U.S. patent application number 10/807162 was filed with the patent office on 2005-03-31 for para-phenylenediamine derivatives comprising a cyclic diaza group substituted with a cationic radical, and use of these derivatives for dyeing keratin fibers.
Invention is credited to Genet, Alain, Leduc, Madeleine, Sabelle, Stephane.
Application Number | 20050066451 10/807162 |
Document ID | / |
Family ID | 34381620 |
Filed Date | 2005-03-31 |
United States Patent
Application |
20050066451 |
Kind Code |
A1 |
Sabelle, Stephane ; et
al. |
March 31, 2005 |
Para-phenylenediamine derivatives comprising a cyclic diaza group
substituted with a cationic radical, and use of these derivatives
for dyeing keratin fibers
Abstract
The disclosure relates to novel para-phenylenediamine
derivatives containing a cyclic diaza group, substituted with a
cationic radical, as well as to the dye compositions comprising
them, and to the method of dyeing keratin fibers using these
compositions. Tthe present invention may make it possible to obtain
a chromatic, strong, relatively unselective and fast coloration on
keratin fibers.
Inventors: |
Sabelle, Stephane; (Paris,
FR) ; Genet, Alain; (Aulnay Sous Bois, FR) ;
Leduc, Madeleine; (Paris, FR) |
Correspondence
Address: |
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW,
GARRETT & DUNNER, L.L.P.
1300 I Street, N.W.
Washington
DC
20005-3315
US
|
Family ID: |
34381620 |
Appl. No.: |
10/807162 |
Filed: |
March 24, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60467123 |
May 2, 2003 |
|
|
|
Current U.S.
Class: |
8/405 |
Current CPC
Class: |
C07D 243/08 20130101;
C07D 403/06 20130101; C07D 233/54 20130101; C07D 295/13
20130101 |
Class at
Publication: |
008/405 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 24, 2003 |
FR |
03 03548 |
Claims
What is claimed is:
1. A compound of formula (I), and the addition salts thereof
42wherein: a ranges from 0 to 4, it being understood that when a is
greater than or equal to 2, then the radicals R.sub.1 may be
identical or different, b ranges from 0 to 4, it being understood
that when b is greater than or equal to 2, then the radicals
R.sub.4 may be identical or different, c is equal to 0 or 1,
R.sub.1 is chosen from a halogen atom; C.sub.1-C.sub.8 aliphatic
and alicyclic, saturated and unsaturated hydrocarbon-based chains,
wherein at least one carbon atom is optionally replaced with at
least one entity chosen from oxygen, nitrogen, silicon, and sulphur
atoms and an SO.sub.2 group; and an onium radical Z; with the
proviso that the radical R.sub.1 does not comprise a peroxide bond
or diazo, nitro or nitroso radicals, R.sub.2 comprises an onium
radical Z, wherein an onium radical is a nitrogen-based quaternary
radical, R.sub.3 is chosen from an alkyl radical; an alkenyl
radical; an alkynyl radical; a hydroxyl radical; a hydroxyalkyl
radical; an alkoxy radical; an alkoxyalkyl radical; an
alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an amino
radical; a monoalkylamino radical; a dialkylamino radical; an
aminoalkyl radical; an aminoalkyl radical wherein the amine is
monosubstituted or disubstituted with at least one radical chosen
from alkyl, acetyl and hydroxyalkyl radicals; a hydroxyl radical; a
aminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a
carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl
radical; a monoalkylaminocarbonyl radical; a dialkylaminocarbonyl
radical; a monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical; R.sub.4 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyalkyl
radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical.
2. The compound according to claim 1, wherein R.sub.1 is chosen
from C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 alkoxyalkyl
radicals, C.sub.1-C.sub.4 hydroxyalkyl radicals, C.sub.1-C.sub.4
aminoalkyl radicals, C.sub.1-C.sub.4 alkoxy radicals,
C.sub.1-C.sub.4 hydroxyalkoxy radicals, and C.sub.1-C.sub.4
carboxyalkyl radicals.
3. The compound according to claim 2, wherein R.sub.1 is chosen
from methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl,
methoxy, isopropyloxy and 2-hydroxyethoxy radicals.
4. The compound according to claim 1, wherein a is equal to 0 or
1.
5. The compound according to claim 1, wherein R.sub.2 is an onium
radical Z of formula (II) 43wherein: D is a linker arm chosen from
a covalent bond and from linear and branched C.sub.1-C.sub.14
alkylene chains, which may comprise at least one hetero atom chosen
from oxygen, sulphur and nitrogen, and which may be substituted
with at least one radical chosen from hydroxyl and amino radicals,
and which may further optionally comprise at least one carbonyl
radical; R.sub.8, R.sub.5 and R.sub.6, which may be identical or
different, are each separately chosen from C.sub.1-C.sub.1-5 alkyl
radicals; C.sub.1-C.sub.6 monohydroxyalkyl radicals;
C.sub.2-C.sub.6 polyhydroxyalkyl radicals;
(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkyl radicals; aryl
radicals; benzyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals; C.sub.1-C.sub.6 aminoalkyl
radicals wherein the amine is mono- or disubstituted with at least
one radical chosen from C.sub.1-C.sub.4 alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; and quaternary ammonium
radicals; R.sub.8, R.sub.5 and R.sub.6 together, in pairs, form,
with the nitrogen atom to which they are attached, a saturated 4-,
5-, 6- or 7-membered carbon-based ring optionally comprising at
least one hetero atom, wherein the ring may optionally be
substituted with a radical chosen from hydroxyl radicals,
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl
radicals, C.sub.2-C.sub.6 polyhydroxyalkyl radicals,
C.sub.1-C.sub.6 alkoxy radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals,
carbamoyl radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, amino radicals, and amino
radicals mono- and disubstituted with at least one radical chosen
from (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcar- bonyl,
carbamoyl and (C.sub.1-C.sub.6)alkylsulphonyl radicals; R.sub.7 is
chosen from C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals; C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; aryl radicals; benzyl radicals; C.sub.1-C.sub.6
aminoalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals wherein
the amine is mono- or disubstituted with at least one radical
chosen from (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl,
carbamoyl and (C.sub.1-C.sub.6)alkylsulphonyl radicals;
C.sub.1-C.sub.6 carboxyalkyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals; C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
and N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; x is equal to 0 or 1, with the proviso that when x=0,
then the linker arm D is attached to the nitrogen atom bearing the
radicals R.sub.5, R.sub.6 and R.sub.8, when x=1, then two of the
radicals R.sub.5, R.sub.6 and R.sub.8 form, together with the
nitrogen atom to which they are attached, a 4-, 5-, 6- or
7-membered saturated ring and the linker arm D is linked to a
carbon atom of the saturated ring; Y.sup.- is a counterion.
6. The compound according to claim 5, wherein: x is equal to 0, and
R.sub.5, R.sub.6 and R.sub.8 are each separately chosen from
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.6 carbamoyl alkyl radicals, and
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.s- ub.6)alkyl radicals,
or wherein R.sub.8 and R.sub.5 together form a ring chosen from
azetidine, pyrrolidine, piperidine, piperazine and morpholine
rings, and wherein R.sub.6 is chosen from C.sub.1-C.sub.6 alkyl
radicals; C.sub.1-C.sub.6 monohydroxyalkyl radicals;
C.sub.2-C.sub.6 polyhydroxyalkyl radicals; C.sub.1-C.sub.6
aminoalkyl radicals; aminoalkyl radicals mono- and disubstituted
with at least one radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)-alkylcarbamoyl(C.sub.1-C.sub.6)alkyl
radicals.
7. The compound according to claim 5, wherein x is equal to 1;
R.sub.7 is chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)a- lkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)alkylcarbamyl(C.sub.1-C.sub.6)alkyl radicals;
R.sub.8 and R.sub.5 together form a ring chosen from azetidine,
pyrrolidine, piperidine, piperazine and morpholine rings; and
R.sub.6 is chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl
radicals.
8. The compound according to claim 5, wherein R.sub.2 comprises a
trialkylammonium alkyl radical, and further wherein the alkyl
linking R.sub.2 to the ring is optionally substituted with at least
one hydroxyl group.
9. The compound according to claim 5, wherein D is chosen from a
covalent bond and an alkylene chain that may optionally be
substituted and/or may comprise a carbonyl group.
10. The compound according to claim 1, wherein R.sub.2 is an onium
radical Z of formula (III) 44wherein: D is a linker arm chosen from
a covalent bond and from linear and branched C.sub.1-C.sub.14
alkylene chains that may optionally comprise at least one hetero
atom chosen from oxygen, sulphur and nitrogen, and that may be
optionally substituted with at least one radical chosen from
hydroxyl and amino radicals, and that may further optionally
comprise at least one carbonyl radical; the ring members E, G, J
and L, which may be identical or different, are chosen from carbon,
oxygen, sulphur and nitrogen atoms to form a ring chosen from
pyrrole, pyrazole, imidazole, triazole, oxazole, isooxazole,
thiazole and isothiazole rings, q is an integer ranging from 1 to
4; R, which may be identical or different, is chosen from a
hydrogen atom, halogen atoms, hydroxyl radicals, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl
radicals, carbamoyl radicals, carboxyl radicals, C.sub.1-C.sub.6
alkylcarbonyl radicals, amino radicals, amino radicals mono- and
disubstituted with a radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals C.sub.2-C.sub.6 polyhydroxyalkyl
radicals, and quaternary ammonium radicals; R.sub.7 is chosen from
C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6 monohydroxyalkyl
radicals; C.sub.2-C.sub.6 polyhydroxyalkyl radicals; aryl radicals;
benzyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals,
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is
substituted with a radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carboxyalkyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)-alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; and quaternary ammonium radicals; x is equal to 0 or 1,
with the proviso that when x=0, the linker arm D is attached to the
nitrogen atom, when x=1, the linker arm D is attached to one of the
ring members E, G, J or L, and Y.sup.- is a counterion.
11. The compound according to claim 10, wherein the ring members E,
G, J and L form a ring chosen from pyrrole, imidazole, pyrazole,
oxazole, thiazole and triazole rings.
12. The compound according to claim 11, wherein the ring members E,
G, J and L form an imidazole ring.
13. The compound according to claim 10, wherein x is equal to 0 and
D is chosen from a covalent bond and an alkylene chain that may be
optionally substituted and/or that may optionally comprise a
carbonyl function.
14. The compound according to claim 10, wherein x is equal to 0 and
R is chosen from a hydrogen atom, hydroxyl radicals,
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl
radicals, C.sub.2-C.sub.6 polyhydroxyalkyl radicals,
C.sub.1-C.sub.6 alkoxy radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals,
carbamoyl radicals, C.sub.1-C.sub.6 alkylcarbonyl radicals, amino
radicals, amino radicals mono- and disubstituted with at least one
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals.
