U.S. patent application number 09/791822 was filed with the patent office on 2001-11-29 for compositions for dyeing keratin fibers, containing cationic indolizine derivatives, and dyeing process.
Invention is credited to Breton, Philippe, Lagrange, Alain, Segala, Fabienne.
Application Number | 20010044974 09/791822 |
Document ID | / |
Family ID | 8847427 |
Filed Date | 2001-11-29 |
United States Patent
Application |
20010044974 |
Kind Code |
A1 |
Breton, Philippe ; et
al. |
November 29, 2001 |
Compositions for dyeing keratin fibers, containing cationic
indolizine derivatives, and dyeing process
Abstract
Compositions for the oxidation dyeing of keratin fibres,
containing at least one oxidation base and at least one coupler
chosen from indolizine derivative comprising at least one cationic
group Z, Z being chosen from quaternized aliphatic chains,
aliphatic chains comprising at least one quaternized saturated
ring, and aliphatic chains comprising at least one quaternized
unsaturated ring. Methods of using these cationic indolizine
derivatives as couplers for the oxidation dyeing of keratin fibres,
in combination with at least one oxidation base, and to dyeing
processes using them. Some of these cationic indolizine derivatives
are novel.
Inventors: |
Breton, Philippe; (Le
Chesnay, FR) ; Segala, Fabienne; (Paris, FR) ;
Lagrange, Alain; (Coupvray, FR) |
Correspondence
Address: |
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW,
GARRETT & DUNNER L.L.P.
1300 I STREET, NW
WASHINGTON
DC
20005
US
|
Family ID: |
8847427 |
Appl. No.: |
09/791822 |
Filed: |
February 26, 2001 |
Current U.S.
Class: |
8/405 ; 8/406;
8/408; 8/421; 8/423 |
Current CPC
Class: |
A61K 8/492 20130101;
A61Q 5/10 20130101; C07D 471/04 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/408; 8/421; 8/423 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 25, 2000 |
FR |
00 02419 |
Claims
What is claimed is:
1. A composition for dyeing keratin fibres, wherein the composition
comprises, in a medium which is suitable for dyeing: (i) at least
one oxidation base; and (ii) at least one coupler chosen from
indolizine derivatives of formula (I) and the acid addition salts
thereof: 7in which: n may be an integer from 0 to 4; R.sub.1 and
R.sub.3, which may be identical or different, are each chosen from
hydrogen atoms; halogen atoms; Z groups; C.sub.1-C.sub.4 alkyl
radicals; C.sub.1-C.sub.4 alkoxy radicals; C.sub.1-C.sub.4
monohydroxyalkyl radicals; C.sub.2-C.sub.4 polyhydroxyalkyl
radicals; C.sub.1-C.sub.4 aminoalkyl radicals; acetylamino
radicals; acetylamino-(C.sub.1-C.sub.4)alkyl radicals;
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals;
mono(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
aminocarboxy(C.sub.1-C.sub.4)alkyl radicals;
acetyl(C.sub.1-C.sub.4)alkyl- amino(C.sub.1-C.sub.4)alkyl radicals;
and aromatic rings which are optionally substituted with at least
one radical chosen from halogen atoms, C.sub.1-C.sub.4 alkyl
radicals, trifluoro-methyl radicals, C.sub.1-C.sub.4 alkoxy
radicals, amino radicals, mono- and disubstituted amino radicals
wherein the substituent is chosen from C.sub.1-C.sub.4 alkyl
radicals, (C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, carboxyl radicals and sulphoxy radicals; R.sub.3 may
optionally further be chosen from 5- and 6-membered unsaturated
heterocycles; R.sub.2 and R.sub.4, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms, Z
groups; C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals, C.sub.1-C.sub.4 aminoalkyl radicals,
mono(C.sub.1-C.sub.4)-alkylamino(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkyl-amino(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals, cyano radicals, carboxy(C.sub.1-C.sub.4)alkyl
radicals, nitro radicals and 5- and 6-membered aromatic rings which
are optionally substituted with at least one radical chosen from
halogen atoms, C.sub.1-C.sub.4 alkyl radicals, trifluoromethyl
radicals, C.sub.1-C.sub.4 alkoxy radicals, amino radicals and mono-
and disubstituted amino radicals wherein the substituent is chosen
from C.sub.1-C.sub.4 alkyl radicals,
(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals and sulphoxy radicals; Z is chosen from the
following unsaturated cationic groups of formulae (II) and (III)
below, and the saturated cationic groups of formula (IV) below: 8in
which: D is a linker arm which is chosen from linear and branched
alkylene chains which may be interrupted by at least one hetero
atom, and which may be substituted with at least one substituent
chosen from hydroxyl and C.sub.1-C.sub.6 alkoxy radicals, and which
may bear at least one ketone function; the ring members E, G, J, L
and M, which may be identical or different, are chosen from carbon,
oxygen, sulphur and nitrogen atoms; b is an integer from 0 to 4; m
is an integer from 0 to 5; the radicals R, which may be identical
or different, are chosen from a second group Z, which may be
identical to or different from the first group Z, 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, nitro radicals, cyano radicals,
cyano(C.sub.1-C.sub.6)alkyl 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, amido radicals, aldehydo radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals, amino radicals protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; NHR" and NR"R'" groups
in which R" and R'", which may be identical or different, are
chosen from C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; R.sub.5 is chosen from C.sub.1-C.sub.6 alkyl radicals,
C.sub.1-C.sub.6 mono-hydroxyalkyl radicals, C.sub.2-C.sub.6
polyhydroxyalkyl radicals, cyano(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)-alkylsilane(C.- sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alk- yl radicals,
carbamyl(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals,
benzyl radicals and second Z groups which may be identical to or
different from the first Z groups; R.sub.6, R.sub.7 and R.sub.8,
which may be identical or different, are each 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)alkoxy(C.sub.1-C.sub.6)alkyl radicals,
cyano(C.sub.1-C.sub.6)alkyl radicals, aryl radicals, benzyl
radicals, amido(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)alkyl- silane(C.sub.1-C.sub.6)alkyl radicals
and C.sub.1-C.sub.6 aminoalkyl radicals in which the amine is
protected with at least one group chosen from
(C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals; two of the radicals R.sub.6, R.sub.7 and
R.sub.8, may also form, together with the nitrogen atom to which
they are attached, 5- and 6-membered saturated carbon-based rings
and rings containing at least one hetero atom, it being possible
for the said ring to be optionally substituted with at least one
substituent chosen from 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, nitro
radicals, cyano radicals, cyano(C.sub.1-C.sub.6)alkyl 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,
amido radicals, aldehydo radicals, carboxyl radicals,
keto(C.sub.1-C.sub.6)alky- l radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals and amino radical protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbo- nyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; one of the radicals
R.sub.6, R.sub.7 and R.sub.8 may optionally be chosen from second Z
groups, which may be identical to or different from the first Z
groups; R.sub.9 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 protected by at least one group
chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and
C.sub.1-C.sub.6 alkylsulphonyl radicals;
carboxy(C.sub.1-C.sub.6)alkyl radicals; cyano(C.sub.1-C.sub.6)alkyl
radicals; carbamyl(C.sub.1-C.sub.6)alkyl 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;
sulphonamido(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbox- y(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)al- kyl radicals;
(C.sub.1-C.sub.6)alkylketo(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 N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; a and y are integers equal to 0 or 1; with the following
provisos: in the unsaturated cationic groups of formula (II): when
a=0, the linker arm D is attached to the nitrogen atom, when a=1,
the linker arm D is attached to one of the ring members E, G, J and
L, y cannot take the value 1 except: 1) when the ring members E, G,
J and L simultaneously represent a carbon atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; or alternatively 2) when at least one of the ring members E,
G, J and L represents a nitrogen atom to which the radical R.sub.5
is attached; when b is at least 2, two adjacent radicals R may also
form together a ring chosen from unsaturated 5- and 6-membered
carbon-based rings and rings containing at least one hetero atom;
in the unsaturated cationic groups of formula (III): when a=0, the
linker arm D is attached to the nitrogen atom, when a=1, the linker
arm D is attached to one of the ring members E, G, J, L and M, y
cannot take the value 1 except when at least one of the ring
members E, G, J, L and M represents a divalent atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; when m is at least 2, two adjacent radicals R may also form
together unsaturated 5- and 6-membered carbon-based rings and rings
containing at least one hetero atom; in the cationic groups of
formula (IV): when a=0, the linker arm D is attached to the
nitrogen atom bearing the radicals R.sub.6 to R.sub.8, when a=1,
two of the radicals R.sub.6 to R.sub.8 form, together with the
nitrogen atom to which they are attached, saturated 5- and
6-membered rings as defined above, and the linker arm D is attached
to a carbon atom of the said saturated ring; X.sup.- is chosen from
monovalent and divalent anions; it being understood that: at least
one of the radicals R.sub.1 and R.sub.3 represents a hydrogen atom;
and the number of cationic groups Z is at least equal to 1.
2. The composition according to claim 1, wherein R.sub.3 is an
unsaturated heterocycle chosen from pyrrole rings, pyridine rings,
pyrimidine rings, imidazole rings, pyrazole rings, oxazole rings,
thiazole rings, triazole rings, pyrazolotriazole rings,
pyrazoloimidazole rings, pyrrolotriazole rings, pyrazolopyrimidine
rings, pyrazolopyridine rings, benzimidazole rings, benzoxazole
rings, benzothiazole rings, indole rings, indoline rings,
indolidine rings, isoindolidine rings, benzotriazoline rings,
pyrazine rings, oxazine rings, triazine rings, quinoline rings,
tetrahydroquinoline rings, benzimidazolidine rings and
benzopyrimidine rings.
3. The composition according to claim 1, wherein the rings in the
unsaturated Z groups of formula (II) are chosen from pyrrole rings,
imidazole rings, pyrazole rings, oxazole rings, thiazole rings,
triazole rings, pyrazoltriazolinium rings, pyrazoloimidazolinium
rings, pyrrolotriazolinium rings, pyrazolopyrimidinium rings,
pyrazolopyridinium rings, benzimidazolinium rings, benzoxazolinium
rings, benzothiazolinium rings, indolinium rings, indolidinium
rings, isoindolinium rings, indazolinium rings and
benzotriazolinium rings.
4. The composition according to claim 1, wherein the rings in the
unsaturated Z groups of formula (III) are chosen from pyridine
rings, pyrimidine rings, pyrazine rings, oxazine rings, triazine
rings, quinolinium rings, tetrahydroquinolinium rings,
benzimidazolidinium rings and benzopyrimidinium rings.
5. The composition according to claim 1, wherein X- is chosen from
halides, hydroxides, hydrogen sulphates and (C.sub.1-C.sub.6)alkyl
sulphates.
