AZOMETHINE DIRECT DYES OR REDUCED PRECURSORS OF THESE
DYES OBTAINED FROM 2-CHLORO-3-AMINO-6-METHYLPHENOL, AND
HAIR DYEING METHOD STARTING FROM THESE DYES AND
PRECURSORS
The invention relates to the dyeing of keratinous
fibres using azomethine direct dyes or reduced
precursors of azomethine direct dyes obtained from 2-
chloro-3-amino-6-methylphenol.
It is known to dye keratinous fibres and in
particular the hair, with dyeing compositions
comprising direct dyes, according to a "direct dyeing"
method.
The method conventionally used in direct dyeing
consists in applying, to the keratinous fibres, direct
dyes or colouring molecules having affinity for the
said fibres, in leaving them to stand and then rinsing
the fibres. The direct dyes used to date are
nitrobenzene dyes, anthraquinones, nitropyridines or
dyes of azo, xanthene, acridine, azine or
triarylmethane benzene derivative type.
Other dyes result from oxidation bases and oxidation
couplers which, once condensed, are applied to the
hair. For example, in the documents FR 233 036,
FR 2 262 022, FR 2 262 024, US 4,221,729 and
FR 2 261 750, diphenylamines, such as leuco derivatives
of indophenols, of indamine and of indoaniline, are
used, either alone or in combination with other dyes,
in dyeing compositions. Other compounds corresponding
to oxidized derivatives of leuco derivatives, such as
those described in the documents FR 2 254 557 and
FR 2 234 277, are also known to dye keratinous fibres.
The colourings which result from direct dyeings are
temporary or semi-permanent colourings, as the nature
of the interactions which bind direct dyes to the

keratinous fibre and their desorption from the surface
and/or from the core of the fibre are responsible for
their low dyeing power and for their poor hold with
regard to washing operations or to perspiration. In
addition, these direct dyes are generally sensitive to
the action of oxidizing agents, such as aqueous
hydrogen peroxide solution, which renders them
generally unusable in lightening direct dyeing
compositions based on aqueous hydrogen peroxide
solution and on a basifying agent, which will be
similar to oxidation dyeings.
Direct dyes also exhibit a certain lack of stability
towards light related to the low resistance of the
chromophore with regard to photochemical attacks. In
addition, their sensitivity to light is dependent on
the distribution of their molecules, uniform or
aggregated, in the" substrate.
Consequently, there exists a real need to find direct
dyes which make it possible to dye keratinous fibres,
which are stable towards light, which are also
resistant to bad weather, to washing operations and to
perspiration, and which are sufficiently stable in the
presence of oxidizing agents, such as aqueous hydrogen
peroxide solution, to be able to obtain simultaneous
lightening of the fibre with the advantages set out
above, while exhibiting an improved toxicological
profile compatible with cosmetic use on keratinous
fibres.
These aims are achieved with the present invention, a
subject-matter of which is a method for dyeing
keratinous fibres starting from the direct dyes of
formula (I):


their organic or inorganic acid salts, their
geometrical isomers, their tautomers and their
solvates, such as hydrates;
in which formula (I):
• R1 represents:
- a chlorine atom;
- a (C1-C3) alkyl radical optionally substituted by
one or more hydroxyl groups;
- a (C1-C3)alkoxy radical optionally substituted by
one or more hydroxyl groups;
• X represents:
a hydroxyl radical;
an -NR4R5 radical with R4 and R5 representing,
independently of one another:
i) a hydrogen atom;
ii) a C1-C5 alkyl radical optionally
substituted by one or more groups chosen
from hydroxyl, (C1-C3)alkoxy, amino, (C1-
C3)alkylamino, di (C1-C3) alkylamino,
aminocarbonyl, carboxyl -COOH,
sulpho -SO3H, tri (C1-C3) alkylammonio and
(C1-C3)alkylimidazolio;
a pyrrolidinyl radical optionally substituted by
a group chosen from hydroxyl, (C1-C3)alkoxy,
amino, (C1-C3) alkylamino, di (C1-C3) alkylamino,
tri (C1-C3) alkylammonio and (C1-
C3)alkylimidazolio;
a piperidinyl radical optionally substituted by

-1
a group chosen from hydroxyl, (C1-C3) alkoxy,
amino, (C1-C3) alkylamino, di(C1-C3) alkylamino,
tri(C1-C3)alkylammonio and (C1-
C3)alkylimidazolio;
• n represents an integer between 0 and 3 inclusive;
• R2 and R3, which are identical or different, are as
defined for R4 and R5;
it being understood that, when X and/or R2 and/or R3
and/or R4 and/or R5 comprise a cationic group, the
electrical neutrality of the compounds of formula (I)
is brought about by a cosmetically acceptable anionic
counterion or a mixture of cosmetically acceptable
anionic counterions, such as, for example, chlorides,
bromides and sulphates.
Another subject-matter of the invention is a dyeing
method starting from colourless reduced precursors of
chlorinated azomethine dyes which, once oxidized,
generate the compounds of formula (I) as defined above.
These precursors correspond to the compounds of formula
(II):

their organic or inorganic acid • salts, their
geometrical isomers, their tautomers and their
solvates, such as hydrates;
in which formula (II) R1, R2, R3, X and n are as defined
above;
it being understood that:
- when X and/or R2 and/or R3 and/or R4 and/or R5 comprise

