a
monohydroxy(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 thioalkyl
radical; a polyhydroxy(C.sub.2-C.sub.4 alkyl)-C.sub.1-C.sub.4
thioalkyl radical; a C.sub.1-C.sub.4 carboxyalkyl radical; a
(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 carbonylalkyl radical; a
C.sub.1-C.sub.4 acetylaminoalkyl radical; a C.sub.1-C.sub.4
cyanoalkyl radical; a C.sub.1-C.sub.4 trifluoroalkyl radical; a
C.sub.1-C.sub.4 haloalkyl radical; a C.sub.1-C.sub.4 phosphoalkyl
radical, and a C.sub.1-C.sub.4 sulphoalkyl radical; R.sub.2 and
R.sub.3, which may be identical or different, are chosen from a
hydrogen or halogen atom; a group Z; a group --NH--Z; a
C.sub.1-C.sub.4 alkyl radical; a carboxyl radical; a
(C.sub.1-C.sub.4 alkoxy)carbonyl radical or a formyl radical;
R.sub.4 and R.sub.5, which may be identical or different, are
chosen from a hydrogen or halogen atom; a group Z; a group --NH--Z;
a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 alkoxy radical;
an acetylamino radical; a C.sub.1-C.sub.5 monohydroxyalkyl radical;
a C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a thiophene radical; a furan
radical; a phenyl radical; an aralkyl radical in which the alkyl
moiety is C.sub.1-C.sub.4; a phenyl radical or aralkyl radical in
which the alkyl moiety is C.sub.1-C.sub.4, each substituted by a
halogen atom, by a C.sub.1-C.sub.4 alkyl radical, by a
trifluoromethyl radical, by a C.sub.1-C.sub.4 alkoxy radical, by an
amino radical or by an amino radical which is mono- or
disubstituted by a C.sub.1-C.sub.4 alkyl radical; a
(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical and a
di(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical; Z is
chosen from the unsaturated cationic groups of formulae (II) and
(III) below and the saturated cationic groups of formula (IV)
below: 8in which: D is a linker which is an alkyl chain which is
linear or branched and can be interrupted by at least one
heteroatom and can be substituted by at least one hydroxyl or
C.sub.1-C.sub.6 alkoxy radical and carry at least one ketone
functional group; the ring members E, G, J, L and M, which may be
identical or different, are chosen from a carbon, oxygen, sulphur
or nitrogen atom; n is an integer ranging from between 0 and 4
inclusive; m is an integer ranging from between 0 and 5 inclusive;
the radicals R, which may be identical or different, are chosen
from a group Z, a halogen atom, a hydroxyl radical, a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro
radical, a cyano radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
C.sub.1-C.sub.6 alkoxy radical, a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, an amido radical, an
aldehydo radical, a carboxyl radical, a C.sub.1-C.sub.6
alkylcarbonyl radical, a thio radical, a C.sub.1-C.sub.6 thioalkyl
radical, a (C.sub.1-C.sub.6 alkyl)thio radical, an amino radical,
an amino radical protected by a (C.sub.1-C.sub.6 alkyl)carbonyl,
carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a group NHR"
or NR"R'" in which R" and R'", which may be identical or different,
are chosen from a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6
monohydroxyalkyl radical and a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; R.sub.6 is chosen from a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 carbamylalkyl radical, a (C.sub.1-C.sub.6
alkyl)-C.sub.1-C.sub.6 carboxyalkyl radical, a benzyl radical and a
group Z of formula (II), (III) or (IV); R.sub.7, R.sub.8 and
R.sub.9 which may be identical or different, are chosen from a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, an aryl radical, a benzyl
radical, a C.sub.1-C.sub.6 amidoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical or a
C.sub.1-C.sub.6 aminoalkyl radical whose amine is protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; where two of the radicals R.sub.7, R.sub.8
and R.sub.9 may also form, together with the nitrogen atom to which
they are attached, a 5- or 6-membered saturated ring containing
carbon or containing at least one additional heteroatom, it being
possible for the said ring to be unsubstituted or substituted by a
halogen atom, a hydroxyl radical, a C.sub.1-C.sub.6 alkyl radical,
a C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a nitro radical, a cyano radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, a C.sub.1-C.sub.6 alkoxy
radical, a tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl
radical, an amido radical, an aldehydo radical, a carboxyl radical,
a C.sub.1-C.sub.6 ketoalkyl radical, a thio radical, a
C.sub.1-C.sub.6 thioalkyl radical, a (C.sub.1-C.sub.6 alkyl)thio
radical, an amino radical, or an amino radical protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; one of the radicals R.sub.7, R.sub.8 and
R.sub.9 may also be chosen from a second group Z which may be
identical to or different from the first said group Z; R.sub.10 is
chosen from a C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
monohydroxyalkyl radical; a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; an aryl radical; a benzyl radical; a C.sub.1-C.sub.6
aminoalkyl radical or a C.sub.1-C.sub.6 aminoalkyl radical whose
amine is protected by a (C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl
or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a C.sub.1-C.sub.6
carboxyalkyl radical; a C.sub.1-C.sub.6 cyanoalkyl radical; a
C.sub.1-C.sub.6 carbamylalkyl radical; a C.sub.1-C.sub.6
trifluoroalkyl radical; a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
sulphonamidoalkyl radical; a
(C.sub.1-C.sub.6-alkyl)carboxy-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphinyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphonyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)keto-C.sub.1-C.sub.6 alkyl radical; an
N--(C.sub.1-C.sub.6 alkyl)carbamyl-C.sub.1-C.sub.6 alkyl radical;
or an N--(C.sub.1-C.sub.6 alkyl)sulphonamido-C.sub.1-C.sub.6 alkyl
radical; x and y are integers equal to 0 or 1; with the following
conditions: in the unsaturated cationic groups of formula (II):
when x is 0, the linker D is attached to the nitrogen atom, when x
is 1, the linker D is attached to one of the ring members E, G, J
or L, y can adopt the value 1 only: 1) when the ring members E, G,
J and L are simultaneously a carbon atom and when the radical
R.sub.6 is carried by the nitrogen atom of the unsaturated ring; or
2) when at least one of the ring members E, G, J and L is a
nitrogen atom to which the radical R.sub.6 is attached; in the
unsaturated cationic groups of formula (III): when x is 0, the
linker D is attached to the nitrogen atom, when x is 1, the linker
D is attached to one of the ring members E, G, J, L or M, y can
adopt the value 1 only when at least one of the ring members E, G,
J, L and M represents a divalent atom and when the radical R.sub.6
is carried by the nitrogen atom of the unsaturated ring; in the
cationic groups of formula (IV): when x is 0, the linker is
attached to the nitrogen atom which carries the radicals R.sub.7 to
R.sub.9, when x is 1, two of the radicals R.sub.7 to R.sub.9 form,
conjointly with the nitrogen atom to which they are attached, a 5-
or 6-membered saturated ring as defined above, and the linker D is
carried by a carbon atom of the said saturated ring; X.sup.- is
chosen from a monovalent or divalent anion; with the proviso that:
the number of cationic groups Z of formula (II), (III) or (IV) is
at least 1.
53. The process for dyeing keratin fibers according to claim 52,
comprising applying said dyeing composition to said fibers, wherein
an oxidizing agent is added to said dyeing composition at the time
of application.
54. The process for dyeing keratin fibers according to claim 52,
comprising applying said dyeing composition to said fibers, wherein
an oxidizing agent is present in an oxidizing composition and said
oxidizing composition is applied simultaneously or sequentially
with said dyeing composition.
