The invention relates to the dyeing of keratin
materials using dichromophore dyes with a carbonyl or
heterocyclic linker.
It is known practice to dye keratin fibers, in
particular human keratin fibers, by direct dyeing. The
process conventionally used in direct dyeing comprises
applying to the keratin fibers direct dyes which are
colored or coloring molecules having an affinity for
the fibers, allowing them to diffuse and then rinsing
the fibers.
The direct dyes which are conventionally used are, for
example, dyes of the nitrobenzene type, anthraquinone
dyes, nitropyridine dyes, or dyes of the azo, xanthene,
acridine, azine or triarylmethane type.
It is also known practice to use hemicyanin styryl
direct dyes to strongly dye keratin fibers. These
benzothiazolium or benzoimidazolium heteroaryl-group
dyes are, for example, those described in patent
applications EP 1166753 and EP 1166757.
The coloring of keratin fibers using these conventional
direct dyes does not make it possible to significantly
lighten keratin fibers.
The lightening of the color of dark keratin fibers to
lighter shades, by optionally modifying the shade
thereof, constitutes an important demand.
Conventionally, in order to obtain a lighter coloring,
a chemical bleaching process is used. This process
comprises treating the keratin fibers, such as the
hair, with a strong oxidizing system, generally

composed of hydrogen peroxide, possibly in combination
with persalts, generally in an alkaline medium.
This bleaching system has the drawback of damaging the
keratin fibers and of detrimentally affecting their
cosmetic properties. The fibers in fact have a tendency
to become rough, more difficult to disentangle and more
brittle. Finally, the lightening or the bleaching of
keratin fibers with oxidizing agents is incompatible
with the treatments for modifying the shape of said
fibers particularly in hair straightening treatments.
Another lightening technique comprises applying
fluorescent direct dyes to dark hair. This technique,
described in particular in documents WO 03/028685 and
WO 2004/091473, makes it possible to retain the quality
of the keratin fiber during the treatment. However,
these fluorescent direct dyes do not exhibit
satisfactory fastness with respect to outside agents.
In order to increase the fastness of direct colorings,
it is known practice to use disulfide dyes, in
particular imidazolium chromophore dyes in patent
applications WO 2005/097051 or EP 1647580, and
pyridinium/indolizinium styryl chromophore dyes in
patent applications WO 2006/134043 and WO 2006/136617.
These dyes use reducing agents to ensure good fastness.
However, the reducing agents may present drawbacks in
terms of odor, in terms of the user perceiving damage
to the keratin fiber and in terms of multistep
applications, including a fixing step with an oxidizing
agent.
The aim of the present invention is to provide new
systems for dyeing keratin materials, in particular
human keratin fibers, especially dark hair, which do
not have the drawbacks of the existing bleaching
processes.

In particular, one aim of the invention is to provide
direct dyeing systems for obtaining colorings, option-
ally with lightening effects or visible colorings,
especially on dark keratin fibers, which are resistant
to successive shampooing operations, which do not damage
the keratin fibers and which do not detrimentally
affect their cosmetic properties.
Another aim of the invention is to dye keratin
materials chromatically, naturally and/or in a manner
which is persistent with respect to outside attacks.
Another aim of the invention is to provide dyes which
are stable in the formulation carriers, and which have
better coloring from the root to the end on all types
of hair, while at the same time being relatively
nonselective.
This aim is achieved with the present invention, a
subject of which is a process for dyeing keratin
materials, in particular keratin fibers, especially
human keratin fibers such as the hair, more
particularly dark hair, comprising applying, to the
keratin materials, a dye composition comprising, in a
cosmetic medium, at least one dichromophore dye with a
carbonyl or heterocyclic linker, chosen from the dyes
of formula (I) below:

the organic or mineral acid salts, optical isomers and
geometric isomers thereof, and the solvates such as
hydrates:
in which formula (I):
• A represents a radical containing at least one
chromophore which is optionally cationic, colored,
or colored and fluorescent;
• L and L', which may be identical or different,

represent:
o a saturated or unsaturated, linear or branched
C1-C20 hydrocarbon-based chain which is optionally
substituted, optionally interrupted and/or
optionally terminated at one or both of its ends
with one or more divalent groups or combinations
thereof chosen from -N(R)-, -O-, -S-, -C(O)- and
-SO2-, with R, R' , which may be identical or
different, being chosen from a hydrogen, and a
C1-C4 alkyl, hydroxyalkyl and aminoalkyl radical;
it being understood that said combination cannot
form a disulfide bond -S-S-;
o an arylene group,
o a heteroarylene group,
o a cycloalkylene group, or
o a heterocycloalkylene group;
• Y represents a carbonyl group -C(0)- or a
heteroaryl group, which is cationic or
noncationic, which comprises 5-13 members, which
is optionally substituted, and which comprises
from 1 to 5 heteroatoms chosen from oxygen, sulfur
or nitrogen atoms; in particular, the divalent
group -Y-(L')p'-Y- is chosen from the divalent
groups for which p' is 1, such as:



in which divalent groups:
- Z1 represents an oxygen or sulfur atom or a
radical NR1,
- Z2 represents a nitrogen atom or a radical CR2,
- Z3 represents a nitrogen atom or a radical CR3,
- Z4 represents a nitrogen atom or a radical CR4,
with R2, R3 and R4 representing a hydrogen or
halogen atom, an optionally substituted
(C1-C4) alkyl group or a (C1-C4) alkoxy, hydroxyl,
(poly)hydroxy(C2-C4)alkoxy or C(O)-N(R') group, in
which R and R' are as defined above, or an amino
group, optionally substituted with one or two
(hydroxy) (C1-C6) alkyl or hetero (C5-C7) cycloalkyl
radicals, which may be identical or different,
such as morpholino, etc.,
or else, two groups R1 with R2 and R3 with R4 form,
together with the nitrogen and/or carbon atoms
which bear them, a condensed aryl group such as
benzo,
- R representing a hydrogen atom or an optionally
substituted (C1-C4)alkyl group;
• p and p', which may be identical or different,
represent an integer equal to 0 or 1;
• Csat represents a linear or branched, optionally
substituted C1-C18 alkylene chain.
Another subject of the invention is a dye composition
for dyeing keratin fibers, comprising, in a cosmetic
medium, at least one dye of formula (I) as defined
above, and optionally a cosmetically acceptable acidic
agent or basic agent; in particular, a basic agent.
A subject of the invention is also novel dyes of

formula (I) as defined above.
Another subject of the invention is a multicompartment
device in which a first compartment contains a dye
composition containing at least one dye of formula (I)
as defined above and a second compartment contains a
cosmetically acceptable acidic or basic agent, in
particular a basic agent.
The process of the invention makes it possible to
obtain a coloring of the hair, without damage thereto,
which is persistent with respect to shampooing
operations, everyday attacks (sunlight, perspiration)
and hair treatments. The dyeing process according to
the invention also makes it possible to visibly color
dark keratin materials, in particular dark human
keratin fibers, especially dark hair. Furthermore, when
the chromophore A is a chromophore derived from a
fluorescent dye, it makes it possible to obtain
lightening of keratin materials such as keratin fibers
which is particularly visible on dark keratin fibers
such as dark hair.
Moreover, the novel dyes according to the invention
exhibit photostability and chemical stability which are
very satisfactory. These dyes are soluble in the
cosmetic media suitable for hair dyeing, and most
particularly in water/ethanol mixtures. This process
also makes it possible to dye bleached keratin fibers
in a strong and chromatic manner.
The dyeing range obtained from the dyes of the inven-
tion also covers the basic shades that are the most
popular in hair dyeing.
For the purpose of the present invention, the term
"dark keratin material" is intended to mean that which
exhibits a lightness L* measured in the CLE. L*a*b*
system of less than or equal to 45, and preferably less
than or equal to 40, given that, moreover, L* = 0 is