a cationic group, the electrical neutrality of the
compounds of formula (II) is brought about by a
cosmetically acceptable anionic counterion or a
mixture of cosmetically acceptable anionic
counterions, such as, for example, chlorides, bromides
and sulphates.
Another subject-matter of the invention is a compound
of formula (I) or (II) as defined above.
Another subject-matter of the invention is a dyeing
composition for the dyeing of keratinous fibres
comprising, in a cosmetic medium, at least one compound
of formula (I) or (II) as defined above.
The direct dyes of formula (I) make it possible to
overcome the disadvantages of the direct dyes
conventionally used previously and result in dyeings by
direct dyeing which have very good resistance to light,
to bad weather, to washing operations, to perspiration
and to rubbing actions. Their good stability with
regard to oxidizing agents, such as aqueous hydrogen
peroxide solution, also makes it possible to use them
in a lightening direct dyeing method.
Furthermore, it has been discovered that the reduced
form of the azomethine derivatives obtained from 2-
chloro-3-amino-6-methylphenol derivatives of formula
(II) , used under oxidizing conditions, can also result
in colourings having very good resistance to light, to
bad weather, to washing operations, to perspiration and
to rubbing actions.
Within the meaning of the present invention and
unless otherwise indicated:
an "organic or inorganic acid salt" is, for

example, chosen from a salt derived i) from
hydrochloric acid HC1, ii) from hydrobromic acid
HBr, iii) from sulphuric acid H2SO4, iv) from
alkylsulphonic acids: Alk-S(O)2OH, such as
methylsulphonic acid and ethylsulphonic acid; v)
from arylsulphonic acids: Ar-S(O)2OH, such as
benzenesulphonic acid and toluenesulphonic acid;
vi) from citric acid; vii) from succinic acid;
viii) from tartaric acid; ix) from lactic acid;
x) from alkoxysulphinic acids: Alk-O-S(O)OH,
such as methoxysulphinic acid and
ethoxysulphinic acid; xi) from aryloxysulphinic
acids, such as tolyloxysulphinic acid and
phenoxysulphinic acid; xii) from phosphoric acid
H3PO4; xiii) from acetic acid CH3C(O)0H; 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)
sulphonates, including C1-C6 alkylsulphonates:
Alk-S(O)2O_, such as methylsulphonate or
mesylate and ethylsulphonate; iv)
arylsulphonates: Ar-S(O)2O-, such as
benzenesulphonate and toluenesulphonate or
tosylate; v) citrate; vi) succinate; vii)
tartrate; viii) lactate; ix) alkyl sulphates:
Alk-O-S(O)O-, such as methyl sulphate and ethyl
sulphate; x) aryl sulphates: Ar-0-S(O)0~, such
as phenyl sulphate and tolyl sulphate; xi)
alkoxy sulphates: Alk-O-S (O) 2O-, such as methoxy
sulphate and ethoxy sulphate; xii) aryloxy
sulphates: Ar-O-S (O)2O-; xiii) phosphate; xiv)

acetate; xv) triflate; and xvi) borates, such as
tetrafluoroborate;
an "alkyl" radical is a saturated, linear or
branched, hydrocarbon radical comprising from 1
to 6 carbon atoms, particularly from 1 to 3
carbon atoms, such as the methyl or ethyl
radical;
an "alkoxy" radical is an "alkyl-oxy" alkyl-O-
radical in which the alkyl part is as defined
above;
the alkyl, alkoxy or heterocycloalkyl radicals
followed by "optionally substituted by ..."
means that the said radicals can have one or
more hydrogen atoms replaced by one or more
substituents in question, particularly one or
two substituents in question.
A subject-matter of the invention is direct dyes of
formula (I) or dyeing precursors of formula (II).
A specific embodiment of the invention relates to
compounds of formula (I) or (II) for which n has a
value zero.
According to another specific embodiment of the
invention, the compound or compounds of formula (I) or
(II) present in the composition according to the
invention are such that n has a value 1 and R1
represents a (C1-C3)alkyl group, such as methyl.
An alternative form relates to compounds of formula
(I) or (II) for which X represents a hydroxyl radical.
Another alternative form of the invention resorts to

compounds of formula (I) or (II) for which X represents
an -NR4R5 radical with R4 and R5 representing,
independently of one another, i) a hydrogen atom or ii)
a C1-C5 alkyl radical optionally substituted by one or
more groups chosen from hydroxyl, (C1-C3)alkoxy, amino,
(C1-C3)alkylamino, di(C1-C3)alkylamino, aminocarbonyl,
carboxyl -COOH, sulpho -SO3H, tri(C1-C3)alkylammonio and
(C1-C3)alkylimidazolio. More particularly, X represents
a group chosen from: i) (di) (C1-C3) (alkyl) amino; ii)
(di) [hydroxy (C1-C3) alkyl] amino; iii) (C1-
C3)alkylimidazolio(C1-C3)alkylamino; iv) [N-(C1-
C3) alkyl, N- (C1-C3) alkylimidazolio (C1-C3) alkyl] amino; v)
tri (C1-C3) alkylammonio (C1-C5) alkylamino and vi)
di [tri (C1-C3) alkylammonio (C1-C5) alkyl] amino .
According to another specific embodiment of the
invention, the compounds of formula (I) or (II) are
such that X represents a pyrrolidinyl group optionally
substituted by a tri (C1-C3) alkylammonio or (C1-
C3)alkylimidazolio group. More particularly, X
represents a pyrrolidino radical optionally substituted
by a tri (C1-C3) alkylammonio or (C1-C3) alkylimidazolio
group.
According to a specific embodiment, the compounds of
formula (I) or (II) are such that NR2R3 represents an
amino NH2 group.
Mention may be made, as example of the compounds of
formula (I) or (II) present in the composition
according to the invention, of the following dyes (la)
to (1t) and precursors (2a) to (2p) , and also their
organic or inorganic acid salts, their geometrical
isomers, their tautomers and their solvates, such as
hydrates:

with An-, which are identical or different, representing
an anionic counterion, such as halide; particularly. An-
represents a chloride.
More particularly, the dyes present in the
composition are chosen from the preceding dyes (la) ,
(1b), (1c), (1d), (1e), (1f), (1g) and (1i) and their
organic or inorganic acid salts, their geometrical
isomers, their tautomers and their solvates, such as
hydrates. According to another specific form of the
invention, the preferred compounds are the compounds
(1m) and (1p).
The compounds of formula (I) or (II) of the
invention are prepared according to the following
general synthetic routes:
1- Access to the compounds corresponding to the
formula (I);
The compounds corresponding to the formula (I) are
obtained in the general way by reacting 2-chloro-3-
amino-6-methylphenol derivatives with a para-
aminophenol derivative (X=OH) or a para-
phenylenediamine derivative (X= -NR4R5) , preferably in a
basic medium, in the presence of an oxidizing agent.

