WO2012069476A1 - Novel direct dyes containing an ascorbic acid-based unit, dye composition comprising them and process for dyeing human keratin materials using these dyes - Google Patents

Novel direct dyes containing an ascorbic acid-based unit, dye composition comprising them and process for dyeing human keratin materials using these dyes Download PDF

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Publication number
WO2012069476A1
WO2012069476A1 PCT/EP2011/070686 EP2011070686W WO2012069476A1 WO 2012069476 A1 WO2012069476 A1 WO 2012069476A1 EP 2011070686 W EP2011070686 W EP 2011070686W WO 2012069476 A1 WO2012069476 A1 WO 2012069476A1
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alkyl
group
radical
hydrogen atom
crc
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PCT/EP2011/070686
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French (fr)
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Andrew Greaves
Nicolas Daubresse
Frédéric Guerin
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L'oreal
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/80—Anthracene dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/82—Azo dyes
    • C09B62/825—Monoazo dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes

Definitions

  • the invention relates to the dyeing of keratin materials using dyes bearing an ascorbic acid-based unit of formula (I), particularly bearing 3,4-dihydroxyfuran-2(5H)- one and 2,3,4(5H)-furantrione units.
  • the direct dyes that are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of the azo, xanthene, acridine, azine or triarylmethane type.
  • the colorations that result from the use of direct dyes are temporary or semi-permanent colorations, 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 poor dyeing power and their poor fastness with respect to washing or to perspiration.
  • Oxidation bases which are colourless before oxidation such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds; and which, in the presence of oxidizing agents, colour the hair.
  • Oxidation bases may be mixed with couplers to obtain varied shades.
  • This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with aqueous hydrogen peroxide solution, as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. Oxidation dyeing systems make it possible to obtain base colorations that are relatively shampoo-fast, but do not make it possible to obtain chromatic shades.
  • a chemical bleaching process is performed. This process consists in treating the keratin fibres, such as the hair, with a strong oxidizing system, generally constituted by hydrogen peroxide optionally combined with persalts, usually in an alkaline medium.
  • This bleaching system has the drawback of degrading keratin fibres and of impairing their cosmetic properties. Specifically, the fibres have a tendency to become coarse, more difficult to disentangle and more brittle. Finally, the lightening or bleaching of keratin fibres with oxidizing agents is incompatible with treatments for changing the shape of said fibres, particularly relaxing treatments.
  • Another lightening technique consists in applying to dark hair fluorescent direct dyes. This technique, described especially in documents WO 03/028 685 and WO 2004/091 473, makes it possible to respect the quality of the keratin fibre during the treatment. However, these fluorescent direct dyes do not have sufficient fastness with respect to external agents.
  • Vitamins are compounds that are essential for the body, one of which, vitamin C, also known as ascorbic acid [50-81-7], l-ascorbic acid, l-xylo-ascorbic acid or l-threo- hex-2-enoic acid ⁇ -lactone, is known for its anti-scurvy virtues.
  • Ascorbic acid is also known as an antioxidant (see, for example, Ullmann's Encylopedia of Industrial Chemistry; "Vitamins", 2005 Wley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a27 443 (pp. 110-122), or US 2006/0 039 937), an antithrombotic protective agent (see, for example, US 4 329 290), or an anticancer agent (see, for example, EP 0 875 246).
  • ascorbic acid derivatives have been used for functionalizing matrices such as ultraviolet screening agents (WO 2008/017346).
  • the aim of the present invention is to provide novel systems for the direct dyeing of keratin materials and for especially lightening dark keratin materials, in particular human keratin fibres such as the hair, which are powerful, remanent and easy to use.
  • one name of the invention is to provide direct dyeing systems for obtaining lightening effects especially on keratin materials such as naturally or artificially dark keratin fibres, which are fast with respect to successive shampooing, which do not degrade the keratin fibres and which do not impair their cosmetic properties.
  • Another aim of the invention is to dye keratin materials, especially keratin fibres such as the hair, in a manner that is intense, strong, chromatic and/or remanent with respect to external attacking factors.
  • the invention is also directed towards providing compounds for dyeing keratin fibres such as the hair with little coloration selectivity between the root and the end, whether it is performed on natural or permanent-waved fibres.
  • organic or mineral acid salts such as hydrates, thereof;
  • A represents a coloured chromophore
  • Asc represents a radical derived from ascorbic acid chosen from ascorbyl and dehydroascorbyl radicals, chosen from formulae (11-1 ) to (II-4), and which is linked to the rest of the molecule via one of the substituents R 5 , Re, R 7 , Re or Rg, or alternatively the said radical is linked to the rest of the molecule directly via one of the carbon atoms bearing the substituents R 5 , R 6 , R , Rs or R 9 , in which case one of these substituents is absent:
  • R 5 , R 6 , R 7 , Re, R9 and R 0 which may be identical or different, represent a hydrogen atom or a group chosen from i) (d-C 8 )alkyl, N) hydroxyl, iii) carboxyl, iv) and -O-protected with a protecting group;
  • R 5 and R 9 together form a divalent group -0-(CR a Rb) n -0- with R a and R , which may be identical or different, representing a hydrogen atom or a group (C C 8 ) alkyl such as methyl or t-butyl, (C C 8 )alkoxy, allyl, (poly)halo(CrC 8 )alkyl such as trifluoromethyl, and n is equal to 1 , 2 or 3, and in particular R 5 and R 9 together form a divalent group -0-CH 2 -CH 2 -0- or -0-C(CH 3 ) 2 -0-;
  • Rn and R 2 which may be identical or different, a hydrogen atom, an alkali metal, an alkaline-earth metal or a protecting group,
  • Rn and R 2 together form a divalent group -(CR a Rb) n - with R a and R , and n as defined previously;
  • ⁇ Y represents an oxygen or sulfur atom
  • X and X' which may be identical or different, represent:
  • the divalent group(s) or combinations thereof are chosen from -0-; -N(R)-; -C(O)- with R chosen from a hydrogen atom and a C C 4 alkyl radical; > p and p', which may be identical or different, represent an integer equal to 0 or 1 ; and
  • C S at represents a linear or branched, optionally cyclic C Ci 8 alkylene chain.
  • Another subject of the invention concerns a process for dyeing and/or lightening keratin materials, particularly keratin fibres, especially dark fibres, in which a suitable dye composition comprising one or more direct dyes bearing a group derived from ascorbic acid of formula (I) as defined previously is applied to the said materials.
  • Another subject of the invention is a dye composition
  • a dye composition comprising, in a cosmetically suitable medium, at least one direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
  • Another subject of the invention concerns a direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
  • the direct dyes of formula (I) afford fast coloration on keratin fibres.
  • the coloration, especially using the compounds of formula (I) with A representing a fluorescent coloured chromophore, is also visible on keratin materials that are even dark, in particular human keratin fibres, especially the hair, without degrading the said material, remanent with respect to shampooing, common attacking factors (sunlight or perspiration), and other hair treatments, even in the absence of a reducing agent.
  • the direct dyes of formula (I) afford lightening of keratin materials such as keratin fibres, particularly dark keratin fibres and more particularly dark hair, in general with a tone depth of less than or equal to 6, preferably less than or equal to 4.
  • the dyes of formula (I) according to the invention are moreover stable with respect to oxidizing agents, and show satisfactory solubility cosmetic dyeing media. These dyes especially broaden the colour range from yellow to blue.
  • the dyes of formula (I) colour keratin materials after application to keratin fibres in a manner that is strong, intense, chromatic and/or remanent with respect to external attacking factors, with low coloration selectivity between the root, and on different types of fibre, do not necessarily oblige a reductive treatment of the fibres or any chemical oxidizing agent, and which are visible on the said materials, even dark materials.
  • the term "dark keratin fibres", particularly naturally or artificially dark hair, means hair whose tone depth is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut-brown).
  • the lightening of the hair is evaluated by the "tone depth” variation before and after application of the compound of formula (I).
  • tone is based on the classification of natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of natural shades are well known to hairstyling professionals and are published in the book Sciences des.s capillaires [Hair treatment sciences] by Charles Zviak, 1988, published by Masson, pp. 215 and 278.
  • the tone depths range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
  • the term "bleached hair” means hair whose tone depth is greater than 4 (chestnut-brown) and preferably greater than 6 (dark blond).
  • One means for measuring the lightening effect given to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of reflectance of the hair.
  • the curve corresponding to the treated hair should show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to the untreated hair.
  • the wavelength at which the difference is maximal between the reflectance curve for the treated hair and that for the untreated hair is in the wavelength range from 500 to 650 nanometers and preferably in the wavelength range from 550 to 620 nanometers.