equivalent to black and L* = 100 is equivalent to
white.
For the purpose of the invention, the expression
"naturally or artificially dark hair" is intended to
mean whose tone height is less than or equal to 6 (dark
blond) and preferably less than or equal to 4
(chestnut-brown).
The lightening of the hair is evaluated by the
variation in "tone height" before and after application
of the compound of formula (I). The notion of "tone" is
based on the classification of the natural shades, one
tone separating each shade from the shade immediately
following or preceding it. This definition and the
classification of the natural shades are well known to
hair styling professionals and are published in the
book "Science des traitements capillaires" [Hair
Treatment Sciences], by Charles Zviak 1988, published
by Masson, pp. 215 and 278.
The tone heights range from 1 (black) to 10 (very light
blond), one unit corresponding to one tone; the higher
the figure, the lighter the shade.
An artificially colored hair is a hair whose color has
been modified by a dyeing treatment, for example dyeing
with direct dyes or oxidation dyes.
For the purpose of the invention, the term "bleached
hair" is intended to mean hair whose tone height is
greater than 6 and preferably greater than 7.
For the purpose of the present invention, and unless
otherwise indicated:
the "aryl" or "heteroaryl" radicals or the aryl or
heteroaryl part of a radical may be substituted
with at least one substituent chosen from:

• a C1-C16, preferably C1-C8, alkyl radical
optionally substituted with one or more radicals
chosen from the radicals: hydroxyl, C1-C2 alkoxy,
C2-C4 (poly)hydroxyalkoxy, acylamino and amino
substituted with two C1-C4 alkyl radicals, which
may be identical or different, optionally bearing
at least one hydroxyl group, or the two radicals
possibly forming, with the nitrogen atom to which
they are attached, a heterocycle comprising from
5 to 7 members, preferably 5 or 6 members, which
is saturated or unsaturated, which is optionally
substituted, and which optionally comprises
another heteroatom which may be identical or
different from the nitrogen;
• a halogen atom such as chlorine, fluorine or
bromine;
• a hydroxyl group;
• a C1-C2 alkoxy radical;
• C1-C2 alkylthio radical;
•a C2-C4 (poly)hydroxyalkoxy radical;
• an amino radical;
. a 5- or 6-membered heterocycloalkyl radical;
• an optionally cationic 5- or 6-membered hetero-
aryl radical, preferably imidazolium, optionally
substituted with a C1-C4 alkyl radical, preferably
methyl;
• an amino radical substituted with one or two C1-C6
alkyl radicals, which may be identical or
different, optionally bearing at least:
i) one hydroxyl group,
ii) one amino group optionally substituted with
one or two optionally substituted C1-C3 alkyl
radicals, said alkyl radicals possibly
forming, with the nitrogen atom to which they
are attached, a heterocycle comprising from 5
to 7 members, which is saturated or
unsaturated, which is optionally substituted,
and which optionally comprises at least one
other heteroatom which may or may not be

different from nitrogen,
. -N(R)-C(O)R' in which the R radical is a hydrogen
atom or a C1-C4 alkyl radical optionally bearing
at least one hydroxyl group, and the R' radical
is a C1-C2 alkyl radical;
• (R)2N-C(O)- in which the R radicals, which may or
may not be identical, represent a hydrogen atom,
or a C1-C4 alkyl radical optionally bearing at
least one hydroxyl group;
. R' SO2-NR- in which the R radical represents a
hydrogen atom or a C1-C4 alkyl radical optionally
bearing at least one hydroxyl group, and the R'
radical represents a C1-C4 alkyl radical or a
phenyl radical;
• (R) 2N-S (O)2- in which the R radicals, which may or
may not be identical, represent a hydrogen atom
or a C1-C4 alkyl radical optionally bearing at
least one hydroxyl group,
• a carboxylic radical in acid or salified form
(preferably with an alkali metal or an ammonium,
which is substituted or unsubstituted);
• a cyano group;
• a polyhaloalkyl group containing from 1 to 6
carbon atoms and from 1 to 6 halogen atoms, which
may be identical or different; the polyhaloalkyl
group is, for example, trifluoromethyl;
the cyclic or heterocyclic part of a nonaromatic
radical may be substituted with at least one
substituent, chosen from the groups:
• hydroxyl;
• C1-C4 alkoxy;
. C1-C4 alkyl;
• C2-C4 (poly)hydroxyalkoxy;
• a C1-C2 alkylthio radical;
. RC(O)-N(R')- in which the R' radical is a
hydrogen atom or a C1-C4 alkyl radical optionally
bearing at least one hydroxyl group, and the R
radical is a C1-C2 alkyl radical or an amino
radical substituted with two C1-C4 alkyl groups,

which may be identical or different, optionally
bearing at least one hydroxyl group;
• RC(O)-O- in which the R radical is a C1-C4 alkyl
radical or an amino radical substituted with one
or two C1-C4 alkyl groups, which may be identical
or different, optionally bearing at least one
hydroxyl group, said alkyl radicals possibly
forming, with the nitrogen atom to which they are
attached, a heterocycle comprising from 5 to 7
members, which is saturated or unsaturated, which
is optionally substituted, and which optionally
comprises at least one other heteroatom which may
or may not be different from nitrogen;
. RO-C(O)- in which the R radical is a C1-C4 alkyl
radical optionally bearing at least one hydroxyl
group;
a cyclic or heterocyclic radical or a nonaromatic
part of an aryl or heteroaryl radical may also be
substituted with one or more oxo or thioxo groups;
an "aryl" radical represents a condensed or
noncondensed, monocyclic or polycyclic group
containing from 6 to 22 carbon atoms, and at least
one ring of which is aromatic; preferably, the
aryl radical is a phenyl, biphenyl, naphthyl,
indenyl, anthracenyl or tetrahydronaphthyl;
a "heteroaryl radical" represents an optionally
cationic, condensed or noncondensed, monocyclic or
polycyclic group comprising from 5 to 22 members
and from 1 to 6 heteroatoms chosen from a
nitrogen, oxygen, sulfur and selenium atom, and at
least one ring of which is aromatic; preferably, a
heteroaryl radical is chosen from acridinyl,
benzimidazolyl, benzobistriazolyl, benzopyrazolyl,
benzopyridazinyl, benzoquinolyl, benzothiazolyl,
benzotriazolyl, benzoxazolyl, pyridinyl,
tetrazolyl, dihydrothiazolyl, imidazopyridinyl,
imidazolyl, indolyl, isoquinolyl, naphtho-
imidazolyl, naphthooxazolyl, naphthopyrazolyl,
oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl,

phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl,
pyrazoyltriazyl, pyridyl, pyridinoimidazolyl,
pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl,
thiazolyl, thiazolopyridinyl, thiazoylimidazolyl,
thiopyrylyl, triazolyl, xanthylyl and its ammonium
salt;
a "cyclic or cycloalkyl radical" is a condensed or
noncondensed, monocyclic or polycyclic, nonaromatic
radical containing from 5 to 22 carbon atoms,
possibly comprising one or more unsaturations; in
particular, the cyclic radical is a cyclohexyl;
a "heterocyclic radical or heterocycle" is a
condensed or noncondensed, monocyclic or poly-
cyclic, nonaromatic radical containing from 5 to
22 members, comprising from 1 to 6 heteroatoms
chosen from nitrogen, oxygen, sulfur and selenium;
the term "arylene", "heteroarylene", "cyclo-
alkylene" and "heterocycloalkylene" is intended to
mean divalent groups derived from the respective
"aryl", "heteroaryl", "cycloalkyl" and "hetero-
cycloalkyl" groups as defined above, it being
possible for said divalent groups to be
substituted with the same groups as those defined
for the "aryl", "heteroaryl", "cycloalkyl" and
"heterocycloalkyl" groups; in particular, the
arylene group is a phenylene group, more
particularly 1,4-phenylene or 1,3-phenylene; in
particular, the arylene group is an indolylene
group; the cycloalkylene group is a cyclohexylene
group, and the heterocycloalkylene group is a
piperazene group;
an "alkyl radical" is a linear or branched, C1-C16,
preferably C1-C8, hydrocarbon-based radical;
an "alkylene chain" represents a divalent C1-C18
chain; in particular C1-C6, more particularly C1-C2
when the chain is linear; optionally substituted
with one or more groups, which may be identical or
different, chosen from hydroxyl, (C1-C2)alkoxy,
(poly)hydroxy (C2-C4) alkoxy (di) (C1-C2) (alkyl) amino,

Ra-Za-C(Zb)- and Ra-Za-S(O)t- groups, with Za, Zb,
which may be identical or different, representing
an oxygen or sulfur atom or a group NRa' , Ra
representing an alkali metal, a hydrogen atom or
an alkyl group, or else it is absent if another
part of the cationic molecule and Ra' representing
a hydrogen atom or an alkyl group, and t is 1 or
2;
a "saturated or unsaturated, optionally substitu-
ted C1-C20 hydrocarbon-based chain" represents a
hydrocarbon-based, in particular C1-C8, chain
optionally comprising one or more π double bonds,
which may or may not be conjugated; in particular,
the hydrocarbon-based chain is saturated; said
chain is optionally substituted with one or more
groups, which may be identical or different,
chosen from hydroxyl, (C1-C2)alkoxy, (poly)hydroxy-
(C2-C4)alkoxy (di) (C1-C2) (alkyl) amino, Ra-Zs-C(Zb)-
and Ra-Za-S(O)t- groups, with Za, Zb, which may be
identical or different, representing an oxygen or
sulfur atom or a group NRa', Ra representing an
alkali metal, a hydrogen atom or an alkyl group,
or else it is absent if another part of the
cationic molecule and Ra' representing a hydrogen
atom or an alkyl group, and t is 1 or 2;
the expression "optionally substituted" assigned
to the alkyl radical implies that said alkyl
radical may be substituted with one or more
radicals chosen from the radicals: i) hydroxyl;
ii) C1-C4 alkoxy; iii) acylamino; iv) amino option-
ally substituted with one or two C1-C4 alkyl
radicals, which may be identical or different,
said alkyl radicals possibly forming, with the
nitrogen atom which bears them, a heterocycle
comprising from 5 to 7 members, optionally
comprising another heteroatom which may or may not
be different from nitrogen; v) or a quaternary
ammonium group -N+R'R''R''', M- for which R', R'',
R'' ', which may be identical or different,

represent a hydrogen atom or a C1-C4 alkyl group,
or else -N+R'R''R''' forms a heteroaryl such as
imidazolium optionally substituted with a C1-C4
alkyl group, and M- represents the anionic
counterion;
an "alkoxy radical" is an alkyloxy or alkyl-O-
radical for which the alkyl radical is a linear or
branched, C1-C16, preferably C1-C8, hydrocarbon-
based radical;
an "alkylthio radical" is an alkyl-S- radical for
which the alkyl radical is a linear or branched,
C1-C16, preferably C1-C8, hydrocarbon-based radical,
when the alkylthio group is optionally
substituted, this implies that the alkyl group is
optionally substituted as defined above;
the limits delimiting the extent of the range of
values are included in this range of values;
an "organic or mineral acid salt" is more
particularly chosen from a salt derived from
cosmetically acceptable acids such as: i) from
hydrochloric acid HC1; ii) from hydrobromic acid
HBr; iii) from sulfuric acid H2SC4; iv) from
alkylsulfonic acids: Alk-S(O)2OH such as methyl-
sulfonic acid and ethylsulfonic acid; v) from
arylsulfonic acids: Ar-S(O)20H such as from
benzenesulfonic acid and from toluenesulfonic
acid; vi) from citric acid; vii) from succinic
acid; viii) from tartaric acid; ix) from lactic
acid; x) from alkoxysulfinic acids: Alk-0-S(O)OH
such as from methoxysulf inic acid and from
ethoxysulfinic acid; xi) from aryloxysulfinic
acids such as from tolueneoxysulf inic acid and
from phenoxysulfinic acid; xii) from phosphoric
acid H3PO4; xiii) from acetic acid CH3C(O)OH;
xiv) from triflic acid CF3SO3H and xv) from
tetrafluoroboric acid HBF4;
an "anionic counterion" is an anion or an anionic
group associated with the cationic charge of the
dye; more particularly, the anionic counterion is

chosen from: i) halides such as chloride or
bromide; ii) nitrates; iii) sulfonates, among
which are C1-C6 alkyl sulfonates: Alk-S(O)2O- such
as methyl sulfonate or mesylate and ethyl
sulfonate; iv) aryl sulfonates: Ar-S(O)2O- such as
benzene sulfonate and toluenesulfonate or
tosylate; v) citrate; vi) succinate; vii) tartrate;
viii) lactate; ix) alkyl sulfates: Alk-O-S(O)O-
such as methyl sulfate and ethyl sulfate;
x) arylsulfates: Ar-O-S(O)O- such as benzenesulfate
and toluenesulfate; xi) alkoxysulfates:
Alk-O-S(O)2O such as methoxy sulfate and ethoxy
sulfate; xii) aryloxysulfates : Ar-O-S (O)2O-;
xiii) phosphate; xiv) acetate; xv) triflate; and
xvi) borates such as tetrafluoroborate;
the "solvates" represent the hydrates and also the
association with linear or branched C1-C4 alcohols
such as ethanol, isopropanol or n-propanol.
The dyes of formula (I) as defined above are dyes, i.e.
compounds comprising chromophores A capable of absorb-
ing light in the visible spectrum. Furthermore, some
dyes of the invention of formula (I) are, in addition,
fluorescent dyes, i.e. they comprise chromophores A
capable of absorbing light in the UV radiation or
visible range at a wavelength λabs of between 250 and
800 nm and capable of re-emitting light in the visible
range at an emission wavelength greater than that
absorbed λabs of between 400 and 800 nm. The difference
between the absorption wavelength and the emission
wavelength is commonly referred to as Stoke's shift,
which is between 1 nm and 100 nm.
Preferably, the dyes which are also fluorescent of
formula (I) of the invention are dyes capable of
absorbing in the visible range λabs of between 400 and
800 nm and of re-emitting in the visible range λabs of
between 400 and 800 nm. More preferably, the dyes of
formula (I) are dyes capable of absorbing at a λabs of