15. The compound according to claim 10, wherein x is equal to 1,
R.sub.7 is chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl radicals, (C.sub.1-C.sub.6)alkylcarbon- yl
radicals, carbamoyl radicals and (C.sub.1-C.sub.6)alkylsulphonyl
radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamyl(C.sub.1-C.sub.6)alkyl radicals;
and R is chosen from a hydrogen atom, a hydroxyl radical,
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl
radicals; C.sub.2-C.sub.6 polyhydroxyalkyl radicals,
C.sub.1-C.sub.6 alkoxy radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
carbamoyl radicals; C.sub.1-C.sub.6 alkylcarbonyl radicals; amino
radicals; amino radicals mono- and disubstituted with at least one
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals.
16. The compound according to claim 15, wherein R is chosen from a
hydrogen atom and alkyl radicals that may optionally be
substituted, and R.sub.7 is an alkyl radical that may optionally be
substituted.
17. The compound according to claim 16, wherein R is chosen from
hydrogen; an alkyl radical; alkyl radicals substituted with at
least one hydroxyl; alkyl radicals substituted with at least one
amino; a carboxyl radical; a carbamoyl radical; an amino radical;
and a hydroxyl radical.
18. The compound according to claim 17, wherein R is chosen from
hydrogen; a hydroxyl radical; a methyl radical; an amino radical; a
hydroxymethyl radical; and an aminomethyl radical.
19. The compound according to claim 1, wherein R.sub.2 is an onium
radical Z of formula (IV) 45wherein: D is a linker arm chosen from
a covalent bond and from linear and branched C.sub.1-C.sub.1-4
alkylene chains, which may comprise at least one hetero atom chosen
from oxygen, sulphur and nitrogen atoms, and which may optionally
be substituted with at least one radical chosen from hydroxyl and
amino radicals, and further may optionally comprise at least one
carbonyl radical; the ring members E, G, J, L and M, which may be
identical or different, are chosen from carbon, oxygen, sulphur and
nitrogen atoms and form a ring chosen from pyridine, pyrimidine,
pyrazine, triazine and pyridazine rings; m is an integer ranging
from 1 to 5; R, which may be identical or different, is chosen from
a hydrogen atom, halogen atoms, hydroxyl radicals, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl
radicals, carbamoyl radicals, carboxyl radicals, C.sub.1-C.sub.6
alkylcarbonyl radicals, amino radicals, amino radicals substituted
with a radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
monohydroxy-alkyl radicals; C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; and quaternary ammonium radicals; R.sub.7 is chosen from
C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6 monohydroxyalkyl
radicals; C.sub.2-C.sub.6 polyhydroxyalkyl radicals; aryl radicals;
benzyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbony- l, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carboxyalkyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(- C.sub.1-C.sub.6)alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; and quaternary ammonium radicals; x is equal to 0 or 1,
with the proviso that when x=0, the linker arm D is attached to the
nitrogen atom, when x=1, the linker arm D is attached to one of the
ring members chosen from E, G, J, L and M; and Y.sup.- is a
counterion.
20. The compound according to claim 19, wherein the ring members E,
G, J, L and M form, with the nitrogen of the ring, a ring chosen
from pyridine and pyrimidine rings.
21. The compound according to claim 19, wherein x is equal to 0,
and R is chosen from a hydrogen atom, hydroxyl radicals,
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl
radicals, C.sub.2-C.sub.6 polyhydroxyalkyl radicals,
C.sub.1-C.sub.6 alkoxy radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals,
carbamoyl radicals, C.sub.1-C.sub.6 alkylcarbonyl radicals, amino
radicals, amino radicals mono- and disubstituted with at least one
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals.
22. The compound according to claim 19, wherein x is equal to 1;
R.sub.7 is chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals,
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl radicals, (C.sub.1-C.sub.6)alkylcarbon- yl
radicals, carbamoyl radicals, and (C.sub.1-C.sub.6)alkylsulphonyl
radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamyl(C.sub.1-C.sub.6)alkyl radicals;
and R is chosen from a hydrogen atom, hydroxyl radicals,
C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6 monohydroxyalkyl
radicals; C.sub.2-C.sub.6 polyhydroxyalkyl radicals;
C.sub.1-C.sub.6 alkoxy radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
carbamoyl radicals; C.sub.1-C.sub.6 alkylcarbonyl radicals; amino
radicals; amino radicals mono- or disubstituted with at least one
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals.
23. The compound according to claim 22, wherein R is chosen from a
hydrogen atom and alkyl radicals that may optionally be
substituted, and R.sub.7 is an alkyl radical that may optionally be
substituted.
24. The compound according to claim 23, wherein R is chosen from
hydrogen; an alkyl radical; alkyl radicals substituted with at
least one hydroxyl; alkyl radicals substituted with at least one
amino; a carboxyl radical; a carbamoyl radical; an amino radical;
and a hydroxyl radical.
25. The compound according to claim 24, wherein R is chosen from
hydrogen and from at least one radical chosen from hydroxyl,
methyl, amino, hydroxymethyl and aminomethyl radicals.
26. The compound according to claim 1, wherein either b is equal to
zero, or R.sub.4 is chosen from an alkyl radical; alkyl radicals
substituted with at least one hydroxyl; alkyl radicals substituted
with at least one amino; a carboxyl radical; and a carbamoyl
radical.
27. The compound according to claim 1, wherein R.sub.3 is chosen
from hydrogen; a hydroxyl radical; an amino radical; an alkyl
radical; alkyl radicals substituted with at least one hydroxyl;
alkyl radicals substituted with at least one amino; a carboxyl
radical; and a carbamoyl radical.
28. The compound according to claim 1, wherein counterion Y.sup.-
is chosen from halogens, a hydroxide, a hydrogen sulphate, an
acetate, a tartrate and (C.sub.1-C.sub.6)alkyl sulphates.
29. The compound according to claim 1, chosen from the following
compounds
7 46 3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]-2-
-oxoethyl}-1-methyl- 3H-imidazol-1-ium chloride 47
3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}-1-methyl-3H-
imidazol-1-ium chloride 48 3-{2-[4-(4-Amino-phenyl)[1,4]d-
iazepan-1-yl]propyl}- trimethylammonium chloride 49
{2-[4-(4-Amino-phenyl)[1,4]diazepan-1- yl]ethyl}trimethylammonium
chloride 50 1-{3-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]pr- opyl}-1-
methylpyrrolidinium chloride 51
{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}-(2-
hydroxyethyl)dimethylammonium chloride 52
{3-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}dimethyl(ethyl-2-
methyl-3H-imidazol-1-ium chloride) ammonium; chloride 53
3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]propyl}-1-methyl-3H-
imidazol-1-ium chloride 54 {2-[4-(4-Amino-phenyl)[1,4]dia-
zepan-1-yl]ethyl}dimethyl-(3- trimethylsilanyl-propyl)ammonium;
chloride 55 3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}-1-(3-
trimethylsilanyl-propyl)-3H-imidazol- 1-ium chloride 56
3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-2-oxoethyl}-1- methyl-3H-imidazol-1-ium
chloride 57 3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]ethyl}-1- methyl-3H-imidazol-1-ium chloride 58
{3-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-propyl}trimethylammon- ium chloride 59
{2-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]ethyl}-
trimethylammonium chloride 60 {3-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-propyl}-1- methyl-3H-imidazol-1-ium chloride
61 {2-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]ethyl}(2-
hydroxyethyl)-dimethylammonium chloride 62
{3-[4-(4-Amino-3-methylphenyl) [1,4]-diazepan-1-yl]ethyl}-dimethyl
(ethyl-2-methyl-3H-imidazol-1-ium chloride)ammonium chloride 63
1-{3-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]propyl}-1-
methyl-pyrrolidinium; chloride 64 {2-[4-(4-Amino-3-methyl- phenyl)
[1,4]-diazepan-1-yl]ethyl}-dimethyl (3-trimethylsilanylpropyl)ammo-
nium chloride 65 3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]diazepan-1-yl]ethyl}-1- (3-trimethylsilanylpropyl)-3H-
imidazol-1-ium chloride 66 {3-[4-(4-Amino-phenyl)[1,4]dia-
zepan-1-yl]-2-hydroxy-propyl}trimethylammonium; chloride 67
{3-[4-(4-Amino-methylphenyl)[1,4-
diazepan-1-yl]-2-hydroxypropyl}trime- thylammonium; chloride 68
3-{2-[4-(4-Amino-phenyl)piperazi- n- 1-yl]-2-oxoethyl}-1-methyl-3H-
imidazol-1-ium chloride 69 {3-[4-(4-Amino-phenyl)piperazin-1-
yl]-2-hydroxypropyl}trimethylammoni- um chloride 70
3-{2-[4-(4-Amino-3-methylphenyl) piperazin-1-yl]-2-oxoethyl}-1-
methyl-3H-imidazol-1-ium chloride 71 3-[4-(4-Amino-3-methylphenyl)
piperazin-1-yl]-2-hydroxypropyl}- trimethylammonium chloride 72
3-{2-[4-(4-Amino-3-phenyl) piperazin-1-yl]ethyl}-1-methyl-3H-
imidazol-1-ium chloride 73 {3-[4-(4-Amino-3-phenyl)
piperazin-1-yl]propyl}trimethylammonium chloride 74
3-{2-[4-(4-Amino-3-methylphenyl) piperazin-1-yl]ethyl}-1-methyl-3H-
imidazol-1-ium chloride 75 {3-[4-(4-Amino-3-methylphenyl)
piperazin-1-yl]-propyl}trimethylammoni- um chloride 76
1-{3-[4-(4-Amino-phenyl) piperazin-1-yl]propyl}-1-
methylpyrrolidinium chloride 77 1-{3-[4-(4-Amino-3-phenyl)
piperazin-1-yl]propyl}-1- methylpyrrolidinium chloride
30. The nitro derivatives of formula (I') 78a ranges from 0 to 4,
it being understood that when a is greater than or equal to 2, then
the radicals R.sub.1 may be identical or different, b ranges from 0
to 4, it being understood that when b is greater than or equal to
2, then the radicals R.sub.4 may be identical or different, c is
equal to 0 or 1, R.sub.1 is chosen from halogen atoms;
C.sub.1-C.sub.8 aliphatic and alicyclic, saturated and unsaturated
hydrocarbon-based chains, wherein at least one carbon atom is
optionally replaced with at least one entity chosen from oxygen,
nitrogen, silicon, and sulphur atoms and an SO.sub.2 group; and an
onium radical Z; with the proviso that the radical R.sub.1 does not
comprise a peroxide bond or diazo, nitro or nitroso radicals,
R.sub.2 comprises an onium radical Z, wherein an onium radical is a
nitrogen-based quaternary radical, R.sub.3 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyl
radical; a hydroxyalkyl radical; an alkoxy radical; an alkoxyalkyl
radical; an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an
amino radical; a monoalkylamino radical; a dialkylamino; an
aminoalkyl radical; an aminoalkyl radical wherein the amine is
monosubstituted or disubstituted with at least one radical chosen
from alkyl, acetyl and hydroxyalkyl radicals; a hydroxyl radical; a
aminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a
carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl
radical; a monoalkylaminocarbonyl radical; a dialkylaminocarbonyl
radical; a monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical; R.sub.4 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyalkyl
radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical.
