Triaromatic azomethine direct dyes, dye composition comprising
at least one such dye, method of implementation and use
The present invention relates to particular triaromatic 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 invention also relates to a composition for dyeing keratin
fibres comprising, in a medium suitable for dyeing, such direct dyes
and also to a method for dyeing using said composition.
A final subject of the invention is the precursors of these direct
dyes, the use thereof for dyeing fibres and a multicompartment device
containing them.
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" method.
The method conventionally used in direct dyeing consists in
applying to the keratin fibres one or more direct dyes, or colouring
molecules, which have an affinity for said fibres, leaving them on for
a time, 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-type
dyes.
These direct dyes may also be applied to the keratin fibres in
the presence of an oxidizing agent if it is desired to obtain a
simultaneous fibre-lightening effect.
However, the colours that result therefrom are temporary or
semi-permanent colours 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.
Furthermore, such direct dyes are generally sensitive to the
action of oxidizing agents, which makes them difficult to use in
particular in lightening direct dye compositions that are formulated
from aqueous hydrogen peroxide solution and an alkalinizing agent,
which are similar to compositions used for oxidation dyeing. In other
words, direct dyes are generally not very compatible with dye
compositions intended to lighten the fibres and, consequently, using
them in a lightening dyeing method, as an alternative to oxidation
dyeing, is not yet entirely satisfactory.
These dyes also have the drawback of lacking light stability,
due to the low resistance of the chromophore to photochemical attacks,
which tends to lead to the colour of the keratin fibres fading over time.
Therefore there is a real need to have direct dyes that not only
enable the keratin fibres to be dyed satisfactorily but that are also
light-stable, capable of resulting in colours that resist the various
attacks that the fibres may be subjected to, such as inclement weather,
washing and perspiration, and further, that are sufficiently stable in
the presence of oxidizing agents such as aqueous hydrogen peroxide
solution to be able to deliver simultaneous lightening of the fibre with
the advantages set out hereinabove.
These objectives are achieved with the present invention,
which relates in particular to azomethine-type direct dyes having a
triaromatic unit of formula (I) below, the organic or inorganic acid or
base salts thereof, the tautomeric, optical isomer or geometric isomer
forms thereof and/or the solvates thereof:
in which formula (I):
• n i and n2 represent, independently of one another, 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 selected from
hydroxyl or imidazolium, An radicals; An denoting a
cosmetically acceptable anion or mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
represents:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- an aminocarbonyl radical;
- a radical of formula (II):
in which formula (II):
o m represents an integer equal to 0, 1, 2, 3 or 4;
o R' represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different
radicals selected from hydroxyl or imidazolium, An
radicals; An denoting a cosmetically acceptable anion or
mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
- a hydroxyl radical;
- an -NR' 3R' 4 radical in which R' 3 and R represent,
independently of one another:
a hydrogen atom;
a linear or branched C1- C 5 alkyl radical, optionally
substituted with one or more hydroxyl or C1-C4 alkoxy
radicals;
o it being understood that, in formula (II) , when m is greater
than or equal to 2, the R ' radicals may be identical or
different;
R2 represents:
- a hydrogen atom;
- a C1- C alkyl radical, optionally substituted with one or more
hydroxyl radicals;
R i and R2 may form, together with the nitrogen atom to which they
are attached, a pyrrolidino, piperidino or morpholino ring;
R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched Ci -C alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- a Ci -C4 alkoxy radical;
X i and X2 represent, independently of one another:
- a hydroxyl radical;
- an -NR " 3R " 4 radical in which:
- R ' ' 3 represents:
■ a hydrogen atom;
■ a linear Ci -C alkyl radical;
- R ' ' 4 represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2 -C alkyl radical substituted with
one or more hydroxyl radicals;
R " 3 and R " 4 may form, together with the nitrogen atom to which
they are attached, a piperidino or morpholino ring;
it being understood that the compounds of formula (I) may not
represent the compounds A to F below:
Compound A
Compound C Compound D
Compound
Compound F
Another subject of the present invention relates to a
composition for dyeing keratin fibres, in particular human keratin
fibres such as the hair, comprising, in a medium suitable for dyeing,
one or more azomethine-type dyes having a triaromatic unit of formula
(I) below:
in which formula (I):
• ni and n2 represent, independently of one another, 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 selected from
hydroxyl or imidazolium, An radicals; An denoting a
cosmetically acceptable anion or mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
• Ri represents:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- an aminocarbonyl radical;
- a radical of formula (II):
in which formula (II):
o m represents an integer equal to 0, 1, 2, 3 or 4;
o R' represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different
radicals selected from hydroxyl or imidazolium, An
radicals; An denoting a cosmetically acceptable anion or
mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
- a hydroxyl radical;
- an -NR' 3R' 4 radical in which R' 3 and R'4 represent,
independently of one another:
a hydrogen atom;
a linear or branched C1-C 5 alkyl radical, optionally
substituted with one or more hydroxyl or C1-C4 alkoxy
radicals;
o it being understood that, in formula (II), when m is greater
than or equal to 2, the R' radicals may be identical or
different;
• R2 represents:
- a hydrogen atom;
- a C1-C alkyl radical, optionally substituted with one or more
hydroxyl radicals;
• R and R2 may form, together with the nitrogen atom to which they
are attached, a pyrrolidino, piperidino or morpholino ring;
• R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched C -C alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- a C1-C4 alkoxy radical;
• X and X2 represent, independently of one another:
- a hydroxyl radical;
- an - R 3R 4 radical in which:
- R' ' 3 represents:
■ a hydrogen atom;
■ a linear C -C alkyl radical;
- R' represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2-C alkyl radical substituted with
one or more hydroxyl radicals;
R" 3 and R " 4 may form, together with the nitrogen atom to which
they are attached, a piperidino or morpholino ring;
it being understood that the compounds of formula (I) may not
represent the compounds A to D below:
In particular, the invention also relates to the use of said dye
composition for colouring keratin fibres, especially human keratin
fibres such as the hair.
The present invention also relates to the use, for dyeing keratin
fibres, in particular human keratin fibres such as the hair, of one or
more azomethine-type dyes having a triaromatic unit of formula (I)
below, the organic or inorganic acid or base salts thereof, the
tautomeric, optical isomer or geometric isomer forms thereof and/or
the solvates thereof:
in which formula (I) nl n2, R, Ri , R2, R 3, R4, i and X2 have the same
meanings as those indicated previously.
The invention additionally relates to a method for dyeing
keratin fibres, in particular human keratin fibres such as the hair, in
which applied to said fibres is a dye composition comprising, in a
medium suitable for dyeing, one or more azomethine-type dyes having
a triaromatic unit of formula (I) below, the organic or inorganic acid
or base salts thereof, the tautomeric, optical isomer or geometric
isomer forms thereof and/or the solvates thereof:
in which formula (I) nl n2, R, Rl R2, R3, R4, Xi and X2 have the same
meanings as those indicated previously ; for a time sufficient to obtain
the desired coloration, after which the fibres are rinsed, optionally
washed with shampoo, rinsed again and the resulting fibres are dried
or left to dry.
Similarly, the invention relates more particularly to a method
for lightening keratin fibres, especially human keratin fibres such as
the hair, in which applied to said fibres are (i) a dye composition free
of oxidizing agent and comprising, in a medium suitable for dyeing,
one or more azomethine-type dyes having a triaromatic unit of formula
(I) below, the organic or inorganic acid or base salts thereof, the
tautomeric, optical isomer or geometric isomer forms thereof and/or
the solvates thereof:
in which formula (I) nl n2, R, Ri , R2, R3, R4, i and X2 have the same
meanings as those indicated previously; and (ii) a cosmetic
composition comprising one or more oxidizing agents; compositions
(i) and (ii) being applied to said keratin fibres sequentially or
simultaneously for a time sufficient to obtain the desired lightening,
after which the fibres are rinsed, optionally washed with shampoo,
rinsed again and the resulting fibres are dried or left to dry.
The azomethine-type direct dyes having a triaromatic unit of
formula (I) according to the invention thus make it possible to result
in colours that resist the various attacks that the keratin fibres may be
subject to, such as inclement weather, light, washing and perspiration.
Furthermore, the direct dyes according to the invention enable
the keratin fibres to be dyed satisfactorily, especially by resulting in
powerful, chromatic and sparingly selective colours and lead to an
improved uptake of the colouration.
The direct dyes according to the invention are light-stable and
can be used in the presence of an oxidizing agent, which facilitates
their use in lightening direct dye compositions based on oxidizing
agents.
In other words, the direct dyes according to the present
invention lead to long-lasting colours and are compatible with dye
compositions that are intended to lighten keratin fibres.
Furthermore, one subject of the invention is colourless or
weakly coloured leuco-type compounds, which correspond to the
reduced form of the azomethine-type direct dyes having a triaromatic
unit according to the invention, of formula (III) below:
(III)
and the organic or inorganic acid or base salts thereof, the tautomeric,
optical isomer or geometric isomer forms thereof and/or the solvates
thereof;
in which formula (III) nl n2, R, Ri , R2, R 3, R4, i and X2 have the
same meanings as those indicated previously in formula (I).
The leuco-type compounds according to the invention may
therefore lead, in the presence of one or more oxidizing agents, to
azomethine-type direct dyes of formula (I).
Thus, the invention also relates to the use of one or more
leuco-type compounds of formula (III) as precursors of the direct dyes
of formula (I).
In particular, the invention relates to the use of one or more
leuco-type compounds of formula (III) in the presence of one or more
oxidizing agents for dyeing keratin fibres, especially human keratin
fibres such as the hair.
The invention also relates to a multicompartment device or kit
containing a first compartment comprising one or more leuco-type
compounds of formula (III) as defined previously and a second
compartment comprising one or more oxidizing agents.
