Particular azomethine direct dyes, dye composition comprising
at least one such compound, implementation process therefore
and use thereof
The present invention relates to particular direct dyes of
azomethine type and also to the use thereof for dyeing keratin
fibres, in particular human keratin fibres such as the hair. The
present invention also relates to a composition for dyeing keratin
fibres, comprising such direct dyes in a suitable dyeing medium.
Similarly, a subject of the invention is a process for dyeing
keratin fibres using the said dye composition, and also a device
comprising the same.
Finally, the present invention also relates to precursors of
these direct dyes.
The present invention relates to the field of dyeing keratin
fibres and more particularly to the field of hair dyeing.
It is known practice to dye keratin fibres, and in particular
the hair, with dye compositions containing one or more direct dyes,
according to a "direct dyeing" process.
The process conventionally used in direct dyeing consists in
applying to keratin fibres one or more direct dyes, or colouring
molecules, which have affinity for the said fibres, leaving them to
stand on the fibres, and then rinsing the fibres. The direct dyes used
hitherto are generally nitrobenzene dyes, anthraquinone dyes,
nitropyridine dyes, dyes of azo, xanthene, acridine or azine type or
triarylmethane-based dyes.
These direct dyes may also be applied to keratin fibres in the
presence of an oxidizing agent if it is desired to obtain simultaneous
lightening of the fibres.
However, the colorations resulting therefrom are temporary
or semi-permanent since the nature of the interactions that bind the
direct dyes to the keratin fibre and their desorption from the surface
and/or the core of the fibre are responsible for their weak dyeing
power and their poor fastness with respect to washing, inclement
weather or perspiration.
Moreover, such direct dyes are generally sensitive to the
action of oxidizing agents such as aqueous hydrogen peroxide
solution, which makes them difficult to use in lightening direct dye
compositions that are formulated with aqueous hydrogen peroxide
solution and a basifying agent, these compositions resembling the
compositions used for oxidation dyeing. In other words, direct dyes
are generally sparingly compatible with dye compositions intended
for lightening fibres, and, consequently, their use in a lightening
dyeing process, as an alternative to oxidation dyeing, is
unsatisfactory.
These dyes also have the drawback of lacking light-fastness,
on account of the poor resistance of the chromophore to
photochemical attack. This lack of stability may lead in certain
cases to fading over time of the coloration of the keratin fibres.
There is thus a real need for direct dyes that can not only
dye keratin fibres satisfactorily, but that are also light-fast, capable
of giving colorations that are both resistant to the various attacking
factors to which the fibres may be subjected, such as inclement
weather, sunlight, washing and perspiration, and that are also
sufficiently stable in the presence of oxidizing agents such as
aqueous hydrogen peroxide solution in order to be able to obtain
simultaneous lightening of the fibre with the advantages outlined
above.
These aims are achieved with the present invention, one
subject of which is especially direct dyes of azomethine type of
formula (I) below, organic or mineral acid salts thereof, tautomeric
forms, optical isomers or geometrical isomers thereof and solvates
thereof:
which formula (I):
n represents an integer equal to 0, 1, 2, 3 or 4 .
R represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different radicals
chosen from hydroxyl or imidazolium radicals, An ; An
denoting a cosmetically acceptable anion or mixture of
anions.
- a C1-C4 alkoxy radical.
- a halogen atom.
Ri represents:
- a linear or branched C1-C10 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R3 can form, together with the nitrogen atom to which they
are attached, a pyrrolidino, piperidino or morpholino ring,
X represents:
- a hydroxyl radical,
- a radical -NR 4R5 in which R 4 and R represent,
independently of each other:
■ a hydrogen atom,
■ a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl or C1- C 4 alkoxy
radicals,
it being understood that the compounds of formula (I) cannot
(E)
In a preferred embodiment according to the invention, direct
dyes of azomethine type are of formula (I) below, organic or
mineral acid salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof and solvates thereof:
I which formula (I):
n represents an integer equal to 0, 1, 2, 3 or 4 .
R represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different radicals
chosen from hydroxyl or imidazolium radicals, An ; An
denoting a cosmetically acceptable anion or mixture of
anions.
- a C1-C4 alkoxy radical.
- a halogen atom.
Ri represents:
- a linear or branched C2-C alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R 3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R 3 can form, together with the nitrogen atom to which they
are attached, a pyrrolidino, piperidino or morpholino ring,
X represents:
- a hydroxyl radical,
- a radical -NR 4R5 in which R 4 and R represent,
independently of each other:
■ a hydrogen atom,
■ a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl or C1- C 4 alkoxy
radicals,
t being understood that the compounds of formula (I) cannot
epresent the following compounds (A) or (B):
Another subject of the present invention concerns the use of
one or more direct dyes of azomethine type of formula (I) as defined
previously for the dyeing of keratin fibres, in particular human
keratin fibres such as the hair.
The present invention also relates to a keratin fibre dye
composition comprising, in a suitable dyeing medium, one or more
direct dyes of azomethine type of formula (I) as defined previously.
In particular, the invention also relates to the use of the said
dye composition for dyeing keratin fibres.
A subject of the invention is also a process for dyeing
keratin fibres, in particular human keratin fibres such as the hair, in
which the said dye composition according to the invention is applied
to the said fibres for a time that is sufficient to obtain the desired
coloration, after which the resulting fibres are rinsed, optionally
washed with shampoo, rinsed again and dried or left to dry.
The present invention also relates to a process for lightening
keratin fibres, in particular human keratin fibres such as the hair, in
which the dye composition according to the invention, free of
oxidizing agent, and an oxidizing composition are sequentially or
simultaneously applied for a time that is sufficient to obtain the
desired lightening, after which the resulting fibres are rinsed,
optionally washed with shampoo, rinsed again and dried or left to
dry.
The invention also relates to a multi-compartment device or
kit using the said dye composition according to the invention.
Moreover, a subject of the invention is colourless or weakly
coloured compounds of leuco type, which are the reduced form of
the direct dyes of azomethine type according to the invention of
formula (II) below, organic or mineral acid salts thereof, tautomeric
forms, optical isomers or geometrical isomers thereof, and solvates
thereof:
in which formula (II) n, R, Rl R2, R3, X, R4 and R have the same
meanings as those indicated in formula (I).
A subject of the invention is also the use of these compounds
of leuco type as precursors of the direct dyes of azomethine type of
formula (I).
Furthermore, a subject of the invention is the use of these
compounds of leuco type for dyeing keratin fibres, such as human
keratin fibres, especially the hair, in the presence of an oxidizing
agent.
Finally, the invention relates to a multi-compartment device
or kit using a dye composition comprising one or more compounds
of leuco type of formula (II).
The direct dyes of azomethine type of formula (I) according
to the invention can give colorations that are very resistant to the
various attacking factors to which keratin fibres may be subjected,
such as inclement weather, light, washing and perspiration.
Furthermore, the direct dyes according to the invention can
satisfactorily dye keratin fibres, especially producing powerful,
chromatic and sparingly selective colorations.
The direct dyes according to the invention are also light-fast
and can be used in the presence of an oxidizing agent, which
facilitates their use in lightening direct dyeing compositions based
on oxidizing agents.
In other words, the direct dyes according to the present
invention lead to fast colorations that are compatible with dye
compositions intended for lightening keratin fibres.
Other characteristics, aspects, subjects and advantages of the
present invention will emerge even more clearly on reading the
description and the example that follows.
Direct dyes of azomethine type
The direct dyes according to the invention comprise in their
structure two aromatic rings and an azomethine bond.
Preferably, in formula (I), direct dyes of azomethine type
according to the invention are such that, taken together or
separately:
• n represents an integer equal to 0, 1 or 2,
• R represents:
- a linear or branched C1-C4 alkyl radical, preferably
methyl,
- a C1-C4 alkoxy radical, preferably a methoxy radical,
- a halogen atom, preferably chlorine;
when n is equal to 2, the groups R are identical or
different,
• Ri represents:
- a linear or branched C2- C alkyl radical, optionally
substituted with one or more hydroxyl radicals,
• R2 and R 3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C4 alkyl radical, preferably
methyl, ethyl or propyl radical,
• R2 and P 3 may form, together with the nitrogen atom to
which they are attached, a pyrrolidino, piperidino or morpholino
ring,
• X represents:
- a hydroxyl radical,
- a radical -NR 4R5 in which R4 and R represent,
independently of each other:
a hydrogen atom,
a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl radicals.
Preferably, An is an anionic counterion chosen from
perchlorate, bromide, iodide, chloride and methosulfate ions or a
mixture of these ions.
An denotes a cosmetically acceptable anion or mixture of
anions, for instance halides, such as chloride, methosulfates,
nitrates; alkylsulfonates: Alk-S(0) 20 such as methanesulfonate or
mesylate, and ethanesulfonate; arylsulfonates: Ar-S(0) 20 such as
benzenesulfonate and toluenesulfonate or tosylate; citrate;
succinate; tartrate; lactate; alkyl sulfates: Alk-0-S(0)0 such as
methylsulfate; arylsulfates such as benzenesulfate and
toluenesulfate; phosphate; acetate; triflate; and borates such as
tetrafluoroborate.