31. A dye composition comprising, as oxidation base, at least one
compound of formula (I), and the addition salts thereof 79wherein:
a ranges from 0 to 4, it being understood that when a is greater
than or equal to 2, then the radicals R.sub.1 may be identical or
different, b ranges from 0 to 4, it being understood that when b is
greater than or equal to 2, then the radicals R.sub.4 may be
identical or different, c is equal to 0 or 1, R.sub.1 is chosen
from halogen atoms; C.sub.1-C.sub.8 aliphatic and alicyclic,
saturated and unsaturated hydrocarbon-based chains, wherein at
least one carbon atom is optionally replaced with at least one
entity chosen from oxygen, nitrogen, silicon, and sulphur atoms and
an SO.sub.2 group; and an onium radical Z; with the proviso that
the radical R.sub.1 does not comprise a peroxide bond or diazo,
nitro or nitroso radicals, R.sub.2 comprises an onium radical Z,
wherein an onium radical is a nitrogen-based quaternary radical,
R.sub.3 is chosen from an alkyl radical; an alkenyl radical; an
alkynyl radical; a hydroxyl radical; a hydroxyalkyl radical; an
alkoxy radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an amino radical; a monoalkylamino
radical; a dialkylamino; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical; R.sub.4 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyalkyl
radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical.
32. The dye composition according to claim 31, further comprising
at least one coupler chosen from meta-phenylenediamines,
meta-aminophenols, meta-diphenols, naphthalene-based couplers,
heterocyclic couplers, and the addition salts thereof.
33. The composition according to claim 31, comprising at least one
additional oxidation base other than the compound of formula (I),
chosen from para-phenylenediamines, bis(phenyl)alkylenediamines,
para-aminophenols, ortho-aminophenols, heterocyclic bases, and the
addition salts thereof.
34. The composition according to claims 33, wherein, for the at
least one compound of formula (I) and for the at least one
additional oxidation base, if present, each oxidation base in the
dye composition is present in an amount ranging from about 0.001%
to about 10% by weight, relative to the total weight of the dye
composition.
35. The dye composition according to claim 32, wherein the at least
one coupler is present in the dye composition in an amount ranging
from about 0.001% to about 10% by weight, relative to the total
weight of the dye composition.
36. The dye composition according to claim 31, further comprising a
cosmetic medium suitable for dyeing keratin fibers.
37. A process for the oxidation dyeing of keratin fibers,
comprising applying a dye composition to the fibers in the presence
of at least one oxidizing agent, for a time sufficient to develop a
desired coloration, wherein the dye composition comprises, as an
oxidation base, at least one compound of formula (I), and the
addition salts thereof 80wherein: a ranges from 0 to 4, it being
understood that when a is greater than or equal to 2, then the
radicals R.sub.1 may be identical or different, b ranges from 0 to
4, it being understood that when b is greater than or equal to 2,
then the radicals R.sub.4 may be identical or different, c is equal
to 0 or 1, R.sub.1 is chosen from halogen atoms; C.sub.1-C.sub.8
aliphatic and alicyclic, saturated and unsaturated
hydrocarbon-based chains, wherein at least one carbon atom is
optionally replaced with at least one entity chosen from oxygen,
nitrogen, silicon, and sulphur atoms and an SO.sub.2 group; and an
onium radical Z; with the proviso that the radical R.sub.1 does not
comprise a peroxide bond or diazo, nitro or nitroso radicals,
R.sub.2 comprises an onium radical Z, wherein an onium radical is a
nitrogen-based quaternary radical, R.sub.3 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyl
radical; a hydroxyalkyl radical; an alkoxy radical; an alkoxyalkyl
radical; an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an
amino radical; a monoalkylamino radical; a dialkylamino; an
aminoalkyl radical; an aminoalkyl radical wherein the amine is
monosubstituted or disubstituted with at least one radical chosen
from alkyl, acetyl and hydroxyalkyl radicals; a hydroxyl radical; a
aminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a
carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl
radical; a monoalkylaminocarbonyl radical; a dialkylaminocarbonyl
radical; a monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical; R.sub.4 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyalkyl
radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical.
38. The process according to claim 37, wherein the at least one
oxidizing agent is chosen from hydrogen peroxide, urea peroxide,
alkali metal bromates, persalts, peracids and oxidase enzymes.
39. The process according to claim 37, wherein the at least one
oxidizing agent may be added to the dye composition at the time of
application to the fibers or it may be applied in the form of an
oxidizing composition simultaneously or sequentially with the
application of the dye composition.
40. A multi-compartment kit, wherein at least one first compartment
comprises a dye composition comprising, as an oxidation base, at
least one compound of formula (I), and the addition salts thereof
81wherein: a ranges from 0 to 4, it being understood that when a is
greater than or equal to 2, then the radicals R.sub.1 may be
identical or different, b ranges from 0 to 4, it being understood
that when b is greater than or equal to 2, then the radicals
R.sub.4 may be identical or different, c is equal to 0 or 1,
R.sub.1 is chosen from halogen atoms; C.sub.1-C.sub.8 aliphatic and
alicyclic, saturated and unsaturated hydrocarbon-based chains,
wherein at least one carbon atom is optionally replaced with at
least one entity chosen from oxygen, nitrogen, silicon, and sulphur
atoms and an SO.sub.2 group; and an onium radical Z; with the
proviso that the radical R.sub.1 does not comprise a peroxide bond
or diazo, nitro or nitroso radicals, R.sub.2 comprises an onium
radical Z, wherein an onium radical is a nitrogen-based quaternary
radical, R.sub.3 is chosen from an alkyl radical; an alkenyl
radical; an alkynyl radical; a hydroxyl radical; a hydroxyalkyl
radical; an alkoxy radical; an alkoxyalkyl radical; an
alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an amino
radical; a monoalkylamino radical; a dialkylamino; an aminoalkyl
radical; an aminoalkyl radical wherein the amine is monosubstituted
or disubstituted with at least one radical chosen from alkyl,
acetyl and hydroxyalkyl radicals; a hydroxyl radical; a aminoalkyl
radical; a carboxyl radical; a carboxyalkyl radical; a carbamoyl
radical; a carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical; R.sub.4 is chosen from an alkyl
radical; an alkenyl radical; an alkynyl radical; a hydroxyalkyl
radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a
hydroxyalkoxyalkyl radical; an aminoalkyl radical; an aminoalkyl
radical wherein the amine is monosubstituted or disubstituted with
at least one radical chosen from alkyl, acetyl and hydroxyalkyl
radicals; a hydroxyl radical; a aminoalkyl radical; a carboxyl
radical; a carboxyalkyl radical; a carbamoyl radical; a
carbamoylalkyl radical; an alkoxycarbonyl radical; a
monoalkylaminocarbonyl radical; a dialkylaminocarbonyl radical; a
monoalkylaminocarbonylalkyl radical; and a
dialkylaminocarbonylalkyl radical and at least one second
compartment comprises at least one oxidizing agent.
Description
[0001] This application claims benefit of U.S. Provisional
Application No. 60/467,123, filed May 2, 2003.
[0002] The present disclosure relates to novel
para-phenylenediamine derivatives comprising a cyclic diaza group
substituted with a cationic radical, to the dye compositions
comprising at least one para-phenylenediamine as disclosed herein,
and to a process for dyeing keratin fibers using these dye
compositions.
[0003] It is known practice to dye keratin fibers, for instance,
human hair, with dye compositions containing oxidation dye
precursors, such as ortho- or para-phenylenediamines, ortho- or
para-aminophenols, heterocyclic compounds such as diaminopyrazole
derivatives, pyrazolo[1,5-a]pyrimidine derivatives, pyrimidine
derivatives, pyridine derivatives, 5,6-dihydroxyindole derivatives
and 5,6-dihydroxyindoline derivatives, which may also be referred
to as oxidation bases. Oxidation dye precursors, or oxidation
bases, are colorless or weakly colored compounds that, when
combined with oxidizing products, can give rise to colored
compounds and dyes by a process of oxidative condensation.
[0004] It is also known that the shades obtained with these
oxidation bases may be varied by combining them with couplers or
coloration modifiers, the latter being chosen from, for example,
aromatic meta-diamines, meta-aminophenols, meta-hydroxyphenols and
certain heterocyclic compounds such as, for example,
pyrazolo[1,5-b]-1,2,4-triazo- le derivatives,
pyrazolo[3,2-c]-1,2,4-triazole derivatives,
pyrazolo[1,5-a]pyrimidine derivatives, pyridine derivatives,
pyrazol-5-one derivatives, indoline derivatives and indole
derivatives.
[0005] The variety of molecules that may be used as oxidation bases
and couplers allows a wide range of colors to be obtained.
[0006] The "permanent" coloration obtained with these oxidation
dyes should, moreover, satisfy a certain number of requirements.
For instance, it should have no toxicological drawbacks, allow
shades to be obtained in the desired intensity, and show good
resistance to external agents such as light, bad weather, washing,
permanent-waving, perspiration and rubbing.
[0007] The dyes should also allow white hairs to be covered.
Additionally, the dyes should be as unselective as possible, i.e.,
they must produce the smallest possible color differences along the
same length of keratin fiber, which may be differently sensitized
(i.e., damaged) between its end and its root. They should also show
good chemical stability in the formulations, and have a good
toxicological profile.
[0008] In the field of hair dyeing, para-phenylenediamine and
para-tolylenediamine are oxidation bases that are widely used. They
give varied shades with oxidation couplers.
[0009] However, there is a need in the art for novel oxidation
bases that have a better toxicological profile than
para-phenylenediamine and para-tolylenediamine, while at the same
time giving the hair excellent properties in terms of color
intensity, variety of shades, color uniformity and fastness with
respect to external agents.
[0010] It is already known to use para-phenylenediamine derivatives
substituted with a pyrrolidine group as oxidation bases for dyeing
keratin fibers as replacements for para-phenylene-diamine. For
example, U.S. Pat. No. 5,851,237 describes the use of
1-(4-aminophenyl)pyrrolidine derivatives optionally substituted on
the benzene nucleus. U.S. Pat. No. 5,993,491 proposes the use of
N-(4-aminophenyl)-2-hydroxymethylpyrrolidin- e derivatives
optionally substituted on the benzene nucleus and on the
pyrrolidine heterocycle in position 4 with a hydroxyl radical.