The leuco-type compounds of formula (III) used under
oxidizing conditions thus have the advantage of resulting in colours
that resist the various attacks that the keratin fibres may be subjected
to, such as inclement weather, washing, light or perspiration.
Other features, aspects, subjects and advantages of the present
invention will become even more clearly apparent on reading the
following description and examples.
. Azomethine-type compound having a triaromatic unit
The direct dyes of formula (I) according to the present
invention comprise in their structure at least three aromatic rings and
one azomethine bond.
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 methylsulfonate or mesylate and
ethylsulfonate; arylsulfonates: Ar-S(0) 20 such as benzenesulfonate
and toluenesulfonate or tosylate; citrate; succinate; tartrate; lactate;
alkylsulfates: 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 selected from bromide,
chloride, methylsulfate and toluenesulfonate ions or a mixture of these
ions.
According to one embodiment, in formula (I), azomethine-type
direct dyes according to the invention are such that, taken together or
separately:
• n i and n2 represent, independently of one another, an integer
equal to 0, 1 or 2;
• R represents:
- a linear or branched C1-C4 alkyl radical, preferably a
methyl radical;
- a C1-C4 alkoxy radical, preferably a methoxy radical;
- a halogen atom, preferably chlorine;
• P i represents:
- a hydrogen atom;
a linear or branched Ci-Cs alkyl radical, optionally
substituted with one or more hydroxyl radicals;
an aminocarbonyl radical;
a radical of formula (II):
in which formula (II):
o m represents an integer equal to 0, 1, 2 or 3;
o R' represents:
- a linear or branched C1-C4 alkyl radical, preferably
a methyl radical;
- a C1-C4 alkoxy radical, preferably a methoxy
radical;
- a halogen atom, preferably chlorine;
- a hydroxyl radical;
- an -NR' 3R ' 4 radical in which R' 3 and R' 4 represent,
independently of one another:
a hydrogen atom;
a linear or branched C1- C 5 alkyl radical, optionally
substituted with one or more hydroxyl radicals;
o it being understood that, in formula (II), when m is
greater than or equal to 2, the R' radicals may be
identical or different;
• R2 represents:
- a hydrogen atom;
- a linear or branched Ci-C alkyl radical, a butyl, methyl
or ethyl radical;
• Ri and R2 may form, together with the nitrogen atom to
which they are attached, a pyrrolidino, piperidino or morpholino ring;
• R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, preferably a
methyl or propyl radical;
- a C1- C 4 alkoxy radical, preferably a methoxy radical;
• it being understood that when Ri and R2 represent a
hydrogen atom then R3 and R4 cannot simultaneously denote a
hydrogen atom; and/or
• Xi and X2 represent, independently of one another:
- a hydroxyl radical;
an - R 3R 4 radical in which:
- R' ' 3 represents:
■ a hydrogen atom;
■ a linear Ci-C alkyl radical;
- R' ' 4 represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2 -C alkyl radical substituted with
one or more hydroxyl radicals;
R 3 and R " 4 may form, together with the nitrogen atom
to which they are attached, a piperidino or morpholino
ring.
Preferably, ni and n2 represent an integer equal to 0, 1 or 2,
and more preferably ni and n2 are equal to 0 or 1.
Preferably, R represents a halogen atom, in particular chlorine,
or a linear C1-C4 alkyl radical, in particular a methyl radical.
Preferably, Ri represents a linear or branched C1-C4 alkyl
radical, in particular a methyl, ethyl or butyl radical; a linear C1-C4
alkyl radical substituted with a hydroxyl radical, in particular a 2-
hydroxyethyl radical; an aminocarbonyl radical; a radical of formula
(II) in which m represents 0 or 1 and R' represents an -NR' 3R ' 4
radical in which R' 3 and R' 4 represent a linear or branched C1-C4 alkyl
radical.
More preferably, Ri is selected from a methyl radical; a 2-
hydroxyethyl radical; an aminocarbonyl radical; a radical of formula
(II) in which m represents 0 or 1 with R' representing an -NR' 3R' 4
radical in which R' 3 and R represent a linear or branched C1-C4 alkyl
radical.
In other words, Ri is preferably other than a hydrogen atom.
Preferably, R2 represents a hydrogen atom or a linear C1-C4
alkyl radical, preferably a butyl, methyl or ethyl radical.
More preferably, R2 represents a hydrogen atom or a methyl
radical.
More preferably still, R2 represents a hydrogen atom.
Preferably, R3 represents a hydrogen atom or a C1-C4 alkoxy
radical, preferably a methoxy radical. In particular, R3 represents a
hydrogen atom.
Preferably, R 4 represents a hydrogen atom or a linear or
branched C1-C4 alkyl radical, preferably a methyl radical. More
preferably still, R 4 represents a hydrogen atom.
According to one embodiment, R3 and R 4 represent a hydrogen
atom.
According to one embodiment, Rl R2, R3 and R 4 represent a
hydrogen atom.
Preferably, Xi and X2 represent a hydroxyl radical or an
-NR" 3R" 4 radical in which R" 3 represents a hydrogen atom or a
linear Ci-C alkyl radical and R' represents a hydrogen atom or a
linear or branched C3-C alkyl radical or a C2 - C alkyl radical
substituted with one or more hydroxyl radicals.
Preferentially, Xi and X2 represent a hydroxyl radical or an
-N'R" 3R" 4 radical in which R" 3 represents a hydrogen atom or a
linear Ci-C 3 alkyl radical and R' represents a hydrogen atom or a
linear or branched C3-C4 alkyl radical or a C2-C4 alkyl radical
substituted with one or more hydroxyl radicals. Preferably, R" 3
represents a hydrogen atom or a methyl or ethyl radical and R 4
represents a hydrogen atom or an isopropyl or 2-hydroxyethyl radical.
In other words, X and X2 preferably represent a hydroxyl
radical.
Alternatively, X and X2 represent an - 'R 3R 4 radical in
which R" 3 represents a hydrogen atom or a linear C1-C 3 alkyl radical
and R" 4 represents a hydrogen atom or a linear or branched C3-C4
alkyl radical, or a C2-C4 alkyl radical substituted with one or more
hydroxyl radicals.
According to one embodiment, n and n2 represent an integer
equal to 0 or 1, R is other than a hydrogen atom, R2 represents a
hydrogen atom and R4 represents a hydrogen atom.
According to one particular embodiment, n and n2 represent an
integer equal to 0 or 1, R is other than a hydrogen atom, R2
represents a hydrogen atom, R4 represents a hydrogen atom and X and
X2 represent an -N'R" 3R" 4 radical in which R" 3 represents a
hydrogen atom or a linear C -C3 alkyl radical and R" 4 represents a
hydrogen atom or a linear or branched C3-C4 alkyl radical or a C2-C4
alkyl radical substituted with one or more hydroxyl radicals.
According to another particular embodiment, n and n2
represent an integer equal to 0 or 1, R is other than a hydrogen atom,
R2 represents a hydrogen atom, R4 represents a hydrogen atom and X
and X2 represent a hydroxyl radical.
In accordance with these two particular embodiments, R may
preferably represent a linear or branched C1-C4 alkyl radical; a linear
C1-C4 alkyl radical substituted with a hydroxyl radical; an
aminocarbonyl radical; a radical of formula (II) in which m represents
0 or 1 and R' represents an -NR' 3R'4 radical in which R'3 and R'4
represent a linear or branched C1-C4 alkyl radical.
According to a preferred embodiment, X and X2 represent a
-NR"3R" 4 radical in which R" 3 and R" 4 represent a hydrogen atom.
According to another preferred embodiment, X and X2
represent a -NR" 3R" 4 radical in which R" 3 and R" 4 are different
from a hydrogen atom.
According to a further embodiment, the direct dyes are chosen
among the compounds of formula (I) wherein when X or X2 represent
a -NR" 3R 4 radical, R" 4 preferably represents a hydrogen atom or a
branched or linear C 3-C alkyl radical and R" 3 and R " 4 may form,
together with the nitrogen atom to which they are attached, a
piperidino ring.
According to this embodiment, R" 4 does not represent a linear
of branched C 2-C alkyl radical substituted with one or more hydroxyl
radicals and R" 3 and R " 4 do not form, together with the nitrogen
atom to which they are attached, a morpholino ring.
