Particular quinone direct dyes, dye composition comprising at
least one such dye, implementation process therefor and use
thereof
The present invention relates to particular quinone direct dyes
and also to the use thereof for dyeing keratin fibres, in particular
human keratin fibres such as the hair.
The invention also relates to a composition for dyeing keratin
fibres comprising such quinone direct dyes in a suitable dyeing
medium, and also to a dyeing process using the said composition.
Specifically, a subject of the invention is precursors of these
direct dyes, their use for dyeing fibres and a multi-compartment device
containing them.
The present invention relates to the field of dyeing keratin
fibres and more particularly to the field of hair dyeing.
It is known practice to dye keratin fibres, and in particular the
hair, with dye compositions containing one or more direct dyes,
according to a "direct dyeing" process.
The process conventionally used in direct dyeing consists in
applying to keratin fibres one or more direct dyes, or colouring
molecules, which have affinity for the said fibres, leaving them to
stand on the fibres, and then rinsing the fibres. The direct dyes used
hitherto are generally nitrobenzene dyes, anthraquinone dyes,
nitropyridine dyes, dyes of azo, xanthene, acridine or azine type or
triarylmethane-based dyes.
These direct dyes may also be applied to keratin fibres in the
presence of an oxidizing agent if it is desired to obtain simultaneous
lightening of the fibres.
However, the colorations resulting therefrom are temporary or
semi-permanent since the nature of the interactions that bind the direct
dyes to the keratin fibre and their desorption from the surface and/or
the core of the fibre are responsible for their weak dyeing power and
their poor fastness with respect to washing, inclement weather or
perspiration.
These dyes also have the drawback of lacking stability towards
light, on account of the poor resistance of the chromophore to
photochemical attack, which has a tendency to lead to fading over time
of the coloration of keratin fibres.
There is thus a real need for direct dyes that can not only dye
keratin fibres satisfactorily, but that are also stable towards light, and
are capable of giving colorations that are resistant to the various
attacking factors to which the fibres may be subjected, such as bad
weather, washing and perspiration.
These aims are achieved with the present invention, one subject
of which is especially quinone direct dyes of formula (I) below,
organic or mineral acid or base salts thereof, tautomeric forms, optical
isomers or geometrical isomers thereof and/or solvates thereof:
in which formula (I):
• n represents an integer equal to 0, 1, 2, 3 or 4;
R represents:
- a linear or branched C 1-C4 alkyl radical;
- a linear or branched C 1-C4 alkyl radical, substituted with one
or more identical or different radicals chosen from hydroxyl
and imidazolium radicals, An ; An denoting a cosmetically
acceptable anion or mixture of anions;
- a C 1-C4 alkoxy radical;
- a halogen atom;
R i represents:
- a linear or branched C 1-C5 alkyl radical;
- a linear or branched C 1-C5 alkyl radical, optionally substituted
with one or more hydroxyl radicals;
R2 represents:
- a linear or branched C1-C5 alkyl radical;
- a linear or branched C1-C5 alkyl radical, optionally substituted
with one or more hydroxyl radicals;
• X represents:
- a hydroxyl radical;
- a radical -NR 3R4 in which R3 and R4 represent, independently
of each other:
■ a hydrogen atom;
■ a linear or branched Ci-C alkyl radical;
" a linear or branched Ci-C alkyl radical, substituted with
one or more hydroxyl or C1- C 4 alkoxy radicals.
Another subject of the present invention concerns the use of
one or more quinone direct dyes of formula (I) as defined previously
for the dyeing of keratin fibres, in particular human keratin fibres such
as the hair.
The present invention also relates to a composition for dyeing
keratin fibres, in particular human keratin fibres such as the hair,
comprising, in a suitable dyeing medium, one or more quinone direct
dyes of formula (I) as defined previously.
In particular, the invention also relates to the use of the said
dye composition for dyeing keratin fibres, especially human keratin
fibres such as the hair.
The invention also relates to a process for dyeing keratin
fibres, in particular human keratin fibres such as the hair, in which the
said dye composition according to the invention is applied to the said
fibres for a time that is sufficient to obtain the desired coloration,
after which the resulting fibres are rinsed, optionally washed with
shampoo, rinsed again and dried or left to dry.
Similarly, the invention relates more particularly to a process
for lightening keratin fibres, in particular human keratin fibres such as
the hair, in which (i) the said dye composition, free of oxidizing agent,
and (ii) a cosmetic composition comprising one or more oxidizing
agents are applied to the said fibres; compositions (i) and (ii) being
applied to the said keratin fibres sequentially or simultaneously for a
time that is sufficient to obtain the desired lightening, after which the
fibres are rinsed, optionally washed with shampoo and rinsed again,
and the resulting fibres are dried or left to dry.
The quinone direct dyes of formula (I) according to the
invention can thus give colorations that are resistant to the various
attacking factors to which keratin fibres may be subjected, such as
inclement weather, light, washing and perspiration.
Furthermore, the direct dyes according to the invention can
satisfactorily dye keratin fibres, especially producing powerful,
chromatic, sparingly selective colorations and lead to an improved
uptake of the colouration.
The direct dyes according to the invention have the advantage
of being light-fast and can be used in the presence of an oxidizing
agent, which facilitates their use in lightening direct dyeing
compositions based on oxidizing agents.
In other words, the direct dyes according to the present
invention lead to fast colorations and are compatible with dye
compositions intended for lightening keratin fibres.
Moreover, a subject of the invention is colourless or weakly
coloured compounds of leuco type, which are the reduced form of the
quinone direct dyes according to the invention of formula (II) below,
organic or mineral acid or base salts thereof, tautomeric forms, optical
isomers or geometrical isomers thereof, and/or solvates thereof:
(II)
in which formula (II) n, R, Rl R2 and X have the same meanings as
those indicated in formula (I).
The compounds of leuco type according to the invention lead,
in the presence of one or more oxidizing agents, to the quinone direct
dyes of formula (I).
Thus, the invention also relates to the use of one or more
compounds of leuco type of formula (II) as precursors of the direct
dyes of formula (I).
In particular, the invention relates to the use of one or more
compounds of leuco type of formula (II) in the presence of one or
more oxidizing agents, for dyeing keratin fibres, in particular human
keratin fibres such as the hair.
The present invention also relates to a multi-compartment
device or "kit" containing a first compartment comprising a cosmetic
composition comprising one or more compounds of leuco type of
formula (II) as defined previously, and a second compartment
comprising one or more oxidizing agents.
The compounds of leuco type of formula (II) used under
oxidizing conditions thus have the advantage of giving colorations that
are resistant to the various attacking factors to which keratin fibres
may be subjected, such as inclement weather, washing, light and
perspiration.
Other characteristics, aspects, subjects and advantages of the
present invention will emerge even more clearly on reading the
description and the examples that follow.
. Quinone direct dyes
Preferably, in formula (I), quinone direct dyes according to the
invention are such that, taken together or separately:
• n represents an integer equal to 0, 1 or 2;
• R represents:
- a linear or branched C 1-C4 alkyl radical, preferably
methyl;
- a C 1-C4 alkoxy radical, preferably a methoxy radical;
- a halogen atom, preferably chlorine;
• Ri represents:
- a linear or branched C1-C5 alkyl radical, preferably a
methyl or ethyl radical;
- a linear or branched C1-C5 alkyl radical, substituted with
one or more hydroxyl radicals, preferably a 2-
hydroxyethyl radical;
• R2 represents:
- a linear or branched C1-C5 alkyl radical, preferably a
methyl or ethyl radical;
- a linear or branched C1-C5 alkyl radical, substituted with
one or more hydroxyl radicals, preferably a 2-
hydroxyethyl radical; and/or
• X represents:
- a hydroxyl radical;
- a radical -NR 3R4 in which R3 and R4 represent,
independently of each other:
■ a hydrogen atom;
■ a linear or branched Ci-C alkyl radical;
" a linear or branched Ci-C alkyl radical,
substituted with one or more hydroxyl radicals.