[0011] Patent Application JP 11-158,048 teaches compositions
containing at least one compound chosen from para-phenylene-diamine
derivatives optionally substituted on the benzene nucleus, and one
of the nitrogen atoms of which is included in a 5- to 7-membered
carbon ring.
[0012] Publication DE 197 07 545 describes the use of
para-phenylenediamine compounds in which one of the amino groups
forms a diazacycloheptane, for dyeing keratin fibers.
[0013] However, the compounds described in the above mentioned
references do not make it possible to give the hair a coloration
that is equivalent in quality to that obtained with
para-phenylenediamine or with para-tolylenediamine due to the lack
of intensity and uniformity of color.
[0014] The present inventors, therefore, have developed novel dye
compositions that may not have the drawbacks of the oxidation bases
of the prior art. For example, the present inventors provide herein
novel oxidation bases that simultaneously have a good toxicological
profile and properties such that the dye compositions comprising
them do not degrade keratin fibers, while at the same time being
capable of generating colorations in varied shades that are, for
example, strong, unselective and fast.
[0015] Thus, disclosed herein is a compound of formula (I), wherein
the compound is a para-phenylenediamine derivative substituted with
a cyclic diaza group, and addition salts thereof: 1
[0016] wherein
[0017] a ranges from 0 to 4, it being understood that when a is
greater than or equal to 2, then the radicals R.sub.1 may be
identical or different,
[0018] b ranges from 0 to 4, it being understood that when b is
greater than or equal to 2, then the radicals R.sub.4 may be
identical or different,
[0019] c is equal to 0 or 1,
[0020] R.sub.1 may be chosen from halogen atoms; C.sub.1-C.sub.8
aliphatic and alicyclic, saturated and unsaturated,
hydrocarbon-based chains wherein at least one carbon atom may be
replaced with at least one entity chosen from oxygen, nitrogen,
silicon and sulphur atoms and an SO.sub.2 group; and an onium
radical Z; with the proviso that the radical R1 does not comprise a
peroxide bond or diazo, nitro or nitroso radicals,
[0021] R.sub.2 comprises an onium radical Z, wherein an onium
radical is a nitrogen-based quaternary radical,
[0022] R.sub.3 may be chosen from
[0023] an alkyl radical;
[0024] an alkenyl radical;
[0025] an alkynyl radical;
[0026] a hydroxyl radical;
[0027] a hydroxyalkyl radical;
[0028] an alkoxy radical;
[0029] an alkoxyalkyl radical;
[0030] an alkylcarbonyl radical;
[0031] a hydroxyalkoxyalkyl radical;
[0032] an amino radical;
[0033] a monoalkylamino radical;
[0034] a dialkylamino radical;
[0035] an aminoalkyl radical;
[0036] an aminoalkyl radical wherein the amine is monosubstituted
or disubstituted with at least one radical chosen from alkyl,
acetyl and hydroxyalkyl radicals;
[0037] a hydroxyl radical;
[0038] an aminoalkyl radical;
[0039] a carboxyl radical;
[0040] a carboxyalkyl radical;
[0041] a carbamoyl radical;
[0042] a carbamoylalkyl radical;
[0043] an alkoxycarbonyl radical;
[0044] a monoalkylaminocarbonyl radical;
[0045] a dialkylaminocarbonyl radical;
[0046] a monoalkylaminocarbonylalkyl radical; and
[0047] a dialkylaminocarbonylalkyl radical;
[0048] R.sub.4 may be chosen from
[0049] an alkyl radical;
[0050] an alkenyl radical;
[0051] an alkynyl radical;
[0052] a hydroxyalkyl radical;
[0053] an alkoxyalkyl radical;
[0054] an alkylcarbonyl radical;
[0055] a hydroxyalkoxyalkyl radical;
[0056] an aminoalkyl radical;
[0057] an aminoalkyl radical wherein the amine is monosubstituted
or disubstituted with at least one radical chosen from alkyl,
acetyl and hydroxyalkyl radicals;
[0058] a hydroxyl radical;
[0059] a aminoalkyl radical;
[0060] a carboxyl radical;
[0061] a carboxyalkyl radical;
[0062] a carbamoyl radical;
[0063] a carbamoylalkyl radical;
[0064] an alkoxycarbonyl radical;
[0065] a monoalkylaminocarbonyl radical;
[0066] a dialkylaminocarbonyl radical;
[0067] a monoalkylaminocarbonylalkyl radical; and
[0068] a dialkylaminocarbonylalkyl radical.
[0069] Also disclosed herein are the nitro derivatives of formula
(I') included in the synthesis of the derivatives of formula (I) as
presently disclosed.
[0070] Further disclosed herein is a dye composition comprising at
least one para-phenylenediamine compound of formula (I) as an
oxidation base.
[0071] Yet another aspect of the present disclosure is the use of
the aforementioned composition for dyeing keratin fibers and the
process for dyeing keratin fibers, for instance human keratin
fibers such as hair, using the composition of the present
disclosure.
[0072] The composition of the present disclosure, for example,
makes it possible to obtain a chromatic, powerful, unselective and
fast coloration of keratin fibers.
[0073] In the context of the present disclosure, an aliphatic
hydrocarbon-based chain is a linear or branched chain that may
contain unsaturations of the alkene or alkyne type. An alicyclic
hydrocarbon-based chain is a saturated or unsaturated, branched
chain not containing an aromatic cyclic structure.
[0074] The term "onium" means a nitrogen-based quaternary
radical.
[0075] The compounds of formula (I) are para-phenylenediamines
wherein one amine is included in a ring of 1,4-diazacycloheptane
type, this ring also being referred to in the literature as
1,4-diazepane, or wherein one amine is included in a ring of
1,4-diazacyclohexane type, which is also referred to in the
literature as 1,4-piperazine.
[0076] In formula (I) above, R.sub.1 may be chosen from
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 alkoxyalkyl
radicals, C.sub.1-C.sub.4 hydroxyalkyl radicals, C.sub.1-C.sub.4
aminoalkyl radicals, C.sub.1-C.sub.4 alkoxy radicals,
C.sub.1-C.sub.4 hydroxyalkoxy radicals, and C.sub.1-C.sub.4
carboxyalkyl radicals.
[0077] By way of non-limiting example, R.sub.1 may be chosen from a
chlorine atom, and from methyl, ethyl, isopropyl, vinyl, allyl,
methoxymethyl, 1-hydroxyethyl, 1-carboxymethyl, 1-aminomethyl,
2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl,
1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 1-amino-2-hydroxyethyl,
1,2-diaminoethyl, methoxy, ethoxy, allyloxy and 2-hydroxyethyloxy
radicals.
[0078] According to one aspect of the present disclosure, R.sub.1
may be chosen from chlorine, bromine, and from C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 hydroxyalkyl, C.sub.1-C.sub.4 aminoalkyl,
C.sub.1-C.sub.4 alkoxy and C.sub.1-C.sub.4 hydroxyalkoxy radicals.
R.sub.1 may, for instance, be chosen from methyl, hydroxymethyl,
2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy, isopropyloxy and
2-hydroxyethoxy radicals.
[0079] In one embodiment, a may be equal to 0 or 1, for example, a
may be 0.
[0080] In another embodiment, R.sub.2 comprises an onium radical Z
corresponding to formula (II) 2
[0081] wherein
[0082] D is a linker arm chosen from a covalent bond and from
linear and branched C.sub.1-C.sub.14 alkylene chains which may
comprise at least one hetero atom chosen from oxygen, sulphur and
nitrogen, and which may be substituted with at least one radical
chosen from hydroxyl and amino radicals, and which may further
comprise at least one carbonyl radical;
[0083] R.sub.8, R.sub.5 and R.sub.6, which may be identical or
different, may each be chosen from C.sub.1-C.sub.15 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals;
(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6)alkyl radicals; aryl
radicals; benzyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals; C.sub.1-C.sub.6 aminoalkyl
radicals wherein the amine is mono- or disubstituted with a radical
chosen from C.sub.1-C.sub.4 alkyl, (C.sub.1-C.sub.6)alkylcarbonyl,
carbamoyl and (C.sub.1-C.sub.6)alkylsulphonyl radicals; and
quaternary ammonium radicals;
[0084] R.sub.8, R.sub.5 and R.sub.6 together, in pairs, may form,
with the nitrogen atom to which they are attached, a saturated 4-,
5-, 6- or 7-membered carbon-based ring optionally comprising at
least one hetero atom, wherein the ring may possibly be substituted
with a radical chosen from a hydroxyl radical, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-- C.sub.6)alkyl
radicals, carbamoyl radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, amino radicals, and amino
radicals mono- or disubstituted with at least one radical chosen
from (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl,
carbamoyl and (C.sub.1-C.sub.6)alkylsulphonyl radicals;
[0085] R.sub.7 may be chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; aryl radicals; benzyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals; C.sub.1-C.sub.6 aminoalkyl
radicals wherein the amine is mono- or disubstituted with at least
one radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carboxyalkyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(- C.sub.1-C.sub.6)alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
and N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals;
[0086] x is equal to 0 or 1, provided that
[0087] when x=0, then the linker arm D is attached to the nitrogen
atom bearing the radicals R.sub.5, R.sub.6 and R.sub.8,
[0088] when x=1, then two of the radicals R.sub.5, R.sub.6 and
R.sub.8 form, together with the nitrogen atom to which they are
attached, a 4-, 5-, 6- or 7-membered saturated ring and the linker
arm D is linked to a carbon atom of the saturated ring;
[0089] Y is a counterion.
[0090] According to this aspect of the present disclosure, x may
be, for example, equal to 0, and R.sub.5, R.sub.6 and R.sub.8,
which may be identical or different, may each be chosen from
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.6 carbamoylalkyl radicals, and
tri(C.sub.1-C.sub.6)-alkylsilane(C.sub.1-C.sub.6)alkyl radicals, or
R.sub.8 and R.sub.5 together may form a ring chosen from azetidine,
pyrrolidine, piperidine, piperazine and morpholine, wherein R.sub.6
may be chosen from C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals; C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; C.sub.1-C.sub.6 aminoalkyl radicals, aminoalkyl radicals
mono- or disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl
radicals.
[0091] According to still another aspect, x is equal to 1, and
R.sub.7 may be chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamylalkyl radicals;
tri(C.sub.1-C.sub.6)-alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)alkylcarbamyl(C.sub.1-C.sub.6)alkyl radicals;
R.sub.8 and R.sub.5 together form a ring chosen from azetidine,
pyrrolidine, piperidine, piperazine and morpholine rings, wherein
R.sub.6 may be chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; C.sub.1-C.sub.6 aminoalkyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals wherein the amine is mono- or
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.sub.6)alkyl radicals; and
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl
radicals.
[0092] By way of a non-limiting example according to this aspect of
the disclosure, R.sub.2 may comprise a trialkylammoniumalkyl
radical, wherein the alkyl linking R.sub.2 to the ring may possibly
be substituted with at least one hydroxyl group.