Preferably, An is an anionic counterion chosen from
bromide, chloride, and methylsulfate and toluenesulfonate ions or a
mixture of these ions.
Preferably, n represents an integer equal to 0, 1 or 2, and
more preferentially n is equal to 0 or 2 .
Preferably, R represents a halogen atom, in particular
chlorine, or a linear C1- C 4 alkyl radical, in particular a methyl
radical.
Preferably, Ri represents a linear or branched C2 - C alkyl
radical, in particular a methyl, ethyl or butyl radical or a linear Ci-
C4 alkyl radical substituted with a hydroxyl radical, in particular a
2-hydroxyethyl radical.
Preferably, Ri is chosen from a methyl radical; a butyl
radical and a 2-hydroxyethyl radical.
Preferably, R2 represents a hydrogen atom or a linear C1-C4
alkyl radical, preferably a butyl, methyl or ethyl radical.
More preferentially, R2 represents a hydrogen atom or a
methyl radical.
Even more preferentially, R2 represents a hydrogen atom.
Preferably, R3 represents a hydrogen atom or a linear C1-C4
alkyl radical, preferably a butyl, methyl or ethyl radical.
More preferentially, R3 represents a hydrogen atom or a
methyl radical.
Even more preferentially, R3 represents a hydrogen atom.
According to one embodiment, R3 and R4 represent a
hydrogen atom.
Preferably, X represents a hydroxyl radical or a radical -
NR4R5 in which R4 and R represent, independently of each other, a
hydrogen atom or a linear or branched Ci-C alkyl radical,
optionally substituted with one or more hydroxyl radicals.
Preferentially, X represents a hydroxyl radical or a radical -
NR4R5 in which R4 and R represent, independently of each other, a
linear or branched C1-C4 alkyl radical, optionally substituted with
one or more hydroxyl radicals.
Even more preferentially, X represents a radical -NR 4R5 in
which R4 and R represent, independently of each other, a linear or
branched C1-C4 alkyl radical, optionally substituted with one or
more hydroxyl radicals.
Preferably, R4 and R represent, independently of each other,
a hydrogen atom or a methyl, ethyl, isopropyl or 2-hydroxyethyl
radical.
According to one embodiment, n represents an integer equal
to 0 or 2, Ri is other than a hydrogen atom, R2 represents a
hydrogen atom and R 3 represents a hydrogen atom.
According to one particular embodiment, n represents an
integer equal to 0, Ri is other than a hydrogen atom, R2 represents a
hydrogen atom, R3 represents a hydrogen atom and X represents a
radical -NR4R5 in which R4 and R represent, independently of each
other, a linear or branched C2-C3 alkyl radical, optionally
substituted with one or more hydroxyl radicals.
According to another particular embodiment, n represents an
integer equal to 2, Ri is other than a hydrogen atom, R2 represents a
hydrogen atom, R3 represents a hydrogen atom and X represents a
hydroxyl radical.
Preferably, the direct dyes of azomethine type of formula (I)
according to the invention are chosen from the following
compounds and the geometrical or optical isomer forms thereof, the
tautomers thereof, the organic or mineral acid salts thereof or the
solvates thereof such as hydrates:

2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
O H Compound 7
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 8
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 9
2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 10
6-[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenylamino]hexan-1-ol
Compound 11
4-propoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1,4-dienylamine
Compound 12
2- {[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
OH Compound 13
6-(4-Aminophenylimino)-4-propoxy-3-
iminocyclohexa-1,4-dienylamine
Compound 14
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 15
6-(4-Amino-2,3-dimethylphenylimino)-4-
propoxy-3-iminocyclohexa- 1,4-dienylamine
Compound 16
2-[[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
OH
Compound 17
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 18
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 19
2-[[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
OH Compound 20
4-ethoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1,4-dienylamine
Compound 2 1
2- {[4-(2-Amino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 22
6-(4-Aminophenylimino)-4-ethoxy-3-
iminocyclohexa-1,4-dienylamine
Compound 23
4-(2-Amino-5-ethoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 24

2- {[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 31
6-(4-Aminophenylimino)-4-pentyloxy-3-
iminocyclohexa-1,4-dienylamine
Compound 32
4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenol
Compound 33
6-(4-Amino-2,3-dimethylphenylimino)-4-
pentyloxy-3-iminocyclohexa-l,4-
dienylamine
Compound 34
2-[[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl
(2-hydroxyethyl)amino]ethanol
OH
Compound 35
4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-2-
chlorophenol
Compound 36

6-(4-Amino-2,3-dimethylphenylimino)-4-
hexyloxy-3-iminocyclohexa-l,4-
dienylamine
Compound 43
2-[[4-(2-Amino-5-hexyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl
(2-hydroxyethyl)amino]ethanol
OH
Compound 44
4-(2-Amino-5-hexyloxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 45
4-(2-Amino-5-hexyloxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 46
2-[[4-(2-Amino-5-hexyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 47
N-(5-Ethoxy-4-imino-2-pyrrolidin- 1-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-N'-
isopropylbenzene-1,4-diamine
Compound 48
N-(5-Ethoxy-4-imino-2-piperidin- 1-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-
N'-isopropylbenzene- 1,4-diamine
Compound 49
NH
N-(5-Ethoxy-4-imino-2-morpholin-4-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-
N'-isopropylbenzene- 1,4-diamine
Compound 50
NH
N-(2-Diethylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-N'-ethyl
-N'-isopropylbenzene-1,4-diamine
Compound 51
NH
N-(2-methylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-N'-ethyl
-N'-isopropylbenzene-1,4-diamine
Compound 52
NH, N-(5-Ethoxy-4-imino-2-pyrrolidin- 1-
ylcyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene- 1,4-diamine
NH Compound 53
NH, N-(5-Ethoxy-4-imino-2-piperidin- 1-
ylcyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene- 1,4-diamine
Compound 54

Preferably, the direct dyes of formula (I) according to the
present invention are chosen from the direct dyes 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 65 and 66, and more preferentially 1, 2, 3, 8, 10, 65
and 66.
The direct dyes of formula (I) may be obtained according to
the procedure below:
R'=NO 1b (I)
The compounds of formula (I) are generally obtained by
reacting the derivatives l a or l b with the meta-phenylenediamines 2
in basic medium in the presence of an oxidizing agent. The base
used is preferentially an aqueous solution of ammonia or of sodium
hydroxide and the oxidizing agent is preferentially chosen from
aqueous hydrogen peroxide solution, potassium ferricyanide, air,
ammonium persulfate and manganese oxide.
Synthetic approaches similar to this reaction scheme are
described in patents FR 2 234 277, FR 2 047 932, FR 2 106 66 1 and
FR 2 12 1 101.
Use of the direct dye
The present invention also relates to the use of one or more
compounds of azomethine type of formula (I) as defined previously
for dyeing keratin fibres, in particular human keratin fibres such as
the hair.
Composition
A subject o f the invention is also the composition in
particular for dyeing keratin fibres, in particular human keratin
fibres such as the hair, comprising one or more azomethine
compounds o f formula (I) as defined previously.
The direct dye(s) as defined previously may be present in the
dye composition in a content ranging from 0.00 1% to 10% by
weight and preferably in a content ranging from 0.005% to 6% by
weight, relative to the total weight of the dye composition.
The dye composition according to the invention may also
comprise one or more oxidation dyes.
The oxidation dyes are generally chosen from oxidation
bases optionally combined with one or more couplers.
By way o f example, the oxidation bases are chosen from
para-phenylenediamines, bis(phenyl)alkylenediamines, paraaminophenols,
ortho-aminophenols and heterocyclic bases, and the
addition salts thereof.
Among the para-phenylenediamines that may be mentioned,
for example, are para-phenylenediamine, para-tolylenediamine, 2-
chloro-para-phenylenediamine, 2,3-dimethyl-par aphenylenediamine,
2,6-dimethyl-para-phenylenediamine, 2,6-
diethyl-para-phenylenediamine, 2,5-dimethyl-par aphenylenediamine,
,-dimethyl-para-phenylenediamine, N,Ndiethyl-
para-phenylenediamine, N,N-dipropyl-paraphenylenediamine,
4-amino-N,N-diethyl-3-methylaniline, N,Nbis
(P-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis ( -
hydroxy ethyl) amino -2-met hylaniline, 4-N,N-bis ( -
hydroxy ethyl) amino -2-chloro aniline, 2--hydroxy ethyl-par aphenylenediamine,
2-fluoro-para-phenylenediamine, 2-isopropylpara-
phenylenediamine, N-(P-hydroxypropyl)-paraphenylenediamine,
2-hydroxymethyl-para-phenylenediamine, N,Ndimethyl-
3-methyl-para-phenylene diamine, N-ethyl-N -( -
hydroxyethyl)-para-phenylenediamine, N-(P,y-dihydroxypropyl)-
para-phenylenediamine, N-(4 '-amino phenyl) -paraphenylenediamine,
N-phenyl-para-phenylenediamine, 2--
hydroxyethyloxy-para-phenylenediamine, 2-P-acetylaminoethyloxypara-
phenylenediamine, N-(-methoxy ethyl) -par aphenylenediamine,
4-aminophenylpyrrolidine, 2-thienyl-paraphenylenediamine,
2-P-hydroxyethylamino-5-aminotoluene and 3-
hydroxy- l -(4'-aminophenyl)pyrrolidine, and addition salts thereof
with an acid.