An denotes a cosmetically acceptable anion or mixture of
anions, for instance halides, such as chloride, methosulfates, nitrates;
alkylsulfonates: Alk-S(0) 20 such as methanesulfonate or mesylate,
and ethanesulfonate; arylsulfonates: Ar-S(0) 20 such as
benzenesulfonate and toluenesulfonate or tosylate; citrate; succinate;
tartrate; lactate; alkyl sulfates: Alk-0-S(0)0 such as methylsulfate;
arylsulfates such as benzenesulfate and toluenesulfate; phosphate;
acetate; triflate; and borates such as tetrafluoroborate.
Preferably, An is an anionic counterion chosen from bromide,
chloride, and methylsulfate and toluenesulfonate ions or a mixture of
these ions.
Preferably, n represents an integer equal to 0, 1 or 2, and more
particularly n is equal to 0 or 2 .
Preferably, R represents a linear or branched C1- C 4 alkyl
radical, a C1- C 4 alkoxy radical or a halogen atom. More preferentially,
R is chosen from a methyl radical, a methoxy radical and a chlorine
atom.
Preferably, Ri represents a linear or branched C1-C5 alkyl
radical and R2 represents a linear or branched C1-C5 alkyl radical,
substituted with one or more hydroxyl radicals, or vice versa.
More preferentially, Ri is chosen from a methyl radical and an
ethyl radical, and R2 is a 2-hydroxyethyl radical, or vice versa.
Preferably, X represents a hydroxyl radical.
As a variant, X represents a radical -NR 3R4 in which R3 and R4
represent, independently of each other, a hydrogen atom or a linear or
branched Ci-C alkyl radical, optionally substituted with one or more
hydroxyl radicals.
Preferably, R3 and R4 represent, independently of each other, a
hydrogen atom or a methyl, ethyl, isopropyl or 2-hydroxyethyl radical.
According to one embodiment, n represents an integer equal to
0, 1 or 2 and Ri represents a linear or branched C1-C5 alkyl radical
and R2 represents a linear or branched C1-C5 alkyl radical, substituted
with one or more hydroxyl radicals, or vice versa.
In accordance with this embodiment, n is preferably equal to 2,
Ri is chosen from a methyl radical and an ethyl radical, and R2 is a 2-
hydroxyethyl radical, or vice versa.
In particular, n is equal to 2, R represents a linear or branched
C1-C4 alkyl radical or a C1-C4 alkoxy radical and Ri is chosen from a
methyl radical and an ethyl radical and R2 is a 2-hydroxyethyl radical,
or vice versa.
According to another embodiment, n is equal to 0 and Ri
represents a linear or branched C1-C5 alkyl radical and R2 represents a
linear or branched C1-C5 alkyl radical, substituted with one or more
hydroxyl radicals, or vice versa.
According to another embodiment, n is equal to 1 and Ri
represents a linear or branched C1-C5 alkyl radical and R2 represents a
linear or branched C1-C5 alkyl radical, substituted with one or more
hydroxyl radicals, or vice versa.
Preferably, the quinone direct dyes of formula (I) according to
the invention are chosen from the following compounds and the
geometrical or optical isomer forms thereof, the tautomers thereof, the
organic or mineral acid or base salts thereof or the solvates thereof
such as hydrates:
Compound 7
H
2-(4-Amino-3-methylphenylamino)-
5-
[(2- 2 1 hydro xyethyl)methylamino] [ 1,4]
CH3 benzoquinone
Compound 8
OH
2-(4-Amino-2,3,5,6-
tetramethylphenylamino)-5-[(2-
hydroxyethyl)methylamino] [ 1,4]
benzoquinone
Compound 9
Compound 11
2-(4-Aminophenylamino)-5-[(2-
hydroxyethyl)ethylamino] [1,4]
benzoquinone
Compound 12
2-[(2-Hydroxyethyl)ethylamino]-5-
(4-hydroxyphenylamino)[ 1,4]
benzoquinone
Compound 13
xxf xxr 2- {4-[Bis(2-
hydro xyethyl) amino Jphenylamino}
-5-[(2-hydroxyethyl)
ethylamino] [1,4]benzoquinone
OH
Compound 14
2-(3-Chloro-4-
hydroxyphenylamino)-
5-[(2-
hydroxyethyl)ethylamino] [1,4]benzoquinone
quinone
2-(4-Amino-2-methoxy-5-
methylphenylamino)-5-[(2-
hydroxyethyl)methylamino] [ 1,4]
benzoquinone
with An as defined previously
2-Dimethylamino-5-(4-
hydroxyphenylamino)[ 1,4]
benzoquinone
Compound 28
2-(4-Aminophenylamino)-5-
dimethylamino[ 1,4]benzoquinone
Compound 29
2-(4-Amino-2,3-
dimethylphenylamino)-5-
dimethylamino[ 1,4]benzoquinone
Compound 30
2-Dimethylamino-5-[4-
(ethylisopropylamino)phenylamino]
[ 1,4]benzoquinone
Compound 31
Preferably, the direct dyes of formula (I) according to the
present invention are chosen from the quinone direct dyes 1, 2, 3, 4, 5,
6, 7, 8, 9, 10, 11, 19, 20, 21, 22, 23, 24, 25, 32 and 33 .
Even more preferentially, the quinone direct dyes of formula
(I) according to the invention are chosen from the quinone direct dyes
1, 2, 3, 4, 7, 10, 11 and 32.
The quinone direct dyes of formula (I) may be obtained
The compounds corresponding to formula (I) are generally
obtained by reacting the derivatives l a with the morpholine derivatives
2 in basic medium in the presence of an oxidizing agent. The base used
is preferentially an aqueous solution of ammonia or of sodium
hydroxide and the oxidizing agent is preferentially chosen from
hydrogen peroxide, potassium ferricyanide, air, ammonium persulfate
and manganese oxide.
Synthetic approaches similar to that described previously are
described in patents FR 2 234 277, FR 2 047 932, FR 2 106 66 1 and FR
2 12 1 101.
The quinone direct dyes of formula (I) may also be obtained
according to the procedure as described below:
The compounds corresponding to formula (I) are generally
obtained by reacting the derivatives l a or I d with the metaaminophenols
3 in basic medium in the presence of an oxidizing agent.
The base used is preferentially an aqueous solution of ammonia or of
sodium hydroxide and the oxidizing agent is preferentially chosen from
hydrogen peroxide, potassium ferricyanide, air, ammonium persulfate
and manganese oxide.
Similar synthetic approaches are described in patent
application FR 21189380.
The invention also relates to the use of one or more quinone
direct dyes of formula (I) as described previously for dyeing keratin
fibres, in particular human keratin fibres such as the hair.
. Dye composition
The present invention also relates to a composition for dyeing
keratin fibres, in particular human keratin fibres such as the hair,
comprising, in a suitable dyeing medium, one or more direct dyes of
formula (I) as defined previously.
Preferably, the dye composition comprises one or more
quinone direct dyes of formula (I) chosen from compounds 1, 2, 3, 4,
5, 6, 7, 8, 9, 10, 11, 19, 20, 21, 22, 23, 24, 25, 32 and 33, and also
mixtures thereof.
Even more preferentially, the dye composition comprises one
or more quinone direct dyes of formula (I) chosen from compounds 1,
2, 3, 4, 7, 10, 11 and 32, and mixtures thereof.
The direct dye(s) as defined previously may be present in the
dye composition according to the invention in a content ranging from
0.00 1% to 10% by weight and preferably in a content ranging from
0.005% to 6%o by weight, relative to the total weight of the dye
composition.
The dye composition of the invention may also comprise one or
more oxidation dyes.