6. The composition according to claim 1, (wherein the indolizine
derivatives of formula (I) are chosen from:
N,N-dimethyl-2-phenyl-N-(phen- ylmethyl)-1-indolizinepropanaminium;
N,N,N-trimethyl-2-phenyl-1-indolizine- thanaminium
N,N,N-trimethyl-2-phenyl-1-indolizinepropanaminium bromide;
4-methyl-4-[2-(2-phenyl-1-indolizinyl )ethyl]morpholinium bromide;
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium
nitrate;
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium
chloride; N,N,N-trimethyl-2-phenyl-1-indolizinethanaminium methyl
sulphate; trimethyl[2-(2-phenyl-1-indolizinyl)ethyl]ammonium
iodide; trimethyl[2-(2-phenyl-l -indolizinyl)ethyl]ammonium
bromide;
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium
methyl sulphate;
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3H--
imidazol-1-ium chloride;
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl-
]-3H-imidazol-1-ium chloride;
1-{2-[2-(4-methoxyphenyl)-8-methylindolizin--
3-yl]-2-oxoethyl}-3-methyl-3H-imidazol-1-ium chloride;
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}-3
H-imidazol-1-ium chloride;
1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoet- hyl}pyridinium
chloride; 1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridini- um
chloride; 1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium
chloride;
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxo-
ethyl}-2-methylpyridinium chloride; 2-phenylindolizin-3-yl
)-2-oxoethyl]pyridinium methyl chloride;
[2-(8-methyl-2-phenylindolizin-3- -yl)-2-oxoethyl]pyridinium
chloride; 2-methyl-1-{2-[2-(3-nitrophenyl)indol-
izin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-oxo-2-(2-phenylin- dolizin-3-yl)ethyl]pyridinium
chloride; 2-methyl-1-{2-[8-methyl-2-(3-nitro-
phenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
2-methyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium
chloride;
3-methoxycarbonyl-1-{2-[2-(3-nitropheny)indolizin-3-yl]-2-oxoet-
hyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3- -yl
)ethyl]pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl
)-8-methylindolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyrid-
inium chloride;
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-
-oxoethyl]pyridinium chloride; and the addition salts thereof with
an acid.
7. The composition according to claim 1, wherein said at least one
coupler is present in an amount ranging from 0.0005% to 12% by
weight relative to the total weight of said composition.
8. The composition according to claim 7, wherein said at least one
coupler is present in an amount ranging from 0.005% to 6% by weight
relative to the total weight of said composition.
9. The composition according to claim 1, wherein said at least one
oxidation base is chosen from para-phenylenediamines, double bases,
para-aminophenols, ortho-aminophenols and heterocyclic oxidation
bases, and the acid addition salts of the foregoing.
10. The composition according to claim 9, wherein the
para-phenylenediamines are chosen from the compounds of formula (V)
below, and the addition salts thereof with an acid: 9in which:
R.sub.10 is chosen from a hydrogen atom, C.sub.1-C.sub.4 alkyl
radicals, C.sub.1-C.sub.4 monohydroxyalkyl radicals,
C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.4 alkyl radicals substituted with at least one
radical chosen from nitrogen-containing radicals, phenyl radicals
and 4'-aminophenyl radicals; R.sub.11 is chosen from a hydrogen
atom, C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals
and C.sub.1-C.sub.4 alkyl radicals substituted with at least one
nitrogen-containing radical; R.sub.12 is chosen from a hydrogen
atom, halogen atoms, C.sub.1-C.sub.4 alkyl radicals,
C.sub.1-C.sub.4 monohydroxyalkyl radicals, C.sub.1-C.sub.4
hydroxyalkoxy radicals, acetylamino(C.sub.1-C.sub.4)alkoxy
radicals, mesylamino(C.sub.1-C.sub.4)a- lkoxy radicals and
carbamoylamino(C.sub.1-C.sub.4)alkoxy radicals; R.sub.13 is chosen
from a hydrogen atom, halogen atoms and C.sub.1-C.sub.4 alkyl
radicals.
11. The composition according to claim 10, wherein said halides are
chosen from chloride, bromides iodide, and fluoride.
12. The composition according to claim 10, wherein said
nitrogen-containing radicals are chosen from amino radicals,
mono(C.sub.1-C.sub.4)alkylamino radicals,
di(C.sub.1-C.sub.4)alkylamino radicals,
tri(C.sub.1-C.sub.4)alkylamino radicals,
monohydroxy(C.sub.1-C.sub.4)alkylamino radicals, imidazolinium
radicals and ammonium radicals.
13. The composition according to claim 9, wherein the
para-phenylenediamines are chosen from para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(-hydroxyethyl)-para-phenylenediamine,
4-N,N-bis(-hydroxyethyl)ami- no-2-methylaniline,
4-N,N-bis(-hydroxyethyl)amino-2-chloroaniline,
2-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,
N-(-hydroxypropyl)-para-phenylenediami- ne,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phen- ylenediamine,
N-ethyl-N-(-hydroxyethyl)-para-phenylenediamine,
N-(-dihydroxypropyl)-para-phenylenediamine,
N-(4'-aminophenyl)-para-pheny- lenediamine,
N-phenyl-para-phenylenediamine, 2-hydroxyethyloxy-para-phenyl-
enediamine, 2-acetylaminoethyloxy-para-phenylenediamine and
N-(-methoxyethyl)-para-phenylenediamine, and the addition salts
thereof with an acid.
14. The composition according to claim 13, wherein said
para-phenylenediamines are chosen from para-phenylenediamine,
para-tolylenediamine, 2-iso-propyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-par- a-phenylened iamine,
2,6-dimethyl-para-phenylened iamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine,
2-.beta.-acetylaminoethyloxy-para-phenyle- nediamine, and the acid
addition salts of any of the foregoing.
15. The composition according to claim 9, wherein the double bases
are chosen from the compounds corresponding to formula (VI) below,
and the acid addition salts thereof: 10wherein: B.sub.1 and
B.sub.2, which may be identical or different, are each chosen from
hydroxyl radicals and --NH.sub.2 radicals, optionally substituted
with at least one radical chosen from C.sub.1-C.sub.4 alkyl
radicals and linker arms Y; linker arm Y is chosen from linear and
branched divalent alkylene chains comprising from 1 to 14 carbon
atoms, wherein said divalent alkylene chains may optionally be
interrupted by at least one nitrogen-containing radical and
optionally interrupted by at least one hetero atom such as an
oxygen atom, a sulphur atom or a nitrogen atom, further wherein
said divalent alkylene chains may optionally be terminated with at
least one nitrogen-containing radical and optionally interrupted by
at least one heteroatom such as an oxygen atom, a sulphur atom or a
nitrogen atom, and further wherein said divalent alkylene chains
may optionally be substituted with at least one radical chosen from
hydroxyl radicals and C.sub.1-C.sub.6 alkoxy radicals; R.sub.14 and
R.sub.15, which may be identical or different, are each chosen from
a hydrogen atom, halogen atoms, C.sub.1-C.sub.4 alkyl radicals,
C.sub.1-C.sub.4 monohydroxyalkyl radicals, C.sub.2-C.sub.4
polyhydroxyalkyl radicals, C.sub.1-C.sub.4 aminoalkyl radicals and
linker arms Y; R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.20 and
R.sub.21, which may be identical or different, are each chosen from
a hydrogen atom, linker arms Y and C.sub.1-C.sub.4 alkyl radicals;
with the proviso that only one linker arm Y is present in each
compound of formula (VI).
16. The composition according to claim 15, wherein the double bases
of formula (VI) are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-am-
inophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'--
aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(p-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(4-methylaminophenyl )tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition
salts of any of the foregoing.
17. A composition according to claim 16, wherein said double bases
are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-di-
aminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and the
acid addition salts of any of the foregoing.
18. The composition according to claim 9, wherein the
para-aminophenols are chosen from the compounds corresponding to
formula (VII) below, and the acid addition salts thereof:
11wherein: R.sub.22 is chosen from a hydrogen atom, halogen atoms,
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, (C.sub.1-C.sub.4)alkoxy(C.sub.- 1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals and
hydroxy(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
and R.sub.23 is chosen from a hydrogen atom, halogen atoms,
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals, cyano(C.sub.1-C.sub.4)alkyl
radicals and (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl
radicals, with the proviso that at least one of R.sub.22 and
R.sub.23 is a hydrogen atom.
19. The composition according to claim 18, wherein the
para-aminophenols are chosen from para-aminophenol,
4-amino-3-methylphenol, 4-amino-3-fluorophenol,
4-amino-3-hydroxymethylphenol, 4-amino-2-methyl phenol,
4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,
4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)ph- enol and
4-amino-2-fluorophenol, and the acid addition salts of any of the
foregoing.
20. A composition according to claim 9, wherein said
ortho-aminophenols are chosen from 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetamido-2-aminophenol and the acid addition salts of any of the
foregoing.16. The composition according to claim 8, wherein the
heterocyclic bases are chosen from pyridine derivatives, pyrimidine
derivatives and pyrazole derivatives, and the addition salts
thereof with an acid.
21. The composition according to claim 1, wherein the at least one
oxidation base is present in an amount generally ranging from
0.0005% to 12% by weight relative to the total weight of the dye
composition.
22. The composition according to claim 1, wherein said composition
contains at least one additional coupler and at least one direct
dye.
23. The composition according to claim 22, wherein the at least one
additional coupler is chosen from meta-phenylenediamines,
meta-aminophenols, meta-diphenols and heterocyclic couplers.
24. The composition according to claim 22, wherein the at least one
additional coupler is present in an amount generally ranging from
0.0001% to 10% relative to the total weight of the dye
composition.
25. The composition according to claim 1, wherein the acid addition
salts are chosen from the hydrochlorides, hydrobromides, sulphates,
tartrates, lactates and acetates.
26. The composition according to claim 1, wherein said composition
is in the form of a liquid, a cream or a gel.
27. The composition according to claim 1, wherein said linker arm D
is chosen from linear and branched alkylene chains containing from
1 to 14 carbon atoms.