[0093] For instance, D may be chosen from a covalent bond and an
alkylene chain that may be substituted and that may comprise a
carbonyl group.
[0094] According to yet another aspect of the present disclosure,
R.sub.2 comprises an onium radical Z corresponding to formula
(III): 3
[0095] wherein
[0096] D is a linker arm chosen from a covalent bond and from
linear and branched C.sub.1-C.sub.14 alkylene chains, which may
comprise at least one hetero atom chosen from oxygen, sulphur and
nitrogen, and which may be substituted with at least one radical
chosen from hydroxyl and amino radicals, and which further may
comprise at least one carbonyl radical;
[0097] the ring members E, G, J and L, which may be identical or
different, may be chosen from carbon, oxygen, sulphur and nitrogen
atoms to form a ring chosen from pyrrole, pyrazole, imidazole,
triazole, oxazole, isoxazole, thiazole and isothiazole rings,
[0098] q is an integer ranging from 1 to 4;
[0099] R, which may be identical or different, may be chosen from a
hydrogen atom, halogen atoms, hydroxyl radicals, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl
radicals, carbamoyl radicals, carboxyl radicals, C.sub.1-C.sub.6
alkylcarbonyl radicals, amino radicals, amino radicals mono- and
disubstituted with at least one radical chosen from
(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbony- l, carbamoyl
and (C.sub.1-C.sub.6)alkylsulphonyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals C.sub.2-C.sub.6 polyhydroxyalkyl
radicals, and quaternary ammonium radicals;
[0100] R.sub.7 may be chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; aryl radicals; benzyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals, C.sub.1-C.sub.6 aminoalkyl
radicals wherein the amine is substituted with a radical chosen
from (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl,
carbamoyl and (C.sub.1-C.sub.6)alkylsulphonyl radicals;
C.sub.1-C.sub.6 carboxyalkyl radicals; C.sub.1-C.sub.6
carbamoylalkyl radicals; C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; and quaternary ammonium radicals;
[0101] x is equal to 0 or 1, with the proviso that
[0102] when x=0, the linker arm D is attached to the nitrogen
atom,
[0103] when x=1, the linker arm D is attached to one of the ring
members E, G, J or L, and
[0104] Y is a counterion.
[0105] According to this aspect of the disclosure, the ring members
E, G, J and L form, for example, a ring chosen from pyrrole,
imidazole, pyrazole, oxazole, thiazole and triazole rings. For
instance, the ring members E, G, J and L may form an imidazole
ring.
[0106] When x is equal to 0, D may be, for example, chosen from a
covalent bond and an alkylene chain that may be substituted and/or
that may comprise a carbonyl function.
[0107] According to yet still another aspect of the present
disclosure, R.sub.2 comprises an onium radical Z corresponding to
formula (IV): 4
[0108] wherein:
[0109] D is a linker arm chosen from a covalent bond and from
linear and branched C.sub.1-C.sub.14 alkylene chains, which may
comprise at least one hetero atom chosen from oxygen, sulphur and
nitrogen atoms, and which may be substituted with at least one
radical chosen from hydroxyl and amino radicals, and which further
may comprise at least one carbonyl radical;
[0110] the ring members E, G, J, L and M, which may be identical or
different, may be chosen from carbon, oxygen, sulphur and nitrogen
atoms, and thus form a ring chosen from pyridine, pyrimidine,
pyrazine, triazine and pyridazine rings;
[0111] m is an integer ranging from 1 to 5;
[0112] R, which may be identical or different, may be chosen from a
hydrogen atom, halogen atoms, hydroxyl radicals, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl
radicals, carbamoyl radicals, carboxyl radicals, C.sub.1-C.sub.6
alkylcarbonyl radicals, amino radicals, amino radicals substituted
with a radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals, C.sub.2-C.sub.6 polyhydroxyalkyl
radicals, and quaternary ammonium radicals;
[0113] R.sub.7 is chosen from C.sub.1-C.sub.6 alkyl radicals;
C.sub.1-C.sub.6 monohydroxyalkyl radicals; C.sub.2-C.sub.6
polyhydroxyalkyl radicals; aryl radicals; benzyl radicals;
C.sub.1-C.sub.6 aminoalkyl radicals; C.sub.1-C.sub.6 aminoalkyl
radicals wherein the amine is mono- and disubstituted with a
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
carboxyalkyl radicals; C.sub.1-C.sub.6 carbamoylalkyl radicals;
C.sub.1-C.sub.6 trifluoroalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)- alkyl radicals;
C.sub.1-C.sub.6 sulphonamidoalkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphinyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylsulphonyl(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylcarbamoyl(C.sub.1-C.sub.6)alkyl radicals;
N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; and quaternary ammonium radicals;
[0114] x is equal to 0 or 1, with the proviso that
[0115] when x=0, the linker arm D is attached to the nitrogen
atom,
[0116] when x=1, the linker arm D is attached to one of the ring
members E, G, J, L or M, and
[0117] Y.sup.- is a counterion.
[0118] In this aspect, the ring members E, G, J, L and M may form,
for example, with the nitrogen of the ring, a ring chosen from
pyridine and pyrimidine rings.
[0119] For further example, when x is equal to 0, then R may be
chosen from a hydrogen atom, hydroxyl radicals, C.sub.1-C.sub.6
alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl radicals,
C.sub.2-C.sub.6 polyhydroxyalkyl radicals, C.sub.1-C.sub.6 alkoxy
radicals, tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl
radicals, carbamoyl radicals, C.sub.1-C.sub.6 alkylcarbonyl
radicals, amino radicals, amino radicals mono- and disubstituted
with at least one radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbonyl, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals.
[0120] As yet another example, when x is equal to 1, R.sub.7 may be
chosen from C.sub.1-C.sub.6 alkyl radicals; C.sub.1-C.sub.6
monohydroxyalkyl radicals; C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; C.sub.1-C.sub.6 aminoalkyl radicals; C.sub.1-C.sub.6
aminoalkyl radicals wherein the amine is mono- or disubstituted
with at least one radical chosen from (C.sub.1-C.sub.6)alkyl
radicals, (C.sub.1-C.sub.6)alkylcarbonyl radicals, a carbamoyl
radical and (C.sub.1-C.sub.6)alkylsulphonyl radicals;
C.sub.1-C.sub.6 carbamoylalkyl radicals;
tri(C.sub.1-C.sub.6)alkylsilane(- C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbonyl(C.sub.1-C.s- ub.6)alkyl radicals;
and N-(C.sub.1-C.sub.6)alkylcarbamyl(C.sub.1-C.sub.6)- alkyl
radicals; R may be chosen from a hydrogen atom, hydroxyl radicals,
C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6 monohydroxyalkyl
radicals, C.sub.2-C.sub.6 polyhydroxyalkyl radicals,
C.sub.1-C.sub.6 alkoxy radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.sub.1-C.sub.6)alkyl radicals,
carbamoyl radicals, C.sub.1-C.sub.6 alkylcarbonyl radicals, amino
radicals, amino radicals mono- and disubstituted with at least one
radical chosen from (C.sub.1-C.sub.6)alkyl,
(C.sub.1-C.sub.6)alkylcarbony- l, carbamoyl and
(C.sub.1-C.sub.6)alkylsulphonyl radicals.
[0121] For instance, R may be chosen from a hydrogen atom and alkyl
radicals that may be substituted, and R.sub.7 comprises an alkyl
radical that may be substituted.
[0122] According to another aspect of the present disclosure, R may
be chosen from hydrogen; alkyl radicals; alkyl radicals substituted
with at least one hydroxyl; alkyl radicals substituted with at
least one amino; carboxyl radicals; and carbamoyl radicals. By way
of non-limiting example, mention may be made of when R is chosen
from hydrogen and from at least one radical chosen from hydroxyl,
methyl, amino, hydroxymethyl, and aminomethyl radicals. In one
embodiment, R is hydrogen.
[0123] In formula (I) above, for instance, b may be equal to 0, or
R.sub.4 may be chosen from alkyl radicals; alkyl radicals
substituted with at least one hydroxyl; alkyl radicals substituted
with at least one amino; carboxyl radicals; and carbamoyl radicals.
For example, R.sub.4 may be hydrogen.
[0124] In formula (I) above, R.sub.3 may be, for instance, chosen
from hydrogen; hydroxyl radicals; amino radicals; alkyl radicals;
alkyl radicals substituted with at least one hydroxyl; alkyl
radicals substituted with at least one amino; carboxyl radicals;
and carbamoyl radicals. For example, R.sub.3 may be hydrogen.
[0125] The carbon substituted with R.sub.3 or with R.sub.4 may be
of (R) and (S) configuration.
[0126] The counterions Y.sup.- may be chosen, for example, from a
halogen atom, a hydroxide, a hydrogen sulphate, an acetate, a
tartrate and a (C.sub.1-C.sub.6)alkyl sulphate. For instance,
Y.sup.- may be chosen from a methyl sulphate and an ethyl
sulphate.