The oxidation dyes are generally chosen from oxidation bases
optionally combined with one or more couplers.
By way of example, the oxidation bases are chosen from paraphenylenediamines,
bis (phenyl) alky lenedi amines, par a-amino phenols,
ortho-aminophenols and heterocyclic bases, and the addition salts
thereof.
Among the para-phenylenediamines that may b e mentioned, for
example, are para-phenylenediamine, para-tolylenediamine, 2-chloropara-
phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-
dimethyl-para-phenylene diamine, 2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine, N, -dimethyl-par aphenylenediamine,
,-diethyl-para-phenylenediamine, N,N-dipropylpara-
phenylenediamine, 4-amino -N,N- diethyl- 3-methylaniline, N,Nbis
(P-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis ( -
hydroxy ethyl) amino -2-methylaniline, 4-N,N-bis ( -
hy droxy ethyl) amino -2-chloro aniline, 2-P-hydroxyethyl-paraphenylenediamine,
2- fluoro -para-phenylenediamine, 2-isopropyl-paraphenylenediamine,
N-(P-hydroxypropyl)-para-phenylenediamine, 2-
hydroxymethyl-para-phenylenediamine, N, -dimethyl- 3-methyl-par aphenylenediamine,
N-ethyl-N -( -hydroxy ethyl) -paraphenylenediamine,
N-(P,y-dihydroxypropyl)-para-phenylenediamine,
N-(4 '-amino phenyl) -para-phenylenediamine, N-phenyl-paraphenylenediamine,
2-P-hydroxyethyloxy-para-phenylenediamine, 2--
acetylaminoethyloxy-para-phenylenediamine, N-(-methoxy ethyl) -
para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-paraphenylenediamine,
2-P-hydroxyethylamino-5-aminotoluene and 3-
hydroxy- l -(4'-aminophenyl)pyrrolidine, and addition salts thereof
with an acid.
Preference i s particularly given, among the abovementioned
para-phenylenediamines, to para-phenylenediamine, paratolylenediamine,
2-isopropyl-para-phenylenediamine, 2-( -
hydroxy ethyl) -para-phenylenediamine, 2-( -hydroxy ethylo xy) -paraphenylenediamine,
2,6-dimethyl-para-phenylenediamine, 2,6-diethylpara-
phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,Nbis
(P-hydroxyethyl)-para-phenylenediamine, 2-chloro-paraphenylenediamine,
2-(P-acetylaminoethyloxy)-para-phenylenediamine
and their addition salts with an acid.
Among the bis(phenyl)alkylenediamines that may b e
mentioned, for example, are N,N'-bis (P-hydroxyethyl)-N,N'-bis(4'-
aminophenyl)- l ,3-diaminopropanol, N,N'-bis (P-hydroxyethyl)-N,N'-
bis (4'-aminophenyl) ethylene diamine, N,N'-bis(4-
aminophenyl)tetramethylenediamine, N,N'-bis ( -hydroxy ethyl) -N,N '-
bis(4- amino phenyl)tetramethylenediamine, N,N'-bis(4-
methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-
bis(4'-amino-3'-methylphenyl)ethylenediamine and l ,8-bis(2,5-
diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.
Mention may be made, among para-aminophenols, by way of
example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-
fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-
(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-
(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino -
2-(aminomethyl)phenol, 4-amino -2-[( -
hydroxyethyl)aminomethyl]phenol, 4-amino-2-fluorophenol and their
addition salts with an acid.
Mention may be made, among ortho-aminophenols, by way o f
example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-
methylphenol, 5-acetamido-2-aminophenol and their addition salts.
Mention may be made, among heterocyclic bases, by way o f
example, of pyridine derivatives, pyrimidine derivatives and pyrazole
derivatives.
Mention may be made, among pyridine derivatives, o f the
compounds described, for example, in patents GB 1 026 978 and
GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-
methoxyphenyl)amino-3-aminopyridine, 3,4-diaminopyridine and their
addition salts.
Other pyridine oxidation bases o f use in the present invention
are the 3-aminopyrazolo[ 1,5-a]pyridine oxidation bases or their
addition salts described, for example, in patent application FR 2 80 1
308. Mention may be made, by way o f example, of pyrazolo[ 1,5-
a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[ 1,5-a]pyrid-3-ylamine, 2-
(morpholin-4-yl)pyrazolo[ 1,5-a]pyrid-3-ylamine, 3-
aminopyrazolo[ 1,5-a]pyridine-2-carboxylic acid, 2-
methoxypyrazolo[ 1,5-a]pyrid-3-ylamine, (3-aminopyrazolo[ l ,5-
a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)ethanol,
2-(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[ 1,5-
a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[ 1,5-a]pyridine, 3,4-
diaminopyrazolo[ 1,5-a]pyridine, pyrazolo[ l ,5-a]pyridine-3,7-diamine,
7-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-ylamine, pyrazolo[ l ,5-
a]pyridine-3, 5-diamine, 5-(morpholin-4-yl)pyrazolo[ l ,5-a]pyrid-3-
ylamine, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-5-yl)(2-
hydroxyethyl)amino]ethanol, 2-[(3-aminopyrazolo[ 1,5-a]pyrid-7-yl)(2-
hydroxyethyl)amino]ethanol, 3-aminopyrazolo[ 1,5-a]pyrid-5-ol, 3-
aminopyrazolo[ 1,5-a]pyrid-4-ol, 3-aminopyrazolo[ 1,5-a]pyrid-6-ol, 3-
aminopyrazolo[ 1,5-a]pyrid-7-ol and their addition salts.
Mention may be made, among pyrimidine derivatives, of the
compounds described, for example, in patents DE 2359399, JP 88-
16957 1, JP 05-63 124 and EP 0 770 375 or patent application WO
96/1 5765 , such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-
triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-
dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their
addition salts and their tautomeric forms, when a tautomeric
equilibrium exists.
Mention may be made, among pyrazole derivatives, of the
compounds described in patents DE 3843892 and DE 4 133957 and
patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and
DE 195 43 988, such as 4,5-diamino- 1-methylpyrazole, 4,5-diamino- 1-
(P-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino- 1-(4 '-
chlorobenzyl)pyrazole, 4,5-diamino- 1,3-dimethylpyrazole, 4,5-
diamino -3-methyl- 1-phenylpyrazole, 4,5-diamino - 1-methyl- 3-
phenylpyrazole, 4-amino - 1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-
4,5-diamino -3-methylpyrazole, 4,5-diamino-3 -(t r t -butyl)- 1-
methylpyrazole, 4,5-diamino- 1-(t r t -butyl)-3 -methylpyrazole, 4,5-
diamino- 1-(-hydroxy ethyl)-3 -methylpyrazole, 4,5-diamino -1-ethy 1-3-
methylpyrazole, 4,5-diamino -1-ethy1-3- (4'-methoxyphenyl)pyrazole,
4,5-diamino -1-ethy1-3 -(hydroxymethyl)pyrazole, 4,5-diamino -3-
hydroxymethyl- 1-methylpyrazole, 4,5-diamino-3-hydroxymethyl- 1-
isopropylpyrazole, 4,5-diamino-3-methyl- 1-isopropylpyrazole, 4-
amino-5-(2'-aminoethyl)amino- 1,3-dimethylpyrazole, 3,4,5-
triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino- 1-
methyl-4-(methylamino)pyrazole, 3,5-diamino-4-(Phydroxyethyl)
amino- 1-methylpyrazole and their addition salts. 4,5-
Diamino- 1-(P-methoxyethyl)pyrazole may also be used.
Use will preferably be made of a 4,5-diaminopyrazole and even
more preferentially of 4,5-diamino- 1-(P-hydroxyethyl)pyrazole and/or
a salt thereof.