55. The process for dyeing keratin fibers according to claim 52,
further comprising rinsing said fibers, washing said fibers with
shampoo, a second rinsing of said fibers and drying of said
fibers.
56. A multi-compartment dyeing kit, comprising at least two
separate compartments, wherein a first compartment contains a first
compartment and a second compartment contains a second composition,
wherein said first composition comprises at least one coupler
chosen from compounds of formula (I) below and the addition salts
thereof with an acid: 9in which: R.sub.1 is chosen from a hydrogen
atom; a group Z; a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4
monohydroxyalkyl radical; a C.sub.2-C.sub.4 polyhydroxyalkyl
radical; a (C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical;
a hydroxy(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical; a
C.sub.1-C.sub.4 aminoalkyl radical; a C.sub.1-C.sub.4 aminoalkyl
radical whose amine is mono- or disubstituted by a C.sub.1-C.sub.4
alkyl radical, by an acetyl radical, by a C.sub.1-C.sub.4
monohydroxyalkyl radical or by a C.sub.2-C.sub.4 polyhydroxyalkyl
radical; a (C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 thioalkyl
radical, a monohydroxy(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4
thioalkyl radical; a polyhydroxy(C.sub.2-C.sub.4
alkyl)-C.sub.1-C.sub.4 thioalkyl radical; a C.sub.1-C.sub.4
carboxyalkyl radical; a (C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4
carbonylalkyl radical; a C.sub.1-C.sub.4 acetylaminoalkyl radical;
a C.sub.1-C.sub.4 cyanoalkyl radical; a C.sub.1-C.sub.4
trifluoroalkyl radical; a C.sub.1-C.sub.4 haloalkyl radical; a
C.sub.1-C.sub.4 phosphoalkyl radical, and a C.sub.1-C.sub.4
sulphoalkyl radical; R.sub.2 and R.sub.3, which may be identical or
different, are chosen from a hydrogen or halogen atom; a group Z; a
group --NH--Z; a C.sub.1-C.sub.4 alkyl radical; a carboxyl radical;
a (C.sub.1-C.sub.4 alkoxy)carbonyl radical or a formyl radical;
R.sub.4 and R.sub.5, which may be identical or different, are
chosen from a hydrogen or halogen atom; a group Z; a group --NH--Z;
a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 alkoxy radical;
an acetylamino radical; a C.sub.1-C.sub.5 monohydroxyalkyl radical;
a C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a thiophene radical; a furan
radical; a phenyl radical; an aralkyl radical in which the alkyl
moiety is C.sub.1-C.sub.4; a phenyl radical or aralkyl radical in
which the alkyl moiety is C.sub.1-C.sub.4, each substituted by a
halogen atom, by a C.sub.1-C.sub.4 alkyl radical, by a
trifluoromethyl radical, by a C.sub.1-C.sub.4 alkoxy radical, by an
amino radical or by an amino radical which is mono- or
disubstituted by a C.sub.1-C.sub.4 alkyl radical; a
(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical and a
di(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical; Z is
chosen from the unsaturated cationic groups of formulae (II) and
(III) below and the saturated cationic groups of formula (IV)
below: 10in which: D is a linker which is an alkyl chain which is
linear or branched and can be interrupted by at least one
heteroatom and can be substituted by at least one hydroxyl or
C.sub.1-C.sub.6 alkoxy radical and carry at least one ketone
functional group; the ring members E, G, J, L and M, which may be
identical or different, are chosen from a carbon, oxygen, sulphur
or nitrogen atom; n is an integer ranging from between 0 and 4
inclusive; m is an integer ranging from between 0 and 5 inclusive;
the radicals R, which may be identical or different, are chosen
from a group Z, a halogen atom, a hydroxyl radical, a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro
radical, a cyano radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
C.sub.1-C.sub.6 alkoxy radical, a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, an amido radical, an
aldehydo radical, a carboxyl radical, a C.sub.1-C.sub.6
alkylcarbonyl radical, a thio radical, a C.sub.1-C.sub.6 thioalkyl
radical, a (C.sub.1-C.sub.6 alkyl)thio radical, an amino radical,
an amino radical protected by a (C.sub.1-C.sub.6 alkyl)carbonyl,
carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a group NHR"
or NR"R'" in which R" and R'", which may be identical or different,
are chosen from a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6
monohydroxyalkyl radical and a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; R.sub.6 is chosen from a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 carbamylalkyl radical, a (C.sub.1-C.sub.6
alkyl)-C.sub.1-C.sub.6 carboxyalkyl radical, a benzyl radical and a
group Z of formula (II), (III) or (IV); R.sub.7, R.sub.8 and
R.sub.9, which may be identical or different, are chosen from a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, an aryl radical, a benzyl
radical, a C.sub.1-C.sub.6 amidoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical or a
C.sub.1-C.sub.6 aminoalkyl radical whose amine is protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; where two of the radicals R.sub.7, R.sub.8
and R.sub.9 may also form, together with the nitrogen atom to which
they are attached, a 5- or 6-membered saturated ring containing
carbon or containing at least one additional heteroatom, it being
possible for the said ring to be unsubstituted or substituted by a
halogen atom, a hydroxyl radical, a C.sub.1-C.sub.6 alkyl radical,
a C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a nitro radical, a cyano radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, a C.sub.1-C.sub.6 alkoxy
radical, a tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl
radical, an amido radical, an aldehydo radical, a carboxyl radical,
a C.sub.1-C.sub.6 ketoalkyl radical, a thio radical, a
C.sub.1-C.sub.6 thioalkyl radical, a (C.sub.1-C.sub.6 alkyl)thio
radical, an amino radical, or an amino radical protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; one of the radicals R.sub.7, R.sub.8 and
R.sub.9 may also be chosen from a second group Z which may be
identical to or different from the first said group Z; R.sub.10 is
chosen from a C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
monohydroxyalkyl radical; a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; an aryl radical; a benzyl radical; a C.sub.1-C.sub.6
aminoalkyl radical or a C.sub.1-C.sub.6 aminoalkyl radical whose
amine is protected by a (C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl
or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a C.sub.1-C.sub.6
carboxyalkyl radical; a C.sub.1-C.sub.6 cyanoalkyl radical; a
C.sub.1-C.sub.6 carbamylalkyl radical; a C.sub.1-C.sub.6
trifluoroalkyl radical; a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
sulphonamidoalkyl radical; a
(C.sub.1-C.sub.6-alkyl)carboxy-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphinyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphonyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)keto-C.sub.1-C.sub.6 alkyl radical; an
N--(C.sub.1-C.sub.6 alkyl)carbamyl-C.sub.1-C.sub.6 alkyl radical;
or an N--(C.sub.1-C.sub.6 alkyl)sulphonamido-C.sub.1-C.sub.6 alkyl
radical; x and y are integers equal to 0 or 1; with the following
conditions: in the unsaturated cationic groups of formula (II):
when x is 0, the linker D is attached to the nitrogen atom, when x
is 1, the linker D is attached to one of the ring members E, G, J
or L, y can adopt the value 1 only: 1) when the ring members E, G,
J and L are simultaneously a carbon atom and when the radical
R.sub.6 is carried by the nitrogen atom of the unsaturated ring; or
2) when at least one of the ring members E, G, J and L is a
nitrogen atom to which the radical R.sub.6 is attached; in the
unsaturated cationic groups of formula (III): when x is 0, the
linker D is attached to the nitrogen atom, when x is 1, the linker
D is attached to one of the ring members E, G, J, L or M, y can
adopt the value 1 only when at least one of the ring members E, G,
J, L and M represents a divalent atom and when the radical R.sub.6
is carried by the nitrogen atom of the unsaturated ring; in the
cationic groups of formula (IV): when x is 0, the linker is
attached to the nitrogen atom which carries the radicals R.sub.7 to
R.sub.9, when x is 1, two of the radicals R.sub.7 to R.sub.9 form,
conjointly with the nitrogen atom to which they are attached, a 5-
or 6-membered saturated ring as defined above, and the linker D is
carried by a carbon atom of the said saturated ring; X.sup.- is
chosen from a monovalent or divalent anion; with the proviso that:
the number of cationic groups Z of formula (II), (III) or (IV) is
at least 1, and wherein said second composition comprises at least
one oxidizing agent.