28. A process for oxidation dyeing of keratin fibres comprising:
applying to said keratin fibres for a sufficient time to develop a
desired color at least one dye composition comprising, in a medium
suitable for dyeing, (i) at least one oxidation base and (ii) at
least one coupler chosen from indolizine derivatives of formula (I)
and the acid addition salts thereof: 12wherein: n may be an integer
from 0 to 4; R.sub.1 and R.sub.3, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms; Z
groups; C.sub.1-C.sub.4 alkyl radicals; C.sub.1-C.sub.4 alkoxy
radicals; C.sub.1-C.sub.4 monohydroxyalkyl radicals;
C.sub.2-C.sub.4 polyhydroxyalkyl radicals; C.sub.1-C.sub.4
aminoalkyl radicals; acetylamino radicals;
acetylamino-(C.sub.1-C.sub.4)a- lkyl radicals;
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals;
mono(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
aminocarboxy(C.sub.1-C.sub.4)alkyl radicals;
acetyl(C.sub.1-C.sub.4)alkyl- amino(C.sub.1-C.sub.4)alkyl radicals;
and aromatic rings which are optionally substituted with at least
one radical chosen from halogen atoms, C.sub.1-C.sub.4 alkyl
radicals, trifluoro-methyl radicals, C.sub.1-C.sub.4 alkoxy
radicals, amino radicals, mono- and disubstituted amino radicals
wherein the substituent is chosen from C.sub.1-C.sub.4 alkyl
radicals, (C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, carboxyl radicals and sulphoxy radicals; R.sub.3 may
optionally further be chosen from 5- and 6-membered unsaturated
heterocycles; R.sub.2 and R.sub.4, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms, Z
groups; C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals, C.sub.1-C.sub.4 aminoalkyl radicals,
mono(C.sub.1-C.sub.4)-alkylamino(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkyl-amino(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals, cyano radicals, carboxy(C.sub.1-C.sub.4)alkyl
radicals, nitro radicals and 5- and 6-membered aromatic rings which
are optionally substituted with at least one radical chosen from
halogen atoms, C.sub.1-C.sub.4 alkyl radicals, trifluoromethyl
radicals, C.sub.1-C.sub.4 alkoxy radicals, amino radicals and mono-
and disubstituted amino radicals wherein the substituent is chosen
from C.sub.1-C.sub.4 alkyl radicals,
(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals and sulphoxy radicals; Z is chosen from the
following unsaturated cationic groups of formulae (II) and (III)
below, and the saturated cationic groups of formula (IV) below:
13in which: D is a linker arm which is chosen from linear and
branched alkylene chains which may be interrupted by at least one
hetero atom, and which may be substituted with at least one
substituent chosen from hydroxyl and C.sub.1-C.sub.6 alkoxy
radicals, and which may bear at least one ketone function; the ring
members E, G, J, L and M, which may be identical or different, are
chosen from carbon, oxygen, sulphur and nitrogen atoms; b is an
integer from 0 to 4; m is an integer from 0 to 5; the radicals R,
which may be identical or different, are chosen from a second group
Z, which may be identical to or different from the first group Z,
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, nitro radicals, cyano radicals,
cyano(C.sub.1-C.sub.6)alkyl 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, amido radicals, aldehydo radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals, amino radicals protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; NHR' and NR"R'" groups
in which R" and R'", which may be identical or different, are
chosen from C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; R.sub.5 is chosen from C.sub.1-C.sub.6 alkyl radicals,
C.sub.1-C.sub.6 mono-hydroxyalkyl radicals, C.sub.2-C.sub.6
polyhydroxyalkyl radicals, cyano(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)-alkylsilane(C.- sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alk- yl radicals,
carbamyl(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals,
benzyl radicals and second Z groups which may be identical to or
different from the first Z groups; R.sub.6, R.sub.7 and R.sub.8,
which may be identical or different, are each 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)alkoxy(C.sub.1-C.sub.6)alkyl radicals,
cyano(C.sub.1-C.sub.6)alkyl radicals, aryl radicals, benzyl
radicals, amido(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)alkyl- silane(C.sub.1-C.sub.6)alkyl radicals
and C.sub.1-C.sub.6 aminoalkyl radicals in which the amine is
protected with at least one group chosen from
(C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals; two of the radicals R.sub.6, R.sub.7 and
R.sub.8, may also form, together with the nitrogen atom to which
they are attached, 5- and 6-membered saturated carbon-based rings
and rings containing at least one hetero atom, it being possible
for the said ring to be optionally substituted with at least one
substituent chosen from 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, nitro
radicals, cyano radicals, cyano(C.sub.1-C.sub.6)alkyl 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,
amido radicals, aldehydo radicals, carboxyl radicals,
keto(C.sub.1-C.sub.6)alky- l radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals and amino radical protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbo- nyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; one of the radicals
R.sub.6, R.sub.7 and R.sub.8 may optionally be chosen from second Z
groups, which may be identical to or different from the first Z
groups; R.sub.9 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 protected by at least one group
chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and
C.sub.1-C.sub.6 alkylsulphonyl radicals;
carboxy(C.sub.1-C.sub.6)alkyl radicals; cyano(C.sub.1-C.sub.6)alkyl
radicals; carbamyl(C.sub.1-C.sub.6)alkyl 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;
sulphonamido(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbox- y(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)al- kyl radicals;
(C.sub.1-C.sub.6)alkylketo(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 N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; a and y are integers equal to 0 or 1; with the following
provisos: in the unsaturated cationic groups of formula (II): when
a=0, the linker arm D is attached to the nitrogen atom, when a=1,
the linker arm D is attached to one of the ring members E, G, J and
L, y cannot take the value 1 except: 1) when the ring members E, G,
J and L simultaneously represent a carbon atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; or alternatively 2) when at least one of the ring members E,
G, J and L represents a nitrogen atom to which the radical R.sub.5
is attached; when b is at least 2, two adjacent radicals R may also
form together a ring chosen from unsaturated 5- and 6-membered
carbon-based rings and rings containing at least one hetero atom;
in the unsaturated cationic groups of formula (III): when a=0, the
linker arm D is attached to the nitrogen atom, when a=1, the linker
arm D is attached to one of the ring members E, G, J, L and M, y
cannot take the value 1 except when at least one of the ring
members E, G, J, L and M represents a divalent atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; when m is at least 2, two adjacent radicals R may also form
together unsaturated 5- and 6-membered carbon-based rings and rings
containing at least one hetero atom; in the cationic groups of
formula (IV): when a=0, the linker arm D is attached to the
nitrogen atom bearing the radicals R.sub.6 to R.sub.8, when a =1,
two of the radicals R.sub.6 to R.sub.8 form, together with the
nitrogen atom to which they are attached, saturated 5- and
6-membered rings as defined above, and the linker arm D is attached
to a carbon atom of the said saturated ring; X.sup.- is chosen from
monovalent and divalent anions; it being understood that: at least
one of the radicals R.sub.1 and R.sub.3 represents a hydrogen atom;
and the number of cationic groups Z is at least equal to 1.
29. The composition according to claim 28, wherein said linker arm
D is chosen from linear and branched alkylene chains containing
from 1 to 14 carbon atoms.
30. The process according to claim 28, wherein said keratin fibres
are human hair.
31. A process according to claim 28, further comprising applying to
said keratin fibres at least one oxidizing composition.
32. A process according to claim 28, wherein said at least one dye
composition further comprises at least one oxidizing agent.
33. A process according to claim 28, wherein said desired color is
developed at acidic, neutral or alkaline pH.
34. A process according to claim 32, wherein said at least one
oxidizing agent is added to said at least one dye composition at
the time of application.
35. A process according to claim 31, wherein said at least one
oxidizing composition comprises at least one oxidizing agent.
36. A process according to claim 31, wherein said at least one
oxidizing composition is applied to said keratin fibres
simultaneously with said at least one dye composition.
37. A process according to claim 31, wherein said at least one
oxidizing composition is applied to said keratin fibres
sequentially with said at least one composition.
38. A process according to claim 31, wherein said at least one
oxidizing composition is mixed with said at least one dye
composition prior to said applying.
39. A process according to claim 28, wherein said keratin fibres
are human keratin fibres.
40. A process accordingly to claim 39, wherein said human keratin
fibres are hair.
41. A process according to claim 32, wherein said at least one
oxidizing agent is chosen from hydrogen peroxide, urea peroxide,
alkali metal bromates, persalts, peracids and enzymes.
42. A process according to claim 41, wherein said persalts are
chosen from perborates and persulphates.
43. A process according to claim 41, wherein said enzymes are
chosen from peroxidases, laccases, tyrosinases and
oxidoreductases.
44. A process according to claim 43, wherein said oxidoreductases
are chosen from pyranose oxidase, glucose oxidase, glycerol
oxidase, lactate oxidase, pyruvate oxidase and uricase.
45. A process according to claim 35, wherein said at least one
oxidizing agent is chosen from hydrogen peroxide, urea peroxide,
alkali metal bromates, persalts, peracids and enzymes.
46. A process according to claim 45, wherein said persalts are
chosen from perborates and persulphates.
47. A process according to claim 46, wherein said enzymes are
chosen from peroxidases, laccases, tyrosinases and
oxidoreductases.
48. A process according to claim 47, wherein said oxidoreductases
are chosen from pyranose oxidase, glucose oxidase, glycerol
oxidase, lactate oxidase, pyruvate oxidase and uricase.
49. A process according to claim 28, wherein said sufficient time
to develop a desired color ranges from 3 minutes to 56 minutes.
50. A process according to claim 49, wherein said sufficient time
to develop a desired color ranges from 5 minutes to 30 minutes.
51. A process according to claim 28, further comprising rinsing
said keratin fibres.
52. A process according to claim 51, further comprising washing
said keratin fibres with shampoo.
53. A process according to claim 52, further comprising rinsing and
drying said keratin fibres.
54. A process according to claim 38, wherein the pH of said at
least one oxidizing composition mixed with said at least one dye
composition ranges from 3 to 12.
55. A process according to claim 54, wherein the pH of said at
least one oxidizing composition mixed with said at least one dye
composition ranges from 5 to 11.
56. A multicompartment device or kit for oxidation dyeing of
keratin fibres comprising a first compartment containing a first
composition comprising, in a medium suitable for dyeing, (i) at
least one oxidation base and (ii) at least one coupler chosen from
indolizine derivatives of formula (I) and the acid addition salts
thereof: 14wherein: n may be an integer from 0 to 4; R.sub.1 and
R.sub.3, which may be identical or different, are each chosen from
hydrogen atoms; halogen atoms; Z groups; C.sub.1-C.sub.4 alkyl
radicals; C.sub.1-C.sub.4 alkoxy radicals; C.sub.1-C.sub.4
monohydroxyalkyl radicals; C.sub.2-C.sub.4 polyhydroxyalkyl
radicals; C.sub.1-C.sub.4 aminoalkyl radicals; acetylamino
radicals; acetylamino-(C.sub.1-C.sub.4)alkyl radicals;
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals;
mono(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
aminocarboxy(C.sub.1-C.sub.4)alkyl radicals;
acetyl(C.sub.1-C.sub.4)alkyl- amino(C.sub.1-C.sub.4)alkyl radicals;
and aromatic rings which are optionally substituted with at least
one radical chosen from halogen atoms, C.sub.1-C.sub.4 alkyl
radicals, trifluoro-methyl radicals, C.sub.1-C.sub.4 alkoxy
radicals, amino radicals, mono- and disubstituted amino radicals
wherein the substituent is chosen from C.sub.1-C.sub.4 alkyl
radicals, (C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl
radicals, carboxyl radicals and sulphoxy radicals; R.sub.3 may
optionally further be chosen from 5- and 6-membered unsaturated
heterocycles; R.sub.2 and R.sub.4, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms, Z
groups; C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals, C.sub.1-C.sub.4 aminoalkyl radicals,
mono(C.sub.1-C.sub.4)-alkylamino(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkyl-amino(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals, cyano radicals, carboxy(C.sub.1-C.sub.4)alkyl
radicals, nitro radicals and 5- and 6-membered aromatic rings which
are optionally substituted with at least one radical chosen from
halogen atoms, C.sub.1-C.sub.4 alkyl radicals, trifluoromethyl
radicals, C.sub.1-C.sub.4 alkoxy radicals, amino radicals and mono-
and disubstituted amino radicals wherein the substituent is chosen
from C.sub.1-C.sub.4 alkyl radicals,
(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals and sulphoxy radicals; Z is chosen from the
following unsaturated cationic groups of formulae (II) and (III)
below, and the saturated cationic groups of formula (IV) below:
15in which: D is a linker arm which is chosen from linear and