Mention may also be made, as pyrazole derivatives, of
diamino-N,N-dihydropyrazolopyrazolones and in particular those
described in application FR-A-2 886 136, such as the following
compounds and their addition salts: 2,3-diamino-6,7-dihydro- lH,5Hpyrazolo[
1,2-a]pyrazol- 1-one, 2-amino-3-ethylamino-6,7-dihydrolH,
5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-isopropylamino-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-(pyrrolidinl
-yl)-6,7-dihydro- lH,5H-pyrazolo[ l ,2-a]pyrazol- l -one, 4,5-diamino -
1,2-dimethyl- l ,2-dihydropyrazol-3-one, 4,5-diamino- 1,2-diethyl- 1,2-
dihydropyrazol-3-one, 4,5-diamino- 1,2-di(2-hydroxy ethyl)- 1,2-
dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydrolH,
5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2-amino-3-dimethylamino-6,7-
dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol- 1-one, 2,3-diamino-5,6,7,8-
tetrahydro- lH,6H-pyridazino[ 1,2-a]pyrazol- 1-one, 4-amino -1,2-
diethyl-5-(pyrrolidin- l -yl)- l ,2-dihydropyrazol-3-one, 4-amino -5-(3 -
dimethylaminopyrrolidin- 1-yl)- 1,2-diethyl- 1,2-dihydropyrazol-3-one
or 2,3-diamino-6-hydroxy-6,7-dihydro- lH,5H-pyrazolo[ 1,2-a]pyrazol-
1-one.
Use will preferably be made of 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or one of its salts.
Use will preferably be made, as heterocyclic bases, of 4,5-
diamino- 1-(P-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydrolH,
5H-pyrazolo[ l ,2-a]pyrazol- l -one and/or one of their salts.
The dye composition may optionally comprise one or more
couplers advantageously chosen from those conventionally used for
the dyeing o f keratin fibres.
Among these couplers, mention may be made especially o f
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthalene-based couplers and heterocyclic couplers, and also the
addition salts thereof.
Mention may be made, for example, o f 1,3-dihydroxybenzene,
1,3-dihydroxy-2-methylbenzene, 4-chloro - 1,3-dihydroxybenzene, 2,4-
diamino- 1-(P-hydroxyethyloxy)benzene, 2-amino -4- (-
hydroxyethylamino)- 1-methoxybenzene, 1,3-diaminobenzene, 1,3-
bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido- l -
dimethylaminobenzene, sesamol, l -P-hydroxyethylamino-3,4-
methylenedioxybenzene, cc-naphthol, 2-methyl- 1-naphthol, 6-
hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-
3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-
dimethoxypyridine, l -N-(P-hydroxyethyl)amino-3,4-
methylenedioxybenzene, 2,6-bis (P-hydroxyethylamino)toluene, 6-
hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, l -H-3-
methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-
dimethylpyrazolo[ 1,5-b]- l ,2,4-triazole, 2,6-dimethyl[3,2-c]- 1,2,4-
triazole and 6-methylpyrazolo[ 1,5-a]benzimidazole, the addition salts
thereof with an acid, and mixtures thereof.
In general, the addition salts o f the oxidation bases and
couplers which can be used in the context of the invention are chosen
in particular from the addition salts with an acid, such as the
hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates,
lactates, tosylates, benzenesulfonates, phosphates and acetates.
The oxidation base(s) each advantageously represent from
0.00 1% to 10% by weight and preferably from 0.005% to 6% by
weight relative to the total weight of the composition.
The content of coupler(s), if they are present, each
advantageously represent from 0.00 1% to 10% by weight relative to
the total weight of the composition, and preferably from 0.005% to 6%
by weight relative to the total weight of the dye composition.
The dye composition according to the invention may also
comprise one or more additional direct dyes other than the quinone
direct dyes according to the present invention.
The additional direct dye(s) according to the invention are
chosen from neutral, acidic or cationic nitrobenzene dyes, neutral,
acidic or cationic azo direct dyes, neutral, acidic or cationic quinone
and in particular anthraquinone direct dyes other than those of the
present invention, azine direct dyes, triarylmethane direct dyes,
azomethine direct dyes and natural direct dyes.
Among the benzenic direct dyes that may be used according to
the invention, mention may be made in a non-limiting manner of the
following compounds:
- 1,4-diamino-2-nitrobenzene;
- 1-amino-2-nitro-4-B-hydroxyethylaminobenzene;
- 1-amino -2-nitro -4-bis( -hydroxyethyl) aminobenzene;
- 1,4-bis(B-hydroxyethylamino)-2-nitrobenzene;
- 1-B-hydroxyethylamino-2-nitro-4-bis(Phydroxyethylamino)
benzene;
- 1-B-hydroxyethylamino-2-nitro-4-aminobenzene;
- 1- -hydroxyethylamino -2-nitro -4-(ethyl) ( fi
lydroxyethyl) aminobenzene;
- 1-amino-3-methyl-4-P-hydroxyethylamino-6-nitrobenzene;
- 1-amino-2-nitro-4-P-hydroxyethylamino-5-chlorobenzene;
- 1,2-diamino-4-nitrobenzene;
- 1-amino -2- -hydro xyethylamino- 5-nitrobenzene;
- 1,2-bis(P-hydroxyethylamino)-4-nitrobenzene;
- 1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene;
- 1-hydro xy-2- amino -5-nitrobenzene;
- 1-hydro xy-2 -amino -4-nitrobenzene;
- 1-hydroxy- 3-nitro -4-amino benzene;
- 1-hydroxy-2-amino-4,6-dinitrobenzene;
- 1--hydroxyethy loxy-2 -P-hydroxyethylamino -5-nitrobenzene;
- 1-met hoxy-2 -P-hydroxyethylamino- 5-nitrobenzene;
- 1- -hy droxyethyloxy- 3-met hylamino -4-nitrobenzene;
- 1- P,y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene;
- 1-P-hydroxyethylamino-4-P,y-dihydroxypropyloxy-2-
nitrobenzene;
- 1-P,y-dihydroxypropylamino-4-trifluoromethyl-2-
nitrobenzene;
- 1-P-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene;
- 1- -hydroxyet hylamino- 3-methy 1-2 -nitrobenzene;
- 1-P-aminoethylamino-5-methoxy-2-nitrobenzene;
- 1-hydro xy-2-chloro-6-ethylamino-4-nitrobenzene;
- 1-hydro xy-2-chloro-6-amino-4-nitrobenzene;
- 1-hy dro xy- 6-bis (P-hydroxyethyl)amino-3-nitrobenzene;
- 1-P-hydroxyethylamino-2-nitrobenzene; and
- 1-hydro xy-4 -P-hydroxyethylamino-3-nitrobenzene.
Among the azo direct dyes that may be used according to the
invention, mention may be made of the cationic azo dyes described in
patent applications WO 95/1 5 144, WO-95/0 1772 and EP-7 14954, the
content of which forms an integral part of the invention.
Among these compounds, the ones that may be mentioned most
particularly are the following dyes:
1,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]- 1Himidazolium
chloride,
1,3-dimethyl-2-[(4-aminophenyl)azo]- lH-imidazolium
chloride,
- 1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium
methyl sulfate.
Among the azo direct dyes that may also be mentioned are the
following dyes, described in the Colour Index International, 3rd
edition: Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22,
Basic Red 76, Basic Red 5 1, Basic Yellow 57, Basic Brown 16, Acid
Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown
17, Acid Yellow 23, Acid Orange 24, Disperse Black 9 .
Mention may also be made o f 1-(4 '-aminodiphenylazo)-2-
methyl-4-bis (P-hydroxyethyl)aminobenzene and 4-hydroxy-3-(2-
methoxyphenylazo)- 1-naphthalenesulfonic acid.