57. A compound of formula (I) below or an addition salt thereof
with an acid: 11in which: R.sub.1 is chosen from a hydrogen atom; a
group Z; a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4
monohydroxyalkyl radical; a C.sub.2-C.sub.4 polyhydroxyalkyl
radical; a (C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical;
a hydroxy(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical; a
C.sub.1-C.sub.4 aminoalkyl radical; a C.sub.1-C.sub.4 aminoalkyl
radical whose amine is mono- or disubstituted by a C.sub.1-C.sub.4
alkyl radical, by an acetyl radical, by a C.sub.1-C.sub.4
monohydroxyalkyl radical or by a C.sub.2-C.sub.4 polyhydroxyalkyl
radical; a (C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 thioalkyl
radical, a monohydroxy(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4
thioalkyl radical; a polyhydroxy(C.sub.2-C.sub.4
alkyl)-C.sub.1-C.sub.4 thioalkyl radical; a C.sub.1-C.sub.4
carboxyalkyl radical; a (C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4
carbonylalkyl radical; a C.sub.1-C.sub.4 acetylaminoalkyl radical;
a C.sub.1-C.sub.4 cyanoalkyl radical; a C.sub.1-C.sub.4
trifluoroalkyl radical; a C.sub.1-C.sub.4 haloalkyl radical; a
C.sub.1-C.sub.4 phosphoalkyl radical, and a C.sub.1-C.sub.4
sulphoalkyl radical; R.sub.2 and R.sub.3, which may be identical or
different, are chosen from a hydrogen or halogen atom; a group Z; a
group --NH--Z; a C.sub.1-C.sub.4 alkyl radical; a carboxyl radical;
a (C.sub.1-C.sub.4 alkoxy)carbonyl radical or a formyl radical;
R.sub.4 and R.sub.5, which may be identical or different, are
chosen from a hydrogen or halogen atom; a group Z; a group --NH--Z;
a C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 alkoxy radical;
an acetylamino radical; a C.sub.1-C.sub.5 monohydroxyalkyl radical;
a C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a thiophene radical; a furan
radical; a phenyl radical; an aralkyl radical in which the alkyl
moiety is C.sub.1-C.sub.4; a phenyl radical or aralkyl radical in
which the alkyl moiety is C.sub.1-C.sub.4, each substituted by a
halogen atom, by a C.sub.1-C.sub.4 alkyl radical, by a
trifluoromethyl radical, by a C.sub.1-C.sub.4 alkoxy radical, by an
amino radical or by an amino radical which is mono- or
disubstituted by a C.sub.1-C.sub.4 alkyl radical; a
(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical and a
di(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical; Z is
chosen from the unsaturated cationic groups of formulae (II) and
(III) below and the saturated cationic groups of formula (IV)
below: 12in which: D is a linker which is an alkyl chain which is
linear or branched and can be interrupted by at least one
heteroatom and can be substituted by at least one hydroxyl or
C.sub.1-C.sub.6 alkoxy radical and carry at least one ketone
functional group; the ring members E, G, J, L and M, which may be
identical or different, are chosen from carbon, oxygen, sulphur and
nitrogen atoms; n is an integer ranging from between 0 and 4
inclusive; m is an integer ranging from between 0 and 5 inclusive;
the radicals R, which may be identical or different, are chosen
from a group Z, a halogen atom, a hydroxyl radical, a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro
radical, a cyano radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
C.sub.1-C.sub.6 alkoxy radical, a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, an amido radical, an
aldehydo radical, a carboxyl radical, a C.sub.1-C.sub.6
alkylcarbonyl radical, a thio radical, a C.sub.1-C.sub.6 thioalkyl
radical, a (C.sub.1-C.sub.6 alkyl)thio radical, an amino radical,
an amino radical protected by a (C.sub.1-C.sub.6 alkyl)carbonyl,
carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a group NHR"
or NR"R'" in which R" and R'", which may be identical or different,
are chosen from a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6
monohydroxyalkyl radical and a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; R.sub.6 is chosen from a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 carbamylalkyl radical, a (C.sub.1-C.sub.6
alkyl)-C.sub.1-C.sub.6 carboxyalkyl radical, a benzyl radical and a
group Z of formula (II), (III) or (IV); R.sub.7, R.sub.8 and
R.sub.9, which may be identical or different, are chosen from a
C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, an aryl radical, a benzyl
radical, a C.sub.1-C.sub.6 amidoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical or a
C.sub.1-C.sub.6 aminoalkyl radical whose amine is protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; where two of the radicals R.sub.7, R.sub.8
and R.sub.9 may also form, together with the nitrogen atom to which
they are attached, a 5- or 6-membered saturated ring containing
carbon or containing at least one additional heteroatom, it being
possible for the said ring to be unsubstituted or substituted by a
halogen atom, a hydroxyl radical, a C.sub.1-C.sub.6 alkyl radical,
a C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a nitro radical, a cyano radical, a
C.sub.1-C.sub.6 cyanoalkyl radical, a C.sub.1-C.sub.6 alkoxy
radical, a tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl
radical, an amido radical, an aldehydo radical, a carboxyl radical,
a C.sub.1-C.sub.6 ketoalkyl radical, a thio radical, a
C.sub.1-C.sub.6 thioalkyl radical, a (C.sub.1-C.sub.6 alkyl)thio
radical, an amino radical, or an amino radical protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; one of the radicals R.sub.7, R.sub.8 and
R.sub.9 may also be chosen from a second group Z which may be
identical to or different from the first said group Z; R.sub.10 is
chosen from a C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
monohydroxyalkyl radical; a C.sub.2-C.sub.6 polyhydroxyalkyl
radical; an aryl radical; a benzyl radical; a C.sub.1-C.sub.6
aminoalkyl radical or a C.sub.1-C.sub.6 aminoalkyl radical whose
amine is protected by a (C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl
or (C.sub.1-C.sub.6 alkyl)sulphonyl radical; a C.sub.1-C.sub.6
carboxyalkyl radical; a C.sub.1-C.sub.6 cyanoalkyl radical; a
C.sub.1-C.sub.6 carbamylalkyl radical; a C.sub.1-C.sub.6
trifluoroalkyl radical; a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
sulphonamidoalkyl radical; a
(C.sub.1-C.sub.6-alkyl)carboxy-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphinyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)sulphonyl-C.sub.1-C.sub.6 alkyl radical; a
(C.sub.1-C.sub.6 alkyl)keto-C.sub.1-C.sub.6 alkyl radical; an
N--(C.sub.1-C.sub.6 alkyl)carbamyl-C.sub.1-C.sub.6 alkyl radical;
or an N--(C.sub.1-C.sub.6 alkyl)sulphonamido-C.sub.1-C.sub.6 alkyl
radical; x and y are integers equal to 0 or 1; with the following
conditions: in the unsaturated cationic groups of formula (II):
when x is 0, the linker D is attached to the nitrogen atom, when x
is 1, the linker D is attached to one of the ring members E, G, J
or L, y can adopt the value 1 only: 1) when the ring members E, G,
J and L are simultaneously a carbon atom and when the radical
R.sub.6 is carried by the nitrogen atom of the unsaturated ring; or
2) when at least one of the ring members E, G, J and L is a
nitrogen atom to which the radical R.sub.6 is attached; in the
unsaturated cationic groups of formula (III): when x is 0, the
linker D is attached to the nitrogen atom, when x is 1, the linker
D is attached to one of the ring members E, G, J, L or M, y can
adopt the value 1 only when at least one of the ring members E, G,
J, L and M represents a divalent atom and when the radical R.sub.6
is carried by the nitrogen atom of the unsaturated ring; in the
cationic groups of formula (IV): when x is 0, the linker is
attached to the nitrogen atom which carries the radicals R.sub.7 to
R.sub.9, when x is 1, two of the radicals R.sub.7 to R.sub.9 form,
conjointly with the nitrogen atom to which they are attached, a 5-
or 6-membered saturated ring as defined above, and the linker D is
carried by a carbon atom of the said saturated ring; X.sup.- is
chosen from a monovalent or divalent anion; with the proviso that:
the number of cationic groups Z of formula (II), (III) or (IV) is
at least 1.