  • aryl or heteroaryl radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
  • a C1-C16 and preferably C C C 8 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C C 2 alkoxy, C 2 -C 4 (poly)hydroxyalkoxy, acylamino, amino substituted with two C C 4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6- membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen;
  • halogen atom such as chlorine, fluorine or bromine
  • an optionally cationic 5- or 6-membered heteroaryl radical preferentially imidazolium, optionally substituted with a (C C 4 )alkyl radical, preferentially methyl;
  • an optionally cationic 5- or 6-membered heteroaryl radical preferentially imidazolium, optionally substituted with a (C C 4 )alkyl radical, preferentially methyl;
  • an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C C 2 alkyl radical;
  • the carboxylic radical possibly being in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);
  • an alkylsulfonylamino radical (R'S0 2 -NR-) in which the radical R represents a hydrogen atom or a C C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C C 4 alkyl radical or a phenyl radical;
  • ⁇ an aminosulfonyl radical ((R) 2 N-S0 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C C 4 alkyl radical optionally bearing at least one hydroxyl group;
  • cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups:
  • alkylcarbonylamino ((RCO-NR'-) in which the radical R' is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R is a C C 2 alkyl radical or an amino radical substituted with two C C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming, with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom;
  • alkylcarbonyloxy in which the radical R is a C C 4 alkyl radical or an amino radical substituted with one or two identical or different C C 4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen;
  • alkylcarbonyloxy in which the radical R is a C C 4 alkyl radical or an amino radical substituted with one or two identical or different C C 4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen; a cyclic or heterocyclic radical, or a non-aromatic portion of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups; a hydrocarbon-based chain is unsaturated when it comprises one or more double bonds and/or one or more triple bonds; an "aryl" radical represents a fused or non-fused monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl radical or an amino radical substitute
  • the charge when the charge is endocyclic, it is included in the electron derealization via the mesomeric effect, for example it is a pyridinium, imidazolium or indolinium
  • R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(CrC 8 )alkyl group such as methyl;
  • G represents a covalent ⁇ bond, or a divalent group or the combination chosen from: -N(R)-; -N + (R')(R")-, Q " ; -0-; -S-; -C(O)-; -S(0) 2 - with R' and R", which may be identical or different, representing a hydrogen atom or a group (hydroxy)(CrC 6 )alkyl and Q " represents an anionic counterion;
  • alk represents an alkylene group
  • G represents -N(R')- with R' chosen from a hydrogen atom and a C C 4 alkyl radical;
  • cationic aryl bearing an exocyclic charge means an aralkyi ring whose cationic group is outside the said ring: it is especially an ammonium or phosphonium substituent R + such as trimethylammonium outside the aryl such as phenyl or naphthyl:
  • a "cyclic radical” is a non-aromatic, monocyclic or polycyclic, fused or non-fused cycloalkyl radical, containing from 5 to 22 carbon atoms, which may comprise one or more unsaturations;
  • a "heterocyclic radical” is a non-aromatic, monocyclic or polycyclic, fused or non- fused 5- to 22-membered radical, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, morpholinyl, thiomorpholinyl, piperidyl, piperazinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydr
  • the said "protecting group” is chosen from:
  • aryl for instance halophenyl such as para-chlorophenyl,
  • heteroaryl such as optionally /V-oxidized pyridine, for instance /V-oxido-3- methyl-2-picolyl or anthryl,
  • tetrahydropyranyl THP tetrahydropyranyl
  • THTP tetrahydrothiopyranyl
  • S- mono or S,S- dioxide tetrahydropyranyl
  • 4-methoxyTHP 4-methoxyTHTP
  • tetrahydrofuryl THF
  • aryl-heteroaryl such as 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl (tritylone),
  • n) mono/di/tri(CrC 8 )alkylsilyl such as trimethylsilyl (TMS), triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, t-butyldimethylsilyl or triisopropylsilyl,
  • triarylsilyl such as triphenylsilyl
  • triaryl(CrC 8 )alkyl such as tribenzylsilyl, (triphenyl)dimethylsilyl, tri-para- xylylsilyl;
  • R-C(Y)- with o R representing 1) a hydrogen atom, or 2) a group (d-C 8 )alkyl such as methyl, 3) (poly)halo(aryl)(CrC 8 )alkyl such as chloromethyl, dichloromethyl, trichloromethyl or trifluoromethyl or chlorodiphenylmethyl, 4) (C C 8 )alkoxy such as methoxy, ethoxy, isobutoxy, 5) (aryl)(C 2 -C 8 )alkenyloxy such as vinyloxy, allyloxy, or cinnamyloxy, 6) (poly)halo(CrC 8 )alkoxy such as trichloroethoxy, 7) (C 2 - C 8 )alkenyl, 6) (Ci-C 8 )alkoxy(CrC 8 )alkyl such as methoxymethyl, 8) (poly)aryl(Ci-C 8 )alkyl such
  • o Y representing an oxygen or sulfur atom or a group R'N or R'R"N + , Q " with R' and R", which may be identical or different, representing a hydrogen atom or a group (CrC 8 )alkyl and Q " representing an organic or mineral anionic counterion;
  • R' and R which may be identical or different, representing 1) a hydrogen atom, or 2) a hydroxyl group, 3) (CrC 8 )alkoxy, 4) (C 2 - C 8 )alkenyloxy such as vinyloxy, 6) aryl such as 2,4,6- trimethylphenyl or mesityl, 7) aryl(CrC 8 )alkyl, the aryl group being optionally substituted with one or more groups (CrC 8 )alkyl such as benzyl or 2,4,6- trimethylbenzyl, 8) aryloxy such as phenoxy, 9) aryloxy(CrC 8 )alkyl such as phenoxymethyl, 10) cycloalkyl such as adamantyl, 11) heterocycloalkyl, 12) heteroaryl, or 13) (di)(CrC 8 )(alkyl)amino such as dimethylamino;
  • alkyl radical is a linear or branched C Ci 6 and preferably C C 8 hydrocarbon-based radical; particularly C C 4 such as methyl or ethyl;
  • the expression "optionally substituted” attributed to the alkyl radical means that the said alkyl radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) C C 4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C C 4 alkyl radicals, the said alkyl radicals possibly forming with the nitrogen atom that bears them a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N + R'R"R"', M " for which R', R" and R'", which may be identical or different, represent a hydrogen atom or a C C 4 alkyl group, or else -N + R'R"R"', forms a heteroaryl such as imidazolium optionally substituted with a C C 4 alkyl group, and M " represents the organic or mineral
  • the compounds of formula (I) according to the invention may be cationic, anionic or neutral;
  • one or more groups in the compound can ensure the electrical neutrality, for example if the rest of the compound is cationic, with groups -O " (oxalate), -COO " (carboxylate), R 3 N + - (ammonium), or R 3 P + - (phosphonium); - when the compound is anionic, then the organic or mineral counterion(s) are cationic, preferentially chosen from mineral cations such as alkali metals or alkaline-earth metals such as Na, Mg, K and Ca, and organic cations such as ammonium NH 4 + or (di/tri)(CrC 8 )alkylammonium,
  • the counterion(s) are anionic species, preferentially chosen from i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including C C 6 alkylsulfonates; Alk-S(0) 2 0 " such as methanesulfonate or mesylate, and ethanesulfonate; iv) arylsulfonates: Ar- S(0) 2 0 " such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfites: Alk-0-S(0)0 " such as methyl sulfite and ethyl sulfite; x) aryl sulfites: Ar-0-S(0)0 " such as benzene s
  • an "organic or mineral acid salt” is more particularly chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 S0 4 , iv) alkylsulfonic acids: Alk-S(0) 2 OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(0) 2 OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-0-S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii)
  • coloured chromophore means a radical derived from a dye, i.e. which has the capacity of colouring and which is in the form of a coloured compound that may be observed with the naked eye (absorbing light at a wavelength in the UV and visible radiation range, i.e. at a wavelength ab s of between 250 and 800 nm, particularly in the visible spectrum between 400 and 700 nm).
  • the dye absorbs in the yellow, orange, red, violet or blue range (see, for example, Ullmann's Encyclopedia of Industrial chemistry "Dyes, General Survey", 2005 Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim10.1002/14356007.a09_073 and Color Chemistry, Synthesis, Properties, and Applications of Organic Dyes and Pigments, H. Zollinger, 2003, 3rd Ed. Verlag Helvetica Chimica Acta, Wiley-VCH, chap. 1.1 and 2.1).
  • the term "fluorescent chromophore” means a radical derived from a fluorescent dye as defined previously, which, besides being a dye, i.e.
  • a fluorescent dye is especially a compound that is capable of absorbing UV or visible radiation at a wavelength ab s of between 400 and 700 nm and capable of re-emitting in the visible range at an emission wavelength em of between 410 and 800 nm.
  • fluorescent compounds are dyes that are capable of absorbing in the visible range ab s between 400 and 800 nm and of re-emitting in the visible range em between 410 and 810 nm. More preferentially, fluorescent dyes are dyes that are capable of absorbing at a ab s of between 420 and 550 nm and of re-emitting in the visible range em between 470 and 600 nm.
  • the radical A of formula (I) may contain one or more chromophores, which may be identical or different, it being understood that at least one chromophore is coloured.
  • coloured chromophores that are useful, mention may be made of those derived from the following dyes: acridines; acridones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanins such as zerocyanins, azacarbocyanins, diazacarbocyanins, diazahemicyanins, hemicyanin, or tetraazacarbocyanins; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines;
  • polymethines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.
  • chromophore A is chosen from those derived from (poly)azo dyes such as (di)azo, hydrazono dyes and (poly)methine dyes such as styryls and anthraquinones.
  • the coloured chromophore A is chosen from cationic chromophores, preferentially those known as
  • Het + represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted with one or more (C C 8 ) alkyl groups such as methyl;
  • Ar + represents an aralkyi radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, particularly tri(CrC 8 )alkylammonium such as trimethylammonium;
  • Ar represents an aryl group, especially phenyl, optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (C C 8 )alkyl, ii) optionally substituted (C C 8 )alkoxy, iii) (di)(CrC 8 )(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(CrC 8 )alkylamino, v) optionally substituted A/-(Ci-C 8 )alkyl-A/-aryl(CrC 8 )alkylamino or alternatively Ar represents a julolidine group;
  • - Ar is an optionally substituted divalent (hetero)alkylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more groups (CrC 8 )alkyl, hydroxyl or (CrC 8 )alkoxy;
  • - Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more groups (CrC 8 )alkyl, hydroxyl, (di)(CrC 8 )(alkyl)amino, (CrC 8 )alkoxy or phenyl;
  • R a and R b which may be identical or different, represent a hydrogen atom or a group (d-Cs)alkyl, which is optionally substituted, preferentially with a hydroxyl group;
  • R a with a substituent of Het + and/or R b with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, R a and R b represent a hydrogen atom or a group (CrC 4 )alkyl, which is optionally substituted with a hydroxyl group;
  • - Q " represents an anionic counterion such as a halide or an alkyl sulfate
  • chromophore (III), ( ⁇ ), (IV), (IV) or (V) is linked to the rest of the molecule of formula (I) via Het + , Ar + , Ar or Ar".
  • R 1 representing a group (C C 4 )alkyl such as methyl
  • R 2 and R 3 which may be identical or different, representing a hydrogen atom or a group (Ci-C 4 )alkyl such as methyl;
  • R 4 representing a hydrogen atom or an electron-donating group such as optionally substituted (CrC 8 )alkyl, optionally substituted (C C 8 )alkoxy, or (di)(C
  • R 4 is a hydrogen atom
  • - Z represents a group CH or a nitrogen atom, preferentially CH,
  • the chromophores (111-1 ) and (IV-1 ) are chosen from Basic Red 51 ,
  • the chromophore A is chosen from anionic chromophores, especially those derived from direct dyes known as "Acid dyes". More particularly, the anionic chromophore A is chosen from (poly)azo dyes such as anionic (di)azo, anthraquinone, naphthoquinone, triaryl methane and nitro dyes, xanthene derivatives, quinoline derivatives and indoles.
  • R 7 , R 8 , R9, R10, R'7, R'e, R'9 and R' 0 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R"-S(0) 2 - with R" representing a hydrogen atom, an alkyl group, an aryl group, (di)(CrC 8 )(alkyl)amino, aryl(C C 8 ) (alkyl)amino; preferentially a phenylamino or phenyl group;
  • aryl(CrC 8 )(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 " )-, M + and iv) alkoxy with M + as defined previously;
  • cycloalkyi especially cyclohexyl
  • Ar-N N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C 8 )alkyl, (0) 2 S(0 , M + or phenylamino;
  • W represents a sigma bond ⁇ , an oxygen or sulfur atom, or a divalent radical i)
  • R -NR- with R as defined previously, or ii) methylene -C(R a )(Rb)- with R a and R , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively R a and R form, with the carbon atom that bears them, a spiro cycloalkyi; preferentially W represents a sulfur atom or R a and R together form a cyclohexyl;
  • the chromophore (VI) or (VII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical (O)CO " -, M + on one of the rings A, B, or C; preferentially sodium sulfate;
  • chromophores of formula (VI) derived from dyes, mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
  • chromophores of formula (VII) derived from dyes mention may be made of: Acid Red 11 1 , Acid Red 134, Acid yellow 38. b) the anionic pyrazolone azo chromophores of formula (VIII) or (IX):
  • Rii, Ri2 and R 3 which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0) 2 S(0 " ), M + with M + as defined previously;
  • ⁇ Ri4 represents a hydrogen atom, a group (d-C 8 )alkyl or a group -C(0)0 " , M + with M + as defined previously;
  • ⁇ Ri5 represents a hydrogen atom
  • Ri 6 represents an oxo group, in which case R' 16 is absent, or alternatively R 5 with Ri 6 together form a double bond;
  • R 7 and R 8 which may be identical or different, represent a hydrogen atom, or a group chosen from:
  • Ar-0-S(0) 2 - with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C 8 )alkyl;
  • Ri 9 and R 2 o together form either a double bond, or a benzo group D, which is optionally substituted;
  • R'i6, R'i9 and R' 2 o which may be identical or different, represent a hydrogen atom or a group (CrC 8 )alkyl, or hydroxyl;
  • R 2 i represents a hydrogen atom or a group (CrC 8 )alkyl or (CrC 8 )alkoxy;
  • R a and R a which may be identical or different, are as defined previously, preferentially R a represents a hydrogen atom and R represents an aryl group;
  • ⁇ Y represents either a hydroxyl group or an oxo group
  • ⁇ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that:
  • the chromophore (VIII) or (IX) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + on one of the rings D or E; preferentially sodium sulfonate;
  • chromophores of formula (VIII) derived from dyes mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of chromophores of formula (IX) derived from dyes, mention may be made of: Acid Yellow 17.