between 420 and 550 nm and of re-emitting in the
visible range at a λem of between 470 and 600 nm.
By way of chromophores A which can be used in the
present invention, mention may be made of the radicals
derived from acridine, acridone, anthranthrone, anthra-
pyrimidine, anthraquinone, azine, azo, azomethine,
benzanthrone, benzimidazole, benzimidazolone, benz-
indole, benzoxazole, benzopyran, benzothiazole,
benzoquinone, bisazine, bisisoindoline, carboxanilide,
coumarin, cyanin (such as azacarbocyanin, diazacarbo-
cyanin, diazahemicyanin/hydrazone, hemicyanin/styryl,
tetraazacarbocyanin) , diazine, diketopyrrolopyrrole,
dioxazine, diphenylamine, diphenylmethane, dithiazine,
flavonoid, such as flavanthrone and flavone,
fluorindine, formazan, hydrazone, in particular
arylhydrazone, hydroxy ketone, indamine, indanthrone,
indigoid and pseudoindigoid, indophenol, indoaniline,
isoindoline, isoindolinone, isoviolanthrone, lactone,
methine, naphthalimide, naphthanilide, naphtholactam,
naphthoquinone, nitro, in particular nitro(hetero)-
aromatic, oxadiazole, oxazine, perilone, perinone,
perylene, phenazine, phenothiazine, phthalocyanin,
polyene/carotenoid, porphyrin, pyranthrone, pyrazol-
anthrone, pyrazolone, pyrimidinoanthrone, pyronine,
quinacridone, quinoline, quinophthalone, squarane,
stilbene, thiazine, thioindigo, thiopyronine, triaryl-
methane and xanthene dyes.
By way of fluorescent chromophores A that can be used
in the present invention, mention may be made of the
radicals derived from benzimidazolone, benzoxazole,
coumarin, difluoro-{2-[(2H-pyrrol-2-ylidene-kN)methyl]-
lH-pyrrolato-kN}boron (BODIPY®), diketopyrrolopyrrols,
fluorindine, (poly)methine (in particular cyanin and
styryl/hemicyanin), naphthalimide, naphthanilide,
naphthylamine (such as dansyl), oxadiazole, oxazine,
perilone, perinone, stilbene and xanthene dyes.

Mention may also be made of the fluorescent dyes
described in documents EP 1133975, WO 03/029359,
EP 860636, WO 95/01772, WO 95/15144, EP 714954 and
those listed in the encyclopedia "The chemistry of
synthetic dye" by K. Venkataraman, 1952, Academic Press
vol. 1 to 7, in the encyclopedia "Kirk Othmer"
"Chemical technology", chapter "Dyes and Dye
Intermediate", 1993, Wiley and Sons, and in various
chapters of the encyclopedia "Ullmann's Encyclopedia of
Industrial Chemistry" 7th edition, Wiley and Sons, in
The Handbook — A Guide to Fluorescent Probes and
Labeling Technologies, 10th ed. Molecular
Probes/Invitrogen - Oregon 2005 available on the
Internet or in the previous printed editions.
Among the nitro chromophores A that can be used
according to the invention, mention may be made, in a
nonlimiting manner, of the radicals derived from the
following dyes:
1, 4-diamino-2-nitrobenzene
1-amino-2-nitro-4-β-hydroxyethylaminobenzene
1-amino-2-nitro-4-bis (β-hydroxyethyl) aminobenzene
1,4-bis(β-hydroxyethylamino)-2-nitrobenzene
1-β-hydroxyethylamino-2-nitro-4-bis(β-hydroxyethyl-
amino) benzene
1-β-hydroxyethylamino-2-nitro-4-aminobenzene
1-β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxy-
ethyl)aminobenzene
1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene
l-amino-2-nitro-4-β-hydroxyethylamino-5-chloro-
benzene
1,2-diamino-4-nitrobenzene
1-amino-2-p-hydroxyethylamino-5-nitrobenzene
1,2-bis(p-hydroxyethylamino)-4-nitrobenzene
l-amino-2-tris(hydroxymethyl)methylamino-5-nitro-
benzene
1-hydroxy-2-amino-5-nitrobenzene
l-hydroxy-2-amino-4-nitrobenzene
l-hydroxy-3-nitro-4-aminobenzene

l-hydroxy-2-amino-4,6-dinitrobenzene
1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitro-
benzene
1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene
1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene
1-β, y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene
1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-
2-nitrobenzene
1-β,γ-dihydroxypropylamino-4-trifluoromethyl-
2-nitrobenzene
1-β-hydroxyethylamino-4-trifluoromethyl-2-nitro-
benzene
1-β-hydroxyethylamino-3-methy1-2-nitrobenzene
1-β-aminoethylamino-5-methoxy-2-nitrobenzene
1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene
l-hydroxy-2-chloro-6-amino-4-nitrobenzene
l-hydroxy-6-bis(β-hydroxyethyl)amino-3-nitrobenzene
1-β-hydroxyethylamino-2-nitrobenzene
l-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.
Among the azo chromophores that can be used according
to the invention, mention may be made of the radicals
derived from the cationic azo dyes described in patent
applications WO 95/15144, WO 95/01772 and EP 714954.
Among the azo chromophores, mention may also be made of
those described in the Colour Index International
3rd edition, and in particular the following compounds:
Disperse Red 17
- Acid Yellow 9
- Acid Black 1
- Basic Red 22
- Basic Red 76
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 of 1- (4' -aminodiphenylazo) -
2-methyl-4-bis(β-hydroxyethyl) aminobenzene and
4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic
acid.
Among the quinone chromophores A, those mentioned in
the abovementioned Colour Index International are
suitable, and among the latter, mention may be made,
inter alia, of the radicals derived from 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:
l-N-methylmorpholiniumpropylamino-4-hydroxyanthra-
quinone
1-aminopropylamino-4-methylaminoanthraquinone
1-aminopropylaminoanthraquinone
5-β-hydroxyethyl-1,4-diaminoanthraquinone
2-aminoethylaminoanthraquinone
1,4-bis (β,γ-dihydroxypropylamino)anthraquinone.

Among the azine chromophores A, those listed in the
International Colour Index are suitable, and for
example the radicals derived from the following dyes:
Basic Blue 17
Basic Red 2.
Among the triarylmethane chromophores A that can be
used according to the invention, mention may be made,
in addition to those listed in the Colour Index, of the
radicals derived from the following dyes:
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 indoamine chromophores A that can be used
according to the invention, mention may be made of the
radicals derived from the following dyes:
2-β-hydroxyethylamino-5- [bis (β-4' -hydroxyethyl) -
amino]anilino-1,4-benzoquinone
2-β-hydroxyethylamino-5-(2'-methoxy-4' -amino)-
anilino-1,4-benzoquinone
3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-
6-methoxy-1,4-benzoquinone imine
3-N-(3'-chloro-4'-methylamino)phenylureido-6-methyl-
1,4-benzoquinone imine
3-[4' -N-(ethylcarbamylmethyl)amino]phenylureido-
6-methyl-1,4-benzoquinone imine.
Mention may also be made of the chromophores described
in documents US 5888252, EP 1133975, WO 03/029359,
EP 860636, WO 95/01772, WO 95/15144 and EP 714954.
Mention may also be made of those listed in the
encyclopedia "The chemistry of synthetic dye" by
K. Venkataraman, 1952, Academic Press vol. 1 to 7, in