Among the quinone direct dyes, mention may be made o f the
following dyes: Disperse Red 15, Solvent Violet 13, Acid Violet 43,
Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet
8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7,
Basic Blue 22, Disperse Violet 15, Basic Blue 99, and also the
following compounds:
1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone
1-aminopropylamino-4-methylaminoanthraquinone
1-aminopropylaminoanthraquinone
-5 -hydroxyethyl-1,4-diaminoanthraquinone
-2-aminoethylaminoanthraquinone
1,4-bis (P,y-dihydroxypropylamino)anthraquinone.
Among the azine dyes, mention may be made o f the following
compounds: Basic Blue 17, Basic Red 2 .
Among the triarylmethane dyes that may be used according to
the invention, mention may be made of the following compounds:
Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic
Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7 .
Among the azomethine dyes that may be used according to the
invention, mention may be made of the following compounds:
-2-P-hydroxyethlyamino-5-[bis(P-4'-
hydroxyethyl)amino]anilino- 1,4-benzoquinone;
-2-P-hydroxyethylamino-5-(2'-methoxy-4 ' -amino) anilino- 1,4-
benzoquinone;
-3-N-(2'-chloro-4'-hydroxy)phenylacetylamino-6-methoxy- 1,4-
benzoquinone imine;
-3-N-(3 '-chloro-4'-methylamino)phenylureido-6-methyl- 1,4-
benzoquinone imine; and
-3-[4 '-N- (ethyl, carbamylmethyl) amino ]phenylureido- 6-methyl-
1,4-benzoquinoneimine.
Among the natural direct dyes that may be used according to
the invention, mention may be made of lawsone, juglone, alizarin,
purpurin, carminic acid, kermesic acid, purpurogallin,
protocatechaldehyde, indigo, isatin, curcumin, spinulosin and
apigenidin. Extracts or decoctions containing these natural dyes and in
particular henna-based poultices or extracts may also be used.
The additional direct dye(s) may be present in the dye
composition in a content ranging from 0.00 1% to 10% by weight and
preferably in a content ranging from 0.005% to 6% by weight, relative
to the total weight of the composition.
Preferably, the dye composition comprises one or more
quinone direct dyes of formula (I) and one or more azomethine direct
dyes.
The medium that is suitable for dyeing, also known as the dye
support, is a cosmetic medium generally formed from water or a
mixture of water and of at least one organic solvent. Examples of
organic solvents that may be mentioned include C 1- C 4 lower alkanols,
such as ethanol and isopropanol; polyols and polyol ethers, for
instance 2-butoxyethanol, propylene glycol, propylene glycol
monomethyl ether, diethylene glycol monoethyl ether and monomethyl
ether, and also aromatic alcohols, for instance benzyl alcohol or
phenoxyethanol, and mixtures thereof.
When they are present, the solvents are present in proportions
preferably of between 1% and 99% by weight approximately and even
more preferentially between 5% and 95% by weight approximately
relative to the total weight of the dye composition.
The dye composition may also contain various adjuvants
conventionally used in hair dye compositions, such as anionic,
cationic, nonionic or amphoteric surfactants or mixtures thereof,
anionic, cationic, nonionic or amphoteric polymers or mixtures
thereof, mineral or organic thickeners, and in particular anionic,
cationic, nonionic and amphoteric polymeric associative thickeners,
antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants,
solubilizers, conditioning agents, for instance volatile or non-volatile,
modified or unmodified silicones such as amino silicones, filmforming
agents, ceramides, preserving agents and opacifiers.
The above adjuvants are generally present in an amount, for
each of them, of between 0.0 1% and 20% by weight relative to the
weight of the composition.
Needless to say, a person skilled in the art will take care to
select this or these optional additional compound(s) such that the
advantageous properties intrinsically associated with the dye
composition in accordance with the invention are not, or are not
substantially, adversely affected by the envisaged addition(s).
The pH of the dye composition in accordance with the
invention is generally between 3 and 12 approximately, particularly
between 5 and 11 approximately and even more particularly from 6 to
9 .
Preferably, the pH of the dye composition in accordance with
the invention ranges from 9 to 12, more preferably from 9 to 10 .
It may be adjusted to the desired value by means of acidifying
or basifying agents commonly used in the dyeing of keratin fibres, or
alternatively using standard buffer systems.
Among the acidifying agents that may be mentioned, for
example, are mineral or organic acids, for instance hydrochloric acid,
orthophosphoric acid or sulfuric acid, carboxylic acids, for instance
acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Among the basifying agents that may be mentioned, for
example, are aqueous ammonia, alkali metal carbonates, alkanolamines
such as monoethanolamine, diethanolamine and triethanolamine, and
also derivatives thereof, sodium hydroxide, potassium hydroxide and
the compounds of formula (III) below:
Rd
(III)
in which W is a propylene residue optionally substituted with a
hydroxyl group or a C1-C4 alkyl radical; and Ra, Rb, Rc and Rd, which
may be identical or different, represent a hydrogen atom or a C1-C4
alkyl or C1-C4 hydroxyalkyl radical.
The dye composition according to the invention may be in
various forms, such as in the form of liquids, creams or gels, or in any
other form that is suitable for dyeing keratin fibres, and especially
human hair.
As indicated previously, the invention also relates to the use of
the dye composition as defined previously for dyeing keratin fibres, in
particular human keratin fibres such as the hair.
III. Dyeing process
The dyeing process according to the present invention consists
in applying to wet or dry keratin fibres a dye composition as defined
previously for a time that is sufficient to obtain the desired coloration,
and the fibres are then rinsed, optionally washed with shampoo and
rinsed again, and the resulting fibres are dried or left to dry.
Preferably, the leave-on time for the dye composition is
between 1 and 60 minutes, preferably between 5 and 40 minutes and
even more preferably between 10 and 30 minutes.
The dye composition is generally applied to the keratin fibres
at room temperature, preferably between 25 and 55°C.
According to one embodiment, the dye composition according
to the invention is applied to the keratin fibres in the presence of one
or more oxidizing agents for a time that is sufficient to obtain the
desired lightening.
The oxidizing agent may be present in the dye composition or
may be used separately in a cosmetic composition.
Preferably, the oxidizing agent is used separately in a cosmetic
composition.
Thus, the present invention also relates to a process for
lightening keratin fibres, in particular human keratin fibres such as the
hair, in which (i) the dye composition as defined previously, free of
oxidizing agent, and (ii) a cosmetic composition comprising one or
more oxidizing agents are applied to the said fibres; compositions (i)
and (ii) being applied to the said keratin fibres sequentially or
simultaneously for a time that is sufficient to obtain the desired
lightening, and the fibres are then rinsed, optionally washed with
shampoo and rinsed again, and the resulting fibres are dried or left to
dry.
The purposes of the present invention, the term "sequentially"
means that the oxidizing composition is applied before or after the dye
composition, i.e. as a pretreatment or a post-treatment.
The oxidizing agents used are chosen from hydrogen peroxide,
urea peroxide, alkali metal bromates, persalts such as perborates and
persulfates, peracids, and oxidase enzymes (with the possible
cofactors thereof), among which mention may be made of peroxidases,
2-electron oxidoreductases such as uricases, and 4-electron
oxygenases, for instance laccases.
The oxidizing agent is preferably hydrogen peroxide.
The oxidizing composition may also contain various adjuvants
conventionally used in compositions for dyeing the hair and as defined
previously.
The pH of the oxidizing composition containing the oxidizing
agent is such that, after mixing with the dye composition, the pH of
the resulting composition applied to the keratin fibres preferably
ranges between 3 and 12 approximately, even more preferentially
between 5 and 11 and even more particularly between 6 and 8.5 . It
may be adjusted to the desired value by means of acidifying or
basifying agents usually used in the dyeing of keratin fibres and as
defined previously.