Preferably, the azomethine-type direct dyes having a
triaromatic unit of formula (I) according to the invention are selected
from the following compound, and also the geometric or optical
isomer forms thereof, the organic or inorganic acid or base salts
thereof, or the solvates thereof, such as the hydrates:
2-[4-(Ethylisopropylamino)
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-
Compound 1 methylaminocyclohexa-
2,5-dienone
3-Amino-6-(4-piperidin- 1-
ylphenylamino)-4-[4-
piperidin- l -ylphenylimino]-
2-propyl-
Compound 2 cyclohexa-2,5-dienone
2-(4-Aminophenyl amino) -
4-(4-aminophenylimino)-
5-(2-
hydroxyethylamino)-
cyclohexa-2,5-dienone
Compound 3
5-Dibutylamino-2-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)-
0 phenylimino]cyclohexa-2,5-
Compound 5 dienone
5-Dimethylamino-2-[4-(ethylisopropylamino)
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]cyclohexa-2,5-
0 dienone
Compound 6
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-pyrrolidin- 1-
0 ylcyclohexa-2,5-dienone
Compound 7
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-piperidin- 1-
0 ylcyclohexa-2,5-dienone
Compound 8
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-morpholin-4-
0 ylcyclohexa-2,5-dienone
Compound 9
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-5-
methylaminocyclohexa-2,5-
dienone
Compound 10
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-2,3-
dimethylphenylimino)-5-
pyrrolidin- 1-ylcyclohexa-2,5-
' dienone
Compound 11
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-2,3-
dimethylphenylimino)-5-
piperidin- l -ylcyclohexa-2,5-
dienone
Compound 12
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-2,3-
dimethylphenylimino)-5-
morpholin-4-ylcyclohexa-2,5-
dienone
Compound 13
2-(4-Aminophenyl amino) -4-
(4-amino-
/ phenylimino)-5-
methylaminocyclohexa-2,5-
Compound 14 dienone
2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3(or 2)-methyl-
H phenylimino)-5-
Compound 15 methylaminocyclohexa-2,5-
dienone
5-Amino-2-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)
phenylimino]-
cyclohexa-
2,5-dienone
5-Amino -2-(4 -amino -2,
dimethylphenylamino)-4
amino -2, 3-dimethy 1-
phenylimino]cyclohexadienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-5-
dimethylaminocyclohexa-
2,5-dienone
3,6-Bis[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)
phenylimino]-2-
methoxycyclohexa-2,5-
dienone
Compound 28
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-
phenylaminocyclohexa-2,5-
Compound 29 dienone
2- {4-[ethyl-(2-hydroxyethyl)
amino]-2-methylphenylamino}
-4- {4-[ethyl-
(2-hydroxy ethyl) amino] -2-
methylphenylimino}
-5-
phenylaminocyclohexa-2,5-
Compound 30
dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-
5-phenylaminocyclohexa-
2,5-dienone
Compound 31
(4-Aminophenylamino)-4-(4-
aminophenylimino)-
5-
phenylaminocyclohexa-2,5-
dienone
Compound 32
2-(4-Hydroxyphenylamino)-
4-(4-
hydroxyphenylimino)-5-
phenylaminocyclohexa-2,5-
dienone
Compound 33
2-(3-Chloro-4-hydroxyphenylamino)-
4-(3-chloro-4-hydroxyphenylimino)-
5-phenylaminocyclohexa-
2,5-dienone
Compound 34
Compound 36
H
3,6-Bis(4-amino-3-methylphenylamino)-
4-(4-amino-3-
methylphenylimino)-2-
methoxycyclohexa-2,5-
NH2
dienone
Compound 39
3,6-Bis(4-hydroxyphenylamino)-
4-(4-hydroxyphenylimino)
-2-methoxy
cyclohexa-2,5 -dienone
OH
Compound 40
C I 5-Amino-2-(2-chloro-4-
hydroxyphenylamino)-4-
[2-chloro-4-hydroxyphenylimino]
cyclohexa-
2,5-dienone
Compound 41
3,6-Bis(4-amino-2,3-
dimethylphenylamino)-4-
(4-amino-2,3-dimethylphenylimino)
-2-methoxy
NH2
cyclohexa-2,5 -dienone
Compound 42
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-o-
Compound 43 tolylaminocyclohexa-2,5-
dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-
5-o-tolylaminocyclohexa-
2,5-dienone
Compound 44
2-(4-Aminophenyl amino) -4-
(4-aminophenylimino)-
5-otolylaminocyclohexa-
2,5-
Compound 45 dienone
H 2-(4-Hydroxyphenylamino)-
4-(4-hydroxyphenylimino)-
5-o-tolylaminocyclohexa-
2,5-dienone
Compound 46
H
2-(3-Chloro-4-hydroxyphenylamino)-
4-(3-chloro-4-hydroxyphenylimino)-
5-o-tolylaminocyclohexa-
Compound 47 2,5-dienone
2-(2-Chloro-4-hydroxyphenylamino)-
4-(2-chloro-4-hydroxyphenylimino)-
5-o-tolylaminocyclohexa-
2,5-dienone
Compound 48
2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3(or 2)-methylphenylimino)-
5-o-
Compound 49 tolylaminocyclohexa-2,5-
dienone
5-Amino-2-(4-morpholin-4-
ylphenylamino)-4-[4-
morpholin-4-ylphenylimino]
cyclohexa-
Compound 50 2,5-dienone
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-ptolylaminocyclohexa-
2,5-
dienone
Compound 51
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-
5-p-tolylaminocyclohexa-
2,5-dienone
Compound 52
2-(4-Aminophenyl amino) -4-
(4-aminophenylimino)-
5-ptolylaminocyclohexa-
2,5-
dienone
Compound 53
2-(4-Hydroxyphenylamino)-
4-(4-
hydroxyphenylimino)-5-ptolylaminocyclohexa-
2,5-
dienone
Compound 54

2,5-Bis[4-(ethylisopropylamino)
phenylamino]-4-[4-
(ethylisopropylamino)
phenylimino]-
cyclohexa-2,5-dienone
Compound 67
2,5-Bis(4-amino-2,3-
dimethylphenylamino)-4-
(4-amino-2,3-dimethylphenylimino)
cyclohexa-
2,5-dienone
Compound 68
2,5-Bis(4-aminophenylamino)-
4-(4-
aminophenylimino)-
cyclohexa-2,5-dienone
Compound 69
2,5-Bis(4-hydroxyphenylamino)-
4-
(4-hydroxyphenylimino)-
cyclohexa-2,5-dienone
OH
Compound 70
2,5-Bis(3-chloro-4-
hydroxyphenylamino)-4-(3-
chloro-4-hydroxyphenylimino)
cyclohexa-
2,5-dienone
OH
Compound 71
2,5-Bis(2-chloro-4-hydroxyphenylamino)-
4-(2-chloro-4-
hydroxyphenylimino)-
cyclohexa-2,5-dienone
OH
Compound 72
H 2,5-Bis(4-amino-3-methylphenylamino)-
4-(4-amino-
3-methylphenylimino)-
cyclohexa-2,5-dienone
NH
Compound 73
5-Amino-3-methyl-2-(4-
piperidin- l -ylphenylamino)-
4-[4-
piperidin-
1-ylphenylimino]-
Compound 74 cyclohexa-2,5-dienone
3-Amino-6-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)-
phenylimino]-2-propylcyclohexa-
2,5-dienone
Compound 75

5-Amino -2-(4 -amino -2,3 -
dimethylphenylamino)-4-(4-
amino-2,3-dimethylphenylimino)-
3-methylcyclohexa-
2,5-
dienone
Compound 80
5-Amino-2-(3-chloro-4-
hydroxyphenylamino)-4-(3-
chloro-4-hydroxyphenylimino)-
3-methyl-
Compound 81 cyclohexa-2,5-dienone
C I C I 5-Amino-2-(2-chloro-4-
hydroxyphenylamino)-4-(2-
chloro-4-hydroxyphenylimino)-
3-methylcyclohexa-
2,5-dienone
Compound 82
Preferably, the direct dyes of formula (I) according to the
present invention are selected from azomethine-type compounds 1, 4,
6, 16, 20, 28, 29 and 30.
The direct dyes of formula (I) may be obtained according to the
procedure described below:
Y=NH2, NO
The azomethine-type direct dyes corresponding to formula (I)
are generally obtained by reacting derivatives l a and l b with metaaminophenol
compounds 2 in a basic medium in the presence of an
oxidizing agent. The base used is preferably an aqueous solution of
ammonia or of sodium hydroxide and the oxidizing agent is preferably
selected from aqueous hydrogen peroxide solution, potassium
ferricyanide, air, ammonium persulfate and manganese oxide.
Methods similar to this reaction scheme are described in patent
applications FR 2234277, FR 2047932, FR 210666 1 and FR 212 1101.
In particular, the azomethine-type direct dyes corresponding to
formula (I) in which Ri corresponds to a radical of formula (II) may
be obtained according to the procedure below:
The compounds corresponding to formula () are generally
obtained by reacting derivatives 1 with ta-methoxyphenols 3 in a
basic medium in the presence of an oxidizing agent. The base used is
preferably an aqueous solution of ammonia or of sodium hydroxide
and the oxidizing agent is preferably selected from aqueous hydrogen
peroxide solution, potassium ferricyanide, air, ammonium persulfate
and manganese oxide.
77. Dye composition
As indicated previously, the present invention also relates to a
dye composition for keratin fibres, in particular human keratin fibres
such as the hair, comprising, in a medium suitable for dyeing, one or
more direct dyes of formula (I) as defined previously.
The azomethine-type dyes having a triaromatic unit of formula
(I) in the above composition dyeing composition preferably may not
also represent the compounds E and F previously mentioned.
Preferably, the dye composition comprises one or more direct
dyes of formula (I) selected from azomethine-type compounds 1, 4, 6,
16, 20, 28, 29 and 30 and also mixtures thereof.
The direct dye(s) as defined previously may be present in the
dye composition according to the invention in a content ranging from
0.00 1% to 10% by weight, preferably in a content ranging from
0.005% to 6%o 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 selected from oxidation bases
optionally combined with one or more couplers.
By way of example, the oxidation bases are selected from
/?ara-phenylenediamines, bis(phenyl)alkylenediamines, paraaminophenols,
r t/zo-aminophenols and heterocyclic bases, and the
addition salts thereof.