the encyclopedia "Kirk Othmer" "Chemical technology",
chapter "Dyes and Dye Intermediate", 1993, Wiley and
Sons, and in various chapters of the encyclopedia
"Ullmann's Encyclopedia of Industrial Chemistry"
7th edition, Wiley and Sons.
Preferably, the chromophores A are chosen from those
derived from dyes of azo, anthraquinone and hydrazone
type.
Preferably, the fluorescent chromophores A are chosen
from those derived from dyes of coumarin, (poly)methine
(in particular cyanin and styryl/hemicyanin) and
naphthalimide type.
According to one variant, A of formula (I) contain at
least one cationic radical borne by or included in at
least one of the chromophores.
Preferably, the cationic radical is a quaternary
ammonium.
These cationic radicals are, for example, an alkyl-
ammonium, acridinium, benzimidazolium, benzobistria-
zolium, benzopyrazolium, benzopyridazinium, benzoquino-
lium, benzothiazolium, benzotriazolium, benzoxazolium,
bipyridinium, bistetrazolium, dihydrothiazolium,
imidazopyridinium, imidazolium, indolium, isoquinolium,
naphthoimidazolium, naphthooxazolium, naphthopyrazolium,
oxadiazolium, oxazolium, oxazolopyridinium, oxonium,
phenazinium, phenooxazolium, pyrazinium, pyrazolium,
pyrazoyltriazolium, pyridinium, pyridinoimidazolium,
pyrrolium, pyrylium, quinolium, tetrazolium, thia-
diazolium, thiazolium, thiazolopyridinium, thiazoyl-
imidazolium, thiopyrylium, triazolium or xanthylium
radical.
Examples of cationic chromophores A that can be used in
the present invention have been mentioned above. Other

examples are given in patent applications WO 95/01772,
WO 95/15144, EP 714954, EP 318294 and WO 03/029359.
According to a specific embodiment, the radicals A, A'
in formula (I) or (II) comprise at least one cationic
azo chromophore, described, for example, in EP 850636,
FR 2788433, EP 920856, WO 9948465, FR 2757385,
EP 850637, EP 918053, WO 9744004, FR 2570946,
FR 2285851, DE 2538363, FR 2189006, FR 1560664,
FR 1540423, FR 1567219, FR 1516943, FR 1221122,
DE 4220388, DE 4137005, WO 0166646, US 5708151,
WO 9501772, WO 515144, GB 1195386, US 3524842,
US 5879413, EP 1062940, EP 1133976, GB 738585,
DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem.
(1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5;
Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chim.
(Rome) (1975), 65(5-6), 305-14; Journal of the Chinese
Chemical Society (Taipei) (1998), 45(1), 209-211; Rev.
Roum. Chim. (1988), 33(4), 377-83; Text. Res. J.
(1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9),
600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger.
Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res.
Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence
(1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1), 69-79;
Dyes Pigm. (1989), 11(3), 163-72.
Preferably, the chromophores are chosen from those
derived from dyes of azo, azomethine and cyanin type
(such as azacarbocyanin, diazacarbocyanin, diaza-
hemicyanin/hydrazone, hemicyanin/styryl dyes) .
According to one variant of the invention, the dyes of
formula (I) are cationic dyes comprising at least one
quaternary ammonium radical A which represents:

with:
W representing a heteroaryl, comprising a quaternary

ammonium, optionally substituted preferably with one or
more (C1-C4) alkyl groups;
Ar represents i) a 5- or 6-membered (hetero)aryl radical
of phenyl or pyridium type, or ii) a (hetero)aromatic
bicycle of naphthyl, benzopyridinyl, indolinyl or
benzoindolinyl type, optionally substituted with one or
more halogen atoms, preferably chlorine or fluorine;
with one or more preferably C1-C4 alkyl groups; with one
or more hydroxyl groups; with one or more alkoxy
groups, with one or more hydroxyalkyl groups, with one
or more amino or (di)alkylamino groups, preferably with
the alkyl part being C1-C4;
Z representing an oxygen or sulfur atom, or a group NR'
with R' representing a (hydroxy)(C1-C4)alkyl group.
According to another specific embodiment of the inven-
tion, the cationic fluorescent dyes of the invention of
formula (I) comprise at least one fluorescent chromo-
phore and a quaternary ammonium radical:
A represents:

with:
W representing a heterocycle or a heteroaryl, compris-
ing a quaternary ammonium;
Ar represents i) a 5- or 6-membered (hetero)aryl radical
of phenyl or pyridinium type, or ii) a (hetero)aromatic
bicycle of naphthyl, benzopyrydinium, indolinyl or
benzoindolinyl type, optionally substituted with one or
more halogen atoms, preferably chlorine or fluorine;
with one or more preferably C1-C4 alkyl groups; with one
or more hydroxyl groups; with one or more alkoxy
groups, with one or more hydroxyalkyl groups, with one
or more amino or (di)alkylamino groups, preferably with
the alkyl part being C1-C4, with one or more acylamino
groups; with one or more heterocycloalkyl or heteroaryl
groups comprising 5 or 6 members, preferably chosen
from pyrrolidinyl, piperazinyl, piperidinyl and

imidazolinyl;
Rc, Rd, which may be identical or different, represent a
hydrogen atom or a C1-C4 alkyl group;
Z representing an oxygen or sulfur atom, or a group NR'
with R' representing a (hydroxy)(C1-C4)alkyl group.
According to a specific embodiment, Z is in the para-
position on Ar relative to the azo function or of the
double bond -C (Rc) =C (Rd)-.
Another specific embodiment of the invention relates to
the dyes of formula (I) for which p is 0. Another
embodiment relates to the dyes of formula (I) for which
p is 1.
According to a specific embodiment of the invention,
the dyes of formula (I) are such that Y represents a
carbonyl group, L' represents a C2-C6 alkylene, such as
ethylene, or arylene, such as phenylene, group
optionally interrupted with 1 or 2 heteroatoms such as
oxygen and optionally terminated at each of its ends
with a heteroatom, such as oxygen, or NR with R
representing a hydrogen atom or a (C1-C4)alkyl group.
By way of example, mention may be made of the dyes of
formula (I) :



with An representing an anionic counterion.
For all the exemplary embodiments, which follow, for
preparation of the novel dyes of formula (I), those
skilled in the art know how to pre-protect the reactive
functions such as ketone functions and then to
deprotect them for the needs of the synthesis reaction,
by the known conventional methods of
protection/deprotection such as those described in the
books mentioned above by T.W. Greene John Willey & Sons
ed., NY, 1981, or P. Kocienski "Protecting Croups",
P. Kocienski, Thieme, 3rd ed., 2005.
These dyes can be prepared according to methods known
to those skilled in the art, such as, for example,
"Colour Chemistry, Heinrich Zollinger, Wiley-VCH,
Weinheim, 2003".
According to a first possibility, a compound C1

comprising at least two nucleophilic functions Nu can
be reacted with a sufficient amount of a "reactive
chromophore A" or of a compound comprising such a
"reactive chromophore", in other words comprising an
electrophilic function E, so as to form a covalent bond
or a divalent linking group 2:

with Nu representing a nucleophilic group; E represent-
ing an electrophilic group; A, Y, L, L', Csat, P and p'
as defined above, and, by way of example, the covalent
bonds or divalent groups 2 that can be generated are
listed in the table below based on condensation of
electrophiles with nucleophiles:
Electrophiles E Nucleophiles Nu 2 Covalent bonds
Activated esters* Amines Carboxamides
Acyl nitrides** Amines Carboxamides
Acyl halides Amines Carboxamides
Acyl halides Alcohols Esters
Acyl cyanides Alcohols Esters
Acyl cyanides Amines Carboxamides
Alkyl halides Amines Alkylamines
Alkyl halides Carboxylic acids Esters
Alkyl halides Thiols Thioesters
Alkyl halides Alcohols Ethers
Sulfonic acids and Thiols Thioethers
salts thereof
Sulfonic acids and Carboxylic acids Esters
salts thereof
Sulfonic acids and Alcohols Ethers
salts thereof
Anhydrides Alcohols Esters
Anhydrides Amines Carboxamides
Aryl halides Thiols Thioethers
Aryl halides Amines Arylamines