58. The compound or salt thereof according to claim 57, wherein
said linker D of said group Z is an alkyl chain that comprises 1 to
14 carbon atoms.
59 The compound or salt thereof according to claim 57, wherein said
alkyl and alkoxy radicals of said formula (I) are linear or
branched.
60. The compound or salt thereof according to claim 57, wherein
said at least one heteroatom of said unsaturated cationic groups of
formulae (II), (III) and (IV) is chosen from oxygen, sulphur and
nitrogen atoms.
61. The compound or salt thereof according to claim 57, wherein
said 5- or 6-membered saturated ring containing carbon or
containing at least one additional heteroatom formed by two of said
radicals R.sub.7, R.sub.8, and R.sub.9 and nitrogen is chosen from
a pyrrolidine ring, a piperidine ring, a piperazine ring and a
morpholine ring.
62. The compound or salt thereof according to claim 57, wherein
said unsaturated groups Z of formula (II) are chosen from pyrrole,
imidazole, pyrazole, oxazole, thiazole and triazole rings.
63. The compound or salt thereof according to claim 57, wherein
said rings of said unsaturated groups Z of formula (III) are chosen
from pyridine, pyrimidine, pyrazine, oxazine and triazine
rings.
64. The compound or salt thereof according to claim 57, wherein
said X.sup.- is chosen from a halogen atom, a hydroxide, a hydrogen
sulphate and a C.sub.1-C.sub.6 alkyl sulphate.
65. The compound according to claim 57, wherein said compound of
formula (I) is chosen from:
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpy- ridinium
methosulphate; 4-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methy-
lpyridinium methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)-4-ylmeth-
ylindol-1-yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
4-(4-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-ylmethyl)-1-methylpyridinium
methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)-5-ylmethyl-indol-1--
yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
3-[4-hydroxy-5-(1-methy-
lpyridinium)-3-ylmethyl-indol-1-ylmethyl]-1-methylpyridinium
dimethosulphate;
3-[3-(5-benzyl-4-hydroxyindol-1-yl)propyl]-1-methyl-3H-i-
midazol-1-ium methosulphate;
[2-(4-hydroxy-1H-indol-3-yl)ethyl]trimethyl-a- mmonium
methosulphate; [2-(4-hydroxy-1-methyl-1 H-indol-3-yl)ethyl]-trimet-
hylammonium methosulphate;
(4-hydroxy-1-methyl-1H-indol-3-ylmethyl)-trimet- hylammonium
methosulphate; (4-hydroxy-1H-indol-3-ylmethyl)trimethylammoniu- m
methosulphate;
{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]propyl}-trimeth-
ylammonium methosulphate; {3-[(4-hydroxy-1-methyl-1H-indole
-2-carbonyl)-amino]propyl}trimethylammonium methosulphate;
{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}trimethylammon-
ium methosulphate;
{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]-
propyl}trimethylammonium methosulphate;
3-{3-[(4-hydroxy-1H-indole-2-carbo-
nyl)amino]-propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-methyl-3H-
-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-5-methyl-1H-indole-2-carbo-
nyl)-amino]propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}-1-methyl-
-3H-imidazol-1-ium methosulphate;
{3-[(4-hydroxy-1H-indole-6-carbonyl)amin-
o]propyl}-trimethylammonium monochloride;
{3-[(4-hydroxy-1-methyl-1H-indol-
e-6-carbonyl)-amino]propyl}trimethylammonium monochloride; or an
addition salt thereof with an acid.
66. The compound or salt thereof according to claim 1, wherein said
addition salts with an acid are chosen from hydrochlorides,
hydrobromides, sulphates, citrates, succinates, tartrates, lactates
and acetates.
Description
[0001] The invention relates to novel 4-hydroxyindole derivatives
comprising at least one cationic group Z, Z being selected from
quaternized aliphatic chains, aliphatic chains containing at least
one quaternized saturated ring, and aliphatic chains containing at
least one quaternized unsaturated ring, to their use as a coupler
for the oxidation dyeing of keratinous fibers, to the dyeing
compositions comprising them, and to the methods of oxidation
dyeing which employ them.
[0002] It is known to dye keratinous fibers, and especially human
hair, with dyeing compositions comprising oxidation dye precursors,
especially para-phenylenediamines, ortho- or para-aminophenols, and
heterocyclic compounds, such as diaminopyrazole derivatives, which
are referred to generally as oxidation bases. The oxidation dye
precursors or oxidation bases are colourless or slightly coloured
compounds which, when combined with oxidizing products, have the
capacity to give rise to coloured compounds and dyes by virtue of a
process of oxidative condensation.
[0003] It is also known that the shades obtained with these
oxidation bases can be varied by combining them with couplers or
coloration modifiers, the latter being selected in particular from
aromatic meta-diamines, meta-aminophenols, meta-diphenols and
certain heterocyclic compounds such as, for example, indole
couplers.
[0004] The variety of molecules employed as oxidation bases and
couplers makes it possible to obtain a wide range of colours.
[0005] The so-called permanent coloration obtained by virtue of
these oxidation dyes should, moreover, satisfy certain conditions.
Hence it should have no toxicological drawbacks, should allow
shades of the desired intensity to be obtained, and should have
good resistance to external agents (light, inclement weather,
washing, permanent-waving, perspiration and friction).
[0006] The dyes should also allow white hair to be covered and,
finally, they should be as unselective as possible; in other words,
they should allow the smallest possible differences in coloration
to be produced over the entire length of a single keratinous fibre,
which may in fact be sensitized (i.e. damaged) differently between
its tip and its root.