The base used is preferably an aqueous ammonia or
sodium hydroxide solution and the oxidizing agent is
preferably chosen from aqueous hydrogen peroxide
solution, potassium ferricyanide, air, ammonium
persulphate and manganese oxide.
n

Similar synthetic approaches are described in Patents
FR 2 234 277, FR 2 047 932, FR 2 106 661 and
FR 2 121 101.
2- Access to the compounds corresponding to the
formula (II):
The compounds corresponding to the formula (II) are
obtained in a general way by reacting the compounds of
formula (I) with a reducing agent. This preferred
reducing agent is sodium hydrosulphite.

Similar synthetic approaches are described in Patents
FR 2 056 799, FR 2 047 932, FR 2 165 965 and
FR 2 262 023.
Another subject-matter of the invention relates to a
dyeing composition for dyeing keratinous fibres, in
particular human keratinous fibres, such as the hair,
comprising, in a cosmetic medium, direct dyes of
formula (I) or dyeing precursors of formula (II).

The dyeing composition of use in the invention
generally comprises an amount of dye of formula (I) or
of precursor of formula (II) of between 0.001 and 30%
by weight, with respect to the total weight of the
composition. Preferably, this amount is between 0.005
and 10% by weight and more preferably still between
0.01 and 6% by weight, with respect to the total weight
of the composition.
The dyeing composition comprising the dye of formula
(I) or, preferably, the precursor of formula (II) can
also comprise an oxidizing agent, such as hydrogen
peroxide, urea hydrogen peroxide, alkali metal
bromates, persalts, peracids and oxidase enzymes.
The dyeing composition can additionally comprise
additional direct dyes other than those of formula (I)
or (II). These direct dyes are, for example, chosen
from neutral, acid or cationic nitrobenzene direct
dyes, neutral, acid or cationic azo direct dyes,
tetraazapentamethine dyes, neutral, acid or cationic
quinone and in particular anthraquinone dyes, azine
direct dyes, triarylmethane direct dyes, indoamine
direct dyes and natural direct dyes.
Mention may be made, among nitrobenzene direct dyes,
without implying limitation, of the following
compounds:
1,4-Diamino-2-nitrobenzene, 1-amino-2-nitro-4-(β-
hydroxyethylamino)benzene, 1-amino-2-nitro-4-[bis(β-
hydroxyethyl) aminojbenzene, 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) -(βhydroxyethyl)amino]benzene,. 1-amino-3-
methy1-4-(β-hydroxyethylamino)-6-nitrobenzene, 1-amino-
2-nitro-4-(β-hydroxyethylamino)-5-chlorobenzene, 1, 2-
diamino-4-nitrobenzene, 1-amino-2-(β-
hydroxyethylamino)-5-nitrobenzene, 1,2-bis-(β-
hydroxyethylamino)-4-nitrobenzene, 1-amino-2-
[tris(hydroxymethyl)methylamino]-5-nitrobenzene, 1-
hydroxy-2-amino-5-nitrobenzene, 1-hydroxy-2-amino-4-
nitrobenzene, 1-hydroxy-3-nitro-4-aminobenzene, 1-
hydroxy-2-amino-4, 6-dinitrobenzene, 1-(β
hydroxyethyloxy)-2-(β-hydroxyethylamino)-5-
nitrobenzene, 1-methoxy-2-(β-hydroxyethylamino)-5-
nitrobenzene, 1-(β-hydroxyethyloxy-3-methylamino)-4-
nitrobenzene, 1- (β,γ-dihydroxypropyloxy)-3-methylamino-
4-nitrobenzene, 1-(β-hydroxyethylamino)-4-(β,γ-
dihydroxypropyloxy)-2-nitrobenzene, 1-(β,γ-
dihydroxypropylamino)-4-trifluoromethy1-2-nitrobenzene,
1---hydroxyethylamino)-4-trifluoromethy1-2-
nitrobenzene, 1-(β-hydroxyethylamino)-3-methy1-2-
nitrobenzene, 1-(β-aminoethylamino)-5-methoxy-2-
nitrobenzene, 1-hydroxy-2-chloro-6-ethylamino-4-
nitrobenzene, 1-hydroxy-2-chloro-6-amino-4-
nitrobenzene, 1-hydroxy-6-[bis--hydroxyethyl)amino]-3-
nitrobenzene, 1-(β-hydroxyethylamino)-2-nitrobenzene or
1-hydroxy-4-(β-hydroxyethylamino)-3-nitrobenzene.
Mention may be made, among azo direct dyes, of the
cationic azo dyes described in Patent Applications
WO 95/15144, WO-95/01772 and EP-714 954, the contents
of which form an integral part of the invention.
Mention may very particularly be made, among these
compounds, of the following dyes: 1,3-dimethy1-2-[[4-
(dimethylamino)phenyl]azo]-1H-imidazolium chloride,