IV. Compound of leuco type
The present invention also relates to compounds of leuco type
of formula (II) below, organic or mineral acid or base salts thereof,
tautomeric forms, optical isomers or geometrical isomers thereof
and/or solvates thereof:
in which n, R, Rl R2 and X have the same meanings as those
indicated in formula (I).
In particular, the preferred variants of n, R, Rl R2 and X in
formula (II) of the compounds of leuco type correspond to those
indicated in formula (I) of the direct dyes.
The compounds of leuco type corresponding to formula (II) are
generally obtained by reacting the compounds of quinone type of
formula (I) with a reducing agent according to the reaction scheme
below:
Synthetic approaches similar to this scheme are described in
patent applications FR 2 056 799, FR 2 047 932, FR 2 165 965 and FR
2 262 023 .
The compounds of leuco type of formula (II) are used as
precursors of the direct dyes of formula (I).
Preferably, the compounds of leuco type of formula (II) are
chosen from the compounds corresponding to the reduced form of the
quinone direct dyes 1 to 33 mentioned previously.
In other words, the compounds of leuco type of formula (II) are
chosen from the precursors of the quinone direct dyes 1 to 33 .
Even more preferentially, the compounds of leuco type of
formula (II) are chosen from precursors of the direct dyes 1, 2, 3, 4, 5,
6, 7, 8, 9, 10, 11, 19, 20, 21, 22, 23, 24, 25, 32 and 33 and
preferentially the precursors of the quinone direct dyes 1, 2, 3, 4, 7,
10, 11 and 32.
In particular, the invention relates to a cosmetic composition
comprising one or more compounds of leuco type of formula (II) as
defined previously.
The present invention also relates to a dyeing process in which
a cosmetic composition comprising one or more compounds of leuco
type of the abovementioned formula (II) is applied to keratin fibres in
the presence of one or more oxidizing agents for a time that is
sufficient to develop the desired coloration, after which the fibres are
rinsed, optionally washed with shampoo and rinsed again, and the
resulting fibres are dried or left to dry.
The oxidizing agent may be atmospheric oxygen or may be
chosen from the oxidizing agents mentioned previously.
In particular, when the oxidizing agent is atmospheric oxygen,
simple exposure to air of the keratin fibres treated with the
composition comprising the compound(s) of leuco type makes it
possible to generate the colouring species and, consequently, to colour
the fibres.
According to one variant, the oxidizing agent(s) may be applied
simultaneously or sequentially to the cosmetic composition comprising
the compounds of leuco type.
Thus, the cosmetic composition comprising the oxidizing
agent(s) may be applied to the keratin fibres before, simultaneously
with or after the cosmetic composition comprising the compounds of
leuco type of formula (II) according to the invention.
According to another variant, a ready-to-use composition which
results from the mixing of a cosmetic composition comprising one or
more compounds of leuco type of the abovementioned formula (II) and
of a cosmetic composition comprising one or more oxidizing agents is
applied to the keratin fibres.
According to one embodiment, the invention relates to a
composition, in particular for dyeing keratin fibres such as the hair,
comprising one or more compounds of formula (II) as defined
previously and optionally comprising one or more oxidizing agents.
The ready-to-use composition that is thus applied to the keratin
fibres may be in various forms, such as in the form of liquids, creams
or gels, or in any other form that is suitable for dyeing keratin fibres,
and in particular human hair.
The leave-on time for the composition(s) ranges from 1 to 60
minutes, preferably from 5 to 40 minutes and even more preferentially
from 10 to 30 minutes.
The cosmetic composition comprising such compounds of leuco
type is generally applied to the keratin fibres at room temperature,
preferably between 25 and 55°C.
IV. Dyeing device
The present invention also relates to a multi-compartment
device or "kit" comprising a first compartment containing a cosmetic
composition comprising one or more compounds of formula (I) as
defined previously or containing one or more compounds of leuco type
of formula (III) as defined previously, and optionally a second
compartment comprising one or more oxidizing agents.
In particular, the invention relates to a multi-compartment
dyeing device or "kit" comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes of formula
(I) as defined previously or containing one or more compounds of
leuco type of formula (III) as defined previously, and a second
compartment comprising one or more oxidizing agents.
More particularly, the invention relates to a multi-compartment
dyeing device or "kit" comprising a first compartment containing a
cosmetic composition comprising one or more direct dyes of formula
(I) as defined previously, free of oxidizing agent, and a second
compartment containing a cosmetic composition comprising one or
more oxidizing agents.
The invention also relates to a multi-compartment dyeing
device or "kit" comprising a first compartment containing a cosmetic
composition comprising one or more compounds of leuco type of the
abovementioned formula (II), and a second compartment containing a
cosmetic composition comprising one or more oxidizing agents.
According to one particular embodiment, the device may
comprise at least one compartment comprising a cosmetic composition
comprising one or more compounds of leuco type of the
abovementioned formula (II).
In this case, the composition comprising the compound(s) of
leuco type as defined above is applied to the keratin fibres, which
become coloured due to their exposure to air.
The devices mentioned above are suitable for dyeing keratin
fibres.
The evaluation of the coloration can be done visually or read
on a spectrocolorimeter (such as Minolta CM3600d, illuminant D65,
angle 10°, SCI values) for the L*, a*, b* colorimetric measurements. In
this L*, a*, b* system, L* represents the intensity of the color, a*
indicates the green/red color axis and b* indicates the blue/yellow
color axis. The lower the value of L, the darker or more intense the
color is. The higher the value of a , the redder the shade is; the higher
the value of b , the yellower the shade is.
The variation in coloring between the colored locks of natural
white hair which is untreated (control) and after treatment or
coloration is defined by , corresponding to the color uptake on
keratin fibers, according to the following equation:
* = - (L* —Lo
* )2 + ( a * —a 0
* + ( * - b 0
* )2 (i)
In this equation, L*, a* and b* represent the values measured
after dyeing the natural hair comprising 90% of white hairs and L o ,
a o and b o represent the values measured for the untreated natural hair
comprising 90% of white hairs.
The greater the value of , the greater the difference in color
between the control locks and the dyed locks and the greater color
uptake is. Chromaticity in the CIE L*, a*, b * colorimetric system is
calculated according to the following equation:
The greater the value of C*, the greater the chromaticity is.
The examples that follow serve to illustrate the invention
ithout, however, being limiting in nature.
I - Examples of synthesis
Example 1:
Synthesis of 2-(4-amino-2,3-dimethylphenylamino)-5-[(2-
hydroxyethyl)methylamino] [1,4]benzoquinone (compound 1)
To a solution of 1.04 g (0.005 mol) of 2,3-dimethylbenzene-
1,4-diamine dihydrochloride in 5 ml of water and 3 ml of 20%
aqueous ammonia is added a solution of 1.23 g (0.005 mol) of 4-
methyl-3,4-dihydro-2H- l ,4-benzoxazin-6-ol hydrobromide in 2 ml of
water, 1 ml of 20% aqueous ammonia and 10 ml of acetone. 17ml of
6 % aqueous hydrogen peroxide solution are added and the mixture is
stirred at room temperature for 4 hours 30 minutes. After filtering off
and drying the precipitate formed, 0.49 g of 2-(4-amino-2,3-
dimethylphenylamino)-5-[(2-hydroxyethyl)methylamino]-
[1,4]benzoquinone (compound 1) are obtained in the form of a brown
powder.
The molecular ion 316 (ES+) is detected by mass
spectrometry.