Among the /?ara-phenylenediamines, mention may be made, by
way of example, of /?ara-phenylenediamine, /?ara-toluenediamine, 2-
chloro-/?ara-phenylenediamine, 2,3-dimethyl-/?ara-phenylenediamine,
2,6-dimethyl-/?ara-phenylenediamine, 2,6-diethyl-/?ara-phenylenediamine,
2,5-dimethyl-/?ara-phenylenediamine, N,N-dimethyl-/?araphenylenediamine,
N,N-diethyl-/?ara-phenylenediamine, N,Ndipropyl-
para -phenylene diamine, 4-amino -N,N- diethyl- 3-methylaniline,
N,N-bis ( -hydroxyethyl)- ara-phenylenediamine, 4-N,Nbis
( -hydroxy ethyl) amino -2-met hylaniline, 4-N,N-bis (P-hydroxyethyl)
amino -2-chloro aniline, 2- -hydroxyethyl- ara-phenylenediamine,
2-fluoro-/?ara-phenylenediamine, 2-isopropyl-/?araphenylenediamine,
N-( -hydroxypropyl)- ara-phenylenediamine, 2-
hydroxymethyl-para -phenylene diamine, N, -dimethyl- 3-methyl-para -
phenylene diamine, N- ethyl-N -( -hydroxy ethyl) -para -phenylenediamine,
N-(P,y-dihydroxypropyl)-para-phenylenediamine, N-(4 ' -
amino phenyl) -para-phenylene diamine, N-phenyl-para-phenylenediamine,
2-P-hydroxyethyloxy-para-phenylenediamine, 2-P-acetylaminoethyloxy-
para -phenylene diamine, N-( -met hoxy ethyl) -paraphenylenediamine,
4-aminophenylpyrrolidine, 2-thienyl-paraphenylenediamine,
2-P-hydroxyethylamino-5-aminotoluene and 3-
hydroxy- l -(4'-aminophenyl)pyrrolidine, and addition salts thereof
with an acid.
Among the /?ara-phenylenediamines mentioned above, paraphenylenediamine,
/?ara-toluenediamine, 2-isopropyl-para-phenylenediamine,
2-P-hydroxyethyl-para-phenylenediamine, 2-P-hydroxyethyloxy-
para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-paraphenylenediamine,
N,N-bis ( -hydroxyethyl)- ara-phenylenediamine,
2-chloro -para-phenylene diamine and 2-P-acetylaminoethyloxy-paraphenylenediamine,
and the addition salts thereof with an acid, are
particularly preferred.
Among the bis(phenyl)alkylenediamines, mention may b e
made, by way o f example, o f N,N'-bis (P-hydroxyethyl)-N,N'-bis(4'-
aminophenyl)- l ,3-diaminopropanol, N,N'-bis (P-hydroxyethyl)-N,N'-
bis (4'-amino phenyl) ethylene diamine, N,N'-bis(4- amino phenyl) -
tetramethylene diamine, N,N'-bis ( -hydroxy ethyl) -N,N'-bis(4- amino -
phenyl) tetramethylene diamine, N,N'-bis(4 -met hylamino phenyl)-
tetramethylene diamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)
ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,6-
dioxaoctane, and the addition salts thereof.
Among the /?ara-aminophenols, mention may be made, by way
of example, of /?ara-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 -[(P-hydroxyethyl)aminomethyl]phenol, 4-amino-2-fluorophenol
and the addition salts thereof with an acid.
Among the r t/zo-aminophenols, mention may be made, by way
of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-
methylphenol, 5-acetamido-2-aminophenol and the addition salts
thereof.
Among the heterocyclic bases, mention may be made, by way
of example, o f pyridine derivatives, pyrimidine derivatives and
pyrazole derivatives.
Mention may be made, among pyridine derivatives, o f 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 the addition salts
thereof.
Other pyridine oxidation bases o f use in the present invention
are the 3-aminopyrazolo[ 1,5-a]pyridine oxidation bases or the addition
salts thereof described, for example, in patent application FR 2 80 1
308. Mention may be made, by way o f 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[ 1,5-a]pyridine-2-carboxylic acid, 2-
methoxypyrazolo[ l ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[ l ,5-
a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)ethanol,
2-(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[ 1,5-
a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[ 1,5-a]pyridine, 3,4-
diaminopyrazolo[ 1,5-a]pyridine, pyrazolo[ l ,5-a]pyridine-3,7-diamine,
7-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-ylamine, pyrazolo[ l ,5-
a]pyridine-3, 5-diamine, 5-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-
ylamine, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)(2-
hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)(2-
hydroxyethyl)amino]ethanol, 3-aminopyrazolo[ 1,5-a]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 the addition salts thereof.
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 the
addition salts thereof and the tautomeric forms thereof, when a
tautomeric equilibrium exists.
Mention may be made, among pyrazole derivatives, of the
compounds described in patents DE 3843892 and 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- 1-
(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-pheny 1-
pyrazole, 4-amino - 1,3-dimethyl-5-hydrazinopyrazole, 1-benzy 1-4,5 -
diamino- 3-methylpyrazole, 4,5-diamino -3-(t r t -butyl) - 1-methylpyrazole,
4,5-diamino- l -(t r t -butyl)-3-methylpyrazole, 4,5-diamino- 1-
(P-hydroxyethyl)-3 -methylpyrazole, 4,5-diamino - 1-ethyl- 3-methyl
pyrazole, 4,5-diamino - 1- ethyl- 3-(4'-methoxyphenyl)pyrazole, 4,5-
diamino- 1-ethyl- 3-(hydroxymethyl)pyrazole, 4,5 -diamino -3-hydro xymethyl-
1-methylpyrazole, 4,5-diamino-3-hydroxymethyl- 1-isopropylpyrazole,
4,5-diamino-3-methyl- l -isopropylpyrazole, 4-amino-5-(2'-
amino ethyl) amino - 1,3-dimethylpyrazole, 3,4,5 -triamino pyrazole, 1-
met hy1-3, 4,5-triamino pyrazole, 3,5-diamino - 1-methyl-4-
(methylamino)pyrazole, 3,5-diamino -4-(P-hydroxyethyl) amino - 1-
methylpyrazole and the addition salts thereof. 4,5-Diamino- 1-(-
methoxyethyl)pyrazole may also be used.
Use will preferably be made of a 4,5-diaminopyrazole and
more preferably still o f 4,5-diamino- 1-(P-hydroxyethyl)pyrazole
and/or a salt thereof.
Mention may also be made, as pyrazole derivatives, of
diamino-N,N-dihydropyrazolopyrazolones and in particular those
described in application FR-A-2 886 136, such as the following
compounds and the addition salts thereof: 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ 1,2-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- 1-one, 2-
amino-3-(pyrrolidin- l -yl)-6,7-dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol-
1-one, 4,5-diamino- l ,2-dimethyl- l ,2-dihydropyrazol-3-one, 4,5-
diamino- 1,2-diethyl- 1,2-dihydropyrazol-3-one, 4,5-diamino- l ,2-di(2-
hydroxy ethyl) - 1,2-dihydropyrazol-3-one, 2-amino-3-(2-
hydroxyethyl)amino-6,7-dihydro- lH,5H-pyrazolo[ 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[ l ,2-
ajpyrazol- 1-one, 4-amino - 1,2-diethyl-5-(pyrrolidin- 1-yl)- 1,2-
dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin- 1-yl)-
1,2-diethyl- 1,2-dihydropyrazo 1-3 -one or 2,3-diamino-6-hydroxy-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one.
Use will preferably be made of 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, of 4,5-
diamino- l -(P-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or a salt thereof.
The dye composition may optionally comprise one or more
couplers advantageously selected from those conventionally used for
dyeing keratin fibres.
Among these couplers, mention may especially be made o f
ta-phenylenediamines, ta-aminophenols, ta-diphenols,
naphthalene-based couplers and heterocyclic couplers, and also the
addition salts thereof.
Mention may be made, for example, o f 1,3-dihydroxybenzene,
1,3-dihydroxy-2-methylbenzene, 4-chloro - 1,3-dihydroxybenzene, 2,4-
diamino- 1-(P-hydroxyethyloxy)benzene, 2-amino-4 -( -
hydroxyethylamino)- 1-methoxybenzene, 1,3-diaminobenzene, 1,3-
bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- l -
(dimethylamino)benzene, sesamol, 1-(P-hydroxyethylamino)-3,4-
methylenedioxybenzene, cc-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-(-hydroxy ethyl) amino -3,4-
methylenedioxybenzene, 2,6-bis (P-hydroxyethylamino)toluene, 6-
hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-
methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-
dimethylpyrazolo[ 1,5-b]- l ,2,4-triazole, 2,6-dimethyl[3,2-c]- 1,2,4-
triazole, 6-methylpyrazolo[ 1,5-a]benzimidazole, the addition salts
thereof with an acid, and mixtures thereof.
In general, the addition salts o f the oxidation bases and
couplers which can be used in the context of the invention are selected
in particular 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), i f it is (they are) present, each
advantageously represents 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 according to the invention may also
comprise one or more additional direct dyes other than the
azomethine-type direct dyes defined previously.
The additional direct dye(s) according to the invention are
selected 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 benzene direct dyes that can b e used according to
the invention, mention may be made, in a non-limiting manner, of the
following compounds:
- 1,4-diamino-2-nitrobenzene;
- 1-amino - -nitro -4--hydroxyethylamino benzene;
- 1-amino -2-nitro -4-bis ( -hydroxy ethyl) aminobenzene;
- 1,4-bis (P-hydroxyethylamino)-2-nitrobenzene;
- 1--hydroxy ethylamino -2-nitro -4-bis ( -
hydro xyethylamino)benzene;
- 1--hydroxy ethylamino -2-nitro -4-amino benzene;
- 1- -hydroxy ethylamino -2-nitro-4-(ethy 1)( -
hydroxyethyl)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- -hydroxy ethylamino -5-nitrobenzene;
- 1,2-bis^-hydroxyethylamino)-4-nitrobenzene;
- 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene;
- 1-hydro xy-2 -amino -5-nitrobenzene;
- 1-hydro xy-2 -amino -4-nitrobenzene;
- 1-hydroxy- 3-nitro -4-amino benzene;
- 1-hydro xy-2 -amino -4, 6-dinitrobenzene;
- 1--hydroxyethy loxy-2- -hydroxy ethylamino -5-
nitrobenzene;
- 1-met hoxy-2- -hydroxy ethylamino -5-nitrobenzene;
- 1- -hy droxy ethyloxy- 3-met hylamino -4-nitrobenzene;
- 1-,-dihy droxypropyloxy- 3-methy lamino -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- -hydroxyethylamino- 3-methy 1-2 -nitrobenzene;
- 1-P-aminoethylamino-5-methoxy-2-nitrobenzene;
- 1-hydro xy-2-chloro-6-ethylamino-4-nitrobenzene;
- 1-hydro xy-2-chloro-6-amino-4-nitrobenzene;
- 1-hydroxy-6-bis (P-hydroxyethyl)amino-3-nitrobenzene;
- 1-P-hydroxyethylamino-2-nitrobenzene; and
- 1-hydro xy-4 - -hydroxyethylamino -3-nitrobenzene.