Preference i s particularly given, among the abovementioned
para-phenylenediamines, to para-phenylenediamine, paratolylenediamine,
2-isopropyl-para-phenylenediamine, 2-( -
hydroxy ethyl) -para-phenylenediamine, 2-(P-hydroxyethyloxy)-paraphenylenediamine,
2,6-dimethyl-para-phenylenediamine, 2,6-
diethyl-para-phenylenediamine, 2,3-dimethyl-par aphenylenediamine,
N,N-bis (P-hydroxyethy^-paraphenylenediamine,
2-chloro-para-phenylenediamine, 2-( -
acetylaminoethyloxy)-para-phenylenediamine and their addition
salts with an acid.
Among the bis(phenyl)alkylenediamines that may be
mentioned, for example, are N,N'-bis (P-hydroxyethyl)-N,N'-bis(4'-
aminophenyl)- l ,3-diaminopropanol, N,N'-bis (P-hydroxyethyl)-N,N'-
bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-
aminophenyl)tetramethylenediamine, N,N'-bis (P-hydroxyethyl) -
N,N'-bis(4-aminophenyl)tetramethylene diamine, N,N'-bis(4-
methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-
bis(4'-amino-3'-methylphenyl)ethylenediamine and l ,8-bis(2,5-
diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.
Mention may be made, among para-aminophenols, by way o f
example, o f para-aminophenol, 4-amino-3-methylphenol, 4-amino-
3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-
(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-
(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-
amino-2-(aminomethyl)phenol, 4-amino -2- [(-
hydroxyethyl)aminomethyl]phenol, 4-amino-2-fluorophenol and
their addition salts with an acid.
Mention may be made, among ortho-aminophenols, by way
of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-
methylphenol, 5-acetamido-2-aminophenol and their addition salts.
Mention may be made, among heterocyclic bases, by way of
example, of pyridine derivatives, pyrimidine derivatives and
pyrazole derivatives.
Mention may be made, among pyridine derivatives, of the
compounds described, for example, in patents GB 1 026 978 and
GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-
methoxyphenyl)amino-3-aminopyridine, 3,4-diaminopyridine and
their addition salts.
Other pyridine oxidation bases of use in the present
invention are the 3-aminopyrazolo[ l ,5-a]pyridine oxidation bases or
their addition salts described, for example, in Patent Application
FR 2 80 1 308. Mention may be made, by way of example, of
pyrazolo[ 1,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[ 1,5-
a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[ 1,5-a]pyrid-3-
ylamine, 3-aminopyrazolo[ l ,5-a]pyridine-2-carboxylic acid, 2-
methoxypyrazolo[ 1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[ 1,5-
a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[ l ,5-a]pyrid-5-
yl)ethanol, 2-(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)ethanol, (3-
aminopyrazolo[ 1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[ 1,5-
ajpyridine, 3,4-diaminopyrazolo[ 1,5-a]pyridine, pyrazolo[ 1,5-
a]pyridine-3,7-diamine, 7-(morpholin-4-yl)pyrazolo[ 1,5-a]pyrid-3-
ylamine, pyrazolo[ l ,5-a]pyridine-3,5-diamine, 5-(morpholin-4-
yl)pyrazolo[ 1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo[ l ,5-
a]pyrid- 5-yl) (2-hydroxy ethyl) amino Jethanol, 2-[(3-
aminopyrazolo[ 1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino]ethanol, 3-
aminopyrazolo[ 1,5-a]pyridin-5-ol, 3-aminopyrazolo[ 1,5-a]pyridin-
4-ol, 3-aminopyrazolo[ 1,5-a]pyridin-6-ol, 3-aminopyrazolo[ 1,5-
a]pyridin-7-ol and their addition salts.
Mention may be made, among pyrimidine derivatives, of the
compounds described, for example, in patents DE 2359399, JP 88-
16957 1, JP 05-63 124 and EP 0 770 375 or patent application WO
96/1 5765, 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
their addition salts and their tautomeric forms, when a tautomeric
equilibrium exists.
Among the pyrazole derivatives that may be mentioned are
the compounds described in the patents DE 3843892, DE 4 133957
and patent applications WO 94/08969, WO 94/08970, FR-A-2 733
749 and DE 195 43 988, such as 4,5-diamino- 1-methylpyrazole, 4,5-
diamino- l -(P-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-
diamino- 1-(4 '-chlorobenzyl)pyrazole, 4,5-diamino - 1,3-
dimethylpyrazole, 4,5-diamino-3-methyl- 1-phenylpyrazole, 4,5-
diamino- 1-methyl- 3-phenylpyrazole, 4-amino - 1,3-dimethyl-5-
hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-
diamino-3-tert-butyl- 1-methylpyrazole, 4,5-diamino - 1-t r t -butyl-3 -
methylpyrazole, 4,5-diamino - 1-(P-hydroxyethyl)-3 -methylpyrazole,
4,5-diamino - 1-ethy 1-3 -methylpyrazole, 4,5-diamino - 1-ethy 1-3 -(4 '-
methoxyphenyl)pyrazole, 4,5-diamino - 1-ethy 1-3-
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'-
amino ethyl) amino - 1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-
methyl-3,4,5-triaminopyrazole, 3,5-diamino- 1-methyl-4-
methylaminopyrazole, 3,5-diamino-4 -(P-hydroxyethyl)amino- 1-
methylpyrazole, and the addition salts thereof.
4,5-Diamino- 1-(P-methoxyethyl)pyrazole may also be used.
Use will preferably be made o f a 4,5-diaminopyrazole and
even more preferentially of 4,5-diamino- 1-(P-hydroxyethyl)pyrazole
and/or a salt thereof.
Pyrazole derivatives that may also be mentioned include
diamino-N,N-dihydropyrazolopyrazolones and especially those
described in patent application FR-A-2 886 136, such as the
following compounds and the addition salts thereof: 2,3-diamino6,7-
dihydro- lH,5H-pyrazolo[ l ,2-a]pyrazol- 1-one, 2-amino-3-
ethylamino-6,7-dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-
amino-3-isopropylamino-6,7-dihydro- lH,5H-pyrazolo[ 1,2-
a]pyrazol- l -one, 2-amino-3-(pyrrolidin- l -yl)-6,7-dihydro- lH,5Hpyrazolo[
l ,2-a]pyrazol- l -one, 4,5-diamino- 1,2-dimethyl- 1,2-
dihydropyrazol-3-one, 4,5-diamino- 1,2-diethyl- 1,2-dihy dropyrazol-
3-one, 4,5-diamino- 1,2-di(2-hydroxy ethyl)- 1,2-dihy dropyrazol- 3-
one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro- 1H,5Hpyrazolo[
1,2-a]pyrazol- 1-one, 2-amino-3-dimethylamino-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2,3-diamino-5,6,7,8-
tetrahydro- lH,6H-pyridazino[ 1,2-a]pyrazol- 1-one, 4-amino - 1,2-
diethyl-5-(pyrrolidin- l -yl)- l ,2-dihy dropyrazo 1-3 -one, 4-amino-5-(3-
dimethylaminopyrrolidin- 1-yl)- 1,2-diethyl- 1,2-dihydropyrazol-3-
one, 2,3-diamino-6-hydroxy-6,7-dihydro- lH,5H-pyrazolo[ l ,2-
ajpyrazol- 1-one.
Use will preferably be made o f 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or a salt thereof.
Use will preferably be made, as heterocyclic bases, o f 4,5-
diamino- 1-(P-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-
dihydro- lH,5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or one o f their
salts.
The dye composition may optionally comprise one or more
couplers advantageously chosen from those conventionally used for
the dyeing of keratin fibres.
Among these couplers, mention may be made especially o f
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthalene-based couplers and heterocyclic couplers, and also the
addition salts thereof.
Mention may be made, for example, of 1,3-
dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro- 1,3-
dihydroxybenzene, 2,4-diamino- 1-(P-hydroxyethyloxy)benzene, 2-
amino-4 -(P-hydroxyethylamino)- 1-methoxybenzene, 1,3-
diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-
ureidoaniline, 3-ureido- 1-dimethylaminobenzene, sesamol, 1--
hydroxyethylamino-3,4-methylenedioxybenzene, -naphthol, 2-
methyl- 1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-
N-methylindole, 2-amino-3-hydroxypyridine, 6-
hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-
(P-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis ( -
hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-
methylpyridine, 1-H-3-methylpyrazol-5-one, l -phenyl-3-
methylpyrazol-5-one, 2,6-dimethylpyrazolo[ 1,5-b]- 1,2,4-triazole,
2,6-dimethyl[3,2-c]- l ,2,4-triazole and 6-methylpyrazolo[ l ,5-
ajbenzimidazole, the addition salts thereof with an acid, and
mixtures thereof.