Aziridines Thiols Thioethers
Carboxylic acids Amines Carboxamides
Carboxylic acids Alcohols Esters
Carbodiimides Carboxylic acids N-acylureas
Diazoalkanes Carboxylic acids Esters
Epoxides Thiols Thioethers
Haloacetamides Thiols Thioethers
Imide esters Amines Amidines
Isocyanates Amines Ureas
Isocyanates Alcohols Urethanes
Isothiocyanates Amines Thioureas
Maleimides Thiols Thioethers
Sulfonic esters Amines Alkylamines
Sulfonic esters Thiols Thioethers
Sulfonic esters Carboxylic acids Esters
Sulfonic esters Alcohols Ethers
Sulfonyl halides Amines Sulfonamides
*the activated esters of general formula -CO-Part
with Part representing a leaving group such as
oxysuccinimidyl, oxybenzotriazolyl, aryloxy which
is optionally substituted;
**the acyl nitrides may rearrange to give
isocyanates.
Reference may be made especially to the book Advanced
Organic Chemistry, J. March, 4th Ed., John Willey &
Sons, 1992.
In accordance with other variants, it is possible to
synthesize the dyes of the invention according to the
following reaction schemes:

with A, Y, L, L', p, p', Csat, £, Nu and E as defined
above;


with A, Y, L, L', p, p', Csat and Σ as defined above; Lg
represents a nucleofuge leaving group such as halide,
in particular bromide or chloride, mesylate or
tosylate;

with A, Y, L, L', p, p', Csat, Σ, Nu and E as defined
above; '

with Y' representing a thiol-function-protecting group,
and A, L, p, CSat, Σ, Nu and E as defined above;

with A, Y, L, L', p, p', Csat, Lg and Σ as defined
above.
Another subject of the invention relates to a
composition comprising at least one dye of formula (I).
In addition to the presence of at least one dye of
formula (I), the composition of the invention may also
contain a cosmetically acceptable acidic or basic
agent; in particular a basic agent.
The pH of the dye composition is generally between 5
and 12 approximately, preferably between 9 and 11. It
can be adjusted to the desired value by means of
acidifying or basifying agents as defined below,
normally used in the dyeing of keratin fibers, or
alternatively using conventional buffer systems.

Among the cosmetically acceptable acidic or acidifying
agents, mention may be made of mineral or organic acids
such as hydrochloric acid HC1, hydrobromic acid HBr,
sulfuric acid H2SO4, phosphoric acid H3PO4,
alkylsulfonic acids: Alk-S(O)2OH such as methylsulfonic
acid and ethylsulfonic acid, arylsulfonic acids: Ar-
S(O)2OH such as benzenesulfonic acid and
toluenesulfonic acid, citric acid, succinic acid;
tartaric acid; lactic acid; alkoxysulfinic acids: Alk-
O-S(O)OH such as methoxysulfinic acid and
ethoxysulfinic acid; aryloxysulfinic acids such as
tolueneoxysulfinic acid and phenoxysulfinic acid;
carboxylic acids such as acetic acid CH3C(O)OH,
tartaric acid, citric acid, lactic acid, triflic acid;
CF3SO3H and tetrafluoroboric acid HBF4.
Among the cosmetically acceptable basic or basifying
agents, mention may be made, by way of example, of
aqueous ammonia, alkali metal carbonates, alkanolamines
such as mono-, di- and triethanolamines and also
derivatives thereof, sodium hydroxide or potassium
hydroxide, and the compounds of formula (y) below:

in which Wa is a propylene residue optionally
substituted with a hydroxyl group or a C1-C4 alkyl
radical; Ral, Ra2, Ra3 and Ra4, which may be identical or
different, represent a hydrogen atom, or a C1-C4 alkyl
or C1-C4 hydroxyalkyl radical.
The dye composition that can be used in the invention
generally contains an amount of dye of formula (I) of
between 0.001% and 50% relative to the total weight of
the composition. Preferably, this amount is between
0.005% and 20% by weight, and even more preferably

between 0.01% and 5% by weight, relative to the total
weight of the composition.
The dye composition may also contain additional direct
dyes. These direct dyes are, for example, chosen from
neutral, acidic or cationic nitrobenzene direct dyes,
neutral, acidic or cationic azo direct dyes,
tetraazapentamethine dyes, neutral, acidic or cationic
guinone, in particular anthraguinone dyes, azine direct
dyes, triarylmethane direct dyes, indoamine direct dyes
and natural direct dyes.
Among the natural direct dyes, mention may be made of
lawsone, juglone, alizarin, purpurin, carminic acid,
kermesic acid, purpurogallin, protocatechaldehyde,
indigo, isatin, curcumin, spinulosin and apigenindin.
Extracts or decoctions containing these natural dyes,
and in particular poultices or henna-based extracts,
may also be used.
The dye composition may contain one or more oxidation
bases and/or one or more couplers conventionally used
for dyeing keratin fibers.
Among the oxidation bases, mention may be made of para-
phenylenediamines, bisphenylalkylenediamines, para-
aminophenols, bis-para-aminophenols, orthoaminophenols,
heterocyclic bases, and addition salts thereof.
Among these couplers, mention may in particular be made
of meta-phenylenediamines, meta-aminophenols, meta-
diphenols, naphthalene couplers, heterocyclic couplers,
and addition salts thereof.
The coupler(s) is (are) each generally present in an
amount of between 0.001% and 10% by weight of the total
weight of the dye composition, preferably between
0.005% and 6%.

The oxidation base(s) present in the dye composition is
(are) in general each present in an amount of between
0.001% and 10% by weight of the total weight of the dye
composition, preferably between 0.005% and 6% by
weight.
In general, the addition salts of the oxidation bases
and of the couplers that can be used in the context of
the invention are in particular chosen from addition
salts with an acid, such as hydrochlorides, hydro-
bromides, sulfates, citrates, succinates, tartrates,
lactates, tosylates, benzenesulfonates, phosphates and
acetates, and addition salts with a base, such as
hydroxides of an alkali metal such as sodium or
potassium, aqueous ammonia, amines or alkanolamines.
The medium suitable for dyeing, also called dye
support, is a cosmetic medium generally containing
water or a mixture of water and at least one organic
solvent. By way of organic solvent, mention may, for
example, be made of C1-C4 lower alkanols, such as
ethanol and isopropanol; polyols and polyol ethers,
such as 2-butoxyethanol, propylene glycol, propylene
glycol monomethyl ether, diethylene glycol monoethyl
ether and diethylene glycol monomethyl ether, and also
aromatic alcohols such as benzyl alcohol or
phenoxyethanol, and mixtures thereof.
The solvents, when they are present, are preferably
present in proportions of preferably between 1% and 99%
by weight approximately, relative to the total weight
of the dye composition, and even more preferably
between 5% and 95% by weight approximately.
The dye composition may also contain various adjuvants
conventionally used in hair-dyeing compositions, such
as anionic, cationic, nonionic, amphoteric or
zwitterionic surfactants or mixtures thereof, anionic,
cationic, nonionic, amphoteric or zwitterionic polymers,