Among the azo direct dyes that can be used according to the
invention, mention may be made of 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, mention may be made very
particularly of 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 o f 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 and Basic Red 2 .
Among the triarylmethane dyes that can 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 and Acid Blue 7 .
Among the azomethine dyes that can be used according to the
invention, mention may be made of the following compounds:
- 2-P-hydroxyethylamino-5-[bis(P-4'-
hydroxyethyl)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.
Among the natural direct dyes that can 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. Use may also be made of extracts or decoctions containing
these natural dyes and in particular henna-based extracts or poultices.
Preferably, the dye composition comprises, in a medium
suitable for dyeing, one or more direct dyes of formula (I) and one or
more azomethine direct dyes other than the direct dyes of formula (I).
The additional direct dye(s) may be present in the dye
composition in a content ranging from 0.00 1% to 10% by weight,
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 more
preferably still of 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, inorganic or organic thickeners, and in particular anionic,
cationic, nonionic and amphoteric polymeric associative thickeners,
antioxidants, penetrants, sequestrants, solubilizers, fragrances,
buffers, dispersants, conditioning agents, for instance volatile or non
volatile, modified or unmodified silicones such as amino silicones,
film-forming agents, ceramides, preserving agents and opacifiers.
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 pH of the dye composition in accordance with the
invention is generally between 3 and 12 approximately, preferably
between 5 and 11 approximately and more particularly still from 6 to
9.5 . It may be adjusted to the desired value by means of acidifying or
alkalinizing agents customarily 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 inorganic or organic acids, such as hydrochloric acid,
orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic
acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
Among the alkalinizing agents, mention may be made, by way
of example, of aqueous ammonia, alkali metal carbonates,
alkanolamines, such as mono-, di- and triethanolamines and
derivatives thereof, sodium hydroxide, potassium hydroxide and the
compounds of formula (IV) below:
.Rb
N-W-N'
Rc Rd
(IV)
in which W is a propylene residue optionally substituted with a
hydroxyl group or a C 1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may
be identical or different, represent a hydrogen atom, a C 1-C4 alkyl
radical or a C 1-C4 hydroxyalkyl radical.
The dye composition according to the invention 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.
As indicated previously, the invention also relates to the use of
the dye composition as defined previously for colouring keratin fibres,
in particular human keratin fibres such as the hair.
III. Use of azomethine-type compounds
Likewise, the present invention consists of the use, for dyeing
keratin fibres, in particular human keratin fibres such as the hair, of
one or more azomethine-type direct dyes having a triaromatic unit of
formula (I) below, the organic or inorganic acid or base salts thereof,
the tautomeric, optical isomer or geometric isomer forms thereof
and/or the solvates thereof:
in which formula (I) nl n2, R, Ri , R2, R3, R4, i and X2 have the same
meanings as those indicated previously.
The compounds A, B, C and D are not used for dyeing keratin
fibres.
The compounds E and F may also not be used for dyeing
keratin fibres.
IV. Dyeing method
The dyeing method according to the present invention consists
in applying a dye composition as defined previously to the keratin
fibres for a time sufficient to obtain the desired coloration, after which
the fibres are rinsed, optionally washed with shampoo, rinsed again
and the resulting fibres are dried or left to dry.
The dye composition used during the keratin fibre dyeing
method does not comprise the compounds A, B, C, D. Preferably, the
dye composition used during the method of the present invention may
also not comprise the compounds E and F.
Preferably, the leave-on time for the dye composition is
between 1 and 60 minutes, preferably between 5 and 40 minutes and
more preferably still between 10 and 30 minutes.
The dye composition is generally applied to the keratin fibres
at ambient temperature, preferably between 25°C 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 method for
lightening keratin fibres, in particular human keratin fibres such as the
hair, in which applied to said fibres are (i) the dye composition as
defined previously free of oxidizing agent and (ii) a cosmetic
composition comprising one or more oxidizing agents; compositions
(i) and (ii) being applied to said keratin fibres sequentially or
simultaneously for a time sufficient to obtain the desired lightening,
after which the fibres are rinsed, optionally washed with shampoo,
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 post-treatment.
The oxidizing agents used are selected 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, and more preferably still
between 5 and 11 and more particularly still between 6 and 9.5 . It may
be adjusted to the desired value by means of acidifying or alkalinizing
agents usually used in the dyeing of keratin fibres and as defined
previously.
V. Leuco-type compound
Furthermore, the present invention relates to leuco-type
compounds of formula (III) below, the organic or inorganic acid or
base salts thereof, the tautomeric, optical isomer or geometric isomer
forms thereof and/or the solvates thereof:
in which formula (III) nl n2, R, Ri , R2, R3, R4, i and X2 have the
same meanings as those indicated in formula (I).
In particular, the preferred variants of nl n2, R, Ri , R2, R3, R4,
Xi and X2 in formula (III) for the leuco-type compounds correspond to
those indicated in formula (I) for the direct dyes.
The leuco-type compounds corresponding to formula (III) are
generally obtained by reacting the azomethine-type compounds of
formula (I) with a reducing agent according to the reaction scheme
below:
Synthesis approaches similar to this reaction scheme are
described in patent applications FR 2 056 799, FR 2 047 932, FR 2 165
965 and FR 2 262 023 .
The leuco-type compounds of formula (III) are used as
precursors of direct dyes of formula (I).
Preferably, the leuco-type compounds of formula (III) are
selected from the compounds corresponding to the reduced form of the
azomethine-type direct dyes 1 to 82 mentioned previously.
In other words, the leuco-type compounds of formula (III) are
selected from the precursors of azomethine-type direct dyes 1 to 82.
More preferably still, the leuco-type compounds of formula
(III) are selected from the precursors of direct dyes 1, 4, 6, 16, 20, 28,
29 and 30.
In particular, the invention relates to a cosmetic composition
comprising one or more leuco-type compounds of formula (III) as
defined previously.
The present invention also relates to a dyeing method in which
a cosmetic composition comprising one or more leuco-type compounds
of the abovementioned formula (III) are 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, rinsed again, and the resulting fibres
are dried or left to dry.
The oxidizing agent may be atmospheric oxygen or may be
selected from the aforementioned oxidizing agents.
In particular, when the oxidizing agent is atmospheric oxygen,
simply exposing the keratin fibres treated with the composition
comprising the leuco-type compound(s) to air 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
to the keratin fibres simultaneously with or sequentially to the
cosmetic composition comprising the leuco-type compounds.
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 leuco-type
compounds of formula (III) according to the invention.
According to another variant, a ready-to-use composition that
results from the mixing of a cosmetic composition comprising one or
more leuco-type compounds of the aforementioned formula (III) and of
a cosmetic composition comprising one or more oxidizing agents is
applied to keratin fibres.
The ready-to-use composition which is thus applied to the
keratin fibres may be in a variety of forms, such as in the form of
liquids, creams or gels or in any other form appropriate for dyeing
keratin fibres, and in particular human hair.
The leave-on time of the composition(s) varies from 1 to 60
minutes, preferably from 5 to 40 minutes and more preferably from 10
to 30 minutes.
The cosmetic composition comprising such leuco-type
compounds is generally applied to the keratin fibres at ambient
temperature, preferably between 25°C and 55°C.
Thus, the present invention also relates to a cosmetic
composition, in particular for dyeing keratin fibres such as the hair,
comprising one or more compounds of formula (III) as defined
previously and optionally comprising one or more oxidizing agents.
VI. Dyeing device
The present invention also relates to a multicompartment
device or "kit" comprising a first compartment containing a cosmetic
composition comprising one or more dyes of formula (I) as defined
previously or containing one or more leuco-type compounds of formula
(III) as defined previously, and optionally a second compartment
comprising one or more oxidizing agents.
In particular, the invention relates to a multicompartment
dyeing device or kit comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes of formula
(I) as defined previously or containing one or more leuco-type
compounds of formula (III) as defined previously, and a second
compartment comprising one or more oxidizing agents.
More particularly, the invention relates to a multicompartment
dyeing device or kit comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes of the
aforementioned formula (I) free of oxidizing agent and a second
compartment containing a cosmetic composition comprising one or
more oxidizing agents.
The invention also relates to a multicompartment dyeing device
or kit comprising a first compartment containing a cosmetic
composition comprising one or more leuco-type compounds of the
aforementioned formula (III), and a second compartment containing a
cosmetic composition 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 leuco-type compounds of the aforementioned
formula (III).
In this case, the composition comprising the leuco-type
compound(s) as defined above is applied to the keratin fibres that are
coloured by means of the exposure thereof to air.
The devices mentioned above are suitable for dyeing keratin
fibres.
The evaluation of the coloration can be done visually or read
on a spectrocolorimeter (such as Minolta CM3600d, illuminant D65,
angle 10°, SCI values) for the L*, a*, b* colorimetric measurements. In
this L*, a*, b* system, L* represents the intensity of the color, a*
indicates the green/red color axis and b indicates the blue/yellow
color axis. The lower the value of L, the darker or more intense the
color is. The higher the value of a , the redder the shade is; the higher
the value of b , the yellower the shade is.