In general, the addition salts of the oxidation bases and
couplers that can be used within the context of the invention are
especially chosen from the addition salts with an acid such as the
hydrochlorides, hydrobromides, sulfates, citrates, succinates,
tartrates, lactates, tosylates, benzenesulfonates, phosphates and
acetates.
The oxidation base(s) each advantageously represent from
0.00 1% to 10% by weight and preferably from 0.005% to 6% by
weight relative to the total weight of the composition.
The content of coupler(s), if they are present, each
advantageously represent from 0.00 1% to 10% by weight relative to
the total weight of the composition, and preferably from 0.005% to
6% by weight relative to the total weight of the dye composition.
The dye composition may also comprise one or more
additional direct dyes other than the direct dyes of azomethine type
defined previously.
The additional direct dye(s) according to the invention are
chosen from neutral, acidic or cationic nitrobenzene dyes, neutral,
acidic or cationic azo direct dyes, neutral, acidic or cationic
quinone and in particular anthraquinone direct dyes, azine direct
dyes, triarylmethane direct dyes, azomethine direct dyes and natural
direct dyes.
Among the benzenic direct dyes that may be used according
t o the invention, mention may be made in a non-limiting manner o f
the following compounds:
- 1,4-diamino-2-nitrobenzene;
- 1-amino-2-nitro-4-B-hydroxyethylaminobenzene;
- 1-amino -2-nitro -4-bis ( -hydroxy ethyl) aminobenzene;
- 1,4-bis (P-hydroxyethylamino)-2-nitrobenzene;
- 1- -hydroxy ethylamino -2-nitro -4-bis ( -
hydroxyethylamino)benzene;
- 1- -hydro xyethylamino -2-nitro -4-amino benzene;
- 1-P-hydroxyethylamino-2-nitro-4-(ethyl)(Phydroxyethyl)
aminobenzene;
- 1-amino -3-methy 1-4- -hydroxy ethylamino- 6-nitrobenzene;
- 1-amino -2-nitro -4- -hydroxy ethylamino -5-chlorobenzene;
- 1,2-diamino-4-nitrobenzene;
- 1-amino -2- -hy droxy ethylamino -5-nitrobenzene;
- 1,2-bis (P-hydroxyethylamino)-4-nitrobenzene;
- 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene;
- 1-hydro xy-2- amino -5-nitrobenzene;
- 1-hydroxy-2-amino-4-nitrobenzene;
- 1-hydroxy- 3-nitro -4-amino benzene;
- 1-hydro xy-2 -amino -4, 6-dinitrobenzene;
- 1-P-hydroxyethyloxy-2-P-hydroxyethylamino-5-nitrobenzene;
- 1-methoxy-2 -P-hydroxyethylamino-5-nitrobenzene;
- 1-P-hydroxyethyloxy-3-methylamino-4-nitrobenzene;
- 1-P,y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene;
- 1-P-hydroxyethylamino-4-P,y-dihydroxypropyloxy-2-
nitrobenzene;
- 1-P,y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene;
- 1-P-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene;
- 1-P-hydroxyethylamino-3-methyl-2-nitrobenzene;
- 1--amino ethylamino -5-methoxy-2 -nitrobenzene;
- 1-hydro xy-2-chloro-6-ethylamino-4-nitrobenzene;
- 1-hydro xy-2-chloro-6-amino-4-nitrobenzene;
- 1-hy dro xy- 6-bis (P-hydroxyethyl)amino- 3-nitrobenzene;
- 1-P-hydroxyethylamino-2-nitrobenzene; and
- 1-hydroxy-4 -P-hydroxyethylamino-3-nitrobenzene.
Among the azo direct dyes that may be used according to the
invention, mention may be made o f the cationic azo dyes described
in patent applications WO 95/1 5 144, WO-95/0 1772 and EP-7 14954,
the content of which forms an integral part of the invention.
Among these compounds, the ones that may be mentioned
most particularly are the following dyes:
- 1,3-dimethyl-2-[[4-(dimethylamino)-phenyl]-azo]- 1Himidazolium
chloride,
- 1,3-dimethyl-2-[(4-aminophenyl)azo]- lH-imidazolium chloride,
- 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methyl
sulfate.
Among the azo direct dyes that may also be mentioned are
the following dyes, described in the Colour Index International, 3rd
edition: Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red
22, Basic Red 76, Basic Red 5 1, Basic Yellow 57, Basic Brown 16,
Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic
Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9 .
Mention may also be made o f 1-(4 '-aminodiphenylazo)-2-
methyl-4-bis (P-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-
methoxyphenylazo)- 1-naphthalenesulfonic acid.
Among the quinone direct dyes, mention may be made of the
following dyes: Disperse Red 15, Solvent Violet 13, Acid Violet 43,
Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse
Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse
Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, and also
the following compounds:
- 1-N-methylmorpholiniumpropylamino-4-
hydroxyanthraquinone
- 1-aminopropylamino-4-methylaminoanthraquinone
- 1-aminopropylaminoanthraquinone
-5 -hydroxyethyl-1,4-diaminoanthraquinone
-2-aminoethylaminoanthraquinone
- 1,4-bis (P,y-dihydroxypropylamino)anthraquinone.
Among the azine dyes, mention may be made o f the
following compounds: Basic Blue 17, Basic Red 2 .
Among the triarylmethane dyes that may be used according
to the invention, mention may be made of the following compounds:
Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic
Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7 .
Among the azomethine dyes that may be used according to
the invention, mention may be made of the following compounds:
2-P-hydroxyethylamino-5-[bis(P-4 ' -hydroxy ethyl)amino] anilino-
1,4-benzoquinone;
2-P-hydroxyethylamino-5-(2 '-methoxy-4 ' -amino )anilino- 1,4-
benzoquinone;
- 3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy- 1,4-
benzoquinoneimine;
3-N-(3 '-chloro-4'-methylamino)phenylureido-6-methyl- 1,4-
benzoquinoneimine; and
- 3-[4'-N-(ethyl,carbamylmethyl)amino]phenylureido-6-methyl- 1,4-
benzoquinoneimine.
Preferably, the composition according to the invention
comprises at least one azomethine compound of formula (I) and at
least one azomethine dye other than those of formula (I).
Among the natural direct dyes that may be used according to
the invention, mention may be made o f lawsone, juglone, alizarin,
purpurin, carminic acid, kermesic acid, purpurogallin,
protocatechaldehyde, indigo, isatin, curcumin, spinulosin and
apigenidin. Extracts or decoctions containing these natural dyes and
in particular poultices or henna-based extracts may also b e used.
The additional direct dye(s) may be present in the dye
composition in a content ranging from 0.00 1% to 10% by weight
and preferably in a content ranging from 0.005% to 6% by weight,
relative to the total weight of the composition.
The medium that is suitable for dyeing, also known as the
dye support, is a cosmetic medium generally formed from water or a
mixture of water and of at least one organic solvent. Examples of
organic solvents that may be mentioned include C 1- C 4 lower
alkanols, such as ethanol and isopropanol; polyols and polyol
ethers, for instance 2-butoxyethanol, propylene glycol, propylene
glycol monomethyl ether, diethylene glycol monoethyl ether and
monomethyl ether, and also aromatic alcohols, for instance benzyl
alcohol or phenoxyethanol, and mixtures thereof.
When they are present, the solvents are present in
proportions preferably of between 1% and 99% by weight
approximately and even more preferentially between 5% and 95%
by weight approximately relative to the total weight of the dye
composition.
The dye composition may also contain various adjuvants
conventionally used in hair dye compositions, such as anionic,
cationic, nonionic or amphoteric surfactants or mixtures thereof,
anionic, cationic, nonionic or amphoteric polymers or mixtures
thereof, mineral or organic thickeners, and in particular anionic,
cationic, nonionic and amphoteric polymeric associative thickeners,
antioxidants, penetrants, solubilizers, sequestrants, fragrances,
buffers, dispersants, conditioning agents, for instance volatile or
nonvolatile, modified or unmodified silicones such as amino
silicones, film-forming agents, ceramides, preserving agents,
opacifiers and conductive polymers.
The above adjuvants are generally present in an amount for
each of them of between 0.0 1% and 20% by weight relative to the
weight of the composition.
Needless to say, a person skilled in the art will take care to
select this or these optional additional compound(s) such that the
advantageous properties intrinsically associated with the dye
composition in accordance with the invention are not, or are not
substantially, adversely affected by the envisaged addition(s).
The H of the dye composition in accordance with the
invention is generally between 3 and 12 approximately and
preferably between 5 and 11 approximately. It may be adjusted to
the desired value by means of acidifying or basifying agents
commonly used in the dyeing of keratin fibres, or alternatively
using standard buffer systems.