Example 2: Synthesis of 2-[4-(ethylisopropylamino)phenylamino)-
5-[(2-hydroxyethyl)methylamino][ 1,4]benzoquinone
(compound 2)
To a solution of 1.07 g (0.005 mol) of N-(4-aminophenyl)-Nethyl-
N-isopropylamine hydrochloride in 5 ml of water and 2 ml of
20% aqueous ammonia is added a solution of 1.22 g (0.005 mol) of 4-
methyl-3,4-dihydro-2H- l ,4-benzoxazin-6-ol hydrobromide in 2 ml of
water, 1 ml of 20% aqueous ammonia and 15 ml of acetone. 17 ml of
aqueous hydrogen peroxide solution are added and the mixture is
stirred at room temperature for 4 hours. An oil forms. After 24 hours
at 6°C, the oil forms a gum. This gum is taken up in ethyl acetate.
After drying and concentrating this organic phase, 0.86 g of 2-[4-
(ethylisopropylamino)phenylamino]-5-[(2-
hydroxyethyl)methylamino] [1,4]benzoquinone (compound 2) is
obtained in the form of a black powder.
The molecular ion 358 (ES+) is detected by mass
spectrometry.
Example 3:
Synthesis of 2-(4-amino-2,3-dimethylphenylamino)-5-[(2-
hydroxyethyl)ethylamino] [1,4]benzoquinone (compound 10)
To a solution of 1.05 g (0.005 mol) of 2,3-dimethylbenzene-
1,4-diamine dihydrochloride in 5 ml of water and 3 ml of 20% aqueous
ammonia is added a solution of 1.3 1 g (0.005 mol) of 4-ethyl-3,4-
dihydro-2H- 1,4-benzoxazin-6-ol hydrobromide in 3 ml of water, 1 ml
of 20% aqueous ammonia and 15 ml of acetone. 17 ml of 6% aqueous
hydrogen peroxide solution are added and the mixture is stirred at
room temperature for 6 hours 30 minutes. After 12 hours at 6°C, the
reaction medium is concentrated and left for a further 12 hours at 6°C.
A precipitate forms, which is filtered off. It is purified by
chromatography, eluting with dichloromethane/methanol. 0.0 1 g of 2-
(4-amino-2,3-dimethylphenylamino)-5-[(2-
hydroxyethyl)ethylamino] [l ,4]benzoquinone (compound 10) is
obtained in the form of a brown powder.
The molecular ion 328 (ES-) is detected by mass spectrometry.
Example 4:
Synthesis of 2-[4-(ethylisopropylamino)phenylamino)-5-[(2-
hydroxyethyl)ethylamino] [1,4]benzoquinone (compound 11)
To a solution of 1.10 g (0.005 mol) of N-(4-aminophenyl)-Nethyl-
N-isopropylamine hydrochloride in 5 ml of water and 3 ml of 20%
aqueous ammonia is added a solution of 1.30 g (0.005 mol) of 4-ethyl-
3,4-dihydro-2H- l ,4-benzoxazin-6-ol hydrobromide in 3 ml of water, 1
ml of 20% aqueous ammonia and 15 ml of acetone. 17 ml of aqueous
hydrogen peroxide solution are added and the mixture is stirred at room
temperature for 3 hours 30 minutes. An oil forms. After 12 hours at
6°C, the oil forms a gum. This gum is taken up in ethyl acetate, dried
over disodium sulfate and filtered, and the ethyl acetate is evaporated
off. The product is purified on a column of silica (eluent: 80/20 ethyl
acetate/heptane). The eluent is evaporated off. After 48 hours at 6°C,
the product has crystallized, and is left to dry. 0.52 g of 2-[4-
(ethylisopropylamino)phenylamino)-5-[(2-
hydroxyethyl)ethylamino] [l ,4]benzoquinone (compound 11) is
obtained.
The molecular ion 372 (ES+) is detected by mass spectrometry.
Example : Synthesis of 2-(3-chloro-4-hydroxyphenylamino)
hydroxyethyl)methylamino] [1,4]benzoquinone (compound 7)
To a solution of 0.90 g (0.005 mol) of 4-amino-2-chlorophenol
hydrochloride in 5 ml of water and 2 ml of 20% aqueous ammonia is
added a solution of 1.23 g (0.005 mol) of 4-methyl-3,4-dihydro-2H- l ,4-
benzoxazin-6-ol hydrobromide in 3 ml of water, 1 ml of 20% aqueous
ammonia and 10 ml of acetone. The pH is adjusted to 9.5 with 20%
aqueous ammonia. 17 ml of 6%> aqueous hydrogen peroxide solution are
added. After 3 hours, the precipitate is filtered off. 0.99 g of 2-(3-
chloro-4-hydroxyphenylamino)-5-[(2-
hydroxyethyl)methylamino] [1,4]benzoquinone (compound 7) is
obtained in the form of a brown powder.
The molecular ion 323 (ES+) is detected by mass spectrometry.
Example 6: Synthesis of 2-(2-chloro-4-hydroxyphenylamino)-
5-[(2-hydroxyethyl)methylamino] [1,4]benzoquinone (compound 4)
compoun 4
To a solution of 0.90 g (0.005 mol) of 4-amino-3-chlorophenol
hydrochloride in 8 ml of water and 2 ml of 20% aqueous ammonia is
added a solution of 1.23 g (0.005 mol) of 4-methyl-3,4-dihydro-2H- l ,4-
benzoxazin-6-ol hydrobromide in 3 ml of water, 1 ml of 20% aqueous
ammonia and 10 ml of acetone. 17 ml of 6% aqueous hydrogen peroxide
solution are added and the mixture is stirred at room temperature for 6
hours 30 minutes. After 12 hours at 6°C, the precipitate formed is
filtered off and dried. The product is purified on a column of silica
(eluent: 100% dichloromethane and then dichloromethane/methanol up
to 10% methanol). 0.0 1 g of 2-(2-chloro-4-hydroxyphenylamino)-5-[(2-
hydroxyethyl)methylamino] [1,4]benzoquinone (compound 4) is
obtained.
The molecular ion 323 (ES+) is detected by mass spectrometry.
Example 7:
Synthesis of 2-[(4-amino-2,3-dimethylphenyl)amino]-5-[(2
hydroxyethyl)(methyl)amino]benzene- 1,4-diol (compound 32)
To a solution of 5 mg of 2-(4-amino-2,3-
dimethylphenylamino)-5-[(2-
hydroxyethyl)methylamino][ l ,4]benzoquinone 1 in 2 ml of 0.5M
sodium hydroxide are added 15 mg of dithionite in 2 ml of water, and
the mixture is stirred until decolorized.
The molecular ion 318 (ES+) is detected by mass spectrometry.
II - Dyeing evaluation of the compounds
The following dye compositions were prepared:
500 mg of illustrated compound
79 g of water,
15 g of ethanol,
5 g of benzyl alcohol,
1 g of the mixture is applied to a lock of 0.25 g of grey hair
containing 90% white hairs. After a leave-on time of 30 minutes, the
lock is rinsed, washed with a standard shampoo, rinsed again and then
dried.
The results are collated in the following table:
III. Comparative examples
The following dyes were compared:
The dye compositions were prepared as follows:
5 mg of dye (compound 3 or compound A) were added to 1 g of
dye support constituted of 0,5% by weight of benzoic acid, 5% by
weight of benzyl alcohol, 15% by weight of ethanol and 79,5% by
weight of water relative to the total weight of the dye composition.
The pH of the compositions was adjusted to 9.5 with aqueous
ammonia containing 20% of NH3.
The mixture is applied to a lock of 0.25g of grey hair
containing 90% white hairs. After a leave-on time of 30 minutes at
ambient temperature, the lock is washed with a standard shampoo.
The evaluation of the coloration is done with a
spectrocolorimeter (such as Minolta CM3600d, illuminant D65, angle
10°, SCI values) for the L*, a*, b* colorimetric measurements.
The variation in coloring between the colored locks of natural
white hair which is untreated (control) and after treatment or
coloration defined by is calculated according to equation (i) as
previously mentioned.
Results
According to these results, the dye of the present invention
(compound 3) leads to a more intense and chromatic coloration than
the comparative dye (compound A) in the same dyeing composition.