1,3-dimethy1-2-[(4-aminophenyl)azo]-1H-imidazolium
chloride or 1-methy1-4-[(methylphenylhydrazono) methyl]-
pyridinium methyl sulphate.
Mention may also be made, among azo direct dyes, of
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 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 and
Disperse Black 9.
Mention may also be made of 1-(4'-aminodiphenylazo)-
2-methy1-4-[bis -(β-hydroxyethyl)amino]benzene and 4-
hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulphonic
acid.
Mention may be made, among quinone direct dyes, of
the following dyes:
Disperse Red 15, Solvent Violet 13, Acid Violet 43,
Disperse Violet 1, Disperse Violet 4, Disperse Blue 1,
Disperse Violet 8, Disperse Blue 3, Disperse Red 11,
Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse
Violet 15 and Basic Blue 99, and also the following
compounds: 1-(N-methylmorpholinioprdpylamino)-4-
hydroxyanthraquinone, 1-aminopropylamino-4-
methylaminoanthraquinone, • 1-
aminopropylaminoanthraquinone, 5---hydroxyethyl)-1,4-
diaminoanthraquinone, 2-aminoethylaminoanthraquinone
and 1,4-bis -,y-dihydroxypropylamino)anthraquinone.
Mention may be made, among azine dyes, of the
following compounds:
- Basic Blue 17 and Basic Red 2.
Mention may be made, among triarylmethane dyes, 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.
Mention may be made, among indoamine dyes, of the
following compounds:
2-(β-hydroxyethylamino-5-[bis (β-4'-
hydroxyethyl)amino]anilino-1,4-benzoquinone;
2- --hydroxyethylamino-5-(2'-methoxy-4'-
aminoanilino)-1,4-benzoquinone;
3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-
methoxy-1,4-benzoquinone imine;
3-N- (3'-chloro-4'-methylamino)phenylureido-6-
methy1-1,4-benzoquinone imine;
3-[4'-N-(ethyl,carbamylmethyl)-amino]phenylureido-
6-methyl'-l, 4-benzoquinone imine.
Mention may be made, among natural direct dyes, of
lawsone, juglone, alizarin, purpurin, carminic acid,
kermesic acid, purpurogallin, protocatechualdehyde,
indigo, isatin, curcumin, spinulosin or apigenidine. It
is also possible to use extracts or decoctions
comprising these natural dyes and in particular
cataplasms or henna-based extracts.
The dyeing composition can comprise one or more
oxidation bases and/or one or more couplers
conventionally used for the dyeing of keratinous
fibres.
Mention may be made, among oxidation bases, of para-
phenylenediamines, bisphenylalkylenediamines, para-
aminophenols, bis-para-aminophenols, ortho-
aminophenols, heterocyclic bases and their addition
salts.
Mention may in particular be made, among couplers, of
meta-phenylenediamines, meta-aminophenols, meta-
diphenols, naphthalene couplers, heterocyclic couplers
and their addition salts.
The coupler or couplers are each generally present in

an amount of between 0.001 and 10% by weight of the
total weight of the dyeing composition, preferably
between 0.005 and 6% by weight.
The oxidation base or bases present in the dyeing
composition are generally present each in an amount of
between 0.001 and 10% by weight of the total weight of
the dyeing composition, preferably between 0.005 and 6%
by weight.
Generally, the addition salts of the oxidation bases
and couplers which can be used in the context of the
invention are chosen in particular from the addition
salts with an acid, such as hydrochlorides,
hydrobromides, sulphates, citrates, succinates,
tartrates, lactates, tosylates, benzenesulphonates,
phosphates and acetates, and the addition salts with a
base, such as alkali metal hydroxides, such as sodium
hydroxide or potassium hydroxide, ammonia, amines or
alkanolamines.
The medium appropriate for the dyeing, also known as
dyeing vehicle, is a cosmetic medium generally
comprising water or a mixture of water and of at least
one organic solvent. Mention may be made, as organic
solvent, for example, of lower C1-C4 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, aromatic
alcohols, such as benzyl alcohol or phenoxyethanol, and
their mixtures.
The solvents, when they are present, are preferably
present in proportions preferably of between 1 and 50%
by weight approximately, with respect to the total
weight of the dyeing composition, more preferably still
between 5 and 40% by weight approximately.
The dyeing composition can also include various

adjuvants conventionally used in hair dyeing
compositions, such as anionic, cationic, nonionic,
amphoteric or zwitterionic surface-active agents or
their mixtures, anionic, cationic or nonionic,
amphoteric or zwitterionic polymers or their mixtures,
inorganic or organic thickening agents, in particular
anionic, cationic, nonionic and amphoteric polymeric
associative thickeners, antioxidants, penetrating
agents, sequestering agents, fragrances, buffers,
dispersing agents, conditioning agents, such as, for
example, volatile or non-volatile and modified or
unmodified silicones, such as aminated silicones, film-
forming agents, ceramides, preservatives, opacifying
agents or conducting polymers.
The above adjuvants are generally .present in an
amount of, for each of them, between 0.01 and 20% by
weight, with respect to the weight of the composition.
Of course, a person skilled in the art will take care
to choose this or these optional additional compounds
so that the advantageous properties intrinsically
attached to the dyeing composition in accordance with
the invention are not, or not substantially,
detrimentally affected by the envisaged addition or
additions.
The pH of the dyeing composition is generally between
3 and 14 approximately. It can be adjusted to the
desired value using acidifying or basifying agents
commonly used in dyeing keratinous fibres or else using
conventional buffer systems.
According to a specific form of the invention, when
the dyeing composition comprises at least one dye of
formula (I), the composition has a pH of between 6 and
11. According to another specific form of the
invention, when the composition comprises at least one
dyeing precursor of formula (II), the composition has a