Among the acidifying agents, mention may be made, by way
of example, of mineral or organic acids other than dicarboxylic
acids, such as hydrochloric acid, ortho-phosphoric acid, sulfuric
acid, carboxylic acids such as acetic acid, tartaric acid, citric acid
or lactic acid, and sulfonic acids.
Among the basifying agents, mention may be made, by way
of example, of aqueous ammonia, alkali metal carbonates,
alkanolamines such as mono-, di- and triethanolamines and their
derivatives, sodium hydroxide or potassium hydroxide, and the
compounds of formula:
in which W is a propylene residue optionally substituted
with a hydroxyl group or a C1-C4 alkyl radical; and Ra, Rb, Rc and
Rd, which may be identical or different, represent a hydrogen atom
or a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.
The cosmetic composition according to the invention may be
present in a variety of forms, such as in the form of liquids, creams,
gels, or any other form which is appropriate for carrying out dyeing
of keratin fibres, and in particular of human hair.
As indicated previously, the invention also relates to the use
of the dye composition as defined previously for dyeing keratin
fibres, in particular human keratin fibres such as the hair.
Process
The dyeing process according to the present invention
consists in applying to wet or dry keratin fibres a dye composition
as defined previously for a time that is sufficient to obtain the
desired coloration, and the fibres are then rinsed, optionally washed
with shampoo and rinsed again, and the resulting fibres are dried or
left to dry.
Preferably, the leave-on time for the dye composition is
between 1 and 60 minutes, preferably between 5 and 40 minutes and
even more preferably between 10 and 30 minutes.
The dye composition is generally applied to the keratin
fibres at room temperature, preferably between 25 and 55°C.
According to one embodiment, the dye composition
according to the invention is applied to the keratin fibres in the
presence of one or more oxidizing agents for a time that is sufficient
to obtain the desired lightening.
The oxidizing agent may be present in the dye composition
or may be used separately in a cosmetic composition.
Preferably, the oxidizing agent is used separately in a
cosmetic composition.
Thus, the present invention also relates to a process for
lightening keratin fibres, in particular human keratin fibres such as
the hair, in which (i) the dye composition as defined previously,
free of oxidizing agent, and (ii) a cosmetic composition comprising
one or more oxidizing agents are applied to the said fibres;
compositions (i) and (ii) being applied to the said keratin fibres
sequentially or simultaneously for a time that is sufficient to obtain
the desired lightening, and the fibres are then rinsed, optionally
washed with shampoo and rinsed again, and the resulting fibres are
dried or left to dry.
For the purposes of the present invention, the term
"sequentially" means that the oxidizing composition is applied
before or after the dye composition, i.e. as a pretreatment or a posttreatment.
The oxidizing agents used are chosen from hydrogen
peroxide, urea peroxide, alkali metal bromates, persalts such as
perborates and persulfates, peracids, and oxidase enzymes (with the
possible cofactors thereof), among which mention may be made of
peroxidases, 2-electron oxidoreductases such as uricases, and 4-
electron oxygenases, for instance laccases.
The oxidizing agent is preferably hydrogen peroxide.
The oxidizing composition may also contain various
adjuvants conventionally used in compositions for dyeing the hair
and as defined previously.
The pH of the oxidizing composition containing the
oxidizing agent is such that, after mixing with the dye composition,
the pH of the resulting composition applied to the keratin fibres
preferably ranges between 3 and 12 approximately, even more
preferentially between 5 and 11 and even more particularly between
6 and 8.5 . It may be adjusted to the desired value by means of
acidifying or basifying agents usually used in the dyeing of keratin
fibres and as defined previously.
Kit
The present invention also relates to a multi-compartment
device or "kit" comprising a first compartment containing a
cosmetic composition comprising one or more compounds of
formula (I) as defined previously, free of oxidizing agent, and a
second compartment comprising one or more oxidizing agents.
According to one particular embodiment, the device may
comprise at least one compartment comprising a cosmetic
composition comprising one or more compounds of the
abovementioned formula (I).
Leuco compounds
Moreover, a subject of the invention is compounds of leuco
type, which are the reduced form of the direct dyes of azomethine
type according to the invention of formula (II) below, organic or
mineral acid salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof, and solvates thereof:
in which n, R, Rl R2, R 3 , X, R4 and R have the same meanings as
those indicated in formula (I).
Preferably, the compounds of formula (II) are chosen from
the precursors of compounds 1 to 65 mentioned above.
Even more preferentially, the compounds of leuco type of
formula (II) are chosen from precursors of the direct dyes 1, 2, 3, 4,
5, 6, 7, 8, 9, 10, 11 and 65 and more preferentially 1, 2, 3, 8, 10 and
65 .
The compounds of formula (II) are generally obtained by
reacting the compounds of formula (I) with a reducing agent. This
reducing agent may be preferentially chosen from sodium
hydrosulfite, zinc powder and ascorbic acid. This reducing agent is
preferentially sodium hydrosulfite or zinc.
Synthetic approaches are described in patents FR 2 056 799, FR 2
047 932, FR 2 165 965 and FR 2 262 023 .
The invention also relates to the use of one or more
compounds of formula (II) as defined above for dyeing keratin
fibres, in particular human keratin fibres such as the hair, in the
presence of one or more oxidizing agents.
In particular, the invention relates to a cosmetic composition
comprising one or more compounds of leuco type of formula (II) as
defined previously, and optionally comprising one or more oxidizing
agents.
Process
The present invention also relates to a dyeing process in
which a cosmetic composition comprising one or more compounds
of leuco type of the abovementioned formula (II) is applied to
keratin fibres in the presence of one or more oxidizing agents for a
time that is sufficient to develop the desired coloration, after which
the fibres are rinsed, optionally washed with shampoo and rinsed
again, and the resulting fibres are dried or left to dry.
The oxidizing agent may be atmospheric oxygen or may be
chosen from the oxidizing agents mentioned previously.
In particular, when the oxidizing agent is atmospheric
oxygen, simple exposure to air of the keratin fibres treated with the
composition comprising the compound(s) of leuco type makes it
possible to generate the colouring species and, consequently, to
colour the fibres.
According to one variant, the oxidizing agent(s) may be
applied simultaneously or sequentially to the cosmetic composition
comprising the compounds of leuco type.
Thus, the cosmetic composition comprising the oxidizing
agent(s) may be applied to the keratin fibres before, simultaneously
with or after the cosmetic composition comprising the compounds of
leuco type of formula (II) according to the invention.
According to another variant, a ready-to-use composition
which results from the mixing of a cosmetic composition comprising
one or more compounds of leuco type of the abovementioned
formula (II) and of a cosmetic composition comprising one or more
oxidizing agents is applied to the keratin fibres.
The ready-to-use composition that is thus applied to the
keratin fibres may be in various forms, such as in the form of
liquids, creams or gels or in any other form that is suitable for
dyeing keratin fibres, and especially human hair.
The leave-on time for the composition(s) ranges from 1 to 60
minutes, preferably from 5 to 40 minutes and even more
preferentially from 10 to 30 minutes.
The cosmetic composition comprising such compounds of
leuco type is generally applied to the keratin fibres at room
temperature, preferably between 25 and 55°C.
Kit
The present invention also relates to a multi-compartment
device or "kit" comprising a first compartment containing a
cosmetic composition comprising one or more compounds of leuco
type of formula (II) as defined previously, free of oxidizing agent,
and a second compartment comprising one or more oxidizing agents.
According to one particular embodiment, the device may
comprise at least one compartment comprising a cosmetic
composition comprising one or more compounds of leuco type of the
abovementioned formula (II).
In this case, the composition comprising the compound(s) of
leuco type as defined above is applied to the keratin fibres, which
become coloured due to their exposure to atmospheric oxygen, as
oxidizing agent.
The devices mentioned above are suitable for dyeing keratin
fibres.
The examples that follow serve to illustrate the invention
without, however, being limiting in nature.
EXAMPLES
1/ Synthesis examples :
Example 1: Synthesis of 4-butoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-iminocyclohexa- 1,4-
dienylamine hydrochloride 1
compound 1
To a solution of 0.003 mol of N-methyl-N-isopropyl-4-
aminoaniline hydrochloride and 0.003 mol of 4-butoxybenzene- 1,3-
diamine dihydrochloride in 2 ml of water and 6 ml of ethanol,
brought to pH 9.5 with 20% aqueous ammonia solution, are added
10.2 ml of 20-V 6% aqueous hydrogen peroxide solution; after
stirring for 24 hours at room temperature, a gum forms. The
supernatant is removed and the gum is washed with three times 50
ml of water, 4 ml of ethyl acetate and then with isopropyl ether.
After drying, 260 mg of 4-butoxy-6-[4-
(ethylisopropylamino)phenylamino]-3-iminocyclohexa- 1,4-
dienylamine hydrochloride 1 are obtained in the form of a black
powder.
The molecular ion 355 (ES+) is detected by mass
spectrometry.