Furthermore, the colour uptake is significantly higher with
compound 3 than with compound A.
CLAIMS
1. Quinone direct dye of formula (I) below, organic or mineral
acid or base salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof and/or solvates thereof:
in which formula (I):
• n represents an integer equal to 0, 1, 2, 3 or 4;
• R represents:
a linear or branched C1-C4 alkyl radical;
a linear or branched C1-C4 alkyl radical, substituted with one
or more identical or different radicals chosen from hydroxyl and
imidazolium radicals, An ; An denoting a cosmetically acceptable
anion or mixture of anions;
a C1-C4 alkoxy radical;
a halogen atom;
• R represents:
a linear or branched C1-C5 alkyl radical;
- a linear or branched C1-C5 alkyl radical, optionally substituted
with one or more hydroxyl radicals;
• R2 represents:
a linear or branched C1-C5 alkyl radical;
a linear or branched C1-C5 alkyl radical, optionally substituted
with one or more hydroxyl radicals;
• X represents:
- a hydroxyl radical;
- a radical -NR 3R4 in which R3 and R4 represent, independently
of each other:
■ a hydrogen atom;
■ a linear or branched C -C alkyl radical;
" a linear or branched C -C alkyl radical, substituted with
one or more hydroxyl or C1-C4 alkoxy radicals.
2 . Quinone direct dye of formula (I) according to Claim 1,
characterized in that, taken together or separately:
• n represents an integer equal to 0, 1 or 2;
• R represents:
- a linear or branched C1-C4 alkyl radical, preferably
methyl;
- a C1-C4 alkoxy radical, preferably a methoxy radical;
- a halogen atom, preferably chlorine;
• R represents:
- a linear or branched C1-C5 alkyl radical, preferably a
methyl or ethyl radical;
- a linear or branched C1-C5 alkyl radical, substituted with
one or more hydroxyl radicals, preferably a 2-
hydroxyethyl radical;
• R2 represents:
- a linear or branched C1-C5 alkyl radical, preferably a
methyl or ethyl radical;
- a linear or branched C1-C5 alkyl radical, substituted with
one or more hydroxyl radicals, preferably a 2-
hydroxyethyl radical; and/or
• X represents:
- a hydroxyl radical;
- a radical -NR 3R4 in which R3 and R4 represent,
independently of each other:
• a hydrogen atom;
• a linear or branched C -C alkyl radical;
• a linear or branched Ci-C alkyl radical, substituted
with one or more hydroxyl radicals.
3. Quinone direct dye of formula (I) according to Claim 1 or 2,
characterized in that n represents an integer equal to 0, 1 or 2, and
more particularly n is equal to 0 or 2 .
4 . Quinone direct dye of formula (I) according to any one of
Claims 1 to 3, characterized in that Ri represents a linear or branched
C1-C5 alkyl radical and R2 represents a linear or branched C1-C5 alkyl
radical, substituted with one or more hydroxyl radicals, or vice versa.
5. Quinone direct dye of formula (I) according to any one of
Claims 1 to 4, characterized in that Ri is chosen from a methyl radical
and an ethyl radical and R2 is a 2-hydroxyethyl radical, or vice versa.
6 . Quinone direct dye of formula (I) according to any one of
the preceding claims, characterized in that it is chosen from the
following compounds and the geometrical or optical isomer forms
thereof, the tautomers thereof, the organic or mineral acid or base salts
thereof or the solvates thereof such as hydrates:

2-(2-Chloro-4-
roxyphenylamino)-5-[ethyl-(2
hydroxyethyl)amino] [1,4]
benzoquinone

2-(4-Amino-2-methoxy-5-
methylphenylamino)-5-[ethyl-(2-
hydroxyethyl)amino] [1,4]
benzoquinone
2-(4-Amino-3-
methoxyphenylamino)-5-[ethyl-(2-
hydroxyethyl)amino] [1,4]
benzoquinone
2-(4-Amino-3-
methoxyphenylamino)-5-[(2
hydroxyethyl)methylamino] [ 1
benzoquinone
2-(4-Hydroxy-3,5-
dimethylphenylamino)-5-[(2-
hydroxyethyl)methylamino] [ 1,4]
benzoquinone
2-(4-Hydroxy-2,5-
dimethylphenylamino)-5-[(2-
hydroxyethyl)methylamino] [ 1,4]
benzoquinone
Compound 25
2-Dimethylamino-5-(4-
hydroxyphenylamino)[ 1,4]
benzoquinone
Compound 28
2-(4-Aminophenylamino)-5-
dimethylamino[ 1,4]benzoquinone
mpound 29
2-(4-Amino-2,3-
dimethylphenylamino)-5-
dimethylamino[ 1,4]benzoquinone
Compound 30
2-Dimethylamino-5-[4-
(ethylisopropylamino)phenylamino]
[1,4]benzoquinone
with An denoting a cosmetically acceptable anion or a mixture of
cosmetically acceptable anions.
7 . Use of one or more quinone direct dyes of formula (I) as
defined according to any one of Claims 1 to 6, for dyeing keratin
fibres, in particular human keratin fibres such as the hair.
8. Composition, in particular for dyeing keratin fibres such as
the hair, characterized in that it comprises, in a suitable dyeing
medium, one or more quinone direct dyes of formula (I) as defined
according to any one of Claims 1 to 6 .
9 . Process for dyeing keratin fibres, in particular human keratin
fibres such as the hair, in which a dye composition comprising, in a
suitable dyeing medium, one or more quinone direct dyes of formula
(I) as defined according to any one of Claims 1 to 6 is applied to the
said fibres for a time that is sufficient to obtain the desired coloration,
after which the fibres are rinsed, optionally washed with shampoo and
rinsed again, and the resulting fibres are dried or left to dry.
10 . Process for lightening keratin fibres, in particular human
keratin fibres such as the hair, in which a dye composition comprising,
in a suitable dyeing medium, (i) one or more quinone direct dyes of
formula (I) as defined according to any one of Claims 1 to 6, free of
oxidizing agent, and (ii) a cosmetic composition comprising one or
more oxidizing agents are applied to the said fibres; compositions (i)
and (ii) being applied to the said keratin fibres sequentially or
simultaneously for a time that is sufficient to obtain the desired
lightening, and the fibres are then rinsed, optionally washed with
shampoo and rinsed again, and the resulting fibres are dried or left to
dry.
11. Compound of leuco type of formula (II) below, organic or
mineral acid or base salts thereof, tautomeric forms, optical isomers or
geometrical isomers thereof and/or solvates thereof:
in which formula (II) n, R, Rl R2 and X have the same
meanings as those indicated in formula (I) in any one of Claims 1 to 5.
12. Composition in particular for dyeing keratin fibres such as
the hair, comprising one or more compounds of formula (II) as defined
according to the preceding claim and optionally comprising one or
more oxidizing agents.
13. Process for dyeing keratin fibres, characterized in that a
dye composition comprising one or more compounds of formula (II) as
defined according to Claim 11 and an oxidizing composition
comprising one or more oxidizing agents are applied simultaneously or
sequentially to the said wet or dry fibres.
14. Use of one or more compounds of leuco type of formula
(II) as defined according to Claim 11, as precursors of the quinone
direct dyes of formula (I) as defined according to any one of Claims 1
to 6 .
15. Use of one or more compounds of leuco type of formula
(II) as defined according to Claim 11, in the presence of one or more
oxidizing agents, for dyeing keratin fibres, in particular human keratin
fibres such as the hair.
16 . Multi-compartment device or "kit" comprising a first
compartment containing a composition comprising one or more dyes of
formula (I) as defined in any one of Claims 1 to 6 or containing one or
more compounds of leuco type of formula (II) as defined in Claim 11,
and a second compartment comprising one or more oxidizing agents.