pH of between 6 and 11.
Mention may be made, among acidifying agents, by way
of example, of inorganic or organic acids, such as
hydrochloric acid, orthophosphoric acid, sulphuric
acid, carboxylic acids, such as acetic acid, tartaric
acid, citric acid or lactic acid, or sulphonic acids.
Mention may be made, among basifying agents, by way
of example, of ammonia, alkaline carbonates,
alkanolamines, such as mono-, di- and triethanolamines
and their derivatives, sodium hydroxide, potassium
hydroxide and the compounds of following formula (γ) :

in which Wa is a propylene residue optionally
substituted by a hydroxyl group or a C1-C4 alkyl radical
and Ra1, Ra2, Ra3 and Ra4, which are identical or
different, represent a hydrogen atom, a C1-C4 alkyl
radical or a C1-C4 hydroxyalkyl radical.
The dyeing composition can be provided in various
forms, such as in the liquid, cream or gel form or in
any other form appropriate for carrying out dyeing of
keratinous fibres and in particular the hair.
Another subject-matter of the invention is a method
for dyeing keratinous fibres, in particular the hair,
which consists in applying, to the keratinous
substances, in the presence or absence of an oxidizing
agent, a dyeing composition comprising, in a cosmetic
medium, at least one azomethine dye of formula (I) or a
dyeing precursor of formula (II) as defined above.
After a leave-in time, the keratinous fibres are
rinsed, leaving coloured fibres to appear. The leave-in

time is generally between 3 and 50 minutes
approximately, preferably from 5 to 40 minutes
approximately.
The application of the dyeing composition according
to the invention is generally carried out at ambient
temperature. However, it can be carried out at
temperatures varying from 20 to 80°C.
The examples which follow serve to illustrate the
invention without, however, exhibiting a limiting
nature. The dyes of the examples below were fully
characterized by conventional spectroscopic and
spectrometric methods.
EXAMPLES
SYNTHETIC EXAMPLES
Example 1: Synthesis of 3-amino-2-chloro-4- (4-
hydroxyphenylimino)-6-methylcyclohexa-2,5-
dienone 1 (compound (la))

9.7 g (0.05 mol) of 3-amino-2-chloro-6-methylphenol,
dissolved in 250 ml of water, are added to a solution
comprising 5.45 g (0.05 mol) of para-aminophenol,
150 ml of water and 80 ml of 20% ammonium hydroxide in
water in a conical flask.
A solution of 32.9 g (0.1 mol) of potassium
ferricyanide dissolved in 150 ml of water is
subsequently added and the reaction medium is stirred
at ambient temperature for 2 hours.
The solid formed is filtered off, washed with water and
then recrystallized from an ethanol/water 75/25
mixture. 4.4 g of 3-amino-2-chloro-4-(4-

hydroxyphenylimino)-6-methylcyclohexa-2,5-dienone of
formula (la) are obtained.
Example 2: Synthesis of 3-amino-4-(4-aminophenylimino) -
2-chloro-6-methy lcyclohexa-2, 5-dienone 2_
(compound (lb))
ML!

A solution of 9 g (0.05 mol) of para-phenylenediamine
dihydrochloride in 250 ml of water is mixed in a
conical flask with a solution of 9.7 g (0.05 mol) of 3-
amino-2-chloro-6-methylphenol in 250 ml of water and
80 ml of a 20% aqueous ammonium hydroxide solution.
32.9 g (0.1 mol) of potassium ferricyanide are
subsequently added portionwise and the reaction medium
is diluted with 150 ml of water. After stirring at
ambient temperature for 12 hours, the solid formed is
filtered off and then washed with water.
The crude resulting product is subsequently purified by
chromatography on a silica column (eluent:
dichloromethane - dichloromethane/methanol: 90/10).
2.1 g of 3-amino-4-(4-aminophenylimino)-2-chloro-6-
methylcyclohexa-2,5-dienone of formula (lb) are
obtained.
Example 3 : Synthesis of 3-amino-4- (4-amino-
methylphenylimino)-2-chloro-6-
methylcyclohexa-2,5-dienone 3 (compound of
formula (lc))

9.7 g (0.05 mol) of 3-amino-2-chloro-6-methylphenol,
dissolved in 250 ml of water, are added to a solution

comprising 9.75 g (0.05 mol) of para-toluenediamine,
250 ml of water and 40 ml of 20% ammonium hydroxide in
water in a conical flask.
A solution of 32.9 g (0.1 mol) of potassium
ferricyanide dissolved in 150 ml of water is
subsequently added and the reaction medium is stirred
at ambient temperature for 3 h 20.
The solid formed is filtered off, washed with water and
then purified by chromatography on a silica column
(eluent: dichloromethane/methanol: 99/1). 2.98 g of 3-
amino-4-(4-amino-methylphenylimino)-2-chloro-6-
methylcyclohexa-2,5 dienone of formula (1c) are
obtained.
Example 4 : Synthesis of 3-amino-4- [ (4-
aminophenyl)amino]-2-chloro-6-methylphenol (2b)

10 mg (0.04 mol) of (4Z)-3-amino-4-[(4-
aminophenyl)imino]-2-chloro-6-methylcyclohexa-2,5-dien-
1-one are added to a solution comprising 16 mg of
sodium hydrosulphite in 500 µl of methanol and 5 µl of
an aqueous sodium hydroxide solution. The reaction
medium is stirred and then the solution is treated
according to the usual procedure and characterized.
3-Amino-4-[(4-aminophenyl)amino]-2-chloro-6-
methylphenol) (2b) is obtained.