Example 2: Synthesis of 2- {[4-(2-amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyljethylamino} ethanol 2
compound 2
To a solution of 4.39 g (0.0 15 mol) of 2-[(4-amino-3-
methylphenyl)(ethyl)amino]ethanol sulfate in 5 ml of water and 10
ml of ethanol is added a solution of 4-butoxybenzene- 1,3-diamine
dihydrochloride in 5 ml of water and 10 ml of ethanol. The pH is
adjusted to 9.5 with 15 ml of 20% aqueous ammonia. 51 ml of 6%
aqueous hydrogen peroxide solution are added and the mixture is
stirred for 12 hours. The resulting mixture is extracted with butanol.
The organic phase is washed with water brought to pH 10.5 with
2 0% aqueous ammonia. The organic phase is dried with disodium
sulfate and filtered, and the butanol is then evaporated off. The
product is washed with isopropyl ether and filtered off. 2.8 1 g of 2-
{[4-(2-amino-5-butoxy-4-iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyljethylamino} ethanol 2 are obtained in the form of a
black product.
The molecular ion 37 1 (ES+) is detected by mass
spectrometry.
Example 3: Synthesis of 2-chloro-4-[(2,4-diaminobutoxyphenyl)
imino]cyclohexa-2,5-dien- 1-one 8
compound 8
26 ml of 6%o aqueous hydrogen peroxide solution are added
to a solution of 180 mg (0.00 1 mol) of 4-amino-2-chlorophenol
sulfate and 253 mg (0.00 1 mol) of 4-butoxybenzene- 1,3-diamine
dihydrochloride in 2 ml of water and 2 ml of ethanol, and the
solution is adjusted to pH 9.5 with 20%> aqueous ammonia. After
stirring for 5 hours at room temperature, the precipitate formed is
filtered off, washed with water and dried. A brown powder is
obtained.
The molecular ion 320 (ES+) is detected by mass
spectrometry.
Example 4: Synthesis of 2- {[4-(2-amino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)phenyl]ethylamino} ethanol 3
A solution of 4-ethoxybenzene- l ,3-diamine dihydrochloride
in 4 ml of 0.25N sodium hydroxide is added to a solution of 2-
[ethyl(4-nitrosophenyl)amino]ethanol in 2 ml of water, and the
mixture is heated to 50°C. After concentrating the reaction medium,
taking up the residue in isopropyl ether and filtering off and drying
the precipitate formed, 360 mg of 2- {[4-(2-amino-5-ethoxy-4-
imino cyclohexa-2, 5-dienylideneamino)phenyl]ethylamino} ethanol
dihydrochloride 3 are obtained as a black powder.
The molecular ion 329 (ES+) is mainly detected.
Example 5: Synthesis of 2-[[4-(2-amino-5-butoxy-4-
imino cyclohexa-2, 5-dienylideneamino)phenyl] (2-
hydroxyethyl)amino]ethanol 10
compound 10
To a solution of 0.925 g (0.003 mol) of N-ethyl-N-isopropyl-
4-aminoaniline hydrochloride and 0.76 g (0.003 mol) of 4-
butoxybenzene- 1,3-diamine dihydrochloride in 2 ml of water and 6
ml of ethanol, brought to pH 9.5 with 20% aqueous ammonia, are
added 10.2 ml of 6%> aqueous hydrogen peroxide solution. After
stirring for 24 hours at room temperature, the ethanol is removed
and the coupling product formed is extracted with butanol. After
removal of the butanol under vacuum, the gummy residue is taken
up in ethyl acetate and then in ether. 0.470 g of 2-[[4-(2-amino-5-
butoxy-4-iminocyclohexa-2,5-dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol 10 is obtained in the form of a blueblack
powder after drying.
FIA/MS analysis: the molecular ion 387 (ES+) is mainly
detected.
Example 6: Synthesis of 2- {[4-(2-amino-5-ethoxy-4-
imino cyclohexa-2, 5-dienylideneamino)phenyl]ethylamino} ethanol
hydrochloride 65
A solution of 4-butoxybenzene- 1,3-diamine dihydrochloride
in 4.2 ml of 0.25N sodium hydroxide is added to a solution of 2-
[ethyl(4-nitrosophenyl)amino]ethanol in 4.2 ml of water at 50°C.
After 3 hours at 50°C, the supernatant is removed and the residual
gum is washed with water and then taken up in isopropyl ether. The
solid formed is filtered off and dried. 360 mg of 2- {[4-(2-amino-5-
ethoxy-4-iminocyclohexa-2,5-dienylideneamino)phenyl]-
ethylamino} ethanol hydrochloride 65 are thus obtained in the form
of a black powder.
FIA/MS analysis: the molecular ion 357 (ES+) is detected.
Example 7 : Synthesis of 2- {4-amino-3-[4-
(ethylisopropylamino)phenylimino]-6-imino-cyclohexan- 1,4-
dienyloxy} ethanol hydrochloride 66
compound 66
To a solution of 2 .14 g (0.0 1 mol) of N-ethyl-N-isopropyl-4-
aminoaniline hydrochloride and 2.4 1 g (0.0 1 mol) of 2-(2,4-
diaminophenoxy)ethanol dihydrochloride in 10 ml of water and
10ml of ethanol, brought to pH 9.5 with 20% aqueous ammonia, are
added dropwise 5.7 g of 30% aqueous peroxide hydrogen solution
(0.05 mol). After stirring for 6 hours at room temperature, a gum
forms. The supernatant is removed and the residual gum is washed
with four times of water and then taken up in dichloromethane in
order to perform a chromatography (eluent:
dichloromethane/methanol 98/2 v/v). 510 mg of 2- {4-amino-3-[4-
(ethylisopropylamino)phenylimino]-6-iminocyclohexa- 1,4-
dienyloxy} ethanol hydrochloride 66 are thus obtained in the form of
a black powder.
FIA/MS analysis: the molecular ion 343 (ES+) is detected.
Example 8: Synthesis of 4-methoxy-6-[4 -(N -ethyl -Npylamino)
phenylimino]-3-iminocyclohexa- 1,4-dienyl- 1-amine
To a solution of 191.5 mg (0.00 1 mol) of N-ethyl-N-(propan-
2-yl)-4-nitrosoaniline and 312.4 mg of 4-methoxy- 1,3-
metaphenylenediamine dihydrochloride (0.00 15 mol) in 2 ml of
water and 2 ml of ethanol, is added 1 ml of 2 N sodium hydroxide.
After stirring for 4 hours, the mixture is cooled to 0°C then 2 ml of
20% aqueous ammonia is added and the mixture is stirred for 1
hour. The formed precipitate is filtrated and is washed with water.
258 mg of 4-methoxy-6-[4 -(N -ethyl -Nisopropylamino)
phenylimino]-3-iminocyclohexa- 1,4-dienyl- 1-amine
are thus obtained in the form of a black powder.
LC/MS analysis: the molecular ion 313 (ES+) is detected.
2 1 Dyeing evaluations of the molecules 1, 2 , 3 , 8, 10, 65
synthesized :
The following dye compositions were prepared:
o 1 g of illustrated compound
o 79.5 g of water
o 15 g of ethanol
o 5 g of benzyl alcohol
o 0.5 g of benzoic acid
1 g of the resulting mixture is applied to a lock of 0.25 g of
grey hair containing 90% white hairs. After a leave-on time of 30
minutes, the lock is rinsed, washed with a standard shampoo, rinsed
again and then dried.
Compound 1 Very dark violetblue
Compound 2 Very dark violetblue
Compound 3 Very dark violetblue
Compound 8 Dark orange-brown
Compound 10 Very dark bluegreen
Compound 65 Very dark violetblue
3/ Dyeing evaluations of the molecules 66 and 67 synthesized :
The following dye composition was prepared:
o 0.5 g of illustrated compound
o 74.5 g of water
o 15 g of ethanol
o 5 g of benzyl alcohol
o 5 g of 30% aqueous hydroxyethyldimonium chloride
solution
1.25 g of the resulting mixture is applied to a lock of 0.25 g
of grey hair containing 90% white hairs. After a leave-on time of 30
minutes, the lock is rinsed, washed with a standard shampoo, rinsed
again and then dried.
Compound 66 Very dark blue
Compound 67 Very dark blue
CLAIMS
1. Azomethine compound of formula (I) below, organic or
mineral acid salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof and solvates thereof:
which formula (I):
n represents an integer equal to 0, 1, 2, 3 or 4,
R represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different radicals
chosen from hydroxyl or imidazolium radicals, An ; An
denoting a cosmetically acceptable anion or mixture of
anions,
- a C1-C4 alkoxy radical,
- a halogen atom,
Ri represents:
- a linear or branched C1-C10 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R3 may form, together with the nitrogen atom to which
they are attached, a pyrrolidino, piperidino or morpholino ring,
• X represents:
- a hydroxyl radical,
- a radical -NR 4R5 in which R4 and R represent,
independently of each other:
■ a hydrogen atom,
■ a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl or C1- C 4 alkoxy
radicals,
it being understood that the compounds of formula (I) cannot
represent the following compounds (A) or (B):
(E)
2 . Azomethine compound according to Claim 1,
characterized in that Ri represents a linear or branched C2-C alkyl
radical, optionally substituted with one or more hydroxyl radicals.