branched alkylene chains which may be interrupted by at least one
hetero atom, and which may be substituted with at least one
substituent chosen from hydroxyl and C.sub.1-C.sub.6 alkoxy
radicals, and which may bear at least one ketone function; the ring
members E, G, J, L and M, which may be identical or different, are
chosen from carbon, oxygen, sulphur and nitrogen atoms; b is an
integer from 0 to 4; m is an integer from 0 to 5; the radicals R,
which may be identical or different, are chosen from a second group
Z, which may be identical to or different from the first group Z,
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, nitro radicals, cyano radicals,
cyano(C.sub.1-C.sub.6)alkyl 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, amido radicals, aldehydo radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals, amino radicals protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; NHR" and NR"R'" groups
in which R" and R'", which may be identical or different, are
chosen from C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; R.sub.5 is chosen from C.sub.1-C.sub.6 alkyl radicals,
C.sub.1-C.sub.6 mono-hydroxyalkyl radicals, C.sub.2-C.sub.6
polyhydroxyalkyl radicals, cyano(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)-alkylsilane(C.- sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alk- yl radicals,
carbamyl(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals,
benzyl radicals and second Z groups which may be identical to or
different from the first Z groups; R.sub.6, R.sub.7 and R.sub.8,
which may be identical or different, are each 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)alkoxy(C.sub.1-C.sub.6)alkyl radicals,
cyano(C.sub.1-C.sub.6)alkyl radicals, aryl radicals, benzyl
radicals, amido(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)alkyl- silane(C.sub.1-C.sub.6)alkyl radicals
and C.sub.1-C.sub.6 aminoalkyl radicals in which the amine is
protected with at least one group chosen from
(C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals; two of the radicals R.sub.6, R.sub.7 and
R.sub.8, may also form, together with the nitrogen atom to which
they are attached, 5- and 6-membered saturated carbon-based rings
and rings containing at least one hetero atom, it being possible
for the said ring to be optionally substituted with at least one
substituent chosen from 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, nitro
radicals, cyano radicals, cyano(C.sub.1-C.sub.6)alkyl 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,
amido radicals, aldehydo radicals, carboxyl radicals,
keto(C.sub.1-C.sub.6)alky- l radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals and amino radical protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbo- nyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; one of the radicals
R.sub.6, R.sub.7 and R.sub.8 may optionally be chosen from second Z
groups, which may be identical to or different from the first Z
groups; R.sub.9 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 protected by at least one group
chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and
C.sub.1-C.sub.6 alkylsulphonyl radicals;
carboxy(C.sub.1-C.sub.6)alkyl radicals; cyano(C.sub.1-C.sub.6)alkyl
radicals; carbamyl(C.sub.1-C.sub.6)alkyl 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;
sulphonamido(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbox- y(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)al- kyl radicals;
(C.sub.1-C.sub.6)alkylketo(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 N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; a and y are integers equal to 0 or 1; with the following
provisos: in the unsaturated cationic groups of formula (II): when
a=0, the linker arm D is attached to the nitrogen atom, when a=1,
the linker arm D is attached to one of the ring members E, G, J and
L, y cannot take the value 1 except: 1) when the ring members E, G,
J and L simultaneously represent a carbon atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; or alternatively 2) when at least one of the ring members E,
G, J and L represents a nitrogen atom to which the radical R.sub.5
is attached; when b is at least 2, two adjacent radicals R may also
form together a ring chosen from unsaturated 5- and 6-membered
carbon-based rings and rings containing at least one hetero atom;
in the unsaturated cationic groups of formula (III): when a=0, the
linker arm D is attached to the nitrogen atom, when a=1, the linker
arm D is attached to one of the ring members E, G, J, L and M, y
cannot take the value 1 except when at least one of the ring
members E, G, J, L and M represents a divalent atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; when m is at least 2, two adjacent radicals R may also form
together unsaturated 5- and 6-membered carbon-based rings and rings
containing at least one hetero atom; in the cationic groups of
formula (IV): when a=0, the linker arm D is attached to the
nitrogen atom bearing the radicals R.sub.6 to R.sub.8, when a=1,
two of the radicals R.sub.6 to R.sub.8 form, together with the
nitrogen atom to which they are attached, saturated 5- and
6-membered rings as defined above, and the linker arm D is attached
to a carbon atom of the said saturated ring; X.sup.- is chosen from
monovalent and divalent anions; it being understood that: at least
one of the radicals R.sub.1 and R.sub.3 represents a hydrogen atom;
and the number of cationic groups Z is at least equal to 1; and a
second compartment containing at least one oxidizing
composition.
57. The composition according to claim 56, wherein said linker arm
D is chosen from linear and branched alkylene chains containing
from 1 to 14 carbon atoms.
58. A compound chosen from indolizine derivatives of formula (I),
and acid addition salts thereof, 16wherein: n may be an integer
from 0 to 4; R.sub.1 and R.sub.3, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms; Z
groups; C.sub.1-C.sub.4 alkyl radicals; C.sub.1-C.sub.4 alkoxy
radicals; C.sub.1-C.sub.4 monohydroxyalkyl radicals;
C.sub.2-C.sub.4 polyhydroxyalkyl radicals; C.sub.1-C.sub.4
aminoalkyl radicals; acetylamino radicals;
acetylamino-(C.sub.1-C.sub.4)alkyl radicals;
(C.sub.1-C.sub.4)alkoxy(C.su- b.1-C.sub.4)alkyl radicals;
mono(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.- 4)alkyl radicals;
di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
aminocarboxy(C.sub.1-C.sub.4)alkyl radicals;
acetyl(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
and aromatic rings which are optionally substituted with at least
one radical chosen from halogen atoms, C.sub.1-C.sub.4 alkyl
radicals, trifluoro-methyl radicals, C.sub.1-C.sub.4 alkoxy
radicals, amino radicals, mono- and disubstituted amino radicals
wherein the substituent is chosen from C.sub.1-C.sub.4 alkyl
radicals, (C.sub.1-C.sub.4)alkylamin- o(C.sub.1-C.sub.4)alkyl
radicals, di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.- sub.4)alkyl
radicals, carboxyl radicals and sulphoxy radicals; R.sub.3 may
optionally further be chosen from 5- and 6-membered unsaturated
heterocycles; R.sub.2 and R.sub.4, which may be identical or
different, are each chosen from hydrogen atoms; halogen atoms, Z
groups; C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.2-C.sub.4 polyhydroxyalkyl
radicals, C.sub.1-C.sub.4 aminoalkyl radicals,
mono(C.sub.1-C.sub.4)-alkylamino(C.sub.1-C.sub.4)alk- yl radicals,
di(C.sub.1-C.sub.4)alkyl-amino(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals, cyano radicals, carboxy(C.sub.1-C.sub.4)alky- l
radicals, nitro radicals and 5- and 6-membered aromatic rings which
are optionally substituted with at least one radical chosen from
halogen atoms, C.sub.1-C.sub.4 alkyl radicals, trifluoromethyl
radicals, C.sub.1-C.sub.4 alkoxy radicals, amino radicals and mono-
and disubstituted amino radicals wherein the substituent is chosen
from C.sub.1-C.sub.4 alkyl radicals,
(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.su- b.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals and sulphoxy radicals; Z is chosen from the
following unsaturated cationic groups of formulae (II) and (III)
below, and the saturated cationic groups of formula (IV) below:
17in which: D is a linker arm which is chosen from linear and
branched alkylene chains which may be interrupted by at least one
hetero atom, and which may be substituted with at least one
substituent chosen from hydroxyl and C.sub.1-C.sub.6 alkoxy
radicals, and which may bear at least one ketone function; the ring
members E, G, J, L and M, which may be identical or different, are
chosen from carbon, oxygen, sulphur and nitrogen atoms; b is an
integer from 0 to 4; m is an integer from 0 to 5; the radicals R,
which may be identical or different, are chosen from a second group
Z, which may be identical to or different from the first group Z,
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, nitro radicals, cyano radicals,
cyano(C.sub.1-C.sub.6)alkyl 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, amido radicals, aldehydo radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcarbonyl radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals, amino radicals protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; NHR" and NR"R'" groups
in which R" and R'", which may be identical or different, are
chosen from C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals; R.sub.5 is chosen from C.sub.1-C.sub.6 alkyl radicals,
C.sub.1-C.sub.6 mono-hydroxyalkyl radicals, C.sub.2-C.sub.6
polyhydroxyalkyl radicals, cyano(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)-alkylsilane(C.- sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alk- yl radicals,
carbamyl(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkylcarboxy(C.sub.1-C.sub.6)alkyl radicals,
benzyl radicals and second Z groups which may be identical to or
different from the first Z groups; R.sub.6, R.sub.7 and R.sub.8,
which may be identical or different, are each 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)alkoxy(C.sub.1-C.sub.6)alkyl radicals,
cyano(C.sub.1-C.sub.6)alkyl radicals, aryl radicals, benzyl
radicals, amido(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)alkyl- silane(C.sub.1-C.sub.6)alkyl radicals
and C.sub.1-C.sub.6 aminoalkyl radicals in which the amine is
protected with at least one group chosen from
(C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals; two of the radicals R.sub.6, R.sub.7 and
R.sub.8, may also form, together with the nitrogen atom to which
they are attached, 5- and 6-membered saturated carbon-based rings
and rings containing at least one hetero atom, it being possible
for the said ring to be optionally substituted with at least one
substituent chosen from 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, nitro
radicals, cyano radicals, cyano(C.sub.1-C.sub.6)alkyl 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,
amido radicals, aldehydo radicals, carboxyl radicals,
keto(C.sub.1-C.sub.6)alky- l radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals and amino radical protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbo- nyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; one of the radicals
R.sub.6, R.sub.7 and R.sub.8 may optionally be chosen from second Z
groups, which may be identical to or different from the first Z
groups; R.sub.9 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 protected by at least one group
chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and
C.sub.1-C.sub.6 alkylsulphonyl radicals;
carboxy(C.sub.1-C.sub.6)alkyl radicals; cyano(C.sub.1-C.sub.6)alkyl
radicals; carbamyl(C.sub.1-C.sub.6)alkyl 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;
sulphonamido(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbox- y(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)al- kyl radicals;
(C.sub.1-C.sub.6)alkylketo(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 N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals; a and y are integers equal to 0 or 1; with the following
provisos: in the unsaturated cationic groups of formula (II): when
a=0, the linker arm D is attached to the nitrogen atom, when a=1,
the linker arm D is attached to one of the ring members E, G, J and
L, y cannot take the value 1 except: 1) when the ring members E, G,
J and L simultaneously represent a carbon atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; or alternatively 2) when at least one of the ring members E,
G, J and L represents a nitrogen atom to which the radical R.sub.5
is attached; when b is at least 2, two adjacent radicals R may also
form together a ring chosen from unsaturated 5- and 6-membered
carbon-based rings and rings containing at least one hetero atom;
in the unsaturated cationic groups of formula (III): when a=0, the
linker arm D is attached to the nitrogen atom, when a=1, the linker
arm D is attached to one of the ring members E, G, J, L and M, y
cannot take the value 1 except when at least one of the ring
members E, G, J, L and M represents a divalent atom, and when the
radical R.sub.5 is attached to the nitrogen atom of the unsaturated
ring; when m is at least 2, two adjacent radicals R may also form
together unsaturated 5- and 6-membered carbon-based rings and rings
containing at least one hetero atom; in the cationic groups of
formula (IV): when a=0, the linker arm D is attached to the
nitrogen atom bearing the radicals R.sub.6 to R.sub.8, when a=1,
two of the radicals R.sub.6 to R.sub.8 form, together with the
nitrogen atom to which they are attached, saturated 5- and
6-membered rings as defined above, and the linker arm D is attached
to a carbon atom of the said saturated ring; X.sup.- is chosen from
monovalent and divalent anions; with the following provisos: at
least one of the radicals R.sub.1 and R.sub.3 represents a hydrogen
atom; and the number of cationic groups Z is at least equal to 1; Z
cannot be chosen from the cationic groups of formula (IV); and
4-methyl-4-[2-(2-phenyl-1-indolizinyl)ethyl]morpholinium bromide is
excluded.
59. The composition according to claim 58, wherein said linker arm
D is chosen from linear and branched alkylene chains containing
from 1 to 14 carbon atoms.