[0127] Non-limiting examples of derivatives of formula (I) that may
be mentioned include:
1 Formula Nomenclature 5
3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]-2-oxoethyl}-1-methyl-
3H-imidazol-1-ium chloride 6 3-{2-[4-(4-Amino-phenyl)[1,4-
]diazepan-1-yl]ethyl}-1-methyl-3H- imidazol-1-ium chloride 7
3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]propyl}-
trimethylammonium chloride 8 {2-[4-(4-Amino-phenyl)[1,4]diazepan-1-
yl]ethyl}trimethylammonium chloride 9
1-{3-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]propyl}-1-
methylpyrrolidinium chloride 10
{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethy- l}-(2-
hydroxyethyl)dimethylammonium chloride 11
{3-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}dimethyl(ethyl-2-
methyl-3H-imidazol-1-ium chloride) ammonium; chloride 12
3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]propyl}-1-methyl-3H-
imidazol-1-ium chloride 13 {2-[4-(4-Amino-phenyl)[1,4]dia-
zepan-1-yl]ethyl}dimethyl-(3- trimethylsilanyl-propyl)ammonium;
chloride 14 3-{2-[4-(4-Amino-phenyl)[1,4]diazepan-1-yl]ethyl}-1-(3-
trimethylsilanyl-propyl)-3H-imidazol- 1-ium chloride 15
3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-2-oxoethyl}-1- methyl-3H-imidazol-1-ium
chloride 16 3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]ethyl}-1- methyl-3H-imidazol-1-ium chloride 17
{3-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-propyl}trimethylammon- ium chloride 18
{2-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]ethyl}-
trimethylammonium chloride 19 {3-[4-(4-Amino-3-methylphenyl)
[1,4]-diazepan-1-yl]-propyl}-1- methyl-3H-imidazol-1-ium chloride
20 {2-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]ethyl}(2-
hydroxyethyl)-dimethylammonium chloride 21
{3-[4-(4-Amino-3-methylphenyl) [1,4]-diazepan-1-yl]ethyl}-dimethyl
(ethyl-2-methyl-3H-imidazol-1-ium chloride)ammonium chloride 22
1-{3-[4-(4-Amino-3-methylphenyl) [1,4]diazepan-1-yl]propyl}-1-
methyl-pyrrolidinium; chloride 23 {2-[4-(4-Amino-3-methyl- phenyl)
[1,4]-diazepan-1-yl]ethyl}-dimethyl (3-trimethylsilanylpropyl)ammo-
nium chloride 24 3-{2-[4-(4-Amino-3-methylphenyl)
[1,4]diazepan-1-yl]ethyl}-1- (3-trimethylsilanylpropyl)-3H-
imidazol-1-ium chloride 25 {3-[4-(4-Amino-phenyl)[1,4]dia-
zepan-1-yl]-2-hydroxy-propyl}trimethylammonium; chloride 26
{3-[4-(4-Amino-methylphenyl)[1,4-
diazepan-1-yl]-2-hydroxypropyl}trime- thylammonium; chloride 27
3-{2-[4-(4-Amino-phenyl)piperazi- n- 1-yl]-2-oxoethyl}-1-methyl-3H-
imidazol-1-ium chloride 28 {3-[4-(4-Amino-phenyl)piperazin-1-
yl]-2-hydroxypropyl}trimethylammoni- um chloride 29
3-{2-[4-(4-Amino-3-methylphenyl) piperazin-1-yl]-2-oxoethyl}-1-
methyl-3H-imidazol-1-ium chloride 30 3-[4-(4-Amino-3-methylphenyl)
piperazin-1-yl]-2-hydroxypropyl}- trimethylammonium chloride 31
3-{2-[4-(4-Amino-3-phenyl) piperazin-1-yl]ethyl}-1-methyl-3H-
imidazol-1-ium chloride 32 {3-[4-(4-Amino-3-phenyl)
piperazin-1-yl]propyl}trimethylammonium chloride 33
3-{2-[4-(4-Amino-3-methylphenyl) piperazin-1-yl]ethyl}-1-methyl-3H-
imidazol-1-ium chloride 34 {3-[4-(4-Amino-3-methylphenyl)
piperazin-1-yl]-propyl}trimethylammoni- um chloride 35
1-{3-[4-(4-Amino-phenyl) piperazin-1-yl]propyl}-1-
methylpyrrolidinium chloride 36 1-{3-[4-(4-Amino-3-phenyl)
piperazin-1-yl]propyl}-1- methylpyrrolidinium chloride
[0128] For example, the derivatives of formula (I) may be chosen
from:
[0129]
3-{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]-2-oxoethyl}-1-methyl-3H--
imidazol-1-ium chloride
[0130]
3-{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]ethyl}-1-methyl-3H-imidaz-
ol-1-ium chloride
[0131]
{3-[4-(4-aminophenyl)[1,4]diazepan-1-yl]propyl}trimethylammonium
chloride
[0132]
{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]ethyl}trimethylammonium
chloride
[0133]
1-{3-[4-(4-aminophenyl)[1,4]diazepan-1-yl]propyl}-1-methylpyrrolidi-
nium chloride
[0134]
{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]ethyl}(2-hydroxyethyl)dimet-
hylammonium chloride
[0135]
3-{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]propyl}-1-methyl-3H-imida-
zol-1-ium chloride
[0136]
{3-[4-(4-aminophenyl)[1,4]diazepan-1-yl]-2-hydroxypropyl}trimethyla-
mmonium chloride
[0137]
3-{2-[4-(4-aminophenyl)piperazin-1-yl]-2-oxoethyl}-1-methyl-3H-imid-
azol-1-ium chloride
[0138]
{3-[4-(4-aminophenyl)piperazin-1-yl]-2-hydroxypropyl}trimethylammon-
ium chloride
[0139]
3-{2-[4-(4-aminophenyl)piperazin-1-yl]ethyl}-1-methyl-3H-imidazol-1-
-ium chloride
[0140] {3-[4-(4-aminophenyl)piperazin-1-yl]propyl}trimethylammonium
chloride
[0141]
1-{3-[4-(4-aminophenyl)piperazin-1-yl]propyl}-1-methylpyrrolidinium
chloride.
[0142] The compounds of formula (I) may be obtained, for example,
from the syntheses described in Patent Application FR
2,828,488.
[0143] The cationic compounds of formula (I) may be obtained via
the following synthetic route: 37
[0144] Another aspect of the present invention is also the nitro
compounds that are useful in the synthesis of the compounds of
formula (I). These nitro compounds correspond to formula (I')
38
[0145] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, a, b and c are
as defined above.
[0146] The dye composition of the present disclosure comprises, in
a medium that is suitable for dyeing keratin fibers, such as human
hair, at least one derivative of formula (I) as defined above as an
oxidation base.
[0147] The at least one oxidation base of the present disclosure
may be present in the composition in an amount, for each oxidation
base, if there are more than one, ranging from about 0.001% to
about 10% by weight, relative to the total weight of the dye
composition, such as from about 0.005% to about 6%.
[0148] The dye composition of the present disclosure may comprise
at least one coupler conventionally used for dyeing keratin fibers.
Among these couplers that may be mentioned, for example, are
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthalene-based couplers, heterocyclic couplers, and the addition
salts thereof.
[0149] Non-limiting examples of couplers that may be mentioned
include 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-methylphenol,
6-chloro-2-methyl-5-aminophenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene,
2-amino-4-(.beta.-hydroxye- thylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenox- y)propane,
3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol,
1.beta.-hydroxyethylamino-3,4-methylenedioxybenzene,
.alpha.-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole,
4-hydroxyindole, 4-hydroxy-N-methylindole,
2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine,
3,5-diamino-2,6-dimethoxypyridine,
1-N-(.beta.-hydroxyethyl)amino-3,4-methylenedioxybenzene,
2,6-bis(.beta.-hydroxyethylamino)toluene, and the acid addition
salts thereof.
[0150] In the dye composition disclosed herein, the at least one
coupler may be present in the dye composition in an amount ranging
from about 0.001% to about 10% by weight, relative to the total
weight of the dye composition, such as ranging from about 0.005% to
about 6%.
[0151] The composition of the present disclosure may also
optionally comprise at least one additional oxidation base
conventionally used in oxidation dyeing, other than theose of
formula (I). By way of example, the optional at least one
additional oxidation base may be chosen from para-phenylenediamines
other than those described above, bis(phenyl)alkylenediamines,
para-aminophenols, bis-para-aminophenols, ortho-aminophenols,
heterocyclic bases, and the addition salts thereof.
[0152] For example, without limitation, among the optional at least
one additional para-phenylenediamine mention may be made of
para-phenylenediamine, para-tolylenediamine,
2-chloro-para-phenylenediami- ne,
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,
4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine,
2-.beta.-hydroxyethylamino-5-aminotoluen- e and
3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the acid addition
salts thereof.
[0153] Among the para-phenylenediamines mentioned above, for
example, para-phenylenediamine, para-tolylenediamine,
2-isopropyl-para-phenylenedi- amine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenyle- nediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylened-
iamine, N,N-bis(p-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine,
2-.beta.-acetylaminoethyloxy-para-phenyle- nediamine, and the acid
addition salts thereof may be used.
[0154] Among the bis(phenyl)alkylenediamines that may be used,
non-limiting mention may be made, for example, of
N,N'-bis(.beta.-hydroxy-
ethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,
N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(.beta.-hydroxyethy-
l)N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(4-methylaminophen- yl) tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphen-
yl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane,
and the acid addition salts thereof.
[0155] Among the para-aminophenols which may be used, non-limiting
mention may be made, for 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 the acid addition salts thereof.
[0156] Among the ortho-aminophenols which can be used, non-limiting
mention may be made, for example, of 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetacarbamoyl-2-aminop- henol, and the acid addition salts
thereof.
[0157] Among the heterocyclic bases that may be used, non-limiting
mention may be made, for example, of pyridine derivatives,
pyrimidine derivatives and pyrazole derivatives.
[0158] Among the pyridine derivatives that may be used,
non-limiting mention may be made of the compounds described, for
example, in patents GB 1,026,978 and GB 1,153,196, as well as
2,5-diaminopyridine; 2-(4-methoxyphenyl)amino-3-aminopyridine;
2,3-diamino-6-methoxypyridine;
2-(.beta.-methoxyethyl)amino-3-amino-6-methoxypyridine;
3,4-diaminopyridine; and the acid addition salts thereof.
[0159] Other pyridine oxidation bases that may be useful in the
present dye composition as disclosed herein are the
3-aminopyrazolo[1,5-a]pyridin- e oxidation bases and the addition
salts thereof described, for example, in patent application FR
2,801,308. By way of example, non-limiting mention may be made of
pyrazolo[1,5-a]pyrid-3-ylamine;
2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine;
2-morpholin-4-ylpyrazolo[1,5- -a]pyrid-3-ylamine;
3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid,
2-methoxypyrazolo[1,5-a]pyrid-3-ylamine;
(3-aminopyrazolo[1,5-a]pyrid-7-y- l)methanol;
2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol;
2,3-aminopyrazolo[1,5-a]pyrid-7-yl)ethanol;
(3-aminopyrazolo[1,5-a]pyrid-- 2-yl)-methanol;
3,6-diaminopyrazolo[1,5-a]pyridine;
3,4-diaminopyrazolo[1,5-a]pyridine;
pyrazolo[1,5-a]pyridine-3,7-diamine;
7-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine;
pyrazolo[1,5-a]pyridine-3- ,5-diamine;
5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine;
2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol;
2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)
(2-hydroxyethyl)amino]ethanol; 3-aminopyrazolo-[1,5-a]pyrid-5-ol;
3-aminopyrazolo[1,5-a]pyrid-4-ol; 3-aminopyrazolo[1,5-a]pyrid-6-ol;
3-aminopyrazolo[1,5-a]pyrid-7-ol and also the addition salts
thereof with an acid or with a base.
[0160] Among the pyrimidine compounds which may be used,
non-limiting mention may be made of the compounds described, for
example, in German Patent DE 2,359399, or Japanese Patents JP
88-169,571; JP 05,63,124; EP 0,770,375 or patent application WO
96/15765, such as 2,4,5,6-tetraminopyrimidine,
4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.
Among the pyrazolopyrimidine derivatives that may be used,
non-limiting mention may be made for instance, of those mentioned
in patent application FR-A-2,750,048 and among which mention may be
made of 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-(3-aminopyrazolo[1,5-a]pyrimidin-- 7-ylamino)ethanol;
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;
3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine;
and the acid addition salts thereof and the tautomeric forms
thereof, when a tautomeric equilibrium exists.