  • R22, R23, R24, R25, R ⁇ 6 and R27 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • aryloxy or arylthio optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0) 2 S(0 " )-, M + with M + as defined previously;
  • aryl(CrC 8 )(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0) 2 S(0 " )-, M + with M + as defined previously; - (di) (C C 8 )(alkyl)amino;
  • ⁇ Z' represents a hydrogen atom or a group NR 28 R29 with R 28 and R 29 , which may be identical or different, representing a hydrogen atom or a group chosen from: - (C C 8 )alkyl; polyhydroxy(CrC 8 )alkyl such as hydroxyethyl;
  • aryl optionally substituted with one or more groups, particularly i) (d-C 8 )alkyl such as methyl, n-dodecyl, n-butyl; ii) (0) 2 S(0 , M + with M + as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents a group (CrC 8 )alkyl; cycloakyl; especially cyclohexyl;
  • ⁇ Z represents a group chosen from hydroxyl and NR' 2 8R'29 with R' 28 and R' 29 , which may be identical or different, representing the same atoms or groups as R 28 and R 29 as defined previously;
  • the chromophore (X) or (XI) comprises at least one sulfonate radical (0) 2 S(0 , M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • chromophores of formula (X) derived from dyes mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3;
  • chromophores of formula (XI) derived from dyes mention may be made of: Acid Black 48; d) nitro chromophores of formula (XII) or (XIII):
  • R 30 , R 3 1 and R 32 which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
  • heterocycloalkyl such as piperidino, piperazino or morpholino
  • R30, R31 and R32 represent a hydrogen atom
  • R c and R d which may be identical or different, represent a hydrogen atom or an alkyl group
  • ⁇ W is as defined previously; W particularly represents a group -NH-;
  • ALK represents a linear or branched divalent C C 8 alkylene group; in particular, ALK represents a group -CH 2 -CH 2 -;
  • ⁇ n 1 or 2;
  • ⁇ p represents an integer between 1 and 5 inclusive
  • ⁇ q represents an integer between 1 and 4 inclusive
  • ⁇ u is 0 or 1 ;
  • J represents a nitro or nitroso group; particularly nitro; ⁇ when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0) m - with m representing an integer 1 or 2; preferentially J represents a radical -S0 2 -;
  • ⁇ M' represents a hydrogen atom or an organic or mineral cationic counterion
  • ⁇ may be present or absent, represents a benzo group optionally
  • the chromophore (XII) or (XIII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • chromophores of formula (XII) derived from dyes mention may be made of: Acid Brown 13; Acid Orange 3; as examples of chromophores of formula (XIII) derived from dyes, mention may be made of: Acid Yellow 1 , sodium salt of 2,4- dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitrobenzenesulfonic acid, 2(4'-N,N(2"- hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3- nitrobenzenesulfonic acid; e) the triarylmethane chromophores of formula (XIV):
  • R33, R34, R35 and R 36 which may be identical or different, represent a hydrogen atom or a group chosen from (d-C 8 )alkyl, optionally substituted aryl and optionally substituted aryl(CrC 8 )alkyl; particularly a group (CrC 8 )alkyl and benzyl optionally substituted with a group (0) m S(0 , M + with M + and m as defined previously;
  • R37, R38, R39, R40, R41 , R42, R43 and R 44 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • X, X' and X" which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (CrC 8 )alkyl;
  • R 44 together form a fused benzo group: ⁇ ; with ⁇ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0) 2 S(0 " )-, M + ; iv) hydroxyl; v) mercapto; vi) (di)(C C 8 )(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'- C(X)-; ix) R°-X'-C(X)-X"-; with M + , R°, X, X', X" as defined previously;
  • R 37 to R 40 represent a hydrogen atom
  • R 41 to R 44 which may be identical or different, represent a hydroxyl group or (0) 2 S(0 " )-, M + ; and when R 43 with R 44 together form a benzo group, it is preferentially substituted with a group (0) 2 S(0 " )-; it being understood that:
  • the chromophore (XIV) comprises at least one of the rings G', H', or ⁇ containing at least one sulfonate radical (0) 2 S(0 or a carboxylate radical -C(0)0 " ; preferentially sulfonate;
  • chromophores of formula (XIV) derived from dyes
  • R 45 , R 46 , R47 and R 48 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R 49 , R 50 , R51 and R 52 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • R54, R55 and R 48 represent a hydrogen or halogen atom
  • ⁇ G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom; ⁇ L represents an alkoxide O " , M + ; a thioalkoxide S " , M + or a group NR f , with R f representing a hydrogen atom or a group (d-C 8 )alkyl, and M + as defined previously; M + is particularly sodium or potassium;
  • ⁇ L' represents an oxygen or sulfur atom or an ammonium group: N + R f R g , with R f and R g , which may be identical or different, representing a hydrogen atom, a group (CrC 8 )alkyl, optionally substituted aryl; U represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more groups (CrC 8 )alkyl or (0) m S(0 , M + with m and M + as defined previously;
  • ⁇ Q and Q' which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
  • ⁇ M + is as defined previously;
  • chromophores of formula (XV) derived from dyes
  • R53, R54, R55, R56, R57, R58, R59 and R 60 which may be identical or different, represent a hydrogen atom or a group chosen from:
  • ⁇ G represents an oxygen or sulfur atom or a group NR e with R e as defined previously; particularly G represents an oxygen atom;
  • Rj and R h which may be identical or different, represent a hydrogen atom or a group (C C 8 )alkyl;
  • the chromophore (XVI) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + ; preferentially sodium sulfonate;
  • dyes of formula (XVI) mention may be made of: Acid Blue 74. h) the anionic quinoline-
  • R 6 i represents a hydrogen or halogen atom or a group (CrC 8 )alkyl
  • R62, R63, and R 6 4 which may be identical or different, represent a hydrogen atom or a group (0) 2 S(0 " )-, M + with M + representing a hydrogen atom or an organic or mineral cationic counterion; ⁇ or alternatively R 6 i with R 6 2, or R 6 i with R 6 4, together form a benzo group optionally substituted with one or more groups (0) 2 S(0 " )-, M + with M + representing a hydrogen atom or an organic or mineral cationic counterion; it being understood that:
  • the chromophore (XVII) comprises at least one sulfonate radical (0) 2 S(0 " )-, M + preferentially sodium sulfonate;
  • chromophores of formula (XVII) derived from dyes mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
  • the anionic dyes that are most particularly preferred are the dyes designated in the Color Index under the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9, 10- anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4- hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid), C.I.
  • the anionic chromophore A is chosen from anionic (poly)azo dyes such as (di)azo dyes, anthraquinones, naphthoquinones, triarylmethanes, nitro dyes, and quinoline and indole derivatives, i.e. it does not contain any xanthene derivatives.
  • A is not an anionic fluorescein-based chromophore, more particularly A is not an anionic chromophore obtained from a xanthene derivative of formula (XV) as defined previously.
  • the radical A of formula (I) may contain one or more identical or different fluorescent coloured chromophores.
  • A is is a coloured and fluorescent chromophore.
  • coloured and fluorescent chromophore does not mean “optical brightener” chromophores, or any other fluorescent but colourless compounds, i.e. which do not absorb in the visible spectrum (see Ullmann's Encyclopedia of Industrial Chemistry, in the chapters “Fluorescent Dyes” and “Optical Brighteners”, 2005, Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/143560007.a18_153; and 2005, Wiley-VCH Verlag GmbH & co. KGaA, Weinheim 10.1002/143560007.a1 1_279).
  • fluorescent coloured chromophores that are useful in the present invention, mention may be made of radicals derived from the following dyes: acridines, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro ⁇ 2-[(2/-/-pyrrol-2- ylidene-kN)methyl]-1 H-pyrrolato-kN ⁇ bores (BODIPY ®), dipyrinones, diketopyrrolopyrroles, fluorindines, (poly)methines (especially cyanins and styryls/hemicyanins), naphthalimides, naphthanilides, naphthylamine (such as dansyls), naphtholactams, oxadiazoles, oxazines, perilones
  • the chromophores are chosen from those derived from dyes of coumarin type, of (poly)methine type, especially cyanins and styryl/hemicyanin dyes, and of naphthalimide type.
  • radical A of formula (I) contains at least one cationic radical borne by, or included in, at least one of the chromophores.
  • the cationic radical is a quaternary ammonium; more preferentially, the cationic charge is endocyclic.
  • cationic radicals are, for example, a cationic (di/tri)(CrC 8 )alkylammonium radical bearing an exocyclic charge, or a cationic acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazol
  • W + representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (d-C 8 )alkyl optionally substituted especially with one or more hydroxyl groups;
  • W' + representing a divalent heterocyclic or heteroaryl radical as defined for W + ;
  • Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (CrC 8 )alkyl, preferably of C C 4 such as methyl; iii) one or more groups hydroxyl; iv) one or more groups (C C 8 )alkoxy such as methoxy; v) one or more groups hydroxy(CrC 8 )alkyl such as hydroxyethyl, vi) one or more groups amino or (di)(CrC 8 )alkylamino, preferably with the C C 4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroary
  • Ar' is a divalent aryl radical as defined for Ar
  • m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferentially 1 ;
  • R c and R d which may be identical or different, represent a hydrogen atom or an optionally substituted group (CrC 8 )alkyl, preferentially of C C 4 , or alternatively R c contiguous with W or W and/or R d contiguous with Ar or Ar' form, with the atoms that bear them, a (hetero)cycloalkyl, particularly R c is contiguous with W + or W' + and forms a (hetero)cycloalkyl such as cyclohexyl;
  • the dyes of formula (I) contain a chromophore A that is not an anionic fluorescein-based chromophore, and more particularly A is not an anionic chromophore based on a xanthene derivative of formula (XV) as defined previously.
  • the dye of formula (I) is a quaternized or quaternizable fluorescent dye such that, in formula (I), A represents a naphthalimidyl radical optionally bearing an exocyclic cationic charge, of formula (XX) or (XXI):
  • G' represents an amino group -NR f R e or ammonium group -N + R f R e R h , M " ;
  • G represents a divalent amino group -N(R h )- or ammonium group -N + (R h )(R j )-, M " ;
  • R e , R f , R 9 , R h and R j which may be identical or different, represent a hydrogen atom or a C C 6 alkyl group optionally substituted preferentially with a hydroxyl, amino, di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium group, such as trimethylammonium, M " ; with M " with M " representing an organic or mineral counterion,
  • R 1 which may be identical or different, represents a hydrogen atom, a halogen atom, a (di)(CrC 4 )(alkyl)amino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C 4 )alkoxy, (poly)hydroxy(C 2 -C 6 )alkoxy, (C C 4 )alkylcarbonyloxy, (C C 4 )alkoxycarbonyl or (Ci-C 4 )alkylcarbonylamino radical, an acylamino, carbamoyl or (Ci-C 4 )alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (CrCi 6 )alkyl optionally substituted with a group chosen from (CrC 6 )alkoxy, hydroxyl, cyano, carboxyl and (di)(C C 4 )(alkyl)a
  • G' represents an amino group -NR f R e and G" represents a divalent amino group -N(R h )-
  • R 1 represents a hydrogen atom
  • R e and R 9 represent a Ci-C 6 alkyl group substituted with a group di(CrC 6 )alkylamino or tri(C C 6 )alkylammonium, M "
  • R f , R h represent a hydrogen atom or a C C 6 alkyl group
  • the amino group R f R e N- or -N(R h )- is in position 4 or 5 of the naphthalimidyl radical.
  • W + or W' + is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium optionally substituted with one or more identical or different C C 4 alkyl radicals.
  • C sat represents a linear or branched, optionally substituted, optionally cyclic divalent C Ci 8 alkylene chain.