[0007] The inventors have now discovered, in a manner totally
unexpected and surprising, that a novel class of 4-hydroxyindole
derivatives of formula (I) defined below, containing at least one
cationic group Z, Z being selected from quaternized aliphatic
chains, aliphatic chains containing at least one quaternized
saturated ring, and aliphatic chains containing at least one
quaternized unsaturated ring, are suitable for use as a coupler for
oxidation dyeing and that, furthermore, they make it possible to
obtain dyeing compositions which lead to intense colorations in a
very wide range of shades and have excellent properties of
resistance to the various treatments which the keratinous fibers
may undergo. Finally, these compounds have been found to be readily
synthesizable.
[0008] It is these discoveries which form the basis of the present
invention.
[0009] The invention therefore provides, firstly, 4-hydroxyindole
derivatives of formula (I) below and their addition salts with an
acid: 1
[0010] in which:
[0011] R.sub.1 represents a hydrogen atom; a group Z; a
C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 monohydroxyalkyl
radical; a C.sub.2-C.sub.4 polyhydroxyalkyl radical; a
(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical; a
hydroxy(C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4 alkyl radical; a
C.sub.1-C.sub.4 aminoalkyl radical; a C.sub.1-C.sub.4 aminoalkyl
radical whose amine is mono- or disubstituted by a C.sub.1-C.sub.4
alkyl radical, by an acetyl radical, by a C.sub.1-C.sub.4
monohydroxyalkyl radical or by a C.sub.2-C.sub.4 polyhydroxyalkyl
radical; a (C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 thioalkyl
radical, a monohydroxy(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4
thioalkyl radical; a polyhydroxy(C.sub.2-C.sub.4
alkyl)-C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4
carboxyalkyl radical; a (C.sub.1-C.sub.4 alkoxy)-C.sub.1-C.sub.4
thiocarbonylalkyl radical or a C.sub.1-C.sub.4 acetylaminoalkyl
radical; a C.sub.1-C.sub.4 cyanoalkyl radical; a C.sub.1-C.sub.4
trifluoroalkyl radical; a C.sub.1-C.sub.4 haloalkyl radical; a
C.sub.1-C.sub.4 phosphoalkyl radical, or a C.sub.1-C.sub.4
sulphoalkyl radical;
[0012] R.sub.2 and R.sub.3, which are identical or different,
represent a hydrogen or halogen atom; a group Z; a group --NH--Z; a
C.sub.1-C.sub.4 alkyl radical; a carboxyl radical; a
(C.sub.1-C.sub.4 alkoxy)carbonyl radical or a formyl radical;
[0013] R.sub.4 and R.sub.5, which are identical or different,
represent a hydrogen or halogen atom; a group Z; a group --NH--Z; a
C.sub.1-C.sub.4 alkyl radical; a C.sub.1-C.sub.4 alkoxy radical; an
acetylamino radical; a C.sub.1-C.sub.5 monohydroxyalkyl radical; a
C.sub.2-C.sub.4 polyhydroxyalkyl radical; a (C.sub.1-C.sub.4
alkoxy)-C.sub.1-C.sub.4 alkyl radical; a thiophene radical; a furan
radical; a phenyl radical; an aralkyl radical in which the alkyl
moiety is C.sub.1-C.sub.4; a phenyl radical or aralkyl radical in
which the alkyl moiety is C.sub.1-C.sub.4, each substituted by a
halogen atom, by a C.sub.1-C.sub.4 alkyl radical, by a
trifluoromethyl radical, by a C.sub.1-C.sub.4 alkoxy radical, by an
amino radical or by an amino radical which is mono- or
disubstituted by a C.sub.1-C.sub.4 alkyl radical; a
(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical or a
di(C.sub.1-C.sub.4 alkyl)-C.sub.1-C.sub.4 aminoalkyl radical;
[0014] Z is selected from the unsaturated cationic groups of
formulae (II) and (III) below and the saturated cationic groups of
formula (IV) below:
[0015] in which: 2
[0016] D is a linker which represents an alkyl chain containing
preferably 1 to 14 carbon atoms, which is linear or branched and
can be interrupted by one or more heteroatoms such as oxygen,
sulphur or nitrogen atoms and can be substituted by one or more
hydroxyl or C.sub.1-C.sub.6 alkoxy radicals and can carry one or
more ketone functional groups;
[0017] the ring members E, G, J, L and M, which are identical or
different, represent a carbon, oxygen, sulphur or nitrogen
atom;
[0018] n is an integer of between 0 and 4 inclusive;
[0019] m is an integer of between 0 and 5 inclusive;
[0020] the radicals R, which are identical or different, represent
a group Z, a halogen atom, a hydroxyl radical, a C.sub.1-C.sub.6
alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl radical, a
C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro radical, a cyano
radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a C.sub.1-C.sub.6
alkoxy radical, a tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6
alkyl radical, an amido radical, an aldehydo radical, a carboxyl
radical, a C.sub.1-C.sub.6 alkylcarbonyl radical, a thio radical, a
C.sub.1-C.sub.6 thioalkyl radical, a (C.sub.1-C.sub.6 alkyl)thio
radical, an amino radical, an amino radical protected by a
(C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6
alkyl)sulphonyl radical; a group NHR" or NR"R'" in which R" and
R'", which are identical or different, represent a C.sub.1-C.sub.6
alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl radical or a
C.sub.2-C.sub.6 polyhydroxyalkyl radical;
[0021] R.sub.6 represents a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
tri(C.sub.1-C.sub.6 alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, a
(C.sub.1-C.sub.6 alkoxy)-C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 carbamylalkyl radical, a (C.sub.1-C.sub.6
alkyl)-C.sub.1-C.sub.6 carboxyalkyl radical, a benzyl radical or a
group Z of formula (II), (III) or (IV) as defined above;
[0022] R.sub.7, R.sub.8 and R.sub.9, which are identical or
different, represent a C.sub.1-C.sub.6 alkyl radical, a
C.sub.1-C.sub.6 monohydroxyalkyl radical, a C.sub.2-C.sub.6
polyhydroxyalkyl radical, a (C.sub.1-C.sub.6
alkoxy)-C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 cyanoalkyl
radical, an aryl radical, a benzyl radical, a C.sub.1-C.sub.6
amidoalkyl radical, a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical or a C.sub.1-C.sub.6
aminoalkyl radical whose amine is protected by a (C.sub.1-C.sub.6
alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl
radical; where two of the radicals R.sub.7, R.sub.8 and R.sub.9 may
also form, together with the nitrogen atom to which they are
attached, a 5- or 6-membered saturated ring containing carbon or
containing at least one additonal heteroatoms, such as, for
example, a pyrrolidine ring, a piperidine ring, a piperazine ring
or a morpholine ring, it being possible for the said ring to be
unsubstituted or substituted by a halogen atom, a hydroxyl radical,
a C.sub.1-C.sub.6 alkyl radical, a C.sub.1-C.sub.6 monohydroxyalkyl
radical, a C.sub.2-C.sub.6 polyhydroxyalkyl radical, a nitro
radical, a cyano radical, a C.sub.1-C.sub.6 cyanoalkyl radical, a
C.sub.1-C.sub.6 alkoxy radical, a tri(C.sub.1-C.sub.8
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical, an amido radical, an
aldehydo radical, a carboxyl radical, a C.sub.1-C.sub.6 ketoalkyl
radical, a thio radical, a C.sub.1-C.sub.6 thioalkyl radical, a
(C.sub.1-C.sub.6 alkyl)thio radical, an amino radical, or an amino