[0161] Among the pyrazole derivatives that may be used,
non-limiting mention may be made of the compounds described in
patents DE 3,843,892 and DE 4,133,957 and patent applications WO
94/08969, WO 94/08970, FR-A-2,733,749 and DE 195,43,988, such as
4,5-diamino-1-methylpyrazole;
4,5-diamino-1-(.beta.-hydroxyethyl)pyrazole; 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-phenylpyra- zole;
4-amino-1,3-dimethyl-5-hydrazinopyrazole;
1-benzyl-4,5-diamino-3-met- hylpyrazole;
4,5-diamino-3-tert-butyl-1-methylpyrazole;
4,5-diamino-1-tert-butyl-3-methylpyrazole;
4,5-diamino-1-(.beta.-hydroxye- thyl)-3-methylpyrazole;
4,5-diamino-1-ethyl-3-methylpyrazole;
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole;
4,5-diamino-1-ethyl-3-h- ydroxymethylpyrazole;
4,5-diamino-3-hydroxymethyl-1-methylpyrazole;
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole;
4,5-diamino-3-methyl-1-i- sopropylpyrazole;
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 acid addition salts thereof.
[0162] As defined above, the optional at least one additional
oxidation base, when present, is present in an amount, for each
additional oxidation base, ranging from about 0.001% to about 10%
by weight relative to the total weight of the dye composition, for
example, from about 0.005% to about 6%.
[0163] The addition salts of the oxidation bases and of the
couplers that may be used in the dye compositions disclosed herein
may be chosen from, for example, the addition salts with an acid,
such as the hydrochlorides, hydrobromides, sulphates, citrates,
succinates, tartrates, lactates, tosylates, benzenesulphonates,
phosphates and acetates; and the addition salts with a base, such
as sodium hydroxide, potassium hydroxide, ammonia, amines and
alkanolamines.
[0164] The dye composition in accordance with the present
disclosure may also comprise at least one direct dye that may be
chosen from for example, nitrobenzene dyes, azo direct dyes and
methine direct dyes. The direct dyes may be of nonionic, anionic or
cationic nature.
[0165] A medium suitable for dyeing, also known as the dye support,
comprises water or a mixture of water and at least one organic
solvent to dissolve the compounds that would not be sufficiently
soluble in water. Among the organic solvents that may be used,
non-limiting mention may be made, for example, of C.sub.1-C.sub.4
lower alkanols, such as ethanol and isopropanol; polyols and polyol
ethers such as 2-butoxyethanol, propylene glycol, propylene glycol
monomethyl ether, diethylene glycol monoethyl ether and monomethyl
ether, as well as aromatic alcohols such as benzyl alcohol,
phenoxyethanol, and mixtures thereof.
[0166] The at least one solvent may be present in the dye
composition in an amount, for example, ranging from about 1% to
about 40% by weight, relative to the total weight of the dye
composition, such as ranging from about 5% to about 30% by
weight.
[0167] The dye composition in accordance with the present
disclosure can also comprise various adjuvants conventionally used
in compositions for dyeing the hair, such as anionic, cationic,
nonionic, amphoteric, and zwitterionic surfactants and mixtures
thereof; anionic, cationic, nonionic, amphoteric, and zwitterionic
polymers, and mixtures thereof; inorganic or organic thickeners,
for instance, anionic, cationic, nonionic and amphoteric
associative polymeric thickeners, antioxidants, penetration agents,
sequestering agents, fragrances, buffers, dispersing agents,
packaging agents such as, for example, silicones, which may or may
not be volatile or modified, film-forming agents, ceramides,
preserving agents and opacifiers.
[0168] The above adjuvants may be present in the dye composition in
an amount for each of them ranging from about 0.01% to about 20% by
weight, relative to the total weight of the dye composition.
[0169] Needless to say, a person skilled in the art will take care
to select any of the optional additional compounds such that the
advantageous properties intrinsically associated with the oxidation
dye composition in accordance with the present disclosure are not,
or are not substantially, adversely affected by the addition
envisaged.
[0170] The pH of the dye composition in accordance with the present
disclosure may range from about 3 to about 12, such as from about 5
to about 11. It may be adjusted to the desired value using
acidifying or basifying agents usually used in the dyeing of
keratin fibers, or alternatively using standard buffer systems.
[0171] Among the acidifying agents that may be used, non-limiting
mention may be made, for example, of inorganic and organic acids
such as hydrochloric acid, orthophosphoric acid, sulphuric acid,
carboxylic acids such as acetic acid, tartaric acid, citric acid,
lactic acid, and sulphonic acids.
[0172] Among the basifying agents that may be used, non-limiting
mention may be made, for example, of aqueous ammonia, alkaline
carbonates, alkanolamines such as mono-, di- and triethanolamine
and derivatives thereof, sodium hydroxide, potassium hydroxide and
the compounds of formula (V): 39
[0173] wherein W is a propylene residue that may be unsubstituted,
or substituted with a hydroxyl group or a C.sub.1-C.sub.4 alkyl
radical; R.sub.a, R.sub.b, R.sub.c and R.sub.d, which may be
identical or different, are chosen from a hydrogen atom,
C.sub.1-C.sub.4 alkyl radicals and C.sub.1-C.sub.4 hydroxyalkyl
radicals.
[0174] The dye composition according to the present disclosure may
be in various forms, such as liquids, creams and gels, or in any
other form that is suitable for dyeing keratin fibers, such as
human hair.
[0175] The process of the present disclosure is a process wherein
the dye composition as described above is applied to the fibers,
and the color is developed using an oxidizing agent. The color may
be developed at acidic, neutral or alkaline pH and the oxidizing
agent may be added to the composition as disclosed herein just at
the time of use, or it may be used starting with an oxidizing
composition comprising it, which is applied simultaneously or
sequentially to the composition of the invention.
[0176] According to one aspect, the dye composition according to
the present disclosure is mixed, for example, at the time of use,
with a composition comprising, in a medium that is suitable for
dyeing, at least one oxidizing agent, this oxidizing agent being
present in an amount that is sufficient to develop a coloration.
The mixture obtained is then applied to keratin fibers. After an
action time of 3 to 50 minutes approximately, such as 5 to 30
minutes approximately, the keratin fibers are rinsed, washed with
shampoo, rinsed again and then dried.
[0177] The oxidizing agents conventionally used for the oxidation
dyeing of keratin fibers include, for example, hydrogen peroxide,
urea peroxide, alkali metal bromates, persalts such as perborates
and persulphates, peracids and oxidase enzymes, among which,
non-limiting mention may be made of peroxidases, 2-electron
oxidoreductases such as uricases, and 4-electron oxygenases, for
instance laccases. For example, the oxidizing agent may be hydrogen
peroxide.
[0178] The oxidizing composition may also comprise various
adjuvants conventionally used in compositions for dyeing the hair
and as defined above.
[0179] The pH of the oxidizing composition comprising the oxidizing
agent is such that, after mixing with the dye composition, the pH
of the resulting composition applied to the keratin fibers ranges
for example, from about 3 to about 12, for instance from about 5 to
about 11. The pH may be adjusted to the desired value by means of
acidifying or basifying agents usually used in the dyeing of
keratin fibers and as defined above.
[0180] The ready-to-use composition that is finally applied to the
keratin fibers may be in various forms, such as in the form of
liquids, creams, gels, or any other form that is suitable for
dyeing keratin fibers, such as human hair.
[0181] Another aspect of the present disclosure is a
multi-compartment dyeing device or "kit," in which at least one
first compartment contains the dye composition as disclosed herein,
and at least one second compartment contains an oxidizing
composition. This device may be equipped with a means for applying
the desired mixture to the hair, such as the devices described in
patent FR-2,586,913 in the name of L'Oreal.
[0182] Using this device, it is possible to dye keratin fibers
using a process that includes mixing a dye composition comprising
at least one oxidation base of formula (I) with an oxidizing agent,
and applying the mixture obtained to the keratin fibers for a time
that is sufficient to develop the desired coloration.
[0183] Other than in the examples, or where otherwise indicated,
all numbers expressing quantities of ingredients, reaction
conditions, and so forth used in the specification and claims are
to be understood as being modified in all instances by the term
"about." Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the following specification and
attached claims are approximations that may vary depending upon the
desired properties sought to be obtained herein. At the very least,
and not as an attempt to limit the application of the doctrine of
equivalents to the scope of the claims, each numerical parameter
should be construed in light of the number of significant digits
and ordinary rounding approaches.
[0184] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope are approximations, the numerical
values set forth in the specific examples are reported as precisely
as possible. Any numerical value, however, inherently contain
certain errors necessarily resulting from the standard deviation
found in their respective testing measurements. The following
examples are intended to illustrate the invention without limiting
the scope as a result.
EXAMPLES
Example 1
Preparation of
3-{2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]-2-oxoethyl}-1-me-
thyl-3H-imidazol-1-ium Chloride Dihydrochloride (4)
[0185] 40
1.sup.st Step: Synthesis of
2-chloro-1-[4-(4-nitrophenyl)[1,4]diazepan-1-y- l]ethanone (2)
[0186] 22.1 g (0.1 mol) of 1-(4-nitrophenyl)[1,4]diazepane, 8.3 g
(0.06 mol) of potassium carbonate and 120 ml of dimethylformamide
were mixed together in a reactor. 8.3 ml (0.11 mol) of chloroacetyl
chloride were added to this stirred suspension, while maintaining
the temperature between 15 and 25.degree. C. After stirring for
about ten hours at room temperature, 400 g of slightly hydrochloric
ice-cold water were added to the mixture: a yellow gum
crystallized. After filtering off by suction, washing with water
and drying under vacuum over phosphorus pentoxide, 22.4 g of yellow
crystals were obtained (yield=75%).
[0187] .sup.1H NMR (400 MHz, DMSO D6): 1.83 (m), 1.9 (m), 3.37 (t),
3.47 (t), 3.67 (m), 3.85 (t), 4.28 (s), 4.36 (s), 6.9 (m), 8.04
(m).
2.sup.nd Step: Synthesis of
3-methyl-1-{2-[4-(4-nitrophenyl)[1,4]diazepan--
1-yl]-2-oxoethyl}-3H-imidazol-1-ium chloride (3)
[0188] A mixture of 19.95 g (0.067 mol) of
2-chloro-1-[4-(4-nitrophenyl)[1- ,4]diazepan-1-yl]ethanone obtained
above in the preceding step and 11.5 g (0.14 mol) of
1-methyl-1H-imidazole in 40 ml of isobutanol were refluxed for 1
hour 30 minutes with stirring. After crystallization under cold
conditions, a precipitate of yellow crystals was obtained. This
precipitate was then washed with isobutanol and then with ethyl
ether and dried at 40.degree. C. under vacuum and over phosphorus
pentoxide.
[0189] After recrystallization from 65 ml of refluxing ethanol,
14.0 g of a yellow crystalline compound were obtained
(yield=55%).