or blends thereof, mineral or organic thickeners, and
in particular anionic, cationic, nonionic and ampho-
teric associative polymer thickeners, antioxidants,
penetrating agents, sequestering agents, fragrances,
buffers, dispersing agents, conditioning agents such
as, for example, modified or unmodified, volatile or
nonvolatile silicones, such as amino silicones, film-
forming agents, ceramides, preservatives, opacifiers or
conductive polymers.
The above adjuvants are in general present in an
amount, for each of them, of between 0.01% and 20% by
weight relative to the weight of the composition.
Of course, those skilled in the art will take care to
select this or these possible additional compounds in
such a way that the advantageous properties
intrinsically associated with the dye composition in
accordance with the invention are not, or are not
substantially, impaired by the addition (s) envisaged.
The dye composition may be in various forms, such as in
the form of a liquid, a cream or a gel, or in any other
form suitable for dyeing keratin fibers, and in
particular the hair.
Another subject of the invention is a dyeing process
consisting in applying a cosmetic composition compris-
ing at least one dye of formula (I) as defined above to
the keratin fibers, optionally in the presence of an
acidic or basic agent, preferably a basic agent.
The process for dyeing keratin fibers, in particular
dark keratin fibers, according to the invention
consists in applying, to the keratin materials, a dye
composition comprising, in a suitable cosmetic medium,
at least one dye of formula (I) or at least one
fluorescent dye of formula (I).

According to a specific embodiment, in the process of
the invention, the basic agent is applied as a
post-treatment after the application of the composition
containing at least one dye of formula (I).
This post-treatment may be of short duration, in
particular from 1 second to 30 minutes, preferably from
1 minute to 15 minutes, with an acidic or basic agent.
According to a specific embodiment, in the process of
the invention, the basic agent is applied at the same
time as the application of the composition containing
at least one dye of formula (I).
According to another specific embodiment, in the
process of the invention, a reducing agent is applied
as post-treatment after the application of the
composition containing at least one dye of formula (I).
According to another specific embodiment, in the
process of the invention, a reducing agent is applied
as a pretreatment before the application of the
composition containing at least one dye of formula (I).
According to another specific embodiment, in the
process of the invention, a reducing agent is applied
at the same time as the composition containing at least
one dye of formula (I).
This reducing agent may be chosen from thiols, for
example cysteine, homocysteine or thiolactic acid, the
salts of these thiols, phosphines, bisulfite, sulfites,
thioglycolic acid, and also its esters, in particular
glyceryl monothioglycolate, and thioglycerol. This
reducing agent may also be chosen from borohydrides and
derivatives thereof, for instance the salts of
borohydride, of cyanoborohydride, of triacetoxyboro-
hydride or of trimethoxyborohydride: sodium salts,
lithium salts, potassium salts, calcium salts,

quaternary ammonium (tetramethylammonium, tetraethyl-
ammonium, tetra-n-butylammonium or benzyltriethyl-
ammonium) salts; and catechol borane.
A specific embodiment of the invention relates to a
process in which the fluorescent dye of formula (I) is
applied directly to the hair without reducing agents,
free of acidic or basic post-treatment.
A treatment with an oxidizing agent may optionally be
combined. Preferably the process of dyeing keratin
fibers according to the invention comprises an
additional step consisting in applying an oxidizing
agent to the keratin fibers. Any type of oxidizing
agent conventional in the field may be used. Thus, it
may be chosen from hydrogen peroxide, urea peroxide,
alkali metal bromates, persalts such as perborates and
persulfates, and also enzymes, among which mention may
be made of peroxidases, 2-electron oxidoreductases such
as uricases and 4-electron oxygenases such as laccases.
The use of hydrogen peroxide is particularly preferred.
The duration of such treatment is between 1 second and
40 minutes, preferably between 15 seconds and
15 minutes.
The application of the dye composition according to the
invention is generally carried out at ambient
temperature. It may, however, be carried out at
temperatures ranging from 20 to 180°C.
A subject of the invention is also a multicompartment
dyeing device or dyeing "kit" in which a first
compartment contains a dye composition comprising at
least one of formula (I) and a second compartment
contains a cosmetically acceptable acidic or basic
agent capable of freeing the thiol function of the
heterocyclic or carbonyl linker.
One of these compartments may also contain one or more

other dyes of direct dye or oxidation dye type.

The invention also relates to a multicompartment device
in which a first compartment contains a dye composition
comprising at least one dye of formula (I); a
cosmetically acceptable acidic or basic agent capable
of freeing the thiol function of the carbonyl or
heterocyclic linker; and a third compartment contains
an oxidizing agent.
Each of the devices mentioned above may be equipped
with a means for delivering the desired mixture to the
hair, for example such as the devices described in
patent FR 2 586 913.
The examples which follow serve to illustrate the
invention without, however, being limiting in nature
but in the limit of the scope of the object claimed.
The dyes of the examples hereinafter have been entirely
characterized by conventional spectroscopic and
spectrometric methods.
EXAMPLES
SYNTHESIS EXAMPLES
Example 1: Synthesis of 1,1'-[(1,4-Dioxobutane-1,4-
diyl)bis(sulfanediylethane-2,1-diyl)]bis(4-
{[methyl(phenyl)hydrazono]methyl}pyridinium)
dichloride [1]

Synthesis scheme


Procedure
Stage 1: Synthesis of 4-{[methyl(phenyl)hydrazono]-
methyl}-1-(2-sulfanylethyl)pyridinium
chloride
1 g of compound [a] is dissolved in 50 ml of a 1/1
mixture of water/ethanol. 2 eq. of 3-[bis(2-carboxy-
ethyl)phosphino]propanoic acid hydrochloride hydrate in
solution in 20 ml of water and 4 eq. of sodium
bicarbonate in solution in 10 ml of water are added to
the mixture. After stirring for 30 minutes at 40°C
under an inert atmosphere, the reaction mixture is
poured into 2-propanol and the yellow precipitate is
filtered off.
Stage 2: Synthesis of 1,1'-[(1,4-dioxobutane-1,4-
diyl)bis(sulfanediylethane-2,l-diyl)]bis(4-
{[methyl(phenyl)hydrazono]methyl}pyridinium)
dichloride [1]
200 mg of compound [b] and 2 eq. of trimethylamine are
diluted in 10 ml of N-methylpyrrolidinone (NMP). At
0°C, 0.5 eq. of succinyl chloride (CAS 543-20-4)
diluted in 5 ml of NMP (anhydrous) is added dropwise to
the reaction medium with vigorous stirring. The
stirring is continued at ambient temperature for 6 h
and the reaction mixture is then poured into 2-propanol
and the yellow precipitate is filtered off.

Example 2: Synthesis of 4,4'-{1,4-phenylenebis[carbon-
ylsulfanediylethane-2,1-diyl(methylimino)-4,1-
phenyleneethene-2,1-diyl]}bis(1-methyl-
pyridinium) bis(methyl) sulfate [2]

Procedure
500 mg of compound [C] and 2 eq. of trimethylamine are
diluted in 25 ml of N-methylpyrrolidinone (NMP). At
0°C, 0.5 eq. of dithioterephthalic acid [D] (CAS 1076-
98-8) diluted in 5 ml of NMP (anhydrous) is added
dropwise to the reaction medium with vigorous stirring.
The stirring is continued at ambient temperature for
4 h and the reaction mixture is then poured into
2-propanol and the bright orange precipitate is
filtered off. The analyses indicate the expected
product [2] .