radical protected by a (C.sub.1-C.sub.6 alkyl)carbonyl, carbamyl or
(C.sub.1-C.sub.6 alkyl)sulphonyl radical; one of the radicals
R.sub.7, R.sub.8 and R.sub.9 may also represent a second group Z
which is identical to or different from the first group Z;
[0023] R.sub.10 represents a C.sub.1-C.sub.6 alkyl radical; a
C.sub.1-C.sub.6 monohydroxyalkyl radical; a C.sub.2-C.sub.6
polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a
C.sub.1-C.sub.6 aminoalkyl radical or a C.sub.1-C.sub.6 aminoalkyl
radical whose amine is protected by a (C.sub.1-C.sub.6
alkyl)carbonyl, carbamyl or (C.sub.1-C.sub.6 alkyl)sulphonyl
radical; a C.sub.1-C.sub.6 carboxyalkyl radical; a C.sub.1-C.sub.6
cyanoalkyl radical; a C.sub.1-C.sub.6 carbamylalkyl radical; a
C.sub.1-C.sub.6 trifluoroalkyl radical; a tri(C.sub.1-C.sub.6
alkyl)silyl-C.sub.1-C.sub.6 alkyl radical; a C.sub.1-C.sub.6
sulphonamidoalkyl radical; a (C.sub.1-C.sub.6-alkyl)car-
boxy-C.sub.1-C.sub.6 alkyl radical; a (C.sub.1-C.sub.6
alkyl)sulphinyl-C.sub.1-C.sub.6 alkyl radical; a (C.sub.1-C.sub.6
alkyl)sulphonyl-C.sub.1-C.sub.6 alkyl radical; a (C.sub.1-C.sub.6
alkyl)keto-C.sub.1-C.sub.6 alkyl radical; an N--(C.sub.1-C.sub.6
alkyl)carbamyl-C.sub.1-C.sub.6 alkyl radical; or an
N--(C.sub.1-C.sub.6 alkyl)sulphonamido-C.sub.1-C.sub.6 alkyl
radical;
[0024] x and y are integers equal to 0 or 1; with the following
conditions:
[0025] in the unsaturated cationic groups of formula (II):
[0026] when x is 0, the linker D is attached to the nitrogen
atom,
[0027] when x is 1, the linker D is attached to one of the ring
members E, G, J or L,
[0028] y can adopt the value 1 only:
[0029] 1) when the ring members E, G, J and L represent
simultaneously a carbon atom and when the radical R.sub.6 is
carried by the nitrogen atom of the unsaturated ring; or else
[0030] 2) when at least one of the ring members E, G, J and L
represents a nitrogen atom to which the radical R.sub.6 is
attached;
[0031] in the unsaturated cationic groups of formula (III):
[0032] when x is 0, the linker D is attached to the nitrogen
atom,
[0033] when x is 1, the linker D is attached to one of the ring
members E, G, J, L or M,
[0034] y can adopt the value 1 only when at least one of the ring
members E, G, J, L and M represents a divalent atom and when the
radical R.sub.6 is carried by the nitrogen atom of the unsaturated
ring;
[0035] in the cationic groups of formula (IV):
[0036] when x is 0, the linker is attached to the nitrogen atom
which carries the radicals R.sub.7 to R.sub.9,
[0037] when x is 1, two of the radicals R.sub.7 to R.sub.9 form,
conjointly with the nitrogen atom to which they are attached, a 5-
or 6-membered saturated ring as defined above, and the linker D is
carried by a carbon atom of the said saturated ring;
[0038] X.sup.- represents a monovalent or divalent anion selected
preferably from a halogen atom such as chlorine, bromine, fluorine
or iodine, a hydroxide, a hydrogen sulphate or a
C.sub.1-C.sub.6-alkyl sulphate such as, for example, a methyl
sulphate or an ethyl sulphate;
[0039] with the proviso that:
[0040] the number of cationic groups Z of formula (II), (III) or
(IV) is at least 1.
[0041] As indicated above, the colorations obtained with the
oxidation dyeing composition in accordance with the invention can
be intense and make it possible to obtain shades within a very wide
range of colours. Moreover, they can exhibit excellent properties
of resistance with respect to the action of various external agents
(light, inclement weather, washing, permanent-waving, perspiration,
friction). These properties can be particularly remarkable as
regards, notably, the resistance of the colorations obtained with
respect to the action of light, washing and perspiration.
[0042] In the formula (I) above the alkyl and alkoxy radicals can
be linear or branched.
[0043] Among the rings of the unsaturated groups Z of formula (II)
above, mention may be made in particular, by way of example, of
pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole
rings.
[0044] Among the rings of the unsaturated groups Z of formula (III)
above, mention may be made, in particular, by way of example, of
pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
[0045] Among the compounds of formula (I) above, mention may be
made in particular of:
[0046]
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpyridinium
methosulphate;
[0047]
4-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpyridinium
methosulphate;
[0048]
3-[3-(4-hydroxy-5-(1-methylpyridinium)-4-ylmethylindol-1-yl)propyl]-
-1-methylimidazol-1-ium dimethosulphate;
[0049]
4-(4-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-ylmethyl)-1-methylpyridi-
nium methosulphate;
[0050]
3-[3-(4-hydroxy-5-(1-methylpyridinium)-5-ylmethyl-indol-1-yl)propyl-
]-1-methylimidazol-1-ium dimethosulphate;
[0051]
3-[4-hydroxy-5-(1-methylpyridinium)-3-ylmethyl-indol-1-ylmethyl]-1--
methylpyridinium dimethosulphate;
[0052]
3-[3-(5-benzyl-4-hydroxyindol-1-yl)propyl]-1-methyl-3H-imidazol-1-i-
um methosulphate;
[0053] [2-(4-hydroxy-1H-indol-3-yl)ethyl]trimethyl-ammonium
methosulphate;
[0054]
[2-(4-hydroxy-1-methyl-1H-indol-3-yl)ethyl]-trimethylammonium
methosulphate;
[0055] (4-hydroxy-1-methyl-1H-indol-3-ylmethyl)-trimethylammonium
methosulphate;
[0056] (4-hydroxy-1H-indol-3-ylmethyl)trimethylammonium
methosulphate;
[0057]
{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]propyl}-trimethylammonium
methosulphate;
[0058]
{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-amino]propyl}trimethy-
lammonium methosulphate;
[0059]
{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}trimethy-
lammonium methosulphate;
[0060]
{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}trime-
thylammonium methosulphate;
[0061]
3-{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]-propyl}-1-methyl-3H-im-
idazol-1-ium methosulphate;
[0062]
3-{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-met-
hyl-3H-imidazol-1-ium methosulphate;
[0063]
3-{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-met-
hyl-3H-imidazol-1-ium methosulphate;
[0064]
3-{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}-1--
methyl-3H-imidazol-1-ium methosulphate;
[0065]
{3-[(4-hydroxy-1H-indole-6-carbonyl)amino]propyl}-trimethylammonium
monochloride;
[0066]
{3-[(4-hydroxy-1-methyl-1H-indole-6-carbonyl)-amino]propyl}trimethy-
lammonium monochloride;
[0067] and their addition salts with an acid.
[0068] The compounds of formula (I) in accordance with the
invention can be readily obtained in accordance with well-known
methods of the prior art such as, for example, in accordance with
the preparation process described in the patent application FR-A-2
736 640, the disclosure of which is incorporated by reference
herein, followed by a conventional final quaternization step.
[0069] The invention additionally provides for the use of the
compounds of formula (I) in accordance with the invention as a
coupler for the oxidation dyeing of keratinous fibers and, in
particular, of human keratinous fibers such as the hair.