[0190] .sup.1H NMR (400 MHz, DMSO D6): 1.85-2 (2m, 2H), 3.37-3.5
(2m, 2H), 3.72-3.89-3.95 (2 m+2s, 9H), 5.385-5.389 (2s, 2H), 6.93
(2m, 2H), 7.61 (2dd, 1H), 7.68 (2dd, 1H), 8.05 (2m, 2H), 9.08-9.1
(2dd, 1H).
3.sup.rd Step: Synthesis of
3-[2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]-2-o-
xymethyl]-1-methyl-3H-imidazol-1-ium Chloride Dihydrochloride
(4)
[0191] 13.1 g (0.0345 mol) of
3-methyl-1-{2-[4-(4-nitrophenyl)[1,4]diazepa-
n-1-yl]-2-oxoethyl)-3H-imidazol-1-ium chloride, obtained in the
preceding step, 3 g of palladium-on-charcoal (containing 50%
water), 400 ml of 960 ethanol and 150 ml of water were placed in a
one-liter hydrogenator.
[0192] The reduction was performed over two hours under a hydrogen
pressure of about five bar and at a temperature of 70.degree. C.
After filtering off the catalyst under nitrogen, aqueous
hydrochloric acid was poured onto the mixture.
[0193] After evaporating the filtrate under reduced pressure,
recrystallizing the mixture from refluxing ethanol, hydrochloric
acid, and water, and drying at 40.degree. C. under vacuum and over
potassium hydroxide, 15.9 g (yield=75%) of white crystals were
obtained.
[0194] The elemental analysis calculated for
C.sub.17H.sub.26N.sub.5OCl.su- b.3+H.sub.2O+CH.sub.3CH.sub.2OH
was:
2 C % H % N % O % Cl % Calculated: 48.87 7.04 14.38 9.86 21.85
Found: 46.82 6.89 14.42 9.41 22.39
[0195] The .sup.13C NMR and .sup.1H NMR spectra were in accordance
with the expected structure.
[0196] .sup.1H NMR (400 MHz, D.sub.2O): 2.21-2.47 (2m, 2H),
3.78-3.89 (m, 4H), 3.97-4.09 (m+s, 7H), 5.27-5.42 (2H), 7.33-7.72
(m, 6H), 8.71-8.8 (2s, 1H).
[0197] .sup.13C NMR (D.sub.2O): 23.25; 24.32; 35.89; 41.77; 43.44;
44.96; 45.42; 50.17; 53.98; 55.94; 54.59; 56.5; 118.25; 120.69;
123.1; 123.27; 123.55; 123.68; 124.9; 124.99; 125.53; 128.71; 137;
143.6; 144.8; 166.16; 166.74.
[0198] The mass spectrum showed that the expected cation,
C.sub.17H.sub.24N.sub.5O.sup.+, is mainly detected at m/z=314 in
ES.sub.+.
Example 2
2-hydroxy-N,N,N-trimethyl-3-[4-(4-aminophenyl)-1,4-diazepan-1-yl]propan-1--
aminium Acetate (3)
[0199] 41
Synthesis of 2-hydroxy-N,N,
N-trimethyl-3-[4-(4-nitrophenyl)-1,4-diazepan--
1-yl]propan-1-aminium Acetate (2)
[0200] 1.1 g of 1-(4-nitrophenyl)-1,4-diazepane (0.005 mol), 3 ml
of DMF and 0.76 g (0.00448 mol) of glycidyltrimethylammonium were
placed in a three-necked flask. The mixture was heated at
105.degree. C. for 20 hours. The reaction mixture was then poured
into 50 ml of ethyl acetate. After triturating the gum and removing
the ethyl acetate, the product was taken up in water and extracted
with butanol, and the aqueous phase was concentrated. A sample was
purified by preparative HPLC.
[0201] .sup.1H NMR (DMSO d.sub.6, 200 MHz, ppm) was in accordance
with the expected product: 8.03 (d, 2H); 6.84 (d, 2H); 4.25 (m,
1H); 3.23-3.67 (m, 8H); 3.095 (s, 9H); 2.823 (m, 2H); 2.5-2.615 (m,
2H); 1.83 (m, 2H); 1.69 (s, 3H).
[0202] Mass ESI.sup.+: m/z=337[M.sup.+].
Synthesis of
2-hydroxy-N,N,N-trimethyl-3-[4-(4-aminophenyl)-1,4-diazepan-1-
-yl]propan-1-aminium Acetate (3)
[0203] After reduction with zinc/acetic acid,
2-hydroxy-N,N,N-trimethyl-3--
[4-(4-aminophenyl)-1,4-diazepan-1-yl]propan-1-aminium acetate was
obtained.
[0204] Mass ESI.sup.+: m/z=307[M.sup.+].
EXAMPLES OF DYEING
Examples 1 to 7
Dyeing in Alkaline Medium Using 3-{2-[4-(4-aminophenyl)
[1,4]diazepan-1-yl]-2-oxoethyl}-1-methyl-3H-imidazol-1-ium Chloride
Dihydrochloride
[0205] The dye compositions below were prepared:
3 Examples 1 2 3 4 5 6 7 3-{2-[4-(4-Aminophenyl) 10.sup.-3 mol
10.sup.-3 mol 10.sup.-3 mol -- -- -- -- [1,4]diazepan-1-yl]-2-
oxoethyl}-1-methyl-3H- imidazol-1-ium chloride dihydrochloride
(base) 2-Hydroxy-N,N,N- -- -- -- 10.sup.-3 mol 10.sup.-3 mol
10.sup.-3 mol 10.sup.-3 mol trimethyl-3-[4-(4-amino
phenyl)-1,4-diazepan-1- yl]propan-1-aminium acetate (base)
2-(2,4-Diaminophenoxy) 10.sup.-3 mol -- -- 10.sup.-3 mol -- -- --
ethanol dihydrochloride (coupler) 3-Amino-2-chloro-6- -- 10.sup.-3
mol -- -- 10.sup.-3 mol -- -- methylphenol hydrochloride (coupler)
3,6-Dimethyl-1H- -- -- 10.sup.-3 mol -- -- 10.sup.-3 mol --
pyrazolo [5,1-c]- [1,2,4]triazole (coupler) 2-Methyl-5-aminophenol
10.sup.-3 mol (coupler) Dye support (1) (*) (*) (*) (*) (*) (*) (*)
Demineralized water qs 100 g 100 g 100 g 100 g 100 g 100 g 100 g
(*) Dye support (1) pH 9.5 96.degree. ethyl alcohol 20.8 g Sodium
metabisulphite as an aqueous 35% solution 0.23 g A.M. Pentasodium
salt of diethylene triamine pentacetic acid as an aqueous 40%
solution 0.48 g A.M. C.sub.8-C.sub.10 alkyl polyglucoside as an
aqueous 60% solution 3.6 g A.M. Benzyl alcohol 2.0 g Polyethylene
glycol containing 8 3.0 g ethylene oxide units NH.sub.4Cl 4.32 g
Aqueous ammonia containing 20% NH.sub.3 2.94 g
[0206] At the time of use, each composition was mixed with an equal
weight of 20-volumes aqueous hydrogen peroxide solution (6% by
weight). A final pH of 9.5 was obtained.
[0207] Each mixture obtained was applied to locks of grey hair
containing 90% white hairs. After a leave-in time of 30 minutes,
the locks were rinsed, washed with a standard shampoo, rinsed again
and then dried.
[0208] The following dyeing results were obtained.
4 Examples 1 2 3 4 5 6 7 Shade Blue Blue-violet Chromatic
red-violet Blue Blue-violet Chromatic red-violet Grey-violet
observed
Examples 8 to 16
Dyeing in Acidic Medium Using
3-(2-[4-(4-aminophenyl)[1,4]diazepan-1-yl]-2-
-oxoethyl}-1-methyl-3H-imidazol-1-ium Chloride Dihydrochloride
[0209] The following dye compositions were prepared:
5 Examples 8 9 10 11 3-{2-[4-(4-Amino- 10.sup.-3 mol 10.sup.-3 mol
10.sup.-3 mol 10.sup.-3 mol phenyl)[1,4]diazepan-1-yl]-
2-oxoethyl}-1-methyl-3H- imidazol-1-ium chloride; dihydrochloride
(base) 2-(2,4-Diaminophenoxy)- 10.sup.-3 mol ethanol
dihydrochloride (coupler) 3-Amino-2-chloro-6- 10.sup.-3 mol
methyphenol hydrochloride (coupler) 2-Methyl-5-aminophenol
10.sup.-3 mol (coupler) 2-Aminopyridin-3-ol 10.sup.-3 mol (coupler)
Dye support (2) (*) (*) (*) (*) Demineralized water qs 100 g 100 g
100 g 100 g Examples 12 13 14 15 16 2-Hydroxy-N,N,N- 10.sup.-3 mol
10.sup.-3 mol 10.sup.-3 mol 10.sup.-3 mol 10.sup.-3 mol
trimethyl-3-[4-(4- aminophenyl)-1,4-diazepan- 1-yl]propan-1-
aminium acetate (base) 2-(2,4-Diamino- 10.sup.-3 mol -- -- -- --
phenoxy)ethanol dihydrochloride (coupler) 3-Amino-2-chloro-6- --
10.sup.-3 mol -- -- -- methyphenol hydrochloride (coupler)
2-Methyl-5-aminophenol -- -- 10.sup.-3 mol -- -- (coupler)
2-Aminopyridin-3-ol -- -- -- 10.sup.-3 mol -- (coupler)
6-Hydroxy-1-H-indole -- -- -- -- 10.sup.-3 mol (coupler) Dye
support (2) (*) (*) (*) (*) (*) Demineralized water qs 100 g 100 g
100 g 100 g 100 g (*) Dye support (2) pH 7 96.degree. ethyl alcohol
20.8 g Sodium metabisulphite as an aqueous 35% solution 0.23 g A.M.
Pentasodium salt of diethylene triamine pentacetic acid as an
aqueous 40% solution 0.48 g A.M. C.sub.8-C.sub.10 alkyl
polyglucoside as an aqueous 60% solution 3.6 g A.M. Benzyl alcohol
2.0 g Polyethylene glycol containing 8 3.0 g ethylene oxide units
Na.sub.2HPO.sub.4 0.28 g KH.sub.2PO.sub.4 0.46 g
[0210] At the time of use, each composition was mixed with an equal
weight of 20-volumes aqueous hydrogen peroxide solution (6% by
weight). A final pH of 7 was obtained.
[0211] Each mixture obtained was applied to locks of grey hair
containing 90% white hairs. After a leave-in time of 30 minutes,
the locks were rinsed, washed with a standard shampoo, rinsed again
and then dried.
[0212] The following dyeing results were obtained.
6 Examples 8 9 10 11 12 13 14 15 16 Shade Violet-blue Blue-violet
Violet Grey-violet Blue Violet Brown-violet Brown-grey Brown-grey
observed
* * * * *