60. The compound according to claim 58, wherein said compound is
chosen from:
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium
methyl sulphate;
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoeth-
yl]-3H-imidazol-1-ium chloride;
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-o-
xoethyl]-3H-imidazol-1-ium chloride;
1-{2-[2-(4-methoxyphenyl)-8-methylind-
olizin-3-yl]-2-oxoethyl}-3-methyl-3H-imidazol-1-ium chloride;
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}-3H-
imidazol-1-ium chloride;
1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethy- l}pyridinium
chloride; 1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride; 1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium
chloride;
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-2-m-
ethylpyridinium chloride;
2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium methyl chloride;
[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium
chloride; 2-methyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-ox-
oethyl}pyridinium chloride;
2-methyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)et- hyl]pyridinium
chloride; 2-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizi-
n-3-yl]-2-oxoethyl}pyrid in ium chloride;
2-methyl-1-[2-(8-methyl-2-phenyl-
indolizin-3-yl)-2-oxoethyl]pyridinium chloride;
3-methoxycarbonyl-1-{2-[2--
(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride;
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-
-yl]-2-oxoethyl}pyridinium chloride;
3-methoxycarbonyl-1-{2-[8-methyl-2-(3-
-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyrid in ium chloride;
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]pyrid-
inium chloride; and the addition salts thereof with an acid.
Description
[0001] The invention relates to compositions for the oxidation
dyeing of keratin fibres, comprising at least one oxidation base
and at least one coupler chosen from indolizine derivatives
comprising at least one cationic group Z, wherein Z may be chosen
from quaternized aliphatic chains, aliphatic chains comprising at
least one quaternized saturated ring, and aliphatic chains
comprising at least one quaternized unsaturated ring, to oxidation
dyeing processes using them and to novel cationic indolizine
derivatives.
[0002] Dye compositions comprising oxidation dye precursors are
known in the art for dyeing keratinous fibres, such as human hair.
The oxidation dye precursors include ortho-phenylenediamines,
para-phenylenediamines, ortho-aminophenols, para-aminophenols, and
heterocyclic compounds. These are generally known as oxidation
bases. The oxidation dye precursors, i.e., oxidation bases, are
generally colorless or weakly colored compounds which may give rise
to colored compounds and dyes when combined with oxidizing products
via oxidative coupling.
[0003] The shades obtained with these oxidation bases may be varied
by combining them with couplers or coloration modifiers. Such
coloration modifiers may, for example, be chosen from aromatic
meta-diamines, meta-aminophenols, meta-diphenols, and certain
heterocyclic compounds, such as indole compounds.
[0004] The variety of molecules used as oxidation bases and
couplers may make it possible to obtain a wide range of
colours.
[0005] The so-called "permanent" coloration obtained from using
these oxidation dyes should have at least one of the following
desirable characteristics. The coloration should have no
toxicological drawbacks, the shades obtained should have the
desired intensity, and the coloration should have good resistance
to external agents to which the fibres may be subjected, such as
light, bad weather, washing, permanent-waving, perspiration, and
rubbing. The dyes should allow coverage of white hairs, and should
be as unselective as possible, that is, they should allow only the
smallest possible differences in coloration along the same keratin
fiber, which may be differently sensitized (i.e. damaged) between
its end tip and its root.
[0006] Indazole-type compounds have been used in the field of hair
dyeing. For example, in DE-A-1 492 166, the disclosure of which is
incorporated herein by reference, the polycondensation of such
compounds via oxidation has been proposed; in DE-A-2 623 564, the
disclosure of which is incorporated herein by reference, it has
been proposed to combine hydroxy-indazoles with
tetraaminopyrimidines, and in U.S. Pat. No. 4,013,404, the
disclosure of which is incorporated herein by reference, certain
aminoindazoles and their use as oxidation dye precursors have been
proposed.
[0007] The inventors have discovered, entirely surprisingly and
unexpectedly, that the indolizine derivatives of formula (I)
defined below comprising at least one cationic group Z, Z being
chosen from quaternized aliphatic chains, aliphatic chains
comprising at least one quaternized saturated ring and aliphatic
chains comprising at least one quaternized unsaturated ring, are
not only suitable for use as couplers for oxidation dyeing, but
also make it possible to obtain dye compositions which provide at
least one of intense colorations in a very wide range of shades and
excellent properties of resistance to the various treatments to
which the keratin fibres may be subjected.
[0008] A subject of the invention is thus a composition for dyeing
keratin fibres, such as, for example, human keratin fibres such as
the hair, wherein the composition comprises, in a medium which is
suitable for dyeing:
[0009] (i) at least one oxidation base; and
[0010] (ii)at least one coupler chosen from indolizine derivatives
of formula (I) and the acid addition salts thereof: 1
[0011] in which:
[0012] n may be an integer from 0 to 4;
[0013] R.sub.1 and R.sub.3, which may be identical or different,
are each chosen from hydrogen atoms; halogen atoms; Z groups;
C.sub.1-C.sub.4 alkyl radicals; C.sub.1-C.sub.4 alkoxy radicals;
C.sub.1-C.sub.4 monohydroxyalkyl radicals; C.sub.2-C.sub.4
polyhydroxyalkyl radicals; C.sub.1-C.sub.4 aminoalkyl radicals;
acetylamino radicals; acetylamino-(C.sub.1-C.sub.4)alkyl radicals;
(C.sub.1-C.sub.4)alkoxy(C.su- b.1-C.sub.4)alkyl radicals;
mono(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.- 4)alkyl radicals;
di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
aminocarboxy(C.sub.1-C.sub.4)alkyl radicals;
acetyl(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4)alkyl radicals;
and aromatic rings which are optionally substituted with at least
one radical chosen from halogen atoms, C.sub.1-C.sub.4 alkyl
radicals, trifluoro-methyl radicals, C.sub.1-C.sub.4 alkoxy
radicals, amino radicals, mono- and disubstituted amino radicals
wherein the substituent is chosen from C.sub.1-C.sub.4 alkyl
radicals, (C.sub.1-C.sub.4)alkylamin- o(C.sub.1-C.sub.4)alkyl
radicals, di(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.- sub.4)alkyl
radicals, carboxyl radicals and sulphoxy radicals;
[0014] R.sub.3 may optionally further be chosen from 5- and
6-membered unsaturated heterocycles;
[0015] R.sub.2 and R.sub.4, which may be identical or different,
are each chosen from hydrogen atoms; halogen atoms, Z groups;
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals,
mono(C.sub.1-C.sub.4)-alkylamino(C.sub.1-C.sub.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkyl-amino(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals, cyano radicals, carboxy(C.sub.1-C.sub.4)alkyl
radicals, nitro radicals and 5- and 6-membered aromatic rings which
are optionally substituted with at least one radical chosen from
halogen atoms, C.sub.1-C.sub.4 alkyl radicals, trifluoromethyl
radicals, C.sub.1-C.sub.4 alkoxy radicals, amino radicals and mono-
and disubstituted amino radicals wherein the substituent is chosen
from C.sub.1-C.sub.4 alkyl radicals,
(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.su- b.4)alkyl radicals,
di(C.sub.1-C.sub.4)alkylamino-(C.sub.1-C.sub.4)alkyl radicals,
carboxyl radicals and sulphoxy radicals;
[0016] Z is chosen from the following unsaturated cationic groups
of formulae (II) and (III) below, and the saturated cationic groups
of formula (IV) below: 2
[0017] in which:
[0018] D is a linker arm which is chosen from linear and branched
alkylene chains, preferably containing from 1 to 14 carbon atoms,
which may be interrupted by at least one hetero atom, and which may
be substituted with at least one substituent chosen from hydroxyl
and C.sub.1-C.sub.6 alkoxy radicals, and which may bear at least
one ketone function;
[0019] the ring members E, G, J, L and M, which may be identical or
different, are chosen from carbon, oxygen, sulphur and nitrogen
atoms;
[0020] b is an integer from 0 to 4;
[0021] m is an integer from 0 to 5;
[0022] the radicals R, which may be identical or different, are
chosen from a second group Z, which may be identical to or
different from the first group Z, 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, nitro
radicals, cyano radicals, cyano(C.sub.1-C.sub.6)alkyl 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,
amido radicals, aldehydo radicals, carboxyl radicals,
(C.sub.1-C.sub.6)alkylcar- bonyl radicals, thio radicals,
C.sub.1-C.sub.6 thioalkyl radicals, C.sub.1-C.sub.6 alkylthio
radicals, amino radicals, amino radicals protected with at least
one group chosen from (C.sub.1-C.sub.6)alkylcarbo- nyls, carbamyls
and C.sub.1-C.sub.6 alkylsulphonyl radicals; NHR" and NR'R" groups
in which R" and R'", which may be identical or different, are
chosen from C.sub.1-C.sub.6 alkyl radicals, C.sub.1-C.sub.6
monohydroxyalkyl radicals and C.sub.2-C.sub.6 polyhydroxyalkyl
radicals;
[0023] R.sub.5 is chosen from C.sub.1-C.sub.6 alkyl radicals,
C.sub.1-C.sub.6 mono-hydroxyalkyl radicals, C.sub.2-C.sub.6 polyhyd
roxyalkyl radicals, cyano(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)-alkylsilane(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl radicals,
carbamyl(C.sub.1-C.sub.6)alkyl radicals,
(C.sub.1-C.sub.6)alkylcarboxy(C.- sub.1-C.sub.6)alkyl radicals,
benzyl radicals and second Z groups which may be identical to or
different from the first Z groups;
[0024] R.sub.6, R.sub.7 and R.sub.8, which may be identical or
different, are each 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)alkoxy(C.sub.1-C.sub.6)alkyl radicals,
cyano(C.sub.1-C.sub.6)alkyl radicals, aryl radicals, benzyl
radicals, amido(C.sub.1-C.sub.6)alkyl radicals,
tri(C.sub.1-C.sub.6)alkylsilane(C.s- ub.1-C.sub.6)alkyl radicals
and C.sub.1-C.sub.6 aminoalkyl radicals in which the amine is
protected with at least one group chosen from
(C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals; two of the radicals R.sub.6, R.sub.7 and
R.sub.8, may also form, together with the nitrogen atom to which
they are attached, 5- and 6-membered saturated carbon-based rings
and rings containing at least one hetero atom, such as, for
example, a pyrrolidine ring, a piperidine ring, a piperazine ring
or a morpholine ring, it being possible for the said ring to be
optionally substituted with at least one substituent chosen from
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, nitro radicals, cyano radicals,
cyano(C.sub.1-C.sub.6)alkyl 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, amido radicals, aldehydo radicals, carboxyl radicals,
keto(C.sub.1-C.sub.6)alkyl radicals, thio radicals, C.sub.1-C.sub.6
thioalkyl radicals, C.sub.1-C.sub.6 alkylthio radicals, amino
radicals and amino radical protected with at least one group chosen
from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and C.sub.1-C.sub.6
alkylsulphonyl radicals;
[0025] one of the radicals R.sub.6, R.sub.7 and R.sub.8 may
optionally be chosen from second Z groups, which may be identical
to or different from the first Z groups;
[0026] R.sub.9 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 protected by at least one group
chosen from (C.sub.1-C.sub.6)alkylcarbonyls, carbamyls and
C.sub.1-C.sub.6 alkylsulphonyl radicals;
carboxy(C.sub.1-C.sub.6)alkyl radicals; cyano(C.sub.1-C.sub.6)alkyl
radicals; carbamyl(C.sub.1-C.sub.6)alkyl 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;
sulphonamido(C.sub.1-C.sub.6)alkyl radicals;
(C.sub.1-C.sub.6)alkylcarbox- y(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)al- kyl radicals;
(C.sub.1-C.sub.6)alkylketo(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 N-(C.sub.1-C.sub.6)alkylsulphonamido(C.sub.1-C.sub.6)alkyl
radicals;
[0027] a and y are integers equal to 0 or 1; with the following
provisos:
[0028] in the unsaturated cationic groups of formula (II):
[0029] when a=0, the linker arm D is attached to the nitrogen
atom,
[0030] when a=1, the linker arm D is attached to one of the ring
members E, G, J and L,
[0031] y cannot take the value 1 except:
[0032] 1) when the ring members E, G, J and L simultaneously
represent a carbon atom, and when the radical R.sub.5 is attached
to the nitrogen atom of the unsaturated ring; or alternatively
[0033] 2) when at least one of the ring members E, G, J and L
represents a nitrogen atom to which the radical R.sub.5 is
attached;
[0034] when b is at least 2, two adjacent radicals R may also form
together a ring chosen from unsaturated 5- and 6-membered
carbon-based rings and rings containing at least one hetero
atom;
[0035] in the unsaturated cationic groups of formula (III):
[0036] when a=0, the linker arm D is attached to the nitrogen
atom,
[0037] when a=1, the linker arm D is attached to one of the ring
members E, G, J, L and M,
[0038] y cannot take the value 1 except when at least one of the
ring members E, G, J, L and M represents a divalent atom, and when
the radical R.sub.5 is attached to the nitrogen atom of the
unsaturated ring;
[0039] when m is at least 2, two adjacent radicals R may also form
together unsaturated 5- and 6-membered carbon-based rings and rings
containing at least one hetero atom;
[0040] in the cationic groups of formula (IV):
[0041] when a=0, the linker arm D is attached to the nitrogen atom
bearing the radicals R.sub.6 to R.sub.8,
[0042] when a=1, two of the radicals R.sub.6 to R.sub.8 form,
together with the nitrogen atom to which they are attached,
saturated 5- and 6-membered rings as defined above, and the linker
arm D is attached to a carbon atom of the said saturated ring;
[0043] X.sup.- is chosen from monovalent and divalent anions and
may be chosen, for example, from halides such as chloride, bromide,
fluoride and iodide, hydroxides, hydrogen sulphates and
C.sub.1-C.sub.6 alkyl sulphates such as, for example, methyl
sulphates and ethyl sulphates;
[0044] it being understood that:
[0045] at least one of the radicals R.sub.1 and R.sub.3 represents
a hydrogen atom; and
[0046] the number of cationic groups Z is at least equal to 1.