[0070] The invention also provides a composition for the oxidation
dyeing of keratinous fibers and, in particular, of human keratinous
fibers such as the hair, characterized in that it comprises, in a
medium appropriate for dyeing, at least one compound of formula (I)
in accordance with the invention.
[0071] The compound or compounds of formula (I) in accordance with
the invention and/or its or their addition salt or salts with an
acid represents or represent preferably from 0.0005 to 12% by
weight, approximately, of the total weight of the dyeing
composition, and, more preferably still, from 0.005 to 6% by
weight, approximately, of this weight.
[0072] In accordance with one preferred embodiment of the
invention, the dyeing composition additionally includes one or more
oxidation bases which can be selected from the oxidation bases
conventionally used in oxidation dyeing and among which mention may
be made in particular of para-phenylenediamines,
bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols
and heterocyclic bases.
[0073] Among the para-phenylenediamines, mention may be made more
particularly, by way of example, of para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N-ethyl-N-(.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine and their addition
salts with an acid.
[0074] Among the abovementioned para-phenylenediamines, very
particular preference is given to para-phenylenediamine,
para-tolylenediamine, 2-isopropyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenedi- amine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)parapheny- lenediamine,
2-chloro-para-phenylenediamine, 2-.beta.-acetylaminoethyloxy--
para-phenylenediamine, and their addition salts with an acid.
[0075] Among the bisphenylalkylenediamines, mention may be made,
more particularly, by way of example, of
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bi-
s(4'-aminophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'--
bis(4'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylened- iamine,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylen-
e-diamine, N,N'-bis(4-methylaminophenyl)tetramethylene-diamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition
salts with an acid.
[0076] Among the para-aminophenols, mention may be made more
particularly, by way of example, of 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,
4-amino-2-fluorophenol, and their addition salts with an acid.
[0077] Among the ortho-aminophenols, mention may be made more
particularly, by way of example, of 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetamido-2-aminophenol- , and their addition salts with an
acid.
[0078] Among the heterocyclic bases, mention may be made more
particularly, by way of example, of pyridine derivatives,
pyrimidine derivatives and pyrazole derivatives.
[0079] Among the pyridine derivatives, mention may be made more
particularly of the compounds described, for example, in the
patents GB 1 026 978 and GB 1 153 196, the disclosures of each
which are incorporated by reference herein, such as
2,5-diaminopyridine, 2-(4-methoxyphenyl)amin- o-3-aminopyridine,
2,3-diamino-6-methoxypyridine, 2-(.beta.-methoxyethyl)a-
mino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their
addition salts with an acid.
[0080] Among the pyrimidine derivatives, mention may be made more
particularly of the compounds described, for example, in the German
patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP
91-10659 or patent application WO 96/15765, the disclosures of each
which are incorporated by reference herein, such as
2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and
the pyrazolo-pyrimidine derivatives such as those mentioned in the
patent application FR-A-2 750 048, the disclosure of which is
incorporated by reference herein, and among which mention may be
made of pyrazolo[1,5-a]pyrimidine-3,7-diamine;
2,5-dimethylpyrazolo[1,5-a]pyrimid- ine-3,7-diamine;
pyrazolo[1,5-a]pyrimidine-3-5-diamine;
2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;
3-aminopyrazolo[1,5-a]pyrimidin-7-ol;
3-aminopyrazolo[1,5-a]pyrimidin-5-o- l;
2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]ethanol,
2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,
5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, and
their addition salts and their tautomeric forms, when a tautomeric
equilibrium exists, and their addition salts with an acid.
[0081] Among the pyrazole derivatives, mention may be made more
particularly of the compounds described in the patents DE 3 843
892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970,
FR-A-2 733 749 and DE 195 43 988, the disclosures of each which are
incorporated by reference herein, such as
4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,
4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopy-
razole,1-benzyl-4,5-diamino-3-methylpyrazole,
4,5-diamino-3-tert-butyl-1-m- ethylpyrazole,
4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyph- enyl)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,
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylaminopyrazole,
3,5-diamino-4-(.beta.-hydroxy- ethyl)amino-1-methylpyrazole, and
their addition salts with an acid.
[0082] When they are used, these oxidation bases represent
preferably from 0.0005 to 12% by weight, approximately, of the
total weight of the dyeing composition, and still more preferably
from 0.005 to 6% by weight, approximately, of this weight.
[0083] In addition to the compound or compounds of formula (I)
above, the dyeing composition in accordance with the invention may
also include at least one additional coupler which can be selected
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 their addition salts with an
acid.
[0084] These couplers are selected more particularly from
2-methyl-5-aminophenol,
5-N-(.beta.-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)-ben- zene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6-hydroxy-indole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, and their addition salts with an
acid.
[0085] When they are present, these couplers represent preferably
from 0.0001 to 10% by weight, approximately, of the total weight of
the dyeing composition, and still more preferably from 0.005 to 5%
by weight, approximately, of this weight.
[0086] Generally speaking, the addition salts with an acid which
can be used in the context of the dyeing compositions of the
invention (compounds of formula (I), oxidation bases and additional
couplers) are selected in particular from hydrochlorides,
hydrobromides, sulphates, citrates, succinates, tartrates, lactates
and acetates.
[0087] The medium appropriate for dyeing (or vehicle) generally is
water or a mixture of water and at least one organic solvent for
solubilizing the compounds which would not be sufficiently soluble
in water. By way of organic solvent, mention may be made, for
example, of 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 monoethyl ether and monomethyl ether, and
aromatic alcohols, such as benzyl alcohol or phenoxyethanol,
similar products, and mixtures thereof.
[0088] The solvents can be present in proportions of preferably
between 1 and 40% inclusive by weight, approximately, relative to
the total weight of the dyeing composition, and still more
preferably between 5 and 30% inclusive by weight,
approximately.
[0089] The pH of the dyeing composition according to the invention
is generally between 3 and 12 inclusive, approximately, and
preferably between 5 and 11 inclusive, approximately. It can be
adjusted to the desired value by means of acidifying or basifying
agents which are commonly employed in the dyeing of keratinous
fibers.
[0090] Among the acidifying agents, mention may be made, by way of
example, of mineral acids or organic acids such as hydrochloric
acid, ortho-phosphoric acid, sulphuric acid, carboxylic acids such
as acetic acid, tartaric acid, citric acid and lactic acid, and
sulphonic acids.
[0091] Among the basifying agents, mention may be made, by way of
example, of aqueous ammonia, alkali metal carbonates, alkanolamines
such as mono-, di- and triethanolamines and their derivatives,
sodium hydroxide or potassium hydroxide, and the compounds of
formula (V) below: 3
[0092] in which W is a propylene radical optionally substituted by
a hydroxyl group or a C.sub.1-C.sub.6 alkyl radical; and R.sub.11,
R.sub.12, R.sub.13 and R.sub.14, which are identical or different,
represent a hydrogen atom or a C.sub.1-C.sub.6 alkyl or
C.sub.1-C.sub.6 hydroxyalkyl radical.
[0093] The oxidation dyeing compositions in accordance with the
invention may also include at least one direct dye, in particular
for modifying the shades or enriching them with glints.