  • Substituents that may be mentioned include amino, (C C 4 )alkylamino and di(C C 4 )alkylamino groups, or the group R a -Z a -C(Z b )- (in which Z a , Z b , which may be identical or different, represent an oxygen or sulfur atom, or a group NR a ', and R a represents an alkali metal, a hydrogen atom or a group C C 4 alkyl and R a ' represents a hydrogen atom or a group Ci-C 4 alkyl) preferably present in the beta or gamma position of the ascorbic acid- based radical of formula (11-1 ) to (M-4) as defined previously or of formula ( ⁇ -1 ) to ( ⁇ -4) as defined in point 1.4 below.
  • C sat represents a chain -(CR 1 R 2 ) k - with k representing an integer between 1 and 10 inclusive
  • R 1 and R 2 which may be identical or different, representing a hydrogen atom or a group (C C 4 )alkyl, (C Ci 2 )alkoxy, hydroxyl, cyano, carboxyl or (di)(C C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; preferentially, and R 2 , are hydrogen atoms or an amino group; more preferentially, and R 2 represent a hydrogen atom, thus forming an alkylene chain -(CH 2 ) k — with k' being an integer between 1 and 8 inclusive. More particularly, k' is 1 , 2 or 3.
  • radical(s) X and X' which may be identical or different, represent the following sequence:
  • T and T' which may be identical or different, represent one or more radicals or combinations thereof chosen from: -S(0) 2 -; -0-; -S-; -N(R)-; -N + (R)(R°)-, Q " ;
  • R, R° which may be identical or different, representing a hydrogen atom, a C C 4 alkyl, C C 4 hydroxyalkyl or aryl(C C 4 )alkyl radical and Q " representing an organic or mineral anionic counterion; and a cationic or non- cationic, preferentially monocyclic heterocycloalkyl or heteroaryl radical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, more preferentially imidazolium, piperazinyl or piperidyl;
  • T and T represent one or more radicals or combinations thereof chosen from -0-, -N(R)-, -C(O)-, with R chosen from a hydrogen atom and a (C C 4 )alkyl radical;
  • indices t and t' which may be identical or different, are equal to 0 or 1 ;
  • R 2 which may be identical or different, represent a hydrogen atom or a group (C C 4 )alkyl, (C C 4 )alkoxy, hydroxyl, cyano, carboxyl or (di)(C C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen, such as morpholino or piperidino; and R 2 particularly represent a hydrogen atom;
  • Z represents divalent group chosen from:
  • the ascorbic acid-based radical Asc of the dye of formula (I) represents an ascorbyl or dehydroascorbyl radical chosen from formulae (11-1 ) to (M-4) as defined previously.
  • the ascorbic acid-based radical is chosen from formulae (11-1 ) to (II- 3) such that:
  • R 5 is absent and Asc is linked to the rest of the molecule via the carbon atom bearing R 6 and R 7 ; - R 6 , R 7 and R 8 represent a hydrogen atom
  • R1 0 represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen
  • R 9 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously; preferentially:
  • aryl for instance halophenyl such as para-chlorophenyl,
  • aryl(CrC 8 )alkyl such as benzyl, s) R-C(O)-, with R representing 1) a hydrogen atom, or 2) a group (CrC 8 )alkyl such as methyl, 3) (poly)halo(aryl)(CrC 8 )alkyl such as chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl or chlorodiphenylmethyl, 4) (CrC 8 )alkoxy such as methoxy, ethoxy or isobutoxy, 5) (aryl)(C 2 -C 8 )alkenyloxy such as vinyloxy, allyloxy or cinnamyloxy, 6) (poly)halo(CrC 8 )alkoxy such as trichloroethoxy, 7) (C 2 -C 8 )alkenyl, 6) (C C 8 )alkoxy(CrC 8 )alkyl such as meth
  • R 9 represents a hydroxyl group or the same -O-protected with a protecting group chosen from:
  • R-C(O)- with R representing 1) a hydrogen atom, or 2) a group (C C 8 )alkyl such as methyl.
  • the dye of formula (I) comprises a group Asc of formula (11-1 ) to (M-3) as defined previously with R 9 absent and Asc linked to the rest of the molecule via the carbon atom bearing R 8 ;
  • R 6 , R 7 and R 9 represent a hydrogen atom
  • R-io represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen
  • R 5 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously.
  • Asc is chosen from the groups of formulae ( ⁇ -1 ) to ( ⁇ -3):
  • R' 9 representing a hydrogen atom or a protecting group as defined previously; preferentially, R' 9 represents a hydrogen atom, Rn and R 2 being as defined previously, and • ⁇ / ⁇ - representing the point of attachment of Asc to the rest of the molecule of formula (I).
  • the dye of formula (I) comprises a group Asc of formula (M-4) as defined previously with R 9 absent and Asc linked to the rest of the molecule via the carbon atom bearing Y and R 0 represents a hydrogen atom or a (C C 4 )alkyl, particularly hydrogen, in which case Asc is of formula (M'-4) below:
  • the dyes of formula (I) are such that they correspond to formula ( ⁇ '):
  • Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly (M'-1 ) to (M'-4);
  • C sat represents a (d-C 8 )alkylene chain, such as -(CH 2 ) k - with k being an integer between 1 and 8 inclusive; preferentially, k is 1 , 2 or 3;
  • R 2 are as defined previously, particularly represent a hydrogen atom or a group (CrC 4 )alkyl
  • T a , T b , and T c which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0) 2 - -0-, -S-, -N(R)-, -N + (R)(R°)- M " and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom or a radical (C C 4 )alkyl or hydroxy(C C 4 )alkyl; or an aryl(C C 4 )alkyl such as benzyl, and M " represents an organic or mineral anionic counterion such as a halide;
  • T a represents a group -N(R)- and T c represents a group chosen from a radical -0-, -C(O)- or -N(R)-, or a combination thereof with R, representing a hydrogen atom or a group (C C 4 )alkyl such as methyl; and
  • the radical Het + , W + , or W' + is a group chosen from imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, indolinium and pyrazolium, optionally substituted preferentially with one or more identical or different C C 4 alkyl radicals. More particularly, Het + , W + or W' + , is chosen from pyridinium, imidazolium and indolinium groups optionally substituted with one or more identical or different (C C 4 )alkyl radicals, such as methyl.
  • Ar is an optionally substituted phenyl
  • Ar' is an optionally substituted phenylene
  • Ar + is an optionally substituted phenyl or naphthyl bearing an exocyclic tri(CrC 8 )alkylammonium cationic charge, M- with M- representing an organic or mineral anionic counterion, such as trimethylammonium.
  • the dye bearing an ascorbic acid-based group is a dye chosen from the compounds of formulae (l a ) to (l n ) below:
  • Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly ( ⁇ -1 ) to ( ⁇ -4);
  • G represents a group -NR c R d , or (d-C 6 )alkoxy; preferentially G represents a group -NR c R d , which is preferentially in the para position relative to the styryl, azo or hydrazono group;
  • R a and R' a which may be identical or different, represent an optionally substituted group (CrC 6 )alkyl; preferentially, R a represents a group (CrC 3 )alkyl optionally substituted with a hydroxyl group, preferentially unsubstituted, such as methyl;
  • R b represents a hydrogen atom or an optionally substituted C C 6 alkyl group; preferentially unsubstituted, such as methyl;
  • R c and R d which may be identical or different, represent a hydrogen atom, a group aryl(CrC 4 )alkyl, (CrC 6 )alkoxy or an optionally substituted group (C
  • R c and R d preferentially represent a hydrogen atom or a group (C
  • heterocyclic or heteroaryl group or alternatively two adjacent radicals R c and R d , borne by the same nitrogen atom together form a heterocyclic or heteroaryl group; preferentially, the heterocycle or heteroaryl is monocyclic and 5- to 7-membered; more preferentially, the groups are chosen from imidazolyl and pyrrolidinyl;
  • R c and R d represent identical groups; preferentially R c and R d represent a (CrC 3 )alkyl optionally substituted with a hydroxyl group, such as methyl, hydroxyethyl and 2-hydroxypropyl;
  • R g , R' g , R h and R' h which may be identical or different, represent a hydrogen atom, a halogen atom, a group (di)(C C 4 )(alkyl)amino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino, (C C 4 )alkoxy, (poly)hydroxy(C 2 -
  • G represents -NR c R d two groups R c and R' g ; R d and R g ; together form a saturated heteroaryl or heterocyde, optionally substituted with one or more groups (CrC 6 )alkyl, preferentially a 5- to 7-membered heterocyde containing one or two heteroatoms chosen from nitrogen and oxygen; more preferentially the heterocyde is chosen from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl groups;
  • Ri, R j , R' j and R'j which may be identical or different, represent a hydrogen atom, or a group C C 4 alkyl; more preferentially, R, R j , R' j and R'j represent a hydrogen atom;
  • R s represents a sulfonate radical (0) 2 S(0 " )-, M + or a carboxylate radical -C(0)0 " , M + with M + representing an organic or mineral cationic counterion; preferentially sulfonate such as sodium sulfonate;
  • Ri , R ⁇ , R3 and R 4 which may be identical or different, represent a hydrogen atom or a group (C C 4 )alkyl, (CrCi 2 )alkoxy, hydroxyl, cyano, carboxyl or (di)(Ci-C 4 )(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocyde, optionally comprising another heteroatom identical to or different from nitrogen;
  • R 2 , R 3 and R 4 are hydrogen atoms or an amino group; more preferentially, R ⁇ R 2 , R 3 and R 4 , represent a hydrogen atom;
  • R e , R f , R 9 , and R h which may be identical or different, represent a hydrogen atom or an alkyl C C 6 group optionally substituted preferentially with a group di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium, M " with M " representing an organic or mineral anionic counterion, such as trimethylammonium, M " ;
  • R e and R 9 represent an alkyl C C 6 group substituted with a group di(CrC 6 )alkylamino or tri(CrC 6 )alkylammonium, M " and R f , R h represent a hydrogen atom or a C C 6 alkyl group; and the amino group R f R e N- or -N(R h )- is in position 4 of the naphthalimidyl radical;
  • t and t' which may be identical or different, are equal to 0 or 1 ; preferentially, t' is 0:
  • T a , T b and T c which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0) 2 -, -0-, -S-, -N(R)-, -N + (R)(R°)- M " and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom, a radical (C C 4 )alkyl or hydroxy(C C 4 )alkyl; or an aryl(Ci-C 4 )alkyl, and M " represents an organic or mineral anionic counterion such as halide, preferentially, t' is zero and T c represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C C 4 )alkyl such as methyl; more particularly, T c represents a group -C(0)-0-, -O
  • • """ ⁇ j represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring; when the ring is present, the ring is preferentially a benzo; more preferentially, the ring is absent;
  • the direct dyes are chosen from those of formulae (l a ), (l b ), (l c ), (l f ), (l g ), (1), (lj), (l k ), (L) and (l n ).
  • the dyes according to the invention are chosen from the direct dyes of formulae (I'.), (I' b ), (l' c ), (l' f ), (l' g ), ( ⁇ ',), (I' j ), (l' k ), (l' m ) and (l' n ) below:
  • R a , R j and R' j represent a group (d-C 4 )alkyl such as methyl;
  • R b represents a hydrogen atom or a group (C C 4 )alkyl such as methyl; preferentially, R is a hydrogen atom;
  • R g and R' g are as defined previously and preferentially represent a hydrogen atom
  • R s represents a sulfonate radical (0) 2 S(0 " )-, M + such as sodium sulfonate;
  • R s is ortho to the group R c R d N- of (I' j )
  • T c represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C
  • T c represents a group -C(0)-0- or -N(R)-C(0)-;
  • ⁇ m' is 1 , 2 or 3;
  • n' is an integer between 1 and 10 inclusive, and more particularly between 3 and 6 such as 5;
  • R c and R d represent identical groups (CrC 3 )alkyl optionally substituted with a hydroxyl group, such as methyl or hydroxyethyl;
  • R e and R 9 represent a C C 6 alkyl group substituted with a group di(C C 6 )alkylamino or tri(CrC 6 )alkylammonium, M " ;
  • R f and R h represent a hydrogen atom or a C C 6 alkyl group; preferably the amino group R f R e N- or -N(R h )- is in position 4 of the naphthalimidyl radical; and M' representing an organic or mineral anionic counterion;
  • the styryl, hydrozono or azo function is in position 2 (ortho) or 4 (para) relative to the phenyl, preferentially in position 4 and that the styryl or hydrazono function is in position 2' (ortho) or 4' (para) relative to the pyridinium, or 2' (ortho) or 4' (para) relative to the phenyl for (l' k ), preferentially in position 4'.