Example 5: Synthesis of 3-amino-4- [ (4-amino-2-
methylphenyl)amino]-2-chloro-6-methylphenol/3-amino-
4-[(4-amino-3-methylphenyl)amino]-2-chloro-6-
methylphenol (2c)

10 mg {0.04 mol) of 3-amino-4-[(4-amino-2-
methylphenyl)imino]-2-chloro-6-methylcyclohexa-2, 5-
dien-1-one and 3-amino-4-[(4-amino-3-
methylphenyl)imino]-2-chloro-6-methylcyclohexa-2, 5-
dien-1-one are added to a solution comprising 16 mg of
sodium hydrosulphite in 500 µl of methanol and 5 µl of
an aqueous sodium hydroxide solution. The reaction
medium is stirred and then the solution is treated
according to the usual procedure and characterized. 3-
Amino-4-.[ (4-amino-2-methylphenyl) amino] -2-chloro-6-
methylphenol/3-amino-4-[(4-amino-3-methylphenyl)amino]-
2-chloro-6-methylphenol (2c) are obtained.
Example 6 : Synthesis of 3-amino-2-chloro-4- [ (4-
hydroxyphenyl)amino]-6-methylphenol (2a)

10 mg (0.04 mol) of 3-amino-2-chloro-4-[(4-
hydroxyphenyl)imino]-6-methylcyclohexa-2, 5-dien-1-one
are added to a solution comprising 16 mg of sodium
hydrosulphite in 500 µl of methanol and 5 µl of an
aqueous sodium hydroxide solution. The 'reaction medium
is stirred and then the solution is treated according
to the usual procedure and characterized. 3-Amino-2-
chloro-4-[(4-hydroxyphenyl)amino]-6-methylphenol (2a)
is obtained.

Example 7: Synthesis of 3-amino-2-chloro-4-({4-
[ethyl(2-hydroxyethyl)amino]phenyl}imino)-6-
methylcyclohexa-2,5-dien-1-one (1k)

1.94 g of 3-amino-2-chloro-6-methylphenol hydrochloride
are added to 2.53 g of 2-[(4-
aminophenyl)(ethyl)amino]ethanol hydrochloride in
solution in 20 ml of water and 10 ml of ethanol. The pH
is adjusted to 9.5 with 20% ammonium hydroxide in
water. 36 ml of 9% agueous hydrogen peroxide solution
are subseguently added and the reaction medium is
stirred at ambient temperature for 4 h 30. The solid
form is filtered off and washed with water; 2.44 g of
3-amino-2-chloro-4-({4-[ethyl(2-
hydroxyethyl)amino]phenyl)imino)-6-methylcyclohexa-2,5-
dien-1-one (lk) are obtained.
Example 8: Synthesis of 3-amino-2-chloro-4-{[4-(3-
hydroxypyrrolidin-1-yl)phenyl]imino}-6-methylcyclohexa-
2,5-dien-1-one (11)

1.94 g of 3-amino-2-chloro-6-methylphenol hydrochloride
are added to 2.51 g of 1- (4-aminophenyl)pyrrolidin-3-ol
dihydrochloride in solution in 20 ml of water and 20 ml
of ethanol. The pH is adjusted to 9.5 with 20% ammonium
hydroxide and then 18 ml of 9% aqueous hydrogen
peroxide solution are added. The mixture is left
stirring at ambient temperature for 8 'hours and then
the precipitate formed is filtered off. 2.79 g of 3-
amino-2-chloro-4-{[4-(3-hydroxypyrrolidin-1-
yl)phenyl]imino}-6-methylcyclohexa-2,5-dien-1-one (11)
are thus obtained.

Example 9: Synthesis of 3-amino-2-chloro-6-methy1-4-
[(4-pyrrolidin-1-ylphenyl)imino]cyclohexa-2,5-dien-1-
one (1m)

1.94 g of 3-amino-2-chloro-6-methylphenol hydrochloride
are added to 2.35 g of 4--yrrolidin-1-yl)aniline
dihydrochloride in solution in 15 ml of water and 15 ml
of ethanol. The pH is adjusted to 9.5 with 20% ammonium
hydroxide and then 18 ml of 9% aqueous hydrogen
peroxide solution are added. The mixture is left
stirring at ambient temperature for 4 hours and then
the precipitate formed is filtered off. 1.7 g of
3-amino-2-chloro-6-methy1-4-[(4-pyrrolidin-1-
ylphenyl) imino]cyclohexa-2,5-dien-1-one (lm) are thus
obtained.
Example 10: Synthesis of 3-amino-2-chloro-6-methy1-4-
{[4-(methylamino)phenyl]imino}cyclohexa—2, 5-dien-1-one
(ln)

A mixture of 2 g of N-methylbenzene-1,4-diamine
dihydrochloride, 2 g of 3-amino-2-chloro-6-methylphenol
hydrochloride, 20 ml of water, 20 ml of ethanol and
7.6 ml of 9% aqueous hydrogen peroxide solution, a
mixture brought to pH 9.5 with 20% ammonium hydroxide
in water, is stirred at ambient temperature for 5
hours. 2.5 g of 3-amino-2-chloro-6-methy1-4-{[4-
(methylamino)phenyl]imino}cyclohexa-2, 5-dien-1-one (ln)
are obtained.
Example 11: Synthesis of 3-amino-2-chloro-4-{[4-
(dipentylamino)phenyl]imino}-6-methylcyclohexa-2, 5-