The variation in coloring between the colored locks of natural
white hair which is untreated (control) and after treatment or
coloration is defined by , corresponding to the colour uptake on
keratin fibers, according to the following equation:
* = - (L* —Lo
*)2 + (a *—a 0
* + ( * - b 0
*)2 (i)
In this equation, L*, a* and b* represent the values measured
after dyeing the natural hair comprising 90% of white hairs and L o ,
a o and b o represent the values measured for the untreated natural hair
comprising 90% of white hairs.
The greater the value of , the greater the difference in color
between the control locks and the dyed locks and the greater color
uptake is. Chromaticity in the CIE L*, a*, b * colorimetric system is
calculated according to the following equation:
C* = Va* +b*
The greater the value of C*, the greater the chromaticity is.
The examples that follow serve to illustrate the invention
without, however, being limiting in nature.
EXAMPLES
I . Synthesis examples
Example 1: Synthesis of 2-[4-(ethylisopropylamino)phe
amino]-4-[4-(ethylisopropylamino)phenylimino]-5-methylaminocyclohexa-
2,5-dienone (compound 1)
Added to a solution of 0.85 g (0.004 mol) of N-(4-
aminophenyl)-N-ethyl-N-isopropylamine hydrochloride in 2 ml of water
and 2 ml of ethanol, is a solution of 0.40 g (0.002 mol) of 3-
(methylamino)phenol hydrobromide in 1 ml of water and 2 ml of
ethanol. The pH is adjusted to 9.5 with 2 ml of 20% aqueous ammonia.
7 ml of 6 % aqueous hydrogen peroxide solution are added and the
mixture is stirred for 24 hours. A solid is formed; after filtration, it is
washed with water and then with a water/methanol mixture. The product
is purified on a silica column (eluent: dichloromethane/methanol 95/5).
0.24 g of black powder of 2-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-5-methylaminocyclohexa-
2,5-dienone (compound 1) is obtained.
The molecular ion 474 (ES+) is detected by mass spectrometry.
Example 2: Synthesis of 2-[4-(ethylisopropylamino)phenylamino]-
4-[4-(ethylisopropylamino)phenylimino]-5-(2-hydroxyethylamino)
cyclohexa-2,5-dienone (compound 4)
Added to a solution of 0.42 g (0.002 mol) of N-(4-
aminophenyl)-N-ethyl-N-isopropylamine hydrochloride in 2 ml of water
and 2 ml of ethanol, is a solution of 0 .15 g (0.00 1 mol) of 3-[(2-
hydroxyethyl)amino]phenol. The pH is adjusted to 9.5 with 2 ml of 20%
aqueous ammonia. 7 ml of 6%> aqueous hydrogen peroxide solution are
added and the mixture is stirred for 5 hours at ambient temperature.
The precipitate formed is filtered off, rinsed with water and
dried. Thus, 80 mg of a black powder corresponding to 2-[4-(ethylisopropylamino)
phenylamino]-4-[4-(ethylisopropylamino)-
phenylimino]-5-(2-hydroxyethylamino)cyclohexa-2,5-dienone
(compound 4) are obtained.
The molecular ion 504 (ES+) is detected by mass spectrometry.
Example 3: Synthesis of 5-dimethylamino-2-[4-(ethylisopropylamino)
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-
cyclohexa-2,5-dienone (compound 6)
Added to a solution of 0.53 g (0.003 mol) of N-(4-
aminophenyl)-N-ethyl-N-isopropylamine hydrochloride in 2 ml of water
and 2 ml of ethanol, is 0.4 1g (0.003 mol) of 3-(dimethylamino)phenol.
The pH is adjusted to 9.5 with 1.5 ml of 20% aqueous ammonia. 1 ml of
6% aqueous hydrogen peroxide solution is added and the mixture is
stirred for 48 hours. The solid formed is filtered off and then purified
by chromatography (eluent: dichloromethane/methanol 99/1 ) .
250 mg of brown powder corresponding to 5-dimethylamino-2-
[4-(ethylisopropylamino)phenylamino]-4-[4-(ethylisopropylamino)-
phenylimino]cyclohexa-2,5-dienone (compound 6) are obtained.
The molecular ion 489 (ES+) is detected by mass spectrometry.
Example 4: Synthesis of 3,6-bis[4-(ethylisopropylamino)
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-2-methoxycyclohexa-
2,5-dienone (compound 28)
Added to a solution of 0.64 g (0.003 mol) of N-(4-
aminophenyl)-N-ethyl-N-isopropylamine hydrochloride in 2 ml of water
and 3 ml of ethanol, is a solution of 0.47 g (0.003 mol) of 2,3-
dimethoxyphenol in 1 ml of water and 3 ml of ethanol. The pH is
adjusted to 9.5 with 1.5 ml of 20% aqueous ammonia. 10.5 ml of 6%
aqueous hydrogen peroxide solution are added and the mixture is stirred
for 5 hours 30 minutes. The product is extracted with dichloromethane.
The organic phase is dried with disodium sulfate, filtered and then
concentrated until the solvents are eliminated. The product obtained is
purified by chromatography (eluent: dichloromethane/methanol 95/5).
0 . 12 g of black product corresponding to 3,6-bis[4-(ethylisopropylamino)
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-
2-methoxycyclohexa-2,5-dienone (compound 28) is obtained.
The molecular ion 65 1 (ES+) is detected by mass spectrometry.
The 1H NMR spectrum is in agreement.
Example 5: Synthesis of 2-[4-(ethylisopropylamino)phenylamino]-
4-[4-(ethylisopropylamino)phenylimino]-5-phenylaminocyclohexa-
2,5-dienone (compound 29)
Added to a solution of 1.1 g (0.005 mol) of N-(4-
aminophenyl)-N-ethyl-N-isopropylamine hydrochloride in 5 ml of water
and 5 ml of ethanol, is 0.93 g (0.005 mol) of 3-hydroxydiphenylamine.
The pH is adjusted to 9.5 with 20% aqueous ammonia. 17 ml of 6%
aqueous hydrogen peroxide solution is added and the mixture is stirred
for 48 hours. The gum formed is washed with water and then purified
by chromatography (eluent: dichloromethane).
211 mg of brown powder corresponding to 2-[4-(ethylisopropylamino)
phenylamino]-4-[4-(ethylisopropylamino)phenylimino]-
5-phenylaminocyclohexa-2,5-dienone (compound 29) are obtained.
The molecular ion 535 (ES+) is detected by mass spectrometry.
Example 6: Synthesis of 2- {4-[ethyl-(2-hydroxyethyl)amino]
2-methylphenylamino} -4- {4- [ethy 1- (2-hydroxy ethyl) amino] -2-methyl
phenylimino} -5-phenylaminocyclohexa-2,5-dienone (compound 30)
2
Added to a solution of 4.39 g (0.0 15 mol) of 2-[(4-amino-3-
methylphenyl)(ethyl)amino]ethanol sulfate in 10 ml of water and 30 ml
of ethanol, are 2.78 g (0.0 15 mol) of 3-hydroxydiphenylamine. The pH
is adjusted to 9.5 with 20% aqueous ammonia. 25.5 ml of 6% aqueous
hydrogen peroxide solution are added and the mixture is stirred for 24
hours. The gum formed is washed with water and then purified by
chromatography (eluent: dichloromethane/methanol 9/1). 802 mg of
brown powder corresponding to 2- {4-[ethyl-(2-hydroxyethyl)amino]-2-
methylphenylamino} -4- {4- [ethyl- (2-hydroxy ethyl) amino] -2-methylphenylimino}
-5-phenylaminocyclohexa-2,5-dienone (compound 30) are
obtained.
The molecular ion 568 (ES+) is detected by mass spectrometry.
Example 7:
Synthesis of 5-amino-2-[(4-amino-2,3-dimethylphenyl)amino]-
4-[(4-amino-2,3-dimethylphenyl)imino]cyclohexa-2,5-dien- 1-one
(compound 20)
Added to a solution of 3.14g (0.0 15 mol) of 2,3-
dimethylbenzene- 1,4-diamine and 0.8 17g (0.075 mol) of 3-aminophenol
in 10 mL of water and 20 mL of ethanol whose the pH were adjusted to
9.5 with 20% aqueous ammonia, are 4.25 mL of 30% (0.0375 mol)
aqueous hydrogen peroxide. The mixture is stirred for 24 hours. The
precipitate formed is filtrered off.
The solid is then dissolved in 10 mL of dimethylsulfoxyde, the
obtained solution is filtred and 15 mL of water is added to the filtrate.
The precipitate formed once again is filtrated and is washed
with 8 mL of a mixture of dimethylsulfoxyde/water (50/50) and 100 mL
of water. The product is purified by silica chromatography (eluent
dichloromethane/methanol 98/2).
804 mg of black powder corresponding to 5-amino-2-[(4-
amino-2,3-dimethylphenyl)amino]-4-[(4-amino-2,3-dimethylphenyl)
imino]cyclohexa-2,5-dien- 1-one (compound 20) are obtained.
The molecular ion 376 (ES+) is detected by mass spectrometry.
Example 8:
Synthesis of 5-amino-2-( {4-[ethyl(propan-2-
yl) amino ]phenyl} amino) -4-( (4-[ethyl(propan-2-yl)amino]phenyl}imino)
cyclohexa-2,5-dien- l -one (compound 16)
Added to a solution of 6.44g (0.03 mol) of N-(4-aminophenyl)-
N-ethyl-N-isopropylamine and 1.6 g (0.0 15 mol) of 3-aminophenol in
20 mL of water and 40 mL of ethanol brought to pH 9,5 with 20%
aqueous ammonia, are 15 mL of 30%> aqueous hydrogen peroxide. The
mixture is stirred for 10 hours. A gum is formed.