  • the direct dyes are chosen from those of formulae (l b ), and (l m ) and more particularly (l' b ), and
  • dyes bearing an ascorbic acid-based group mention may be made especially of the following compounds:
  • the dyes of formula (l a ) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2). This reaction is well known to those skilled in the art. It is known as the Knoevenagel reaction and consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemi -471-60180-2). This reaction is illustrated in the scheme below:
  • Compounds (a2) may be synthesized via a nucleophilic substitution reaction between a compound (a3) and a compound (a4).
  • This reaction is known to those skilled in the art and is described in the literature. By way of example, reference may be made to the book Advanced Organic Chemistry (ISBN 0-471-60180-2). This reaction is illus
  • R to R 4 R a , R b , G, m, n, Tb, t' Tc, R,, R',, R h , R' h as defined previously and Hal representing a halogen atom such as fluorine.
  • Compounds (a4) may be synthesized via a reaction between a compound (a5) and a compound (a6). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 , R , m, n, Tb, t' as defined previously; Nu representing a nucleophilic group; ⁇ representing an electrophilic group; and T c the bond generated after attack of the nucleophile on the electrophile.
  • Carbodiimides Carboxylic acids N-Acylureas or anhydrides
  • acyl halides may rearrange to give isocyanates. These reactions are known to those skilled in the art and are described in the literature. Reference may be made to the book Advanced Organic Chemistry (ISBN 0- 471 -60180-2).
  • compounds (a4) may be synthesized via a reaction between a compound (a7) and a compound (a8). This reaction is illustrated in the scheme below:
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu as defined previously;
  • compounds (a2) may be synthesized via a reaction between a compound (a9) and a compound (a10). This reaction is illustrated in the scheme below:
  • T a the bond generated after attack of the nucleophile on the electrophile.
  • the covalent bonds T that may be generated are such as those listed in Table A for T c starting from the condensation of electrophiles with nucleophiles (see Table A above):
  • Hal represents a halogen atom such as fluorine
  • Another synthetic variant consists in reacting a compound (a12) with a heterocyclic compound (a8). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , R h , R' h and M' as defined previously;
  • the dyes of formula (lb) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2).
  • This reaction is well known to those skilled in the art, and is known as the Knoevenagel reaction, which consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is illustrated in the scheme below:
  • Compounds (a23) are known to those skilled in the art and are described in the literature. Some of them are commercially available. Compounds (a24) may be synthesized via a quaternization reaction between an electrophilic compound (a25) and a pyridine compound (a26). This reaction is well known to those skilled in the art.
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu, R,, R', and M' as defined previously;
  • the group Gp' represents a leaving group, which, once it has left, generates an anionic counterion. Mention may be made of halides such as iodide, bromide, chloride or the mesylate, sulfate, phosphate, triflate or tosylate group.
  • the compounds (a25) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below: Q ' (CRi3 ⁇ 4 m ScRjF -T-Asc 1
  • R to R 4 R a , R b , m, n, Tb, t' Tc, ⁇ , Nu as defined previously;
  • compounds (a28) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below:
  • R to R 4 R a , R b , m, n, Gp', Tb, t' Tc, ⁇ , Nu, as defined previously;
  • Compounds (a29) may be synthesized via a reaction between a compound (a30) and a compound (a23). This reaction is illustrated in the scheme below:
  • R-i to R 4 R a , R b , G, m, n, T a , £, 3Vu, R g , R' g , Ri, R'i, R h , R' h , M' as defined previously; compounds (a23) are as defined previously.
  • Compounds (a30) may be synthesized via a reaction between a compound (a27) and a pyridine derivative (a26). This reaction is illustrated by the scheme below: Gp'- (CR, R 2 ) m
  • Another synthetic variant consists in reacting a compound (a31) with compounds (a8)
  • Compounds (a31 ) may be synthesized via a reaction between a compound (a32) and a compound (a23). This reaction is illustrated in the scheme below:
  • the dyes of formula (lc) may be synthesized via the synthetic routes described previously for the dyes of formula (la).
  • the main difference is that compounds (a14), compounds bearing an indolinium unit, are used instead of compounds (a1 ), compounds bearing a pyridinium unit.
  • the reaction with compounds (a14) is illustrated in the scheme below:
  • R ⁇ to R 4 R a , Rb, m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , Ri, R'i, Rn, R'n, Rj, R'j, and M' as defined previously;
  • compounds (lb) may be synthesized via a condensation reaction between a compound (a15) and a compound (a8).
  • the reaction with compounds (a14) is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , m, n, Tb, f Tc, ⁇ , Nu, R g , R' g , Ri, R'i, Rn, R'n, Rj, R'j and M' as defined previously;
  • compounds (l d ) may be synthesized via a reaction between a compound (a36) and a compound (a6). This reaction is illustrated by the scheme below:
  • Compounds (a36) may be synthesized via a reaction between a compound
  • Compounds (a39) may be synthesized via a reaction between a compound (a4
  • compounds (a39) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
  • Compounds (a41 ) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
  • R ⁇ to R 4 R a , R b , G, m, n, Tb, t' Tc, ⁇ , N ⁇ u, Ri, R'i, R j , R' j , M' as defined previously;
  • the group Gp' represents a leaving group, which, once it has been removed, generates an anionic counterion M'. Mention may be made of halides such as iodide, bromide, chloride or the triflate, sulfate, phosphate, mesylate or tosylate group.
  • compounds (1 g) may be synthesized via a reaction between a compound ( heme below:
  • Compounds (a45) may be synthesized via a reaction between a compound (a46) and a compound (a27). This reaction is illustrated in the scheme below:
  • compounds (l g ) may be synthesized via a reaction between a compound ( eme below:
  • Compounds (a45') may be synthesized via a reaction between a compound (a46) an
  • R 4 with to R 4 , R a , G, m, n, Tb, t' Tc, ⁇ , Nu, R g , R' g , R h , R' h and M' as defined previously;
  • the first step, to form compound (a49), is a reaction that is well known to those skilled in the art. It is known as a "diazotization" reaction. This reaction is described in the literature. It consists in diazotizing an aromatic amine (compounds (a48)) and in condensing it with an electron-rich aromatic molecule to form a diazo bond. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471- 60180-2). Compounds (a48) are known to those skilled in the art and are described in the literature.
  • the second step, to form compound (a46), is a reaction that is well known to those skilled in the art. It is known as a "quaternization" reaction. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471 -60180-2).
  • R s represents a sulfonate group (S0 3 " M + ) with M + as defined previously, such as sodium or potassium.
  • Compounds (a8) are as described previously.
  • Compounds (l m ) may be synthesized via a reaction between a compound (a60) and a compound (a61 ), to give the intermediate ( ⁇ '), which may itself react with a nucleophilic group G'H to give (C).
  • the latter group is capable of reacting, for example via esterification, with a hydroxyl group of an ascorbic derivative Asc-OH. This reaction is illustrated in the scheme below:
  • Hal represents a halogen atom such as chlorine, bromine or iodine.
  • composition comprising the dye of formula (I) or (l')
  • Another subject of the invention is a dye composition
  • a dye composition comprising, in a cosmetically suitable medium, at least one fluorescent dye bearing a group derived from ascorbic acid of formula (I) or ( ⁇ ) as defined previously.
  • composition of the invention may also contain a reducing agent.
  • the composition does not contain any reducing agent.
  • the cosmetic composition comprising one or more dyes of formula (I) or ( ⁇ ) does not contain any chemical oxidizing agent.
  • chemical oxidizing agent means any chemical or enzymatic oxidizing agent other than atmospheric oxygen.
  • the dye composition that is useful in the invention generally contains an amount of dye of formula (I) or ( ⁇ ) of between 0.001 % and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005% and 20% by weight and even more preferentially between 0.01 % and 5% by weight relative to the total weight of the composition.
  • the dye composition may also contain additional direct dyes.
  • These direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • the dye composition may contain one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.
  • oxidation bases mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
  • couplers mention may be made especially of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
  • the coupler(s) are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the oxidation base(s) present in the dye composition is (are) each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
  • the addition salts of the oxidation bases and couplers used in the context of the invention are especially chosen from the salts of addition with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the salts of addition with a base, such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates
  • a base such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
  • the medium that is suitable for dyeing is a cosmetic medium generally formed from water or a mixture of water and of at least one organic solvent.
  • organic solvents include C 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.
  • the composition contains an aromatic alcohol such as benzyl alcohol.
  • the solvents are preferably 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, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic 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, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers and conductive polymers.
  • adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic
  • the above adjuvants are generally present in an amount for each of them of between 0.01 % 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 is generally between 3 and 14 approximately and preferably between 4 and 11 approximately, and more particularly the pH is such that 3 ⁇ pH ⁇ 9. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems.
  • the pH of the composition comprising at least one dye of formula (I) is an acidic pH (i.e. 3 ⁇ pH ⁇ 7) and in particular the pH is 4.
  • the pH is basic (i.e. 7 ⁇ pH ⁇ 11), more particularly 7 ⁇ pH ⁇ 9.
  • 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.
  • basifying agents examples that may be mentioned include 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 ( ⁇ ) below:
  • W a is a divalent group (d-C 6 )alkylene optionally interrupted with one or more heteroatoms such as O or N and/or optionally substituted with one or more hydroxyl groups or a C C 4 alkyl radical; particularly, W a represents a propylene group;
  • R a i , a2, Ra3 and R a4 which may be identical or different, represent a hydrogen atom or a C C 4 alkyl or C C 4 hydroxyalkyl radical.
  • the dye composition may be in various forms, such as in the form of a liquid, a cream or gel, or in any other form that is suitable for dyeing keratin fibres, and especially the hair. ///. Dyeing and/or lightening process using a dye of formula (I) or (l')
  • Another subject of the invention is a process for dyeing and/or lightening keratin material, especially dark keratin material, which consists in applying to the said materials a composition comprising at least one dye of formula (I) or ( ⁇ ') as defined previously.
  • the process of optical lightening of dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 involves fluorescent dyes of formula (I) or ( ⁇ '), i.e. dyes in which A represents a fluorescent coloured chromophore. Mention may be made particularly of those defined in point 1.2 above. More particularly, the chromophore A is chosen from those of formulae (XVIII), (XIX), (XX) and (XXI) as defined previously.
  • the fluorescent dyes are chosen from (l' a ), (I'b), (l' c ), (I'm) and (l' n ).
  • the fluorescent dyes used for lightening dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 are within the orange range.
  • a reducing agent may be applied before, at the same time as or after application of the composition containing at least one dye of formula (I).
  • no reducing agent is used in the process according to the invention.
  • the composition containing at least one dye of formula (I) has been applied to the keratin materials
  • the composition is left on for a certain time, and the keratin materials are then rinsed, and/or drained dry and/or undergo a heat treatment and/or are exposed to ultraviolet (UV) light.
  • UV ultraviolet
  • the fibres undergo a heat treatment, especially at a temperature of between 50 and 200°C and preferentially between 80 and 180°C.