0.48 g of 3-amino-2-chloro-6-methylphenOl hydrochloride
is added to 0.8 g of N,N-dipentylbenzene-l,4-diamine
dihydrochloride in solution in 5 ml of water and 40 ml
of ethanol. The pH is adjusted to 9.5 with 20% ammonium
hydroxide and then 1.7 ml of 9% aqueous hydrogen
peroxide solution are added. The mixture is left
stirring at ambient temperature for 5 hours and then
the precipitate formed is filtered off. 0.72 g of 3-
amino-2-chloro-4-{[4-(dipentylamino)phenyl]imino}-6-
methylcyclohexa-2,5-dien-1-one (lo) is thus obtained.
Example 12: Synthesis of 3-amino-4-({4-[bis(2-
hydroxyethyl)amino]phenyl}imino)-2-chloro-6-
methylcyclohexa-2,5-dien-1-one (lp)

1.69 g of 3-amino-2-chloro-6-methylphenol hydrochloride
are added to 2.715 g of 2,2'-[(4-
aminophenyl)imino]diethanol sulphate in solution in
32 ml of water and 32 ml of ethanol. The pH is adjusted
to 9.5 with 20% ammonium hydroxide and then 31.5 ml of
9% aqueous hydrogen peroxide solution are added. The
mixtures is left stirring at ambient temperature for 6
hours and then the precipitate formed is filtered off.
1.68 g of 3-amino-4-({4-[bis(2-
hydroxyethyl)amino]phenyl}imino)-2-chloro-6-
methylcyclohexa-2,5-dien-1-one (lp) are thus obtained.

Example 13: Synthesis of the mixture of 3-amino-4-[(4-
amino-2-methylphenyl)imino]-2-chloro-6-methylcyclohexa-
2, 5-dien-1-one and 3-amino-4-[ (4-amino-3-methy1-
phenyl)imino]-2-chloro-6-methylcyclohexa-2,5-dien-1-one
isomers (1g)
n

9.7 g (0.05 mol) of 3-amino-2-chloro-6-methylphenol,
dissolved in 250 ml of water, are added to a solution
comprising 9.75 g (0.05 mol) of 2-methylbenzene-l,4-
diamine dihydrochloride, 250 ml of water and 40 ml of
20% ammonium hydroxide in water in a conical flask.
A solution of 32.9 g (0.1 mol) of potassium
ferricyanide dissolved in 150 ml of water is
subsequently added dropwise and the reaction medium is
stirred at ambient temperature for 2 hours.
The solid formed is filtered off, washed with water,
dried and then purified by silica chromatography
(eluent:dichloromethane 99/methanol 1). 2.98 g of the
mixture of 3-amino-4-[(4-amino-2-methylphenyl)imino]-2-
chloro-6-methylcyclohexa-2,5-dien-1-one and (3-amino-4-
[ (4-amino-3-methylphenyl) imino] -2-chloro--6-
methylcyclohexa-2,5-dien-1-one isomers (lq) are thus
obtained.
Example 14: Synthesis of 1-[1-(4-{[2-amino-3-chloro-5-
methy1-4-oxocyclohexa-2,5-dien-1-
ylidene]amino}phenyl)pyrrolidin-3-yl]-3-methy1-1H-
imidazo1-3-ium chloride (lr)

315 mg of 1-[1-(4-aminophenyl)pyrrolidin-3-yl]-3-
methy1-lH-imidazo1-3-ium chloride hydrochloride and
194.1 mg of 3-amino-2-chloro-6-methylphenol

hydrochloride are weighed out in a flask, 1 ml of water
is added and the pH is adjusted to 9.5 with 20%
ammonium hydroxide in water.
0.5 ml of 30% aqueous hydrogen peroxide solution is
added dropwise. The reaction is exothermic and the
temperature rises to 60°C.
The mixture is left stirring for 18 hours. The
precipitate is filtered off and rinsed with acetone.
The next morning, a second precipitate has formed in
the filtrate and is filtered off. 81 mg of 1-[1-(4-{[2-
amino-3-chloro-5-methy1-4-oxocyclohexa-2, 5-dien-1-
ylidene]amino}phenyl)pyrrolidin-3-yl]-3-methy1-1H-
imidazo1-3-ium chloride (1r) are thus obtained.
Example 15: Synthesis of 1-(4-{[2-amino-3-chloro-5-
methy1-4-oxocyclohexa-2,5-dien-1-ylidene]amino}phenyl)-
N,N,N-trimethylpyrrolidin-3-aminium chloride (lt)

292.5 mg of 1-(4-aminophenyl)-N,N,N-
trimethylpyrrolidin-3-aminium chloride hydrochloride
and 194.1 mg of 3-amino-2-chloro-6-methylphenol
hydrochloride are weighed out in a flask, 1 ml of water
is added and the pH is adjusted to 9.5 with 20%
ammonium hydroxide in water. 1.1 ml of 30% aqueous
hydrogen peroxide solution are added dropwise. The
mixture is left stirring for 24 hours. The precipitate
is filtered off and rinsed with acetone. 80 mg of 1-(4-
{[2-amino-3-chlorc-5-methy1-4-oxocyclohexa-2,5-dien-1-
ylidene] amino}phenyl)-N,N,N-trimethylpyrrolidin-3-
aminium chloride (lt) are thus obtained.

DYEING EXAMPLES
Dyeing in a neutral medium
The following dyeing compositions (A) and (B) are
prepared from the dyes compound (lb) and
compound (lc) synthesized above.