After decantation of the supernatant, the gum is washed with
20 mL of water/ethanol 50/50 mixture and the gum is added to
methanol. The product crystallized for two days.
The product obtained is purified by silica chromatography
(eluent dichloromethane/methanol 98/2). 1.8 g of black powder
corresponding 5-amino -2-( {4-[ethyl(propan-2-yl)amino]phenyl} amino) -
4-( (4-[ethyl(propan-2-yl)amino]phenyl}imino) cyclohexa-2,5-dien- 1-
one (compound 16) are obtained.
The molecular ion 460 (ES+) is detected by mass spectrometry
II. Dyeing evaluations of the compounds synthesized
The following dye compositions were prepared:
- 500 mg of exemplified compound,
79 grams of water,
15 grams of ethanol,
5 grams of benzyl alcohol,
0.5 gram of benzoic acid.
1 gram of the mixture is applied to a 0.25 gram lock of grey
hair containing 90% white hairs. After a leave-on time of 30 minutes,
the lock is rinsed, washed with a standard shampoo, then rinsed again
and then dried.
The results are collated in the following table:
Compound 1 Medium orange-grey
Compound 4 Light orange-grey
Compound 6 Medium orange-grey
Compound 28 Medium orange-grey
Compound 29 Medium orange-grey
Compound 30 Medium orange-grey
CLAIMS
1. Azomethine-type compound having a triaromatic unit o
formula (I) below, the organic or inorganic acid or base salts thereof
the tautomeric, optical isomer or geometric isomer forms thereo
and/or the solvates thereof:
which formula (I):
ni and n2 represent, independently of one another, 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 selected from
hydroxyl or imidazolium, An radicals; An denoting a
cosmetically acceptable anion or mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
Ri represents:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- an aminocarbonyl radical;
- a radical of formula (II):
(R')m
in which formula (II):
o m represents an integer equal to 0, 1, 2, 3 or 4;
o R' represents:
- a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different
radicals selected from hydroxyl or imidazolium, An
radicals; An denoting a cosmetically acceptable anion or
mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
- a hydroxyl radical;
- an -NR' 3R ' 4 radical in which R' 3 and R' 4 represent,
independently of one another:
a hydrogen atom;
a linear or branched C1- C 5 alkyl radical, optionally
substituted with one or more hydroxyl or C1-C4 alkoxy
radicals;
o it being understood that, in formula (II), when m is greater
than or equal to 2, the R' radicals may be identical or
different;
R2 represents:
- a hydrogen atom;
- a C1- C alkyl radical, optionally substituted with one or more
hydroxyl radicals;
Ri and R2 may form, together with the nitrogen atom to which they
are attached, a pyrrolidine, piperidine or morpholine ring;
R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- a C1-C4 alkoxy radical;
Xi and X2 represent, independently of one another:
- a hydroxyl radical;
- an - R 3R 4 radical in which:
R' ' 3 represents:
■ a hydrogen atom;
■ a linear C -C alkyl radical;
R' represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2-C alkyl radical substituted with
one or more hydroxyl radicals;
R 3 and R " 4 may form, together with the nitrogen atom to which
they are attached, a piperidino or morpholino ring;
it being understood that the compounds of formula (I) may not
represent the compounds A to F below:
Compound E
2 . Azomethine-type compound having a triaromatic unit of
formula (I) according to Claim 1, characterized in that, taken together
or separately:
• n and n2 represent, independently of one another, an integer
equal to 0, 1 or 2;
• R represents:
- a linear or branched C1-C4 alkyl radical, preferably a
methyl radical;
- a C1-C4 alkoxy radical, preferably a methoxy radical;
- a halogen atom, preferably chlorine;
• R represents:
- a hydrogen atom;
- a linear or branched C -C alkyl radical, optionally
substituted with one or more hydroxyl radicals;
- an aminocarbonyl radical;
- a radical of formula (II):
in which formula (II):
o m represents an integer equal to 0, 1, 2 or 3;
o R' represents:
- a linear or branched C1-C4 alkyl radical, preferably
a methyl radical;
- a C1-C4 alkoxy radical, preferably a methoxy
radical;
- a halogen atom, preferably chlorine;
- a hydroxyl radical;
- an -NR' 3R' 4 radical in which R' 3 and R' 4 represent,
independently of one another:
a hydrogen atom;
a linear or branched C1- C 5 alkyl radical, optionally
substituted with one or more hydroxyl radicals;
o it being understood that, in formula (II), when m is
greater than or equal to 2, the R' radicals may be
identical or different;
• R2 represents:
- a hydrogen atom;
- a linear or branched Ci-C alkyl radical, a butyl, methyl
or ethyl radical;
• Ri and R2 may form, together with the nitrogen atom to
which they are attached, a pyrrolidine, piperidine or morpholine ring;
• R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, preferably a
methyl or propyl radical;
- a C1- C 4 alkoxy radical, preferably a methoxy radical;
and/or
• Xi and X2 represent, independently of one another:
- a hydroxyl radical;
- an - R 3R 4 radical in which:
- R' ' 3 represents:
■ a hydrogen atom;
■ a linear Ci-C alkyl radical;
- R' represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2-C alkyl radical substituted with
one or more hydroxyl radicals.
3. Azomethine-type compound having a triaromatic unit of
formula (I) according to Claim 1 or 2, characterized in that ni and n2
represent an integer equal to 0 or 1, R is other than a hydrogen atom,
R2 represents a hydrogen atom and R4 represents a hydrogen atom.
4 . Azomethine-type compound having a triaromatic unit of
formula (I) according to any one of the preceding claims, ni and n2
represent an integer equal to 0 or 1, R is other than a hydrogen atom,
R2 represents a hydrogen atom, R4 represents a hydrogen atom and Xi
and X2 represent an - 'R 3R 4 radical in which R 3 represents a
hydrogen atom or a linear C1-C3 alkyl radical and R' represents a
hydrogen atom or a linear or branched C3-C4 alkyl radical or a C2-C4
alkyl radical substituted with one or more hydroxyl radicals.
5. Azomethine-type compound having a triaromatic unit of
formula (I) according to any one of the preceding claims,
characterized in that ni and n2 represent an integer equal to 0 or 1, R
is other than a hydrogen atom, R2 represents a hydrogen atom, R4
represents a hydrogen atom and Xi and X2 represent a hydroxyl
radical.
6 . Azomthenine-type compound a triaromatic unit of formula
(I) according to any one of the preceding claims, characterized in that
Xi and X2 represent a - R 3R 4 radical wherein R 3 and R'
represent hydrogen atom.
7 . Azomethine-type compound a triaromatic unit of formula (I)
according to any one of claims 1 to 5, characterized in that Xi and X2
represent a - R 3R 4 radical wherein R" 3 and R" 4 are different
from hydrogen atom.