  • the duration of the treatment after application of the composition containing may be short, for example from 0.1 second to 1 hour, particularly between 5 minutes and 50 minutes and more particularly between 10 and 45 minutes, and preferentially the leave-on time is 30 minutes.
  • the duration of the post-treatment with heat may be short, for example from 0.1 to 30 minutes.
  • the temperature is between 40°C and 250°C, more particularly between 50°C and 200°C and preferentially from 80°C to 180°C.
  • the heat treatment of the keratin fibres is performed using an iron for smoothing keratin fibres or using a hairstyling hood, a hairdryer or an infrared ray dispenser.
  • the dyeing and/or lightening process according to the invention consists in applying the composition according to the invention to keratin materials and then in draining them dry and/or subjecting them to a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron.
  • the heat treatment is followed by rinsing.
  • the duration of the post-treatment with UV is between 1 second and 2 hours, preferentially 30 minutes.
  • One particular embodiment of the invention concerns a process in which the compound of formula (I) may be applied directly to the hair without reducing agents, free of pretreatment or post-treatment reducing agents.
  • a treatment with a chemical oxidizing agent may optionally be combined.
  • Any type of chemical oxidizing agent that is standard in the field may be used.
  • it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases such as laccases.
  • the use of hydrogen peroxide is particularly preferred.
  • This oxidizing agent may be applied to the fibres before or after applying the composition containing at least one compound of formula (I).
  • the dyeing or optical lightening process does not involve any chemical oxidizing agent.
  • DMF A/,A/-dimethylformamide
  • Compound (D) is reacted in refluxing acetonitrile in the presence of a large excess of the dye to be grafted (5 equivalents) for at least 12 hours (step iv).
  • Compound (F) commercial compound sold by Sigma-Aldrich.
  • the expected product, dye 3 is thus obtained after purification on a column of silica gel.
  • Compound (J) is obtained by reacting the commercial compound (F) with one equivalent of the ethyl ester of bromobutyric acid in refluxing toluene (step viii), followed by saponification of the ester and purification on an ion-exchange column in water (step ix).

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Abstract

The invention relates to the dyeing of keratin materials using the dyes bearing an ascorbic acid-based unit of formula (I), particularly bearing 3,4-dihydroxyfuran-2(5H)-one and 2,3,4(5H)-furantrione units. The invention relates to a dye composition comprising a dye bearing an ascorbic acid-based group, and to a process for the dyeing, especially with a lightening effect, of keratin materials such as the hair, using the said composition. Similarly, the invention relates to novel dyes bearing an ascorbic acid-based group and to the uses thereof in the lightening of keratin materials. This composition affords colorations that are particularly fast and visible on dark keratin fibres, even in the absence of a chemical oxidizing agent.

Description

NOVEL DIRECT DYES CONTAINING AN ASCORBIC ACID-BASED UNIT, DYE COMPOSITION COMPRISING THEM AND PROCESS FOR DYEING HUMAN KERATIN MATERIALS USING THESE DYES The invention relates to the dyeing of keratin materials using dyes bearing an ascorbic acid-based unit of formula (I), particularly bearing 3,4-dihydroxyfuran-2(5H)- one and 2,3,4(5H)-furantrione units.
It is known practice to dye keratin fibres, especially human keratin fibres, by direct dyeing. The process conventionally used in direct dyeing consists in applying to keratin fibres direct dyes, which are coloured and colouring molecules that have affinity for the fibres, leaving them to diffuse and then rinsing the fibres.
The direct dyes that are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines and dyes of the azo, xanthene, acridine, azine or triarylmethane type. The colorations that result from the use of direct dyes are temporary or semi-permanent colorations, 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 poor dyeing power and their poor fastness with respect to washing or to perspiration.
It is also known practice to obtain permanent colorations with dye compositions containing oxidation dye precursors, which are generally known as oxidation bases, which are colourless before oxidation such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds; and which, in the presence of oxidizing agents, colour the hair. Oxidation bases may be mixed with couplers to obtain varied shades. This oxidation dyeing process consists in applying to the keratin fibres bases or a mixture of bases and couplers with aqueous hydrogen peroxide solution, as oxidizing agent, in leaving it to diffuse, and then in rinsing the fibres. Oxidation dyeing systems make it possible to obtain base colorations that are relatively shampoo-fast, but do not make it possible to obtain chromatic shades.
Furthermore, the dyeing of keratin fibres using standard direct dyes does not make it possible to notably lighten the keratin fibres.
There is great demand for the lightening of the colour of dark keratin fibres towards lighter shades, optionally while modifying the shade thereof, Conventionally, to obtain a lighter coloration, a chemical bleaching process is performed. This process consists in treating the keratin fibres, such as the hair, with a strong oxidizing system, generally constituted by hydrogen peroxide optionally combined with persalts, usually in an alkaline medium.
This bleaching system has the drawback of degrading keratin fibres and of impairing their cosmetic properties. Specifically, the fibres have a tendency to become coarse, more difficult to disentangle and more brittle. Finally, the lightening or bleaching of keratin fibres with oxidizing agents is incompatible with treatments for changing the shape of said fibres, particularly relaxing treatments.
Another lightening technique consists in applying to dark hair fluorescent direct dyes. This technique, described especially in documents WO 03/028 685 and WO 2004/091 473, makes it possible to respect the quality of the keratin fibre during the treatment. However, these fluorescent direct dyes do not have sufficient fastness with respect to external agents.
Thus, in order to improve the remanence, it is known practice to use dyes that are linked together via a "spacer" or "linker" which contains a disulfide function: see, for example, WO 2005/097 051 , EP 1 647 580, WO 2006/134 043, WO 2006/136 617, WO 2007/110 533, WO 2007/110 534, WO 2007/110 535, WO 2007/110 537, WO 2007/110 542. Nevertheless, in order for the fixing of these disulfide dyes to the surface of keratin fibres to function, treatment with a reducing agent is generally simultaneously necessary, before or after applying the disulfide dyes. However, the use of reducing agents in appreciable amount may have the drawback of giving off an unpleasant odour during the treatment of the keratin fibres, and as such there is a real need to reduce the content of reducing agent. Furthermore, it is generally necessary to perform an additional oxidative treatment using a chemical oxidizing agent in order to fix the dyes to the keratin fibres and thus to improve the coloration fastness.
Vitamins are compounds that are essential for the body, one of which, vitamin C, also known as ascorbic acid [50-81-7], l-ascorbic acid, l-xylo-ascorbic acid or l-threo- hex-2-enoic acid γ-lactone, is known for its anti-scurvy virtues. Ascorbic acid is also known as an antioxidant (see, for example, Ullmann's Encylopedia of Industrial Chemistry; "Vitamins", 2005 Wley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a27 443 (pp. 110-122), or US 2006/0 039 937), an antithrombotic protective agent (see, for example, US 4 329 290), or an anticancer agent (see, for example, EP 0 875 246).
Very recently, ascorbic acid derivatives have been used for functionalizing matrices such as ultraviolet screening agents (WO 2008/017346).
The aim of the present invention is to provide novel systems for the direct dyeing of keratin materials and for especially lightening dark keratin materials, in particular human keratin fibres such as the hair, which are powerful, remanent and easy to use.
Particularly, one name of the invention is to provide direct dyeing systems for obtaining lightening effects especially on keratin materials such as naturally or artificially dark keratin fibres, which are fast with respect to successive shampooing, which do not degrade the keratin fibres and which do not impair their cosmetic properties.
Another aim of the invention is to dye keratin materials, especially keratin fibres such as the hair, in a manner that is intense, strong, chromatic and/or remanent with respect to external attacking factors. The invention is also directed towards providing compounds for dyeing keratin fibres such as the hair with little coloration selectivity between the root and the end, whether it is performed on natural or permanent-waved fibres.
These aims are achieved with the present invention, one subject of which is direct dyes bearing a group derived from ascorbic acid of formula (I) below:
A- (X)p - Csat - (X'V - Asc (I)
and also the organic or mineral acid salts, optical isomers, geometrical isomers, tautomers and solvates, such as hydrates, thereof;
in which formula (I):
> A represents a coloured chromophore;
> Asc represents a radical derived from ascorbic acid chosen from ascorbyl and dehydroascorbyl radicals, chosen from formulae (11-1 ) to (II-4), and which is linked to the rest of the molecule via one of the substituents R5, Re, R7, Re or Rg, or alternatively the said radical is linked to the rest of the molecule directly via one of the carbon atoms bearing the substituents R5, R6, R , Rs or R9, in which case one of these substituents is absent:
Figure imgf000005_0001
(II-2) (II-3) (n-4) in which formulae (11-1 ) to (N-4):
■ R5, R6, R7, Re, R9 and R 0, which may be identical or different, represent a hydrogen atom or a group chosen from i) (d-C8)alkyl, N) hydroxyl, iii) carboxyl, iv) and -O-protected with a protecting group;
■ or alternatively R5 and R9 together form a divalent group -0-(CRaRb)n-0- with Ra and R , which may be identical or different, representing a hydrogen atom or a group (C C8) alkyl such as methyl or t-butyl, (C C8)alkoxy, allyl, (poly)halo(CrC8)alkyl such as trifluoromethyl, and n is equal to 1 , 2 or 3, and in particular R5 and R9 together form a divalent group -0-CH2-CH2-0- or -0-C(CH3)2-0-;
■ Rn and R 2, which may be identical or different, a hydrogen atom, an alkali metal, an alkaline-earth metal or a protecting group,
■ or alternatively Rn and R 2 together form a divalent group -(CRaRb)n- with Ra and R , and n as defined previously;
■ Y represents an oxygen or sulfur atom;
X and X', which may be identical or different, represent:
a linear or branched, saturated or unsaturated divalent CrC30 hydrocarbon- based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from:
o -N(R)-; -N+(R)(R')-, Q"; -0-; -S-; -C(O)-; -S(0)2- with R, R\ which may be identical or different, chosen from a hydrogen atom and a C C4 alkyl, hydroxy(CrC8)alkyl or amino(CrC8)alkyl radical and Q" represents an organic or mineral anionic counterion;
o an aromatic or non-aromatic, saturated or unsaturated, fused or non- fused (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms; a divalent group or a combination chosen from: -N(R)-; -N+(R)(R')-, Q"; -0-; -S-; -C(O)-; -S(0)2- with R, R' and Q" as defined previously;
preferentially, the divalent group(s) or combinations thereof are chosen from -0-; -N(R)-; -C(O)- with R chosen from a hydrogen atom and a C C4 alkyl radical; > p and p', which may be identical or different, represent an integer equal to 0 or 1 ; and
> CSat represents a linear or branched, optionally cyclic C Ci8 alkylene chain.
Another subject of the invention concerns a process for dyeing and/or lightening keratin materials, particularly keratin fibres, especially dark fibres, in which a suitable dye composition comprising one or more direct dyes bearing a group derived from ascorbic acid of formula (I) as defined previously is applied to the said materials.
Another subject of the invention is a dye composition comprising, in a cosmetically suitable medium, at least one direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
Another subject of the invention concerns a direct dye bearing a unit derived from ascorbic acid of formula (I) as defined previously.
The direct dyes of formula (I) afford fast coloration on keratin fibres. The coloration, especially using the compounds of formula (I) with A representing a fluorescent coloured chromophore, is also visible on keratin materials that are even dark, in particular human keratin fibres, especially the hair, without degrading the said material, remanent with respect to shampooing, common attacking factors (sunlight or perspiration), and other hair treatments, even in the absence of a reducing agent.
The direct dyes of formula (I) afford lightening of keratin materials such as keratin fibres, particularly dark keratin fibres and more particularly dark hair, in general with a tone depth of less than or equal to 6, preferably less than or equal to 4.
The dyes of formula (I) according to the invention are moreover stable with respect to oxidizing agents, and show satisfactory solubility cosmetic dyeing media. These dyes especially broaden the colour range from yellow to blue.