[0047] Colorations obtained using the inventive dye compositions
may possess at least one of the following desirable
characteristics: unselectivity, powerful, enable a variety of
shades, and excellent properties of resistance to at least one of
atmospheric agents chosen from light and bad weather, perspiration
and treatments to which the hair may be subjected (such as
shampooing, permanent-waving, etc.).
[0048] As used herein, "at least one" means one or more and thus
includes individual components as well as mixtures/combinations.
Further, as used herein, unless otherwise noted, alkyl radicals may
be chosen from substituted, unsubstituted, linear, branched, and
cyclic alkyl radicals. Similarly, as used herein and unless
otherwise noted, the alkyl radicals of alkoxy radicals may be
chosen from substituted, unsubstituted, linear, branched, and
cyclic alkyl radicals.
[0049] Non-limiting examples of aromatic rings of formula (I)
include phenyl rings, nitrophenyl rings, alkylphenyl rings,
alkoxyphenyl rings, polyalkyl-phenylrings and polyalkoxyphenyl
rings.
[0050] Non-limiting examples of unsaturated 5- and 6-membered
heterocycles, such as may be represented by R.sub.3, include
pyrrole rings, pyridine rings, pyrimidine rings, imidazole rings,
pyrazole rings, oxazole rings, thiazole rings, triazole rings,
pyrazolotriazole rings, pyrazoloimidazole rings, pyrrolotriazole
rings, pyrazolopyrimidine rings, pyrazolopyridine rings,
benzimidazole rings, benzoxazole rings, benzothiazole rings, indole
rings, indoline rings, indolidine rings, isoindolidine rings,
benzotriazoline rings, pyrazine rings, oxazine rings, triazine
rings, quinoline rings, tetrahydro-quinoline rings,
benzimidazolidine rings and benzopyrimidine rings.
[0051] Non-limiting examples of unsaturated group Z rings of
formula (II) include pyrrole rings, imidazole rings, pyrazole
rings, oxazole rings, thiazole rings, triazole rings,
pyrazoltri-azolinium rings, pyrazoloimidazolinium rings,
pyrrolotriazolinium rings, pyrazolopyrimidinium rings,
pyrazolopyridinium rings, benzimidazolinium rings, benzoxazolinium
rings, benzothiazolinium rings, indolinium rings, indolidinium
rings, isoindolinium rings, indazolinium rings and
benzotriazolinium rings.
[0052] Non-limiting examples of unsaturated group Z rings of
formula (III) include pyridine rings, pyrimidine rings, pyrazine
rings, oxazine rings, triazine rings, quinolinium rings and
tetrahydroquinolinium rings.
[0053] Non-limiting examples of the compounds of formula (I)
include:
[0054]
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium;
[0055] N,N,N-trimethyl-2-phenyl-1-indolizinethanaminium
[0056] N,N,N-trimethyl-2-phenyl-1-indolizinepropanaminium
bromide;
[0057] 4-methyl-4-[2-(2-phenyl-1-indolizinyl)ethyl]morpholinium
bromide;
[0058]
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium
nitrate;
[0059]
N,N-dimethyl-2-phenyl-N-(phenylmethyl)-1-indolizinepropanaminium
chloride;
[0060] N,N,N-trimethyl-2-phenyl-1-indolizinethanaminium methyl
sulphate;
[0061] trimethyl[2-(2-phenyl-1-indolizinyl)ethyl]ammonium
iodide;
[0062] trimethyl[2-(2-phenyl-1-indolizinyl)ethyl]ammonium
bromide;
[0063]
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium
methyl sulphate;
[0064]
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3H-imid-
azol-1-ium chloride;
[0065]
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-iu-
m chloride;
[0066]
1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-3-met-
hyl-3H-imidazol-1-ium chloride;
[0067]
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}-3H-imidazol-1-ium chloride;
[0068] 1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium
chloride;
[0069] 1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride;
[0070] 1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium
chloride;
[0071]
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethy-
l}-2-methylpyridinium chloride;
[0072] 2-phenylindolizin-3-yl)-2-oxoethyl]pyridinium methyl
chloride;
[0073] [2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium
chloride;
[0074]
2-methyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridini-
um chloride;
[0075] 2-methyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride;
[0076]
2-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}pyridinium chloride;
[0077] 2-methyl-1-[2-(8-methyl-2-phenylindolizin-3-yl
)-2-oxoethyl]pyridinium chloride;
[0078]
3-methoxycarbonyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}pyridinium chloride;
[0079] 3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]
pyridinium chloride;
[0080]
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-
-2-oxoethyl}pyridinium chloride;
[0081]
3-methoxycarbonyl-1-(2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-
-oxoethyl}pyridinium chloride;
[0082]
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl-
] pyridinium chloride; and the acid addition salts thereof.
[0083] According to the present invention, the at least one coupler
may be present in the composition in an amount generally ranging
from 0.0005% to 12% by weight relative to the total weight of the
dye composition, such as from 0.005% to 6% by weight.
[0084] The nature of the at least one oxidation base used in the
present invention may not be critical. In one embodiment, the at
least one oxidation base is chosen from para-phenylenediamines,
double bases, para-aminophenols, ortho-aminophenols, heterocyclic
oxidation bases, and the acid addition salts of any of the
foregoing.
[0085] Non-limiting examples of para-phenylenediamines which can be
used as the at least one oxidation base include compounds of
formula (V) and the acid addition salts thereof: 3
[0086] wherein:
[0087] R.sub.10 is chosen from a hydrogen atom, C.sub.1-C.sub.4
alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl radicals,
C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.4 alkyl radicals substituted with at least one
radical chosen from nitrogen-containing radicals, phenyl radicals
and 4'-aminophenyl radicals;
[0088] R.sub.11 is chosen from a hydrogen atom, C.sub.1-C.sub.4
alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl radicals,
C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals and
C.sub.1-C.sub.4 alkyl radicals substituted with at least one
nitrogen-containing radical;
[0089] R.sub.12 is chosen from a hydrogen atom, halogen atoms such
as a chlorine atom, a bromine atom, an iodine atom and a fluorine
atom, C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4
monohydroxyalkyl radicals, C.sub.1-C.sub.4 hydroxyalkoxy radicals,
acetylamino(C.sub.1-C.s- ub.4)alkoxy radicals,
mesylamino-(C.sub.1-C.sub.4)alkoxy radicals and
carbamoylamino(C.sub.1-C.sub.4)alkoxy radicals;
[0090] R.sub.13 is chosen from a hydrogen atom, halogen atoms and
C.sub.1-C.sub.4 alkyl radicals.
[0091] Non-limiting examples of nitrogen containing radicals of
formula (V) above include amino radicals,
mono(C.sub.1-C.sub.4)alkylamino radicals,
di(C.sub.1-C.sub.4)alkylamino radicals, tri(C.sub.1-C.sub.4)alk-
ylamino radicals, monohydroxy(C.sub.1-C.sub.4)alkylamino radicals,
imidazolinium radicals and ammonium radicals.
[0092] Non-limiting examples of the para-phenylenediamines of
formula (V) above include para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylened
iamine, 4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(-hydroxyethyl)-para-phenylen- ediamine,
4-N,N-bis(-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(-hydroxyethyl)amino-2-chloroaniline,
2-hydroxyethyl-para-phenyl- enediamine,
2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediam-
ine, N-(-hydroxypropyl)-para-phenylenediamine,
2-hydroxymethyl-para-phenyl- enediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N-ethyl-N-(-hydroxyethyl)-para-phenylenediamine,
N-(,-dihydroxy-propyl)-p- ara-phenylenediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-hydroxyethyloxy-para-phenylenediamine,
2-acetylamino-ethyloxy-para-phenylenediamine and
N-(-methoxyethyl)-para-p- henylenediamine, and acid addition salts
of any of the foregoing.
[0093] In one embodiment, para-phenylenediamines of formula (V)
above are chosen from para-phenylenediamine, para-tolylenediamine,
2-isopropyl-para-phenylenediamine,
2-hydroxyethyl-para-phenylenediamine,
2-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenylenediami- ne,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediam- ine and
2-acetylaminoethyloxy-para-phenylenediamine, and the acid addition
salts of any of the foregoing.
[0094] As used herein, "double bases" means compounds comprising at
least two aromatic entities substituted with at least one radical
chosen from amino radicals and hydroxyl radicals.