DYEING EXAMPLES
The dye compositions were prepared in the following
proportions

The dye compositions are obtained by dissolving dye [1]
or [2] indicated above (5 x 10-3 mol/1) in solution 1
and then adding an equivalent volume of buffer solution
2.
Each composition is applied to bleached hair (SA40),
natural gray hair comprising 90% white hairs,
permanent-waved gray hair comprising 90% white hairs
(1 g of lock per 6 g of solution) and dark hair (TH4) .
After a leave-in time of 30 min, the locks are rinsed.
Next, solution 3 is applied to bleached hair (SA40),
natural gray hair comprising 90% white hairs,
permanent-waved gray hair comprising 90% white hairs
and dark hair (TH4) (1 g of lock per 6 g of solution)
and the hair is heated to 45°C. After a leave-in time
of 60 min, the locks are rinsed, washed with a standard
shampoo, rinsed again, and then dried.


The following dyeing results were obtained

Lightening of TH4 keratin fibers:
Lightening of the hair thus treated with dye 2 is
observed: the locks of tone height 4 became visually
lighter than untreated control locks.
Fastness with respect to successive shampooing
operations:
The locks thus treated are divided into two; half are
subjected to 5 successive shampooing operations
according to a cycle which comprises wetting the locks
with water, washing with shampooing operations
(conventional shampoo), rinsing with water, followed by
drying.
Visual observations
During the shampooing operations, there is little
visible bleeding of the color; the shampoo foam and the
rinsing water are virtually uncolored.

The color observed on the locks is retained and the
lightening effect remains visible on the hair of tone
height 4 thus treated.

WE CLAIM :
1. A dye of formula (I):

the organic or mineral acid salts, optical isomers
and geometric isomers thereof, and the solvates
such as hydrates:
in which formula (I):
• A represents a radical containing at least one
chromophore which is optionally cationic, colored,
or colored and fluorescent;
• L and L' , which may be identical or different,
represent:
o a saturated or unsaturated, linear or branched
C1-C20 hydrocarbon-based chain which is optionally
substituted, optionally interrupted and/or
optionally terminated at one or both of its ends
with one or more divalent groups or combinations
thereof chosen from -N(R)-, -O-, -S-, -C(O)- and
-SO2-, with R, R' , which may be identical or
different, being chosen from a hydrogen, and a
C1-C4 alkyl, hydroxyalkyl and aminoalkyl radical;
it being understood that said combination cannot
form a disulfide bond -S-S-;
o an arylene group,
o a heteroarylene group,
o a cycloalkylene group, or
0 a heterocycloalkylene group;
• Y represents a carbonyl group -C(O)- or a
heteroaryl group, which is cationic or
noncationic, which comprises 5-13 members, which
is optionally substituted, and which comprises
from 1 to 5 heteroatoms chosen from oxygen, sulfur
or nitrogen atoms;
• p and p', which may be identical or different,
represent an integer equal to 0 or 1;
• Csat represents an optionally substituted, linear
or branched C1-C18 alkylene chain.

2. The fluorescent dye of formula (I) as claimed in
the preceding claim, in which the chromophore A
represents:

with:
W representing a heteroaryl, comprising a quaternary
ammonium, optionally substituted preferably with one or
more (C1-C4) alkyl groups;
Ar represents i) a 5- or 6-membered (hetero)aryl radical
of phenyl or pyridium type, or ii) a (hetero)aromatic
bicycle of naphthyl, benzopyridinyl, indolinyl or
benzoindolinyl type, optionally substituted with one or
more halogen atoms, with one or more alkyl groups, with
one or more hydroxyl groups, with one or more alkoxy
groups, with one or more hydroxyalkyl groups, with one
or more amino or (di)alkylamino groups;
Z representing an oxygen or sulfur atom, or a group NR'
with R' representing a (hydroxy)(C1-C4)alkyl group.
3. The fluorescent dye of formula (I) as claimed in
claim 1, in which the chromophore A represents:

with:
W representing a heterocycle or a heteroaryl, compris-
ing a quaternary ammonium;
Ar represents i) a 5- or 6-membered (hetero)aryl radical
of phenyl or pyridinium type, or ii) a (hetero)aromatic
bicycle of naphthyl, benzopyrydinium, indolinyl or
benzoindolinyl type, optionally substituted with one or
more halogen atoms, with one or more alkyl groups, with
one or more hydroxyl groups; with one or more alkoxy
groups, with one or more hydroxyalkyl groups, with one
or more amino or (di) alkylamino groups, with one or
more acylamino groups; with one or more
heterocycloalkyl or heteroaryl groups comprising 5 or 6
members;

Rc, Rd, which may be identical or different, represent a
hydrogen atom or a C1-C4 alkyl group;
Z representing an oxygen or sulfur atom, or a group NR'
with R' representing a (hydroxy)(C1-C4)alkyl group.
4. The dye of formula (I) as claimed in any one of
the preceding claims, in which Z is in the para-
position on Ar relative to the azo function or of the
double bond -C (Rc) =C (Rd) -.
5. The fluorescent dye of formula (I) as claimed in
any one of the preceding claims, such that Y represents
a carbonyl group, L' represents a C2-C6 alkylene or
arylene group, optionally interrupted with 1 or 2
heteroatoms and optionally terminated at each of its
ends with a heteroatom, such as oxygen, or NR with R
representing a hydrogen atom or a (C1-C4) alkyl group.
6. The fluorescent dye of formula (I) as claimed in
any one of the preceding claims, chosen from the
following dyes:
r\


7. A dye composition comprising, in a suitable
cosmetic medium, a dye of formula (I) as defined in any
one of claims 1 to 6.
8. The dye composition as claimed in the preceding
claim, comprising, in a suitable cosmetic medium:
o at least one dye of formula (I) as defined in
any one of claims 1 to 6;
o and at least one cosmetically acceptable
basic agent.
9. A process for dyeing keratin materials, in which a
suitable dye composition comprising at least one dye of
formula (I) as claimed in any one of claims 1 to 6 is
applied to the materials.
10. The process for dyeing keratin materials as
claimed in the preceding claim, wherein the keratin
materials are dark keratin fibers having a tone height
of less than or equal to 6.
11. The process as claimed in either one of claims 9
and 10, in which the acidic or basic agent is applied
after the application of the dye of formula (I) as
defined in claims 1 to 6.
12. The process as claimed in any one of claims 9 to
11, in which the composition comprises an oxidizing
agent.

13. A multicompartment device in which a first
compartment contains a dye composition comprising a dye
of formula (I) as defined in claims 1 to 6, and a
second compartment contains a basic agent.
14. The use of the dye of formula (I) as defined in
claims 1 to 6, for dyeing human keratin fibers
particularly dark keratin fiber having a tone height of
less than 6.
15. The use of the fluorescent dye of formula (I) as
claimed in any one of claims 1 and 3 to 6, for
lightening dark keratin fibers particularly having a
tone height of less than 6.

The invention relates to the dyeing of keratin materials using dichromophore dyes with a
carbonyl or heterocyclic linker. The invention relates to a dye composition comprising a
dye with a carbonyl or heterocyclic linker, and to a dyeing process with a lightening
effect on keratin materials, in particular keratin fibers, especially human keratin fibers
such as the hair, using said composition, optionally in the presence of a cosmetically
acceptable acid or base. It similarly relates to novel dyes and to the uses thereof in
lightening keratin materials. This composition makes it possible to obtain a coloring with
a lightening effect which is particularly resistant and visible on dark keratin fibers.