The dyes of formula (I) colour keratin materials after application to keratin fibres in a manner that is strong, intense, chromatic and/or remanent with respect to external attacking factors, with low coloration selectivity between the root, and on different types of fibre, do not necessarily oblige a reductive treatment of the fibres or any chemical oxidizing agent, and which are visible on the said materials, even dark materials.
For the purposes of the invention, the term "dark keratin material" is a material that has a numerical luminescence L* in the CIE system L*a*b*, of less than or equal to 45 and preferably less than or equal to 40, given that, moreover, L* = 0 is equivalent to black and L* = 100 is equivalent to white.
For the purposes of the invention, the term "dark keratin fibres", particularly naturally or artificially dark hair, means hair whose tone depth is less than or equal to 6 (dark blond) and preferably less than or equal to 4 (chestnut-brown).
The lightening of the hair is evaluated by the "tone depth" variation before and after application of the compound of formula (I). The notion of "tone" is based on the classification of natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of natural shades are well known to hairstyling professionals and are published in the book Sciences des traitements capillaires [Hair treatment sciences] by Charles Zviak, 1988, published by Masson, pp. 215 and 278.
The tone depths range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
For the purposes of the invention, the term "bleached hair" means hair whose tone depth is greater than 4 (chestnut-brown) and preferably greater than 6 (dark blond).
One means for measuring the lightening effect given to the hair after application of the fluorescent dyes of the invention is to use the phenomenon of reflectance of the hair.
- What is concerned is the reflectance performance of the hair when it is irradiated with visible light in the wavelength range from 400 to 700 nanometers.
- The curves of reflectance as a function of the wavelength, for hair treated with the composition of the invention and for untreated hair, are then compared.
- The curve corresponding to the treated hair should show a reflectance in the wavelength range from 500 to 700 nanometers higher than the curve corresponding to the untreated hair.
- This means that, in the wavelength range from 500 to 700 nanometers, there is at least one region in which the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair. The term "higher" means a difference in reflectance of at least 0.05% and preferably of at least 0.1 %. This does not prevent there from being in the wavelength range from 540 to 700 nanometers at least one region in which the reflectance curve corresponding to the treated hair is superposable, or lower than the reflectance curve corresponding to the untreated hair.
Preferably, the wavelength at which the difference is maximal between the reflectance curve for the treated hair and that for the untreated hair is in the wavelength range from 500 to 650 nanometers and preferably in the wavelength range from 550 to 620 nanometers.
For the purposes of the present invention, and unless otherwise indicated:
- the "aryl" or "heteroaryl" radicals or the aryl or heteroaryl part of a radical may be substituted with at least one substituent borne by a carbon atom, chosen from:
a C1-C16 and preferably C C8 alkyl radical optionally substituted with one or more radicals chosen from hydroxyl, C C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, acylamino, amino substituted with two C C4 alkyl radicals, which may be identical or different, optionally bearing at least one hydroxyl group, or the two radicals possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6- membered heterocycle optionally comprising another heteroatom identical to or different from nitrogen;
· a halogen atom such as chlorine, fluorine or bromine;
a hydroxyl group;
a C1-C2 alkoxy radical; a C2-C4 (poly)hydroxyalkoxy radical;
an amino radical;
nitro;
a 5- or 6-membered heterocycloalkyl radical;
an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (C C4)alkyl radical, preferentially methyl;
an amino radical substituted with one or two identical or different C C6 alkyl radicals, optionally bearing at least:
i) a hydroxyl group,
ii) an amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen,
iii) a quaternary ammonium group -N+R'R"R"', M" for which R', R" and R'", which may be identical or different, represent a hydrogen atom, or a Ci-C4 alkyl group; and M" represents the organic or mineral counterion such as halide,
iv) an optionally cationic 5- or 6-membered heteroaryl radical, preferentially imidazolium, optionally substituted with a (C C4)alkyl radical, preferentially methyl;
• an acylamino radical (-NR-COR') in which the radical R is a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C C2 alkyl radical;
• a carbamoyl radical ((R)2N-CO)-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group;
· a carboxylic acid or ester radical, (-O-COR') or (-C(O)OR'), in which the radical R' is a hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R' is a C C2 alkyl radical;
• the carboxylic radical possibly being in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);
• an alkylsulfonylamino radical (R'S02-NR-) in which the radical R represents a hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' represents a C C4 alkyl radical or a phenyl radical; · an aminosulfonyl radical ((R)2N-S02-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C C4 alkyl radical optionally bearing at least one hydroxyl group;
• a cyano group (CN);
• a polyhaloalkyl group, preferentially trifluoromethyl (CF3);
- the cyclic or heterocyclic part of a non-aromatic radical may be substituted with at least one substituent borne by a carbon atom, chosen from the groups:
• hydroxyl,
• Ci-C4 alkoxy, C2-C4 (poly)hydroxyalkoxy,
· alkylcarbonylamino ((RCO-NR'-) in which the radical R' is a hydrogen atom or a Ci-C4 alkyl radical optionally bearing at least one hydroxyl group, and the radical R is a C C2 alkyl radical or an amino radical substituted with two C C4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming, with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom;
• alkylcarbonyloxy (RCO-0-) in which the radical R is a C C4 alkyl radical or an amino radical substituted with one or two identical or different C C4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen;
· alkylcarbonyloxy (RO-CO-) in which the radical R is a C C4 alkyl radical or an amino radical substituted with one or two identical or different C C4 alkyl groups optionally bearing at least one hydroxyl group, the said alkyl radicals possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other heteroatom identical to or different from nitrogen; a cyclic or heterocyclic radical, or a non-aromatic portion of an aryl or heteroaryl radical, may also be substituted with one or more oxo groups; a hydrocarbon-based chain is unsaturated when it comprises one or more double bonds and/or one or more triple bonds; an "aryl" radical represents a fused or non-fused monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl; a "heteroaryl radical" represents a fused or non-fused, optionally cationic, 5- to 22-membered monocyclic or polycyclic group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and at least one ring of which is aromatic; preferentially, a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthyl and the ammonium salt thereof; the term "cationic heteroaryl radical" means a heteroaryl group as defined previously, which comprises an endocyclic or exocyclic cationic group,
o when the charge is endocyclic, it is included in the electron derealization via the mesomeric effect, for example it is a pyridinium, imidazolium or indolinium
Figure imgf000012_0001
with R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(CrC8)alkyl group such as methyl;
when the charge is exocyclic, it is not included in the electron derealization via the mesomeric effect, for example it is an ammonium or phosphonium substituent R+ such as trimethylammonium, which is outside the heteroaryl such as ridyl, indolyl, imidazolyl or naphthalimidyl in question;
Figure imgf000012_0002
- with R being a heteroaryl substituent as defined previously and
- R+ an ammonium group RaRbRcN+- or a phosphonium group RaRbRcP+- or a group comprising an ammonium group RaRbRcN+- or phosphonium group RaRbRcP+- such as -G-(CrC6)alk-N+RaRbRc or -G-(CrC6)alk-P+RaRbRc with Ra, Rb and Rc, which may be identical or different, representing a hydrogen atom or a group (CrC8)alkyl such as methyl,
G represents a covalent σ bond, or a divalent group or the combination chosen from: -N(R)-; -N+(R')(R")-, Q"; -0-; -S-; -C(O)-; -S(0)2- with R' and R", which may be identical or different, representing a hydrogen atom or a group (hydroxy)(CrC6)alkyl and Q" represents an anionic counterion;
alk represents an alkylene group;
preferentially, G represents -N(R')- with R' chosen from a hydrogen atom and a C C4 alkyl radical;
- the term "cationic aryl bearing an exocyclic charge" means an aralkyi ring whose cationic group is outside the said ring: it is especially an ammonium or phosphonium substituent R+ such as trimethylammonium outside the aryl such as phenyl or naphthyl:
Figure imgf000013_0001
a "cyclic radical" is a non-aromatic, monocyclic or polycyclic, fused or non-fused cycloalkyl radical, containing from 5 to 22 carbon atoms, which may comprise one or more unsaturations; a "heterocyclic radical" is a non-aromatic, monocyclic or polycyclic, fused or non- fused 5- to 22-membered radical, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, morpholinyl, thiomorpholinyl, piperidyl, piperazinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydrothiophenyl, azepanyl, thioazepanyl; preferentially pyrrolidinyl and morpholino; a "radical derived from ascorbic acid" is a radical that is derived from ascorbic acid of formulae (11-1 ) to (M-4) as defined previously or (ΙΓ-1 ) to (II-4') as defined in point 1.4 below; a "protecting group" is a group that prevents a "parasite" reaction by masking the reactivity of the hydroxyl group towards reagents during the organic synthesis, and which can subsequently be liberated, the said protecting group is chosen especially from those described in the following publications:
Organic synthesis with carbohydrates, G-J Boons and K.J Hale, Sheffield Academic Press 2000, chap. 2, pp. 26-53;
Protective Groups in Organic Synthesis, J.R. Hanson, Sheffield Academic Press 1999, chap. 2, pp. 8-35;
Protective Groups in Organic Synthesis, T.W. Greene, published by John Wley & Sons, NY, 1981 , chap. 2 and 3; and
Protecting Groups, P. Kocienski, Thieme, 3rd ed., 2005, chap. 2, 3 and 4;
preferentially, the said "protecting group" is chosen from:
a) (CrC8)alkyl such as isobutyl (i-butyl) or tert-butyl (t-butyl),
b) (poly)halo(CrC8)alkyl such as trifluoromethyl or trichloroethyl, c) (C2-C8)alkenyl such as allyl (CH2-CH=CH2-),
d) aryl, for instance halophenyl such as para-chlorophenyl,
e) heteroaryl such as optionally /V-oxidized pyridine, for instance /V-oxido-3- methyl-2-picolyl or anthryl,
f) (poly)aryl(CrC8)alkyl, with the alkyl optionally interrupted with a heteroatom, such as benzyl, para-methoxybenzyl, ortho-nitrobenzyl, para-halobenzyl such as para-bromo/chlorobenzyl, para-cyanobenzyl, 2-(phenylselenyl)ethyl, triphenylmethyl, a-naphthyldiphenylmethyl, diphenylmethyl, para- methoxyphenyldiphenylmethyl, or dibenzosuberyl,
g) (poly)aryl(CrC8)alkenyl such as cinnamyl (phenyl-CH=CH-CH2-),
h) (Ci-C8)alkoxy(Ci-C8)alkyl such as methoxymethyl (MOM), 1-ethoxyethyl or 1- methyl-1-methoxyethyl,
i) (CrC8)alkylthio(CrC8)alkyl such as methoxythiomethyl (MTM),
j) (Ci-C8)alkoxy(Ci-C8)alkoxy(CrC8)alkyl such as 2-methoxyethoxymethyl
(MEM),
k) bis[halo(Ci-C8)alkoxy](CrC8)alkyl such as bis(2-chloroethoxy)methyl, I) arylcarbonyl(Ci-C8)alkoxyaryldiphenyl(CrC8)alkyl such as [para-(para- bromophenacyloxy)phenyl]diphenylmethyl;
I) heterocycloalkyl optionally substituted with a (CrC8)alkoxy such as
tetrahydropyranyl THP, tetrahydrothiopyranyl (THTP), THTP S- mono or S,S- dioxide, 4-methoxyTHP, 4-methoxyTHTP, tetrahydrofuryl (THF),