[0095] Non-limiting examples of double bases which may be used as
the at least one oxidation base according to the present invention
include compounds of formula (VI) and the acid addition salts
thereof: 4
[0096] in which:
[0097] B.sub.1 and B.sub.2, which may be identical or different,
are each chosen from hydroxyl radicals and --NH.sub.2 radicals,
optionally substituted with at least one radical chosen from
C.sub.1-C.sub.4 alkyl radicals and linker arms Y;
[0098] linker arm Y is chosen from linear and branched divalent
alkylene chains comprising from 1 to 14 carbon atoms, wherein said
divalent alkylene chains may optionally be interrupted by at least
one nitrogen-containing radical and optionally interrupted by at
least one hetero atom such as an oxygen atom, a sulphur atom or a
nitrogen atom, further wherein said divalent alkylene chains may
optionally be terminated with at least one nitrogen-containing
radical and optionally interrupted by at least one heteroatom such
as an oxygen atom, a sulphur atom or a nitrogen atom, and further
wherein said divalent alkylene chains may optionally be substituted
with at least one radical chosen from hydroxyl radicals and
C.sub.1-C.sub.6 alkoxy radicals;
[0099] R.sub.14 and R.sub.15, which may be identical or different,
are each chosen from a hydrogen atom, halogen atoms,
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals and linker arms Y;
[0100] R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.20 and
R.sub.21, which may be identical or different, are each chosen from
a hydrogen atom, linker arms Y and C.sub.1-C.sub.4 alkyl
radicals;
[0101] with the proviso that only one linker arm Y is present in
each compound of formula (III).
[0102] Non-limiting examples of double bases of formula (VI)include
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropano-
l,
N,N'-bis(.beta.-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-methylaminophe- nyl)tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methyl-phe-
nyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane,
and the acid addition salts of any of the foregoing.
[0103] In one embodiment, double bases of formula (VI)are chosen
from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropano-
l, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and the acid
addition salts of any of the foregoing.
[0104] Non-limiting examples of para-aminophenols which may be used
according to the present invention include compounds of formula
(VII) and the acid addition salts thereof: 5
[0105] wherein:
[0106] R.sub.22 is chosen from a hydrogen atom, halogen atoms,
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals and
hydroxy(C.sub.1-C.sub.4)alkylamin- o(C.sub.1-C.sub.4)alkyl
radicals; and
[0107] R.sub.23 is chosen from a hydrogen atom, halogen atoms,
C.sub.1-C.sub.4 alkyl radicals, C.sub.1-C.sub.4 monohydroxyalkyl
radicals, C.sub.2-C.sub.4 polyhydroxyalkyl radicals,
C.sub.1-C.sub.4 aminoalkyl radicals, cyano(C.sub.1-C.sub.4)alkyl
radicals and (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl
radicals,
[0108] with the proviso that at least one of R.sub.22 and R.sub.23
is a hydrogen atom.
[0109] Non-limiting examples of para-aminophenols of formula (VII)
include 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)ph- enol,
4-amino-2-fluorophenol and the acid addition salts of any of the
foregoing.
[0110] Non-limiting examples of ortho-aminophenols which may be
used as the at least one oxidation base include 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol,
5-acetamido-2-aminophenol and the acid addition salts of any of the
foregoing.
[0111] Non-limiting examples of heterocyclic bases which may be
used as the at least one oxidation base include pyridine
derivatives, pyrimidine derivatives, pyrazole derivatives and the
acid addition salts of any of the foregoing.
[0112] Non-limiting examples of pyridine derivatives include
compounds disclosed, for example, in British Patents GB 1 026 978
and GB 1 153 196, the disclosures of which are incorporated herein
by reference, such as 2,5-diaminopyridine,
2-(4-methoxyphenyl)amino-3-aminopyridine,
2,3-diamino-6-methoxypyridine,
2-(.beta.-methoxyethyl)amino-3-amino-6-met- hoxypyridine,
3,4-diaminopyridine and the acid addition salts of any of the
foregoing.
[0113] Non-limiting examples of pyrimidine derivatives include
compounds described, for example, in German Patent DE 2 359 399,
Japanese Patents JP 88-169 571 and JP 91-10659, and Patent
Application WO 96/15765, the disclosures of which are incorporated
herein by reference, such as 2,4,5,6-tetraaminopyrimidine,
4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and
pyrazolopyrimidine derivatives such as those mentioned in patent
application FR-A-2 750 048, the disclosure of which is incorporated
herein by reference, such as pyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,5-dimethylpyrazolo[1,5-a]pyrimid- ine-3,7-diamine,
pyrazolo[1,5-a]pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo[1
,5-a]pyrimidine-3,5-diamine, 3-aminopyrazolo[1 ,5-a]pyrimidin-7-ol,
3-aminopyrazolo[1,5-a]pyrimidin-5-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 addition salts, tautomeric forms, (when a tautomeric
equilibrium exists) and acid addition salts of any of the
foregoing.
[0114] Further non-limiting examples of pyrazole derivatives
include compounds described in German 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, the disclosures of which are
incorporated hereby by reference, such as
4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,
4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1-(.beta.-hydroxy-et- hyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phe-
nylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole,
1-benzyl-4,5-diamino-3-methylpy- razole,
4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-buty-
l-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyph- enyl)pyrazole,
4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
4,5-diamino-3-hydroxymethyl- -1-isopropylpyrazole,
4,5-diamino-3-methyl-1-isopropylpyrazole,
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylamino-pyrazole,
3,5-diamino-4-(.beta.-hydrox- yethyl)amino-1-methylpyrazole, and
the acid addition salts of any of the foregoing.
[0115] According to the present invention, the at least one
oxidation base may be present in the composition in an amount
generally ranging from 0.0005% to 12% by weight relative to the
total weight of the dye composition, such as from 0.005% to 6% by
weight.
[0116] The dye composition according to the present invention may
optionally further comprise at least one additional coupler
different from the indolizine derivatives of formula (I) and may
optionally further comprise at least one direct dye, for example,
to vary and/or enrich the shade obtained using the at least one
oxidation base with highlights.
[0117] The at least one additional coupler which can be used in the
dye composition according to with the present invention may be
chosen from couplers, such as, for example, meta-phenylenediamines,
meta-aminophenols, meta-diphenols and heterocyclic couplers such
as, for example, indole derivatives, indoline derivatives,
benzimidazole derivatives, benzomorpholine derivatives, sesamol
derivatives, pyridine derivatives, pyrimidine derivatives, pyrazole
derivatives and the acid addition salts thereof.
[0118] In one embodiment, the at least one additional coupler is
chosen from 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-methylpheno- l, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethyloxy)benz- ene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
1-amino-2-methoxy-4,5-methylenedioxybenzene, .alpha.-naphthol,
2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1-H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one and the addition salts of any of the
foregoing.
[0119] When present, the at least one additional coupler may be
present in the composition in an amount generally ranging 0.0001%
to 10% by weight relative to the total weight of the dye
composition, such as from 0.005% to 5% by weight.
[0120] According to the present invention, the acid addition salts
may be chosen from hydrochlorides, hydrobromides, sulphates,
tartrates, lactates and acetates.
[0121] The medium suitable for oxidation dyeing, or support,
according to the present invention may be chosen from water and a
mixture of water and at least one organic solvent in order to
dissolve the compounds which might not be sufficiently soluble in
water alone. Non-limiting examples of the at least one organic
solvent includes C.sub.1-C.sub.4 alkanols such as ethanol and
isopropanol; glycerol; glycols and glycol ethers such as
2-butoxyethanol, propylene glycol, propylene glycol monomethyl
ether, diethylene glycol, diethylene glycol monomethyl ether;
aromatic alcohols such as benzyl alcohol and phenoxyethanol; and
analogous solvents.
[0122] According to the present invention, the at least one organic
solvent maybe present in the composition in an amount generally
ranging from 1% to 40% by weight relative to the total weight of
the dye composition, such as from 5% to 30% by weight.
[0123] The pH of the dye composition in accordance with the present
invention generally ranges from 3 to 12. It can be adjusted to the
desired value by means of at least one agent commonly used in
dyeing keratin fibres chosen from acidifying agents and basifying
agents.
[0124] Non-limiting examples of acidifying agents include inorganic
acids and organic acids such as hydrochloric acid, orthophosphoric
acid, carboxylic acids (such as tartaric acid, citric acid and
lactic acid) and sulphonic acids.
[0125] Non-limiting examples of basifying agents include aqueous
ammonia, alkaline carbonates, alkanolamines such as mono-, di- and
triethanolamines and derivatives thereof, sodium hydroxide,
potassium hydroxide and compounds of formula (VIII): 6
[0126] wherein:
[0127] R.sub.28 is chosen from divalent propylene residues,
optionally substituted with at least one radical chosen from
hydroxyl radicals and C.sub.1-C.sub.4 alkyl radicals; R.sub.24,
R.sub.25, R.sub.26 and R.sub.27, which may be identical or
different, are each chosen from a hydrogen atom, C.sub.1-C.sub.4
alkyl radicals and C.sub.1-C.sub.4 hydroxyalkyl radicals.
[0128] According to the present invention, the dye composition may
further comprise at least one adjuvant chosen from adjuvants
conventionally used in hair dyeing compositions, such as anionic
surfactants, cationic surfactants, nonionic surfactants, amphoteric
surfactants, zwitterionic surfactants, anionic polymers, cationic
polymers, nonionic polymers, amphoteric polymers, zwitterionic
polymers, inorganic thickeners, organic thickeners, antioxidants,
penetration agents, sequestering agents, fragrances, buffers,
dispersing agents, conditioners, such as, for example, silicones,
film-forming agents, preserving agents and opacifiers.
[0129] Needless to say, a person skilled in the art will take care
to choose any optional additional compound(s) such that the
advantageous properties associated with the inventive dye
compositions are not, or not substantially, adversely affected by
the addition(s) envisaged.
[0130] According to the present invention, the dye composition may
be provided in various forms, such as in the form of a liquid, a
cream or a gel, or in any other form suitable for dyeing keratin
fibres, such as human hair.
[0131] Another subject of the present invention is a process for
oxidation dyeing of keratin fibres comprising applying to said
keratin fibres for a sufficient time to obtain a desired color at
least one dye composition comprising, in a medium suitable for
dyeing, (i) at least one coupler chosen from indolizine derivatives
of formula (i) and acid addition salts thereofp; and (ii) at least
one oxidation base. In one embodiment, the keratin fibres are
chosen from human keratin fibres. In another embodiment, the human
keratin fibres are hair.
[0132] In another embodiment, the at least one dye composition is
applied to the keratin fibres, and the desired color may be
developed at a pH chosen from acidic, neutral or alkaline pH.
Further, the at least one dye composition may further comprise at
least one oxidizing agent which may be added to the at least one
dye composition at the time of application, and/or which may be
present in at least one oxidizing composition. In one embodiment,
the at least one oxidizing composition may be applied
simultaneously with said at least one dye composition, while in
another embodiment, the at least one oxidizing composition may be
applied to the keratin fibres sequentially with the at least one
dye composition.
[0133] In a further embodiment, the at least one dye composition is
mixed, at the time of use, with at least one oxidizing composition
comprising, in a medium appropriate for dyeing, at least one
oxidizing agent present in an amount sufficient to develop a
desired coloration. The mixture obtained may subsequently be
applied to the keratin fibres and may be left to stand for 3 to 50
minutes, such as for 5 to 30 minutes. In yet another embodiment,
the fibres are rinsed, and may optionally be washed with a shampoo,
rinsed again and dried.
[0134] According to the present invention, the at least one
oxidizing agent may be chosen from oxidizing agents conventionally
used for the oxidation dyeing of keratin fibres, such as hydrogen
peroxide, urea peroxide, alkali metal bromates, persalts such as
perborates and persulphates, peracids and enzymes such as
peroxidases, laccases, tyrosinases and oxidoreductases (such as
pyranose oxidases, glucose oxidases, glycerol oxidases, lactate
oxidases, pyruvate oxidases and uricases).