3. Azomethine compound according to Claim 1 or 2,
characterized in that:
• n represents an integer equal to 0, 1 or 2,
• R represents:
- a linear or branched C1-C4 alkyl radical, preferably
methyl,
- a C1-C4 alkoxy radical, preferably a methoxy radical,
- a halogen atom, preferably chlorine;
when n is equal to 2, the groups R are identical or
different,
• Ri represents:
- a linear or branched C2-C alkyl radical, optionally
substituted with one or more hydroxyl radicals,
• R2 and R3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C1-C4 alkyl radical, preferably
methyl, ethyl or propyl radical,
• R2 and R3 may form, together with the nitrogen atom to
which they are attached, a pyrrolidino, piperidino or morpholino
ring,
• X represents:
- a hydroxyl radical,
- a radical -NR 4R5 in which R4 and R represent,
independently of each other:
a hydrogen atom,
a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl radicals.
4. Azomethine compound of formula (I) according to any
one of the preceding claims, characterized in that, taken together or
separately:
- n represents an integer equal to 0 or 2,
- R represents a halogen atom, in particular chlorine, or a
linear C1-C4 alkyl radical, in particular a methyl radical,
- Ri represents a linear or branched C2-C alkyl radical, in
particular an ethyl or butyl radical; a linear C1-C4 alkyl radical
substituted with a hydroxyl radical, in particular a 2-hydroxyethyl
radical,
- R2 represents a hydrogen atom or a linear C1-C4 alkyl
radical, preferably a butyl, methyl or ethyl radical,
- R 3 represents a hydrogen atom or a linear C1-C4 alkyl
radical, preferably a butyl, methyl or ethyl radical, and/or
- X represents a hydroxyl radical or a radical -NR 4R5 in
which R4 and R represent, independently of each other, a hydrogen
atom or a linear or branched Ci-C alkyl radical, optionally
substituted with one or more hydroxyl radicals.
5. Azomethine compound of formula (I) according to any
one of the preceding claims, characterized in that it is chosen from
the following compounds:

2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
Compound 7
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 8
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 9
2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 10
6-[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenylamino]hexan-1-ol
Compound 11
4-propoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1,4-dienylamine
Compound 12
2- {[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
OH Compound 13
6-(4-Aminophenylimino)-4-propoxy-3-
iminocyclohexa-1,4-dienylamine
Compound 14
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 15
6-(4-Amino-2,3-dimethylphenylimino)-4-
propoxy-3-iminocyclohexa- 1,4-dienylamine
Compound 16
2-[[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
OH
Compound 17
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 18
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 19
2-[[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
OH Compound 20
4-ethoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1,4-dienylamine
Compound 2 1
2- {[4-(2-Amino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 22
6-(4-Aminophenylimino)-4-ethoxy-3-
iminocyclohexa-1,4-dienylamine
Compound 23
4-(2-Amino-5-ethoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 24

2- {[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 31
6-(4-Aminophenylimino)-4-pentyloxy-3-
iminocyclohexa-1,4-dienylamine
Compound 32
4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenol
Compound 33
6-(4-Amino-2,3-dimethylphenylimino)-4-
pentyloxy-3-iminocyclohexa-l,4-
dienylamine
Compound 34
2-[[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl
(2-hydroxyethyl)amino]ethanol
OH
Compound 35
4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-2-
chlorophenol
Compound 36

6-(4-Amino-2,3-dimethylphenylimino)-4-
hexyloxy-3-iminocyclohexa-l,4-
dienylamine
Compound 43
2-[[4-(2-Amino-5-hexyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl
(2-hydroxyethyl)amino]ethanol
OH
Compound 44
4-(2-Amino-5-hexyloxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 45
4-(2-Amino-5-hexyloxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 46
2-[[4-(2-Amino-5-hexyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 47
N-(5-Ethoxy-4-imino-2-pyrrolidin- 1-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-N'-
isopropylbenzene-1,4-diamine
Compound 48
N-(5-Ethoxy-4-imino-2-piperidin- 1-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-
N'-isopropylbenzene- 1,4-diamine
Compound 49
NH
N-(5-Ethoxy-4-imino-2-morpholin-4-
ylcyclohexa-2,5-dienylidene)-N'-ethyl-
N'-isopropylbenzene- 1,4-diamine
Compound 50
NH
N-(2-Diethylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-N'-ethyl
-N'-isopropylbenzene-1,4-diamine
Compound 51
N-(2-methylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-N'-ethyl
-N'-isopropylbenzene-1,4-diamine
Compound 52
NH
NH, N-(5-Ethoxy-4-imino-2-pyrrolidin- 1-
ylcyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene- 1,4-diamine
NH Compound 53
N-(5-Ethoxy-4-imino-2-piperidin- 1-
ylcyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene- 1,4-diamine
Compound 54
NH

OH 3-Chloro-4-(2-diethylamino-5-ethoxy
-4-iminocyclohexa-2,5-dienylideneamino)
phenol
ί , /
Compound 6 1
- N' NH
OH 3-Chloro-4-(2-dimethylamino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)
phenol
Compound 62
6 . Use of one or more azomethine compounds of formula (I)
as defined according to any one of Claims 1 to 5, for dyeing keratin
fibres, in particular human keratin fibres such as the hair.
7 . Composition in particular for dyeing keratin fibres such
as the hair, comprising one or more azomethine compounds of
formula (I) as defined according to any one of Claims 1 to 5.
8. Process for dyeing keratin fibres, characterized in that a
dye composition comprising one or more azomethine compounds of
formula (I) as defined according to any one of Claims 1 to 5 is
applied to the said wet or dry fibres for a time that is sufficient to
obtain the desired coloration, after which the fibres are rinsed,
optionally washed with shampoo and rinsed again, and the resulting
fibres are dried or left to dry.
9 . Process for lightening keratin fibres, characterized in that
(i) the dye composition as defined in Claim 7, free of oxidizing
agent, and (ii) a cosmetic composition comprising one or more
oxidizing agents are applied to the said fibres; compositions (i) and
(ii) being applied to the said keratin fibres sequentially or
simultaneously for a time that is sufficient to obtain the desired
lightening, and the fibres are then rinsed, optionally washed with
shampoo and rinsed again, and the resulting fibres are dried or left
to dry.
10 . Compound of formula (II) below, organic or mineral acid
salts thereof, tautomers thereof and/or solvates thereof:
in which n, R, Rl R2, R 3 , X, R4 and R have the same meaning as in
Claim 2 .
11. Composition in particular for dyeing keratin fibres such
as the hair, comprising one or more azomethine compounds of
formula (II) as defined according to the preceding claim and
optionally comprising one or more oxidizing agents.
12. Process for dyeing keratin fibres, characterized in that a
dye composition comprising one or more azomethine compounds of
formula (II) as defined according to Claim 10 and an oxidizing
composition comprising one or more oxidizing agents are applied
simultaneously or sequentially to the said wet or dry fibres.
13. Use of one or more compounds of formula (II) as defined
according to Claim 10 for dyeing keratin fibres, in particular human
keratin fibres such as the hair, in the presence of one or more
oxidizing agents.
14. Multi-compartment device or dyeing "kit", characterized
in that it comprises a first compartment containing a composition as
defined according to Claim 7 or 11, free of oxidizing agent, and a
second compartment containing a composition comprising one or
more oxidizing agents.
AMENDED CLAIMS
received by the International Bureau on 04 April 2013 (04.04.2013)
1. Azofnethine compound of formula (I) below, organic or
mineral acid salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof and solvates thereof:
which formula (I):
n represents an integer equal to 0, 1, 2, 3 or 4,
R represents:
- a linear or branched C 1- C alkyl radical, optionally
substituted with one or more identical or different radicals
chosen from hydroxyl or imidazolium radicals, An ; An
denoting a cosmetically acceptable anion or mixture of
anions,
- a C 1-C4 alkoxy radical,
- a halogen atom,
Ri represents:
- a linear or branched C -C O alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R2 and R3 represent, independently of each other:
- a hydrogen atom,
- a linear or branched C 1-C4 alkyl radical, optionally
substituted with one or more hydroxyl radicals,
R and R3 may form, together with the nitrogen atom to which
they are attached, a pyrrolidine piperidino or morpholino ring,
X represents:
- a hydroxyl radical,
- a radical -NR4R5 in which R and represent,
independently of each other:
■ a hydrogen atom,
■ a linear or branched C -C alkyl radical, optionally
substituted with one or more hydroxyl or - C alkoxy
radicals,
it being understood that the compounds of formula (I) cannot
represent the following compounds (A), (B), (C), (D) or (E):
(E)
2. Azomethine compound according to Claim 1,
characterized in that R represents a linear or branched C2-Cg alkyl
radical, optionally substituted with one or more hydroxyl radicals.