8. Azomethine-type compound having a triaromatic unit of
formula (I) according to any one of the preceding claims,
characterized in that it is selected from the following compounds and
also the geometric or optical isomer forms thereof, the organic or
inorganic acid or base salts thereof, or the solvates thereof, such as the
hydrates:
2-[4-(Ethylisopropylamino)
phenylamino]-
4-[4-(ethylisopropylamino)-
Compound 1 phenylimino]-5-
methylaminocyclohexa-
2,5-dienone
3-Amino-6-(4-piperidin-
1-ylphenylamino)-4-[4-
piperidin- l -ylphenylimino]-
2-propyl-
Compound 2 cyclohexa-2,5-dienone
2-(4-Aminophenyl amino) -
4-(4-aminophenylimino)-
5-(2-
hydroxyethylamino)-
HO cyclohexa-2,5-dienone
Compound 3

2-[4-(Ethylisopropylamino)
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-
pyrrolidin- 1-ylcyclohexa-
2,5-dienone
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-piperidinl
-ylcyclohexa-2,5-dienone
Compound 8
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-
morpholin-4-ylcyclohexa-
2,5-dienone
0
Compound 9
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-
5-methylaminocyclohexa-
2,5-dienone
Compound 10

2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3-methyl-
H 2 phenylimino) -5-methylamino
Compound 15 cyclohexa-2,5 -dienone
5-Amino-2-[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)
phenylimino]-
cyclohexa-
2,5-dienone
Compound 16
2-(4-Hydroxyphenylamino)-
4-(4-hydroxyphenylimino)-5-
/ methylaminocyclohexa-2,5-
Compound 17 dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-5-
(2-hydroxy ethylamino) -
HO cyclohexa-2, 5-dienone
Compound 18

2-(4-Amino -2, 3-dimethy 1-
phenylamino)-4-(4-amino-
2,3-dimethylphenylimino)-
5-dimethy laminocy clo hexa-
2,5-dienone
Compound 24
2-(4-Aminophenylamino)-4-
(3-chloro-
4-hydroxyphenylimino)-5-
(2-hydroxy ethylamino) -
cyclohexa-2,5-dienone
Compound 25
4-(3-Chloro-4-hydroxyphenylimino)-
2-(4-hydroxyphenylamino)-
/ 5-methylaminocyclohexa-
2,5-dienone
Compound 26
2,5-Bis(4-hydroxyphenylamino)-
4-(4-hydroxyphenylimino)
cyclohexa-
2,5-dienone
Compound 27

2-(2-Chloro-4-hydroxyphenylamino)-
4-(2-chloro-4-hydroxyphenylimino)-
5-phenylaminocyclohexa-2,5-
dienone
Compound 35
2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3(or 2)-methylphenylimino)-
5-phenylaminocyclohexa-
2,5-dienone
Compound 36
H
5-Amino-2-(4-amino-3-chlorophenylamino)-
4-[4-amino-3-
chlorophenylimino]cyclohexa-
2,5-dienone
Compound 37
3,6-Bis(4-aminophenylamino)-4-
(4-
aminophenylimino)-2-methoxycyclohexa-
2,5-dienone
NH2
Compound 38
H 3,6-Bis(4-amino-3-methylphenylamino)-
4-(4-amino-
3-methylphenylimino)-2-
methoxycyclohexa-2,5-
dienone
NH2
Compound 39
3,6-Bis(4-hydroxyphenylamino)-
4-(4-
hydroxyphenylimino)-2-
methoxycyclohexa-2,5-
dienone
OH
Compound 40
C I 5-Amino-2-(2-chloro-4-
hydroxyphenylamino)-4-[2-
chloro-4-hydroxyphenylimino]
cyclohexa-2,5-
dienone
Compound 41
3,6-Bis(4-amino-2,3-
dimethylphenylamino)-4-
(4-amino-2,3-dimethylphenylimino)-
2-
methoxycyclohexa-2,5-
NH2 dienone
Compound 42
2-[4-(Ethylisopropylamino)
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-otolylaminocyclohexa-
2,5-
dienone
Compound 43
2-(4-Amino-2,3-
dimethylphenylamino)-4-
(4-amino-2,3-dimethylphenylimino)-
5-otolylaminocyclohexa-
2,5-
dienone
Compound 44

2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3(or 2)-methylphenylimino)-
5-otolylaminocyclohexa-
2,5-
dienone
Compound 49
5-Amino-2-(4-morpholin-
4-ylphenylamino)-4-[4-
morpholin-4-ylphenylimino]
cyclohexa-
Compound 50 2,5-dienone
2-[4-(Ethylisopropylamino)-
phenylamino]-
4-[4-(ethylisopropylamino)-
phenylimino]-5-ptolylaminocyclohexa-
2,5-
Compound 51 dienone
2-(4-Amino-2,3-dimethylphenylamino)-
4-(4-amino-
2,3-dimethylphenylimino)-
5-ptolylaminocyclohexa-
2,5-
dienone
Compound 52
2-(4-Aminophenyl amino) -4-
(4-aminophenylimino)-
5-ptolylaminocyclohexa-
2,5-
dienone
Compound 53
2-(4-Hydroxyphenylamino)-
4-(4-
hydroxyphenylimino)-5-ptolylaminocyclohexa-
2,5-
dienone
Compound 54
2-(3-Chloro-4-hydroxyphenylamino)-
4-(3-chloro-4-hydroxyphenylimino)-
5-p-tolylaminocyclohexa-
2,5-dienone
Compound 55
2-(2-Chloro-4-hydroxyphenylamino)-
4-(2-chloro-4-hydroxyphenylimino)-
5-p-tolylaminocyclohexa-
2,5-dienone
Compound 56
2-(4-Amino-3(or 2)-methylphenylamino)-
4-
(4-amino-3(or 2)-methylphenylimino)-
5-ptolylaminocyclohexa-
2,5-
dienone
Compound 57
5-Amino-2-(4-piperidin- 1-
ylphenylamino)-4-[4-
piperidin- 1-ylphenylimino]-
cyclohexa-2,5-dienone
Compound 58

2,5-Bis[4-(ethylisopropylamino)-
phenylamino]-4-[4-(ethylisopropylamino)-
phenylimino]cyclohexa-2,5-
dienone
Compound 67
2,5-Bis(4-amino-2,3-
dimethylphenylamino)-4-
(4-amino-2,3-dimethylphenylimino)
cyclohexa-
2,5-dienone
Compound 68
2,5-Bis(4-aminophenylamino)-
4-(4-
aminophenylimino)-
cyclohexa-2,5-dienone
Compound 69

5-Amino -2-(4 -amino -2,3 -
dimethylphenylamino)-4-(4-
amino-2,3-dimethylphenylimino)-
3-methylcyclohexa-
2,5-
dienone
Compound 80
5-Amino-2-(3-chloro-4-
hydroxyphenylamino)-4-(3-
chloro-4-hydroxyphenylimino)-
3-methylcyclohexa-
2,5-dienone
Compound 81
C I C I 5-Amino-2-(2-chloro-4-
hydroxyphenylamino)-4-(2-
chloro-4-hydroxyphenylimino)-
3-methylcyclohexa-
2,5-dienone
Compound 82
9 . Composition, in particular dye composition, for keratin
fibres such as the hair, characterized in that it comprises, in a medium
suitable for dyeing, one or more compounds of azomethine type having
a triaromatic unit of formula (I) below and also the organic or inorganic
acid or base salts thereof, the tautomeric, optical isomer or geometric
isomer forms thereof and/or the solvates thereof:
which formula (I):
ni and n2 represent, independently of one another, 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 selected from
hydroxyl or imidazolium, An radicals; An denoting a
cosmetically acceptable anion or mixture of anions;
- a C1-C4 alkoxy radical;
- a halogen atom;
Ri represents:
- a hydrogen atom;
- a linear or branched Ci-Cs alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- an aminocarbonyl radical;
- a radical of formula (II):
represents:
a linear or branched C1-C4 alkyl radical, optionally
substituted with one or more identical or different
radicals selected from hydroxyl or imidazolium, An
radicals; An denoting a cosmetically acceptable anion or
mixture of anions;
a C1-C4 alkoxy radical;
a halogen atom;
a hydroxyl radical;
an -NR' 3R' 4 radical in which R' 3 and R represent,
independently of one another:
a hydrogen atom;
a linear or branched C1- C 5 alkyl radical, optionally
substituted with one or more hydroxyl or C1-C4 alkoxy
radicals;
o it being understood that, in formula (II) , when m is greater
than or equal to 2, the R ' radicals may be identical or
different;
R2 represents:
- a hydrogen atom;
- a C1- C alkyl radical, optionally substituted with one or more
hydroxyl radicals;
R i and R2 may form, together with the nitrogen atom to which they
are attached, a pyrrolidine, piperidine or morpholine ring;
R3 and R4 represent, independently of one another:
- a hydrogen atom;
- a linear or branched Ci -C alkyl radical, optionally substituted
with one or more hydroxyl radicals;
- a C1-C4 alkoxy radical;
X i and X2 represent, independently of one another:
- a hydroxyl radical;
- an -NR 3R 4 radical in which:
- R ' ' 3 represents:
■ a hydrogen atom;
■ a linear Ci -C alkyl radical;
- R ' represents:
■ a hydrogen atom;
■ a linear or branched C 3-C alkyl radical;
■ a linear or branched C2 -C alkyl radical substituted with
one or more hydroxyl radicals;
R 3 and R " 4 may form, together with the nitrogen atom to which
they are attached, a piperidino or morpholino ring;
it being understood that the compounds of formula (I) may not
represent the compounds A to below:
10 . Use, for dyeing keratin fibres, in particular human keratin
fibres such as the hair, of one or more direct dyes of formula (I) below
and also the organic or inorganic acid or base salts thereof, the
tautomeric, optical isomer or geometric isomer forms thereof and/or the
solvates thereo
in which formula (I) nl n2, R, Ri , R2, R3, R4, i and X2 have the same
meanings as those indicated in Claim 9 .
11. Method for dyeing keratin fibres, in particular human
keratin fibres such as the hair, in which applied to said fibres is a dye
composition comprising, in a medium suitable for dyeing, one or more
direct dyes of formula (I) below, the organic or inorganic acid or base
salts thereof, the tautomeric, optical isomer or geometric isomer forms
thereof and/or the solvates thereof:
in which nl n2, R, Ri , R2, R 3, R4, i and X2 have the same meanings
as those indicated in Claim 9; for a time sufficient to obtain the
desired coloration, after which the fibres are rinsed, optionally washed
with shampoo, rinsed again and the resulting fibres are dried or left to
dry.
12. Method for lightening keratin fibres, in particular human
keratin fibres such as the hair, in which applied to said fibres are (i)
the dye composition as defined according to Claim 9 free of oxidizing
agent and (ii) a cosmetic composition comprising one or more
oxidizing agents; compositions (i) and (ii) being applied to said
keratin fibres sequentially or simultaneously for a time sufficient to
obtain the desired lightening, after which the fibres are rinsed,
optionally washed with shampoo, rinsed again and the resulting fibres
are dried or left to dry.
13. Leuco-type compound of formula (III) below, the organic
or inorganic acid or base salts thereof, the tautomeric, optical isomer
or geometric isomer forms thereof and/or the solvates thereof:
in which formula (III) nl n2, R, Ri , R2, R 3, R 4, i and X2 have the
same meanings as those indicated in Claim 9 .
14. Composition, in particular for dyeing keratin fibres such as
the hair, comprising one or more compounds of formula (III) as
defined according to the preceding claim and optionally comprising
one or more oxidizing agents.
15. Method for dyeing keratin fibres, characterized in that a
dye composition comprising one or more compounds of formula (III)
as defined according to Claim 13 and an oxidizing composition
comprising one or more oxidizing agents are applied simultaneously or
sequentially to said wet or dry fibres.
15. Use of one or more leuco-type compounds of formula (III)
as defined according to Claim 13 as precursors of the direct dyes as
defined according to any one of Claims 1 to 6 .
16 . Use of one or more leuco-type compounds of formula (III)
as defined according to Claim 13 in the presence of one or more
oxidizing agents for dyeing keratin fibres, in particular human keratin
fibres such as the hair.
17 . Multicompartment device or "kit" comprising a first
compartment containing a cosmetic composition comprising one or
more dyes of formula (I) as defined in Claim 9 or containing one or
more leuco-type compounds of formula (III) as defined according to
Claim 13, and a second compartment comprising one or more
oxidizing agents.