tetrahydrothiofuryl (THTF),
m) aryl-heteroaryl such as 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl (tritylone),
n) mono/di/tri(CrC8)alkylsilyl such as trimethylsilyl (TMS), triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, t-butyldimethylsilyl or triisopropylsilyl,
o) (Ci-C8)alkyldiarylsilyl such as t-butyldiphenyl,
p) di(CrC8)alkylarylsilyl,
q) triarylsilyl such as triphenylsilyl,
r) triaryl(CrC8)alkyl such as tribenzylsilyl, (triphenyl)dimethylsilyl, tri-para- xylylsilyl;
s) R-C(Y)-, with o R representing 1) a hydrogen atom, or 2) a group (d-C8)alkyl such as methyl, 3) (poly)halo(aryl)(CrC8)alkyl such as chloromethyl, dichloromethyl, trichloromethyl or trifluoromethyl or chlorodiphenylmethyl, 4) (C C8)alkoxy such as methoxy, ethoxy, isobutoxy, 5) (aryl)(C2-C8)alkenyloxy such as vinyloxy, allyloxy, or cinnamyloxy, 6) (poly)halo(CrC8)alkoxy such as trichloroethoxy, 7) (C2- C8)alkenyl, 6) (Ci-C8)alkoxy(CrC8)alkyl such as methoxymethyl, 8) (poly)aryl(Ci-C8)alkoxy(CrC8)alkyl such as triphenylmethoxymethyl, 9) (C2-C8)alkenyloxy such as vinyloxy, 10) aryl such as 2,4,6- trimethylphenyl or mesityl, 11) aryl(CrC8)alkoxy such as para- methoxybenzoxy, 3,4-dimethoxybenzoxy, ortho-nitrobenzoxy, para-nitro- benzoxy, 12) (poly)aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl such as benzyl or 2,4,6-trimethylbenzyl, triphenylmethyl, or phenylethyl, 13) aryloxy such as para-nitrophenoxy, phenoxy, 14) aryloxy(CrC8)alkyl such as phenoxymethyl or halophenoxymethyl such as para- chlorophenoxymethyl, 2,6-dichloro-4-methylphenoxymethyl, 15) cycloalkyl such as adamantyl, 16) heterocycloalkyl, 17) heteroaryl such as imidazolyl, especially imidazolo, 18) (di)(CrC8)(alkyl)amino, 19) aryl(Ci-C8)alkylamino(CrC8)alkyl 20) (di)aryl(CrC8)alkylamino, such as phenylamino,
o Y representing an oxygen or sulfur atom or a group R'N or R'R"N+, Q" with R' and R", which may be identical or different, representing a hydrogen atom or a group (CrC8)alkyl and Q" representing an organic or mineral anionic counterion; and
'R"P(Y')-, with
o R' and R", which may be identical or different, representing 1) a hydrogen atom, or 2) a hydroxyl group, 3) (CrC8)alkoxy, 4) (C2- C8)alkenyloxy such as vinyloxy, 6) aryl such as 2,4,6- trimethylphenyl or mesityl, 7) aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl such as benzyl or 2,4,6- trimethylbenzyl, 8) aryloxy such as phenoxy, 9) aryloxy(CrC8)alkyl such as phenoxymethyl, 10) cycloalkyl such as adamantyl, 11) heterocycloalkyl, 12) heteroaryl, or 13) (di)(CrC8)(alkyl)amino such as dimethylamino;
o - Y representing an oxygen or sulfur atom; - and "alkyl radical" is a linear or branched C Ci6 and preferably C C8 hydrocarbon-based radical; particularly C C4 such as methyl or ethyl;
- the expression "optionally substituted" attributed to the alkyl radical means that the said alkyl radical may be substituted with one or more radicals chosen from the following radicals: i) hydroxyl, ii) C C4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C C4 alkyl radicals, the said alkyl radicals possibly forming with the nitrogen atom that bears them a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; v) or a quaternary ammonium group -N+R'R"R"', M" for which R', R" and R'", which may be identical or different, represent a hydrogen atom or a C C4 alkyl group, or else -N+R'R"R"', forms a heteroaryl such as imidazolium optionally substituted with a C C4 alkyl group, and M" represents the organic or mineral anionic counterion such as halide; - and "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a linear or branched C Ci6 and preferentially C C8 hydrocarbon-based radical; particularly Ci-C4 such as methoxy or ethoxy, and when the alkoxy group is optionally substituted, this means that the alkyl group is optionally substituted as defined above.
The compounds of formula (I) according to the invention may be cationic, anionic or neutral;
- when the compound is cationic or anionic, then an organic or mineral counterion, or several counterions or a mixture of counterions, are present to ensure the electrical neutrality,
or alternatively one or more groups in the compound can ensure the electrical neutrality, for example if the rest of the compound is cationic, with groups -O" (oxalate), -COO" (carboxylate), R3N+- (ammonium), or R3P+- (phosphonium); - when the compound is anionic, then the organic or mineral counterion(s) are cationic, preferentially chosen from mineral cations such as alkali metals or alkaline-earth metals such as Na, Mg, K and Ca, and organic cations such as ammonium NH4 + or (di/tri)(CrC8)alkylammonium,
- when the compound is cationic, then the counterion(s) are anionic species, preferentially chosen from i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including C C6 alkylsulfonates; Alk-S(0)20" such as methanesulfonate or mesylate, and ethanesulfonate; iv) arylsulfonates: Ar- S(0)20" such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfites: Alk-0-S(0)0" such as methyl sulfite and ethyl sulfite; x) aryl sulfites: Ar-0-S(0)0" such as benzene sulfite and toluene sulfite; xi) alkyl sulfates: Alk-0-S(0)20- such as methyl sulfate and ethyl sulfate; xii) aryl sulfates: Ar-0-S(0)20"; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate;
- an "organic or mineral acid salt" is more particularly chosen from a salt derived from i) hydrochloric acid HCI, ii) hydrobromic acid HBr, iii) sulfuric acid H2S04, iv) alkylsulfonic acids: Alk-S(0)2OH such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(0)2OH such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-0-S(0)OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3P04; xiii) acetic acid CH3COOH; xiv) triflic acid CF3S03H; and xv) tetrafluoroboric acid HBF4; Furthermore, unless otherwise indicated, the limits delimiting the extent of a range of values are included in this range of values.
According to the present invention, the term "coloured chromophore" means a radical derived from a dye, i.e. which has the capacity of colouring and which is in the form of a coloured compound that may be observed with the naked eye (absorbing light at a wavelength in the UV and visible radiation range, i.e. at a wavelength abs of between 250 and 800 nm, particularly in the visible spectrum between 400 and 700 nm).
More particularly, the dye absorbs in the yellow, orange, red, violet or blue range (see, for example, Ullmann's Encyclopedia of Industrial chemistry "Dyes, General Survey", 2005 Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim10.1002/14356007.a09_073 and Color Chemistry, Synthesis, Properties, and Applications of Organic Dyes and Pigments, H. Zollinger, 2003, 3rd Ed. Verlag Helvetica Chimica Acta, Wiley-VCH, chap. 1.1 and 2.1). According to the present invention, the term "fluorescent chromophore" means a radical derived from a fluorescent dye as defined previously, which, besides being a dye, i.e. coloured and observable with the naked eye, is fluorescent, i.e. it has the capacity of re-emitting at least part of the absorbed light at a wavelength longer than that absorbed. A fluorescent dye is especially a compound that is capable of absorbing UV or visible radiation at a wavelength abs of between 400 and 700 nm and capable of re-emitting in the visible range at an emission wavelength em of between 410 and 800 nm.
Preferably, fluorescent compounds are dyes that are capable of absorbing in the visible range abs between 400 and 800 nm and of re-emitting in the visible range em between 410 and 810 nm. More preferentially, fluorescent dyes are dyes that are capable of absorbing at a abs of between 420 and 550 nm and of re-emitting in the visible range em between 470 and 600 nm.
/. Fluorescent dyes of formula (I)
/.1. Coloured chromophore A
The radical A of formula (I) may contain one or more chromophores, which may be identical or different, it being understood that at least one chromophore is coloured.
As coloured chromophores that are useful, mention may be made of those derived from the following dyes: acridines; acridones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanins such as zerocyanins, azacarbocyanins, diazacarbocyanins, diazahemicyanins, hemicyanin, or tetraazacarbocyanins; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones;
(poly)methines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.
Among the azo compounds, mention may be made more particularly of those in the Kirk Othmer Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, updated on 19/04/2010.
Particularly, chromophore A is chosen from those derived from (poly)azo dyes such as (di)azo, hydrazono dyes and (poly)methine dyes such as styryls and anthraquinones.
According to one preferred embodiment of the invention, the coloured chromophore A is chosen from cationic chromophores, preferentially those known as
"basic dyes".
Mention may be made of the hydrazono cationic chromophores of formulae (III) and (III"), azo cationic chromophores (IV) and (IV) and diazo cationic chromophores
(V) below:
Het+-C(Ra)=N-N(Rb)-Ar, Q" (III),
Het+-C(Ra)=N-N(Rb)-Ar, Q" (Ml),
Het+-N=N-Ar, Q" (IV)
Ar+-N=N-Ar", Q" (IV) and
Het+-N=N-Ar'-N=N-Ar, Q" (V)
in which formulae (III), (III'), (IV), (IV) and (V): Het+ represents a cationic heteroaryl radical, preferably bearing an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, optionally substituted with one or more (C C8) alkyl groups such as methyl;
- Ar+ represents an aralkyi radical, such as phenyl or naphthyl, bearing an exocyclic cationic charge, particularly tri(CrC8)alkylammonium such as trimethylammonium;
- Ar represents an aryl group, especially phenyl, optionally substituted, preferentially with one or more electron-donating groups such as i) optionally substituted (C C8)alkyl, ii) optionally substituted (C C8)alkoxy, iii) (di)(CrC8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group, iv) aryl(CrC8)alkylamino, v) optionally substituted A/-(Ci-C8)alkyl-A/-aryl(CrC8)alkylamino or alternatively Ar represents a julolidine group;
- Ar" is an optionally substituted divalent (hetero)alkylene group such as phenylene, particularly para-phenylene, or naphthalene, which are optionally substituted, preferentially with one or more groups (CrC8)alkyl, hydroxyl or (CrC8)alkoxy;
- Ar" is an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl, which are optionally substituted, preferentially with one or more groups (CrC8)alkyl, hydroxyl, (di)(CrC8)(alkyl)amino, (CrC8)alkoxy or phenyl;
Ra and Rb, which may be identical or different, represent a hydrogen atom or a group (d-Cs)alkyl, which is optionally substituted, preferentially with a hydroxyl group;
or alternatively the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; particularly, Ra and Rb represent a hydrogen atom or a group (CrC4)alkyl, which is optionally substituted with a hydroxyl group;
- Q" represents an anionic counterion such as a halide or an alkyl sulfate;
it being understood that the chromophore (III), (ΙΙΓ), (IV), (IV) or (V) is linked to the rest of the molecule of formula (I) via Het+, Ar+, Ar or Ar".
In particular, mention may be made of the azo and hydrazono chromophores bearing an endocyclic cationic charge of formulae (III), (III') and (IV) as defined previously. More particularly those of formulae (III), (III') and (IV) derived from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.
Preferentially derived from the following derivatives:
Figure imgf000021_0001
-1 ) (IV-1 ) formulae (111-1 ) and (IV-1 ) with:
- R1 representing a group (C C4)alkyl such as methyl;
- R2 and R3, which may be identical or different, representing a hydrogen atom or a group (Ci-C4)alkyl such as methyl; and
- R4 representing a hydrogen atom or an electron-donating group such as optionally substituted (CrC8)alkyl, optionally substituted (C C8)alkoxy, or (di)(C
C8)(alkyl)amino optionally substituted on the alkyl group(s) with a hydroxyl group; particularly, R4 is a hydrogen atom,
- Z represents a group CH or a nitrogen atom, preferentially CH,
- Q" is as defined previously;
it being understood that the chromophore (111-1 ) or (IV-1 ) is linked to the rest of the molecule of formula (I) by R1 or R4, in which case one of the hydrogen atoms of R1 or R