[0094] The dyeing composition in accordance with the invention may
also include various adjuvants which are conventionally employed in
hair-dyeing compositions, such as anionic, cationic, nonionic,
amphoteric or zwitterionic surfactants or mixtures thereof,
anionic, cationic, nonionic, amphoteric or zwitterionic polymers or
mixtures thereof, mineral or organic thickeners, antioxidants,
penetrants, sequestrants, perfumes, buffers, dispersants,
conditioning agents such as, for example, volatile or nonvolatile
silicones, modified or otherwise, film formers, ceramides,
preservatives and opacifiers.
[0095] The person skilled in the art will of course take care to
select this or these optional complementary compounds such that the
advantageous properties associated intrinsically with the oxidation
dyeing composition in accordance with the invention are not, or not
substantially, adversely affected by the intended addition or
additions.
[0096] The dyeing composition according to the invention can be
presented in a variety of forms, such as in the form of liquids,
creams, gels or any other form appropriate for carrying out dyeing
of keratinous fibers and, in particular, of human hair.
[0097] The invention also provides a method of oxidation-dyeing
keratinous fibers and, in particular, human keratinous fibers such
as the hair, employing the dyeing composition as defined above.
[0098] In accordance with this method, at least one dyeing
composition as defined above is applied to the fibers, the colour
being revealed at an acidic, neutral or alkaline pH with the aid of
an oxidizing agent which is added to the dyeing composition right
at the time of use or which is present in an oxidizing composition
which is applied simultaneously or sequentially.
[0099] In accordance with a preferred embodiment of the dyeing
method of the invention, the above-described dyeing composition is
preferably mixed, at the time of use, with an oxidizing composition
comprising, in a medium appropriate for dyeing, at least one
oxidizing agent which is present in an amount sufficient to develop
a coloration. The mixture obtained is subsequently applied to the
keratinous fibers and is left to act for from 3 to 50 minutes,
approximately, preferably from 5 to 30 minutes, approximately,
after which the fibers are rinsed, washed with shampoo, rinsed
again and dried.
[0100] The oxidizing agent can be selected from the oxidizing
agents which are conventionally used for the oxidation dyeing of
keratinous fibers, and among which mention may be made of hydrogen
peroxide, urea peroxide, alkali metal bromates, persalts such as
perborates and persulphates, and enzymes such as peroxidases,
laccases and oxidoreductases having 2 electrons. Hydrogen peroxide
is particularly preferred.
[0101] The pH of the oxidizing composition comprising the oxidizing
agent as defined above is such that, after mixing with the dyeing
composition, the pH of the resultant composition that is applied to
the keratinous fibers varies preferably between 3 and 12 inclusive
, approximately, and still more preferably between 5 and 11
inclusive. It is adjusted to the desired value by means of
acidifying or basifying agents which are commonly employed in
dyeing keratinous fibers, such agents being as defined above.
[0102] The oxidizing composition as defined above may also include
various adjuvants which are conventionally employed in hair-dyeing
compositions, such adjuvants being as defined above.
[0103] The composition which is finally applied to the keratinous
fibers may be presented in various forms, such as in the form of
liquids, creams, gels or any other form appropriate for carrying
out dyeing of keratinous fibers and, in particular, of human
hair.
[0104] The invention also provides a multi-compartment dyeing
device or kit, or any other packaging system having two or more
compartments, of which a first compartment contains the dyeing
composition as defined above and a second compartment contains the
oxidizing composition as defined above. These devices can be
equipped with a means allowing the desired mixture to be delivered
to the hair, such as the devices described in the patent FR-2 586
913, the disclosure of which is incorporated by reference herein,
in the name of the applicant.
[0105] The examples which follow are intended to illustrate the
invention without limiting its scope.
PREPARATION EXAMPLES
Preparation Example 1
Synthesis of
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpyridinium
methosulphate
[0106] 4
[0107] a) Preparation of
1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol
[0108] 500 cm.sup.3 of 2-methyl-2-propanol, 75 g of
pyridine-3-carboxaldehyde and 100 g of
1-methyl-1,5,6,7-tetrahydroindol-4- -one were introduced into a
1-liter reactor equipped with a mechanical stirrer and surmounted
by a condenser and a thermometer. After 10 minutes of stirring, 157
g of potassium tert-butoxide were added in small portions over 15
minutes. Following addition, the temperature was held at 75.degree.
C. for 1 hour.
[0109] The reaction mixture was allowed to return to room
temperature and then was neutralized (pH=6) with 20% hydrochloric
acid. It was poured into 2 kg of ice-water. The precipitate
obtained was filtered off with suction and washed with diisopropyl
ether and with petroleum ether. It was dried over potash under
vacuum at 30.degree. C. This gave 120 g of
1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol with a yield of
74%.
[0110] b) Preparation of
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-meth- ylpyridinium
methosulphate
[0111] 95 g of 1-methyl-5-pyridin-3-ylmethyl-1H-indol-4-ol in 500
cm.sup.3 of ethyl acetate and 53 g of dimethyl sulphate were
introduced into a 1-liter reactor equipped with a mechanical
stirrer and surmounted by a condenser and a thermometer. This
mixture was taken to reflux for 2 hours. The reaction mixture was
allowed to return to room temperature and the precipitate was
isolated by filtration. The precipitate was subsequently washed
with ethyl acetate and with petroleum ether and then dried over
potash under vacuum at 30.degree. C.
[0112] This gave 140 g of
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-met- hylpyridinium
methosulphate with a yield of 96%. This product was subsequently
recrystallized from methanol (2.5 cm.sup.3/g); (yield =80%).
[0113] The elemental analysis calculated for
C.sub.16H.sub.17N.sub.2O.CH.s- ub.3O.sub.4S (MW=364.42 g) was:
1 % C H N O S Calculated 56.03 5.53 7.69 21.95 8.80 Found 56.68
5.54 7.63 21.96 8.83
APPLICATION EXAMPLES
Examples 1 to 4
Dyeing in an Alkaline Medium
[0114] The following dyeing compositions in accordance with the
invention were prepared (amounts in grams):
2 EXAMPLE 1 2 3 4 3-(4-Hydroxy-1-methyl-1H-i- ndol-5- 1.093 1.093
1.093 1.093 ylmethyl)-1-methylpyridinium methosulphate (coupler of
formula (I)) para-Aminophenol (oxidation base) 0.327 -- -- --
2-.beta.-Acetylaminoethoxy-para- -- 0.798 -- -- phenylenediamine,
2HCl (oxidation base) 3-Methyl-4-aminophenol (oxidation base) -- --
0.369 -- para-Phenylenediamine (oxidation base) -- -- -- 0.327
Common dyeing vehicle No. 1 (*) (*) (*) (*) Demineralized water
q.s. to 100 g 100 g 100 g 100 g (*) Common dyeing vehicle No.1:
96.degree. ethyl alcohol 18 g 35% aqueous sodium metabisulphite
solution 0.68 g Pentasodium salt of diethylenetriaminepentaacetic
acid 1.1 g 20% aqueous ammonia 10.0 g
[0115] At the time of use, each of the above dyeing compositions
were mixed, weight for weight, with a 20-volume (6% by weight)
hydrogen peroxide solution with a pH of 3. The mixture obtained was
applied to locks of permed grey hair containing 90% white hairs for
30 minutes. The locks were subsequently rinsed, washed with a
standard shampoo, rinsed again and then dried.
[0116] The shades obtained are given in the table below:
3 EXAMPLE Dyeing pH Shade obtained 1 10 .+-. 0.2 Iridescent red 2
10 .+-. 0.2 Blue 3 10 .+-. 0.2 Iridescent red 4 10 .+-. 0.2 Dark
purplish blue
* * * * *