[0135] The pH of the at least one oxidizing composition comprising
the at least one oxidizing agent after mixing with the at least one
dye composition may generally range from 3 to 12, such as from 5
and 11. Further, the pH may be adjusted to a desired value by means
of at least one agent chosen from acidifying and basifying agents
commonly in dyeing keratin fibres and as defined above.
[0136] The at least one oxidizing composition as defined above may
also contain at least one adjuvant conventionally used in hair
dyeing compositions and as defined above.
[0137] The composition which is applied to the keratin fibres may
be in various forms, such as in the form of a liquid, a cream or a
gel or any other form suitable for carrying out dyeing of keratin
fibres, such as human hair.
[0138] The present invention also provides a multi-compartment
device or kit or any other packaging system, comprising a first
compartment containing a first composition comprising at least one
dye composition as defined above and a second compartment
containing a second composition comprising at least one oxidizing
composition as defined above. These devices may be equipped with a
means allowing the desired mixture to be deposited on the hair,
such as the devices described in French Patent FR-2 586 913, the
disclosure of which is incorporated herein.
[0139] Finally, this invention provides certain novel indolizine
derivatives of formula (I). These novel indolizine derivatives, and
the acid addition salts thereof, correspond to formula (I) as
defined above, with the following additional conditions:
[0140] Z cannot be chosen from the cationic groups of formula (IV)
as defined above;
[0141] providing that
4-methyl-4-[2-(2-phenyl-1-indolizinyl)ethyl]morpholi- nium bromide
is excluded.
[0142] The excluded compounds are known in the pharmaceutical
field, as seen in patents U.S. Pat. No. 3,717,644 and U.S. Pat. No.
3,642,807.
[0143] In one embodiment, these novel indolizine derivatives may be
chosen from:
[0144]
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium
methyl sulphate;
[0145]
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3H-imid-
azol-1-ium chloride;
[0146]
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl]-3H-imidazol-1-iu-
m chloride;
[0147]
1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethyl}-3-met-
hyl-3H-imidazol-1-ium chloride;
[0148]
3-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}-3 H-imidazol-1-ium chloride;
[0149] 1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridinium
chloride;
[0150] 1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride;
[0151] 1-[2-oxo-2-(2-m-tolylindolizin-3-yl)ethyl]pyridinium
chloride;
[0152]
1-[2-(8,1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-2-oxoethy-
l}-2-methylpyridinium chloride;
[0153] 2-phenylindolizin-3-yl )-2-oxoethyl]pyridinium methyl
chloride;
[0154] [2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl] pyridinium
chloride;
[0155]
2-methyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl}pyridini-
um chloride;
[0156] 2-methyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridinium
chloride;
[0157]
2-methyl-1-{2-[8-methyl-2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}pyridinium chloride;
[0158]
2-methyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]pyridini-
um chloride;
[0159]
3-methoxycarbonyl-1-{2-[2-(3-nitrophenyl)indolizin-3-yl]-2-oxoethyl-
}pyridinium chloride;
[0160]
3-methoxycarbonyl-1-[2-oxo-2-(2-phenylindolizin-3-yl)ethyl]pyridini-
um chloride;
[0161]
3-methoxycarbonyl-1-{2-[2-(4-methoxyphenyl)-8-methylindolizin-3-yl]-
-2-oxoethyl}pyridinium chloride;
[0162]
3-methoxycarbonyl-1-{2-[8-methyl-2-(3-nitropheny)indolizin-3-yl]-2--
oxoethyl}pyridinium chloride;
[0163]
3-methoxycarbonyl-1-[2-(8-methyl-2-phenylindolizin-3-yl)-2-oxoethyl-
]pyridinium chloride;
[0164] and the acid addition salts of any of the foregoing. The
addition salts with an acid of the above novel compounds are chosen
from those defined above for the compounds of formula (I).
[0165] These specific compounds may be prepared according to the
synthetic process of indolizines comprising the step of reacting
compounds chosen from alkyl-2 pyridine and aralkyl-2 pyridine with
a haloacetone thus producing a pyridinium salt (Chichibabin, Ber.
1927, 60, 1607; Borrows, Holland, Kenyon, J. Chem. Soc. 1946,
1069). By reacting the salt with a base such as sodium bicarbonate
in aqueous medium, indolinine is produced by cyclisation. Other
methods for producing the indolizine nucleus are disclosed in T.
Uchida et K. Matsumoto, Synthesis, 1976, 209-236. These compounds
are then quaternized according to known conventional quaternization
methods.
[0166] The compounds thus obtained can be purified by known methods
such as distillation and crystallisation.
[0167] Other than in the operating example, 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 by the present
invention. 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.
[0168] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention 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.
PREPARATION EXAMPLES
Preparation Example 1
Synthesis of
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridini- um
Methyl Sulphate
[0169] Starting with the 7-methyl-2-phenylindolizine obtained
according to the synthetic method of Chichibabin (Chichibabin Ber.
1927, 60, 1607), a catalytic addition of vinylpyridine was
performed according to the method described by Pentimalli and
Bozzini Ann. Chimica 1966, 56, 752. The
7-methyl-2-phenyl-3-(2-pyrid-2-ylethyl)indolizine thus obtained was
treated with 3 molar equivalents of dimethyl sulphate in refluxing
ethyl acetate. After reaction for two hours, the precipitate formed
was filtered off and recrystallized from isopropyl alcohol, and the
1-methyl-2-[2-(7-methyl-2-phenylindolizin-3-yl)ethyl]pyridinium
methyl sulphate was obtained in the form of a beige-coloured solid
melting at a temperature of 204.degree. C. (Kofler).
[0170] The .sup.1H NMR analysis (DMSO-d.sub.6, 400 MHz) (.delta.
ppm) was as follows: 2.28 (s, 3H); 3.33 (t, 2H); 3.37 (s, 3H); 3.56
(t, 2H); 3.91 (s, 3H); 6.35 (s, 1 H); 6.53 (dd, 1 H); 7.22 (m, 1
H); 7.26 (m, 1 H); 7.30 (m, 2H); 7.35 (m, 2H); 7.79 (dd, 1H); 7.84
(ddd, 1 H); 8.22 (d, 1 H); 8.30 (ddd, 1 H); 8.78 (dd, 1 H).
Preparation Example 2
Synthesis of
3-methyl-1-[2-(7-methyl-2-phenylindolizin-3-yl)-2-oxoethyl]-3-
H-imidazol-1-ium Chloride
[0171] Starting with the 7-methyl-2-phenylindolizine obtained
according to the synthetic method of Chichibabin (Chichibabin Ber.
1927, 60,1607), acylation with chloroacetyl chloride was performed
under the following conditions:
[0172] 2.8 g (0.025 mol) of chloroacetyl chloride were added to a
solution of 5 g (0.024 mol) of 7-methyl-2-phenylindolizine and 2.4
g (0.024 mol) of triethylamine in 300 ml of 1,2-dichloroethane. The
medium was refluxed for 2 h 30 min and then cooled to room
temperature. The reaction medium was washed 3 times with 100 ml of
water and once with 100 ml of saturated sodium chloride solution.
The organic phase was dried over sodium sulphate, filtered and
concentrated on a rotary evaporator. The oil obtained was used in
the following step without further purification.
[0173] The oil obtained was dissolved in 110 ml of ethyl acetate
and the mixture was brought to reflux. 10 g (0.122 mol) of
N-methylimidazole were added and refluxing was continued for one
hour. The medium was then cooled to room temperature and the
precipitate was filtered off, washed with ethyl acetate and then
recrystallized from isopropyl alcohol. A very pale grey light solid
melting at 250.degree. C. (Kofler) was obtained.
[0174] The .sup.1H NMR analysis (DMSO-d.sub.6, 400 MHz) (.delta.
ppm) was as follows: 2.40 (s, 3H); 3.89 (s, 3H); 5.04 (s, 2H); 6.59
(s, 1H); 7.02 (dd, 1H); 7.48-7.64 (m, 7H); 7.72 (dd, 1H); 9.14 (dd,
1 H); 9.71 (d, 1 H).
Preparation Example 3
Synthesis of
3-methyl-1-[2-(2-methylindolizin-3-yl)-2-oxoethyl]-3H-imidazo-
l-1-ium Chloride
[0175] The 2-methylindolizine obtained according to the Chichibabin
synthesis was treated with chloroacetyl chloride as described
previously in Preparation Example 2 above. The green powder
obtained was used in the following quaternization step without
further purification.
[0176] 7.9 g of this green powder (0.0383 mol) were dissolved in
150 ml of ethyl acetate. 9.6 g (0.116 mol) of N-methylimidazole
were added and the medium was brought to reflux. After refluxing
for 3 hours, a further 9.6 g (0.116 mol) of N-methylimidazole were
added. Refluxing was continued for 1 hour and the reaction medium
was cooled to room temperature. The solid which precipitated was
filtered off, washed with ethyl acetate and then recrystallized
from isopropyl alcohol. A beige-coloured solid melting at a
temperature above 260.degree. C. (Kofler) was obtained.
[0177] The .sup.1H NMR analysis (DMSO-d.sub.6, 400 MHz) (.delta.
ppm) was as follows: 2.69 (s, 3H); 3.98 (s, 3H); 5.90 (s, 2H); 6.62
(s, 1 H); 7.03 (dd, 1 H); 7.76 (unresolved multiplet, 3H); 9.20 (d,
1 H); 9.79 (d, 1 H).
DYEING EXAMPLES
Examples 1 to 4 of Dyeing in Alkaline Medium
[0178] The dye compositions below, in accordance with the
invention, were prepared:
1 EXAMPLE 1 2 3 4 1-Methyl-2-[2-(7-methyl- 3 .times. 10.sup.-3 3
.times. 10.sup.-3 -- -- 2-phenylindolizin-3-yl) mol mol
ethyl]pyridinium methyl sulphate (coupler of formula (I))
3-Methyl-1-[2[(7-methyl- -- -- 3 .times. 10.sup.-3 3 .times.
10.sup.-3 2-phenylindolizin-3-yl)- mol mol 2-oxoethyl]-3H-
imidazol-1-ium chloride (coupler of formula (I))
para-Tolylenediamine 3 .times. 10.sup.-3 -- 3 .times. 10.sup.-3 --
(oxidation base) mol mol 3,7-Diaminopyrazolopy- -- 3 .times.
10.sup.-3 -- 3 .times. 10.sup.-3 rimidinedihydrochloride mol mol
(oxidation base) Common dye support (*) (*) (*) (*) Demineralized
water qs 100 g 100 g 100 g 100 g (*) Common dye support: Ethanol 18
g Aqueous ammonia containing 20% NH.sub.3 10 g Sodium
metabisulphite 0.205 g Sequestering agent qs
[0179] At the time of use, the above dye compositions were mixed
weight for weight with a 20-volumes hydrogen peroxide solution (6%
by weight) of pH 3.
[0180] The mixture obtained had a pH of about 10, and was applied
for 30 minutes to locks of natural grey hair containing 90% white
hairs. The locks were then rinsed, washed with shampoo, rinsed
again and then dried.
[0181] The hair was dyed in a shade given in the table below.
2 EXAMPLE SHADE OBTAINED 1 Very matt golden blond 2 Very ashen
natural blond 3 Slightly ashen golden blond 4 Very ashen iridescent
blond
* * * * *