3. Azomethine compound according to Claim 1 or 2,
characterized in that:
• n represents an integer equal to 0, 1 or 2,
• R represents:
- a linear or branched Ci-C alkyl radical, preferably
methyl,
- a C 1-C4 alkoxy radical, preferably a methoxy radical,
- a halogen atom, preferably chlorine;
when n is equal to 2, the groups R are identical or
different,
• represents:
- a linear or branched C2-C alkyl radical, optionally
substituted with one or more hydroxyl radicals,
• R and R represent, independently of each other:
- a hydrogen atom,
- a linear or branched C 1-C4 alkyl radical, preferably
methyl, ethyl or propyl radical,
• R2 and R3 may form, together with the nitrogen atom to
which they are attached, a pyrrolidino, piperidino or morpholino
ring,
• X represents:
- a hydroxyl radical,
- a radical -NR4R5 in which R4 and R5 represent,
independently of each other:
> a hydrogen atom,
> a linear or branched C -C alkyl radical, optionally
substituted with one or more hydroxyl radicals.
4. Azomethine compound of formula (I) according to any
one of the preceding claims, characterized in that, taken together or
separately:
- n represents an integer equal to 0 or 2,
- R represents a halogen atom, in particular chlorine, or a
linear C 1-C4 alkyl radical, in particular a methyl radical,
- Ri represents a linear or branched C2 -C alkyl radical, in
particular an ethyl or butyl radical; a linear C 1-C4 alkyl radical
substituted with a hydroxyl radical, in particular a 2-hydroxyethyl
radical,
- .2 represents a hydrogen atom or a linear C1-C4 alkyl
radical, preferably a butyl, methyl or ethyl radical,
- R represents a hydrogen atom or a linear C1-C4 alkyl
radical, preferably a butyl, methyl or ethyl radical, and/or
- X represents a hydroxyl radical or a radical -NR4R5 in
which R 4 and R5 represent, independently of each other, a hydrogen
atom or a linear or branched C -C alkyl radical, optionally
substituted with one or more hydroxyl radicals.
5. Azomethine compound of formula (I) according to any
one of the preceding claims, characterized in that it is chosen from
the following compounds:

2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-
cuenylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
OH Compound 7
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 8
C 4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 9
2-[[4-(2-Amino-5-butoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
OH Compound 10
6-[4-(2-A ino-5-b toxy-4
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenylamino]hexan-l -ol
Compound 11
4-propoxy-6-[4-
(ethylisopropylamino)phenylimino] -3-
iminocyclohexa-1 ,4-dienylamine
Compound 2
2- {[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 1
6-(4-Aminophenylimino)-4-propoxy-3-
iminocyclohexa- 1,4-dienylamine
Compound
4-(2-Amino-5-butoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 5
6-(4-Amino-2,3-dimethylphenylimino)-4-
propoxy-3-iminocyclohexa-l ,4-dienylamine
Compound 16
2- f [4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol

Compound 17
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 18
4-(2-Amino-5-propoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound
2-[[4-(2-Amino-5-propoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 20
4-ethoxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1 ,4-dienylamine
Compound 2
2-{[4-(2-Amino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 22
6-(4-Aminophenylimino)-4-ethoxy-3-
iminocyclohexa- 1,4-dienylamine
Compound 23
4-(2-Amino-5-ethoxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 24
6-(4-Amino-2,3-dimethylphenylimino)-4-
ethoxy-3 -iminocyclohexa-1,4-dienylamine
Compound 25
2-[[4-(2-Amino-5-ethoxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl](2-
hydroxyethyl)amino]ethanol
Compound 26
4-(2-Amino-5-ethoxy-4-iminocyclohexa-
2,5-dienylideneamino)-2-chlorophenol
Compound 27
4-(2-Amino-5-ethoxy-4-iminocyclohexa-
2,5-dienylideneamino)-3-chlorophenol
Compound 28
2-[[4-(2-Amino-5 -ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)-3
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 29
4-pentyloxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1,4-dienylamine
Compound 30
2-{[4 -(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 1
6-(4-Aminophenylimino)-4-pentyloxy-3-
iminocyclohexa- 1,4-dienylamine
Compound 32
4-(2-Amino-5 -pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenol
Compound 33
6-(4-Amino-2,3-dimethylphenylimino)-4-
pentyloxy-3-iminocyclohexa-l ,4-
dienylamine
Compound 34
2-[[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-
dienylideneamino)phenyl
(2-hydroxyethyl)amino]ethanol
OH
Compound 35
4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-2-
chlorophenol
Compound 36
4-(2-Amino-5-pentyloxy-4-iminocyclohexa-
2,5-dienyudeneamino)-3-chlorophenol
Compound 37
2-[[4-(2-Amino-5-pentyloxy-4-
iminocyclohexa-2,5-dienyIideneamino)-3-
methylphenyl](2-hydroxyethyl)amino]
ethanol
Compound 38
4-hexyloxy-6-[4-
(ethylisopropylamino)phenylimino]-3-
iminocyclohexa-1 ,4-dienylamine
Compound 39
2-{[4-(2-Amino-5-hexyloxy-4-
iminocyclohexa-2,5-dienylideneamino)-3-
methylphenyl]ethylamino}ethanol
Compound 40
6-(4-Aminophenylimino)-4-hexyloxy-3-
iminocyclohexa-1 ,4-dienylamine
Compound 4
4-{2-Amino-5-hexyloxy-4-iminocyclohexa-
2,5-dienylideneamino)phenol
Compound 42

H, N-(5-Ethoxy-4-imino-2-morpholin-4-
yIcyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene-1 ,4-diamine
Compound 55
NH, N-(2-Diethylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-2,3-
dimethylbenzene-1 ,4-diamine
Compound 56
NH, N-(2-Dimethylamino-5-ethoxy-4-imino
cyclohexa-2,5-dienylidene)-2,3 -
dimethylbenzene-1 ,4-diamine
Compound 57
OH 3-Chloro-4-(5-ethoxy-4-imino-2-
pyrrolidin-1 -ylcyclohexa-2,5-
dienylideneamino)phenol
Compound 5
3-Chloro-4-(5 -ethoxy-4-imino-2-
piperidin-1 -ylcyclohexa-2,5-
dienylideneamino)phenol
Compound 59
3-Chloro-4-(5-ethoxy-4-imino-2-
morpholin-4-ylcyclohexa-2,5-
dienyIideneamino)phenol
Compound 60
3-Chloro-4-(2-diethylamino-5-ethoxy
-4-iminocyclohexa-2,5-dienylideneamino)
phenol
Compound 6
3-Chloro-4-(2-dimethylamino-5-ethoxy-4-
iminocyclohexa-2,5-dienylideneamino)
phenol
Compound 62
6. Use of one or more azomethine compounds of formula (I)
as defined according to any one of Claims 1 to 5, for dyeing keratin
fibres, in particular human keratin fibres such as the hair.
7. Composition in particular for dyeing keratin fibres such
as the hair, comprising one or more azomethine compounds of
formula (I) as defined according to any one of Claims 1 to 5.
8. Process for dyeing keratin fibres, characterized in that a
dye composition comprising one or more azomethine compounds of
formula (I) as defined according to any one of Claims 1 to 5 is
applied to the said wet or dry fibres for a time that is sufficient to
obtain the desired coloration, after which the fibres are rinsed,
optionally washed with shampoo and rinsed again, and the resulting
fibres are dried or left to dry.
9. Process for lightening keratin fibres, characterized in that
(i) the dye composition as defined in Claim 7, free of oxidizing
agent, and (ii) a cosmetic composition comprising one or more
oxidizing agents are applied to the said fibres; compositions (i) and
(ii) being applied to the said keratin fibres sequentially or
simultaneously for a time that is sufficient to obtain the desired
lightening, and the fibres are then rinsed, optionally washed with
shampoo and rinsed again, and the resulting fibres are dried or left
to dry.
10. Compound of formula (II) below, organic or mineral acid
salts thereof, tautomers thereof and/or solvates thereof:
in which n, R, Ri, R2, R 3, X, R and R 5 have the same meaning as in
Claim 2.
11. Composition in particular for dyeing keratin fibres such
as the hair, comprising one or more azomethine compounds of
formula (II) as defined according to the preceding claim and
optionally comprising one or more oxidizing agents.
12. Process for dyeing keratin fibres, characterized in that a
dye composition comprising one or more azomethine compounds of
formula (II) as defined according to Claim 10 and an oxidizing
composition comprising one or more oxidizing agents are applied
simultaneously or sequentially to the said wet or dry fibres.
13. Use of one or more compounds of formula (II) as defined
according to Claim 0 for dyeing keratin fibres, in particular human
keratin fibres such as the hair, in the presence of one or more
oxidizing agents.
14. Multi-compartment device or dyeing "kit", characterized
in that it comprises a first compartment containing a composition as
defined according to Claim 7 or 1 , free of oxidizing agent, and a
second compartment containing a composition comprising one or
more oxidizing agents.