Compositions (A) and (B) are applied to locks of
white hair comprising 90% of white hairs. After a
leave-in time of 30 minutes, the locks are rinsed,
washed with a standard shampoo, rinsed again and then
dried.
The shades obtained appear in the table below:




Compositions (C) to (E) are applied to locks of white
hair comprising 90% of white hairs. After a leave-in
time of 30 minutes, the locks are rinsed, washed with a
standard shampoo, rinsed again and then dried.
The shades obtained appear in the table below:


WE CLAIM:
1. Compound of formula (I) or (II):

its organic or inorganic acid salts, its geometrical
isomers, its tautomers and its solvates, such as
hydrates;
in which formula (I) or (II):
• R1 represents:
- a chlorine atom;
- a (C1-C3)alkyl radical optionally substituted by
one or more hydroxy1 groups;
- a (C1-C3)alkoxy radical optionally substituted by
one or more hydroxyl groups;
• X represents:
a hydroxyl radical;
an -NR4R5 radical with R4 and R5 representing,
independently of one another:
i) a hydrogen atom;
ii) a C1-C5 alkyl radical optionally
substituted by one or more groups chosen
from hydroxyl, (C1-C3) alkoxy, amino, (C1-
C3)alkylamino, di (C1-C3)alkylamino,
aminocarbonyl, carboxyl -COOH,
sulpho -SO3H, tri (C1-C3) alkylammonio and
(C1-C3) alkylimidazolio;
a pyrrolidinyl radical optionally substituted by
a group chosen from hydroxyl, (C1-C3) alkoxy,
amino, (C1-C3) alkylamino, di (C1-C3) alkylamino,

tri (C1-C3) alkylammonio and (C1-
C3)alkylimidazolio;
a piperidinyl radical optionally substituted by
a group chosen from hydroxyl, (C1-C3) alkoxy,
amino, (C1-C3) alkylamino, di (C1-C3) alkylamino,
tri (C1-C3) alkylammonio and (C1-
C3)alkylimidazolio;
• n represents an integer between 0 and 3 inclusive;
• R2 and R3, which are identical or different, are as
defined for R4 and R5;
it being understood that, when X and/or R2 and/or R3
and/or R4 and/or R5 comprise a cationic group, the
electrical neutrality of the compounds of formula (I)
or (II) is brought about by a cosmetically acceptable
anionic counterion or a mixture of cosmetically
acceptable anionic counterions.
2. Compound of formula (I) or (II) for which n has a
value 1 and R1 represents a (C1-C3)alkyl radical.
3. Compound of formula (I) or (II) for which n is
zero.
4. Compound of formula (I) or (II) according to any
one of the preceding claims, for which X represents a
hydroxyl radical.
5. Compound of formula (I) or (II) according to any
one of Claims 1 to 3, for which X represents an -NR4R5
radical with R4 and R5 representing, independently of
one another, i) a hydrogen atom or ii) a C1-C5 alkyl
radical optionally substituted by one or more groups
chosen from hydroxyl, (C1-C3) alkoxy, amino, (C1-
C3)alkylamino, di (C1-C3)alkylamino, aminocarbonyl,

carboxyl -COOH, sulpho -SO3H, tri(C1-C3)alkylammonio and
(C1-C3) alkylimidazolio.
6. Compound of formula (I) or (II) according to any
one of Claims 1 to 3 for which X represents a
pyrrolidinyl group optionally substituted by a tri(C1-
C3)alkylammonio or (C1-C3)alkylimidazolio group.
7. Compound of formula (I) or (II) which is chosen
from the following compounds:

with An , which are identical or different, representing
an anionic counterion.
8. Dyeing composition for dyeing keratinous fibres,
comprising, in a cosmetic medium, at least one compound
of formula (I) or (II) according to any one of the
preceding claims.
9. Composition according to the preceding claim, in
which the compound of formula (I) or (II) is present in
an amount of between 0.001 and 30% by weight, with
respect to the total weight of the composition.
10. Composition according to either one of Claims 8
and 9, in which, when the composition comprises at
least one compound of formula (I), the composition has
a pH of between 6 and 11.
11. Composition according to either one of Claims 8
and 9, in which, when the composition comprises at
least one compound of formula (II), the composition has
a pH of between 6 and 11.

12. Composition according to any one of Claims 8 to
11, which additionally comprises at least one oxidizing
agent.
13. Composition according to the preceding claim, in
which the oxidizing agent is chosen from hydrogen
peroxide, urea hydrogen peroxide, alkali metal
bromates, persalts, peracids and oxidase enzymes.
14. Composition according to any one of Claims 8 to
13 which additionally comprises at least one direct dye
other than those of formula (I) or (II), chosen from
neutral, acid or cationic nitrobenzene direct dyes,
neutral, acid or cationic azo direct dyes,
tetraazapentamethine dyes, neutral, acid or cationic
quinone and in particular anthraquinone dyes, azine
direct dyes, triarylmethane direct dyes, indoamine
direct dyes and natural direct dyes.
15. Composition according to any one of Claims 8 to
14 which additionally comprises at least one adjuvant
chosen from anionic, cationic, nonionic, amphoteric or
zwitterionic surface-active agents or their mixtures,
anionic, cationic, nonionic, amphoteric or zwitterionic
polymers or their mixtures, inorganic or organic
thickening agents, antioxidants, penetrating agents,
sequestering agents, fragrances, buffers, dispersing
agents, conditioning agents, film-forming agents,
ceramides, preservatives, opacifying agents and
conducting polymers.
16. Method for dyeing keratinous fibres, in which an
appropriate dye composition according to any one of the
preceding claims is applied to the substances.

17. Use of the compound of formula (I) or (II) as
defined in any one of Claims 1 to 7 for the dyeing of
keratinous fibres.

The invention relates to the dyeing of keratinous fibres using azomethine direct dyes of
formula (I) or reduced precursors of azomethine direct dyes of formula (II) obtained from 2-
chloro-3-amino-6-methylphenol. A subject-matter of the invention is a dyeing composition
comprising at least one chlorinated azomethine direct dye or one reduced precursor of a
chlorinated azomethine direct dye, a method for dyeing keratinous fibres which employs the
said composition and their uses in the dyeing of keratinous fibres. This composition makes it
possible to obtain a particularly stable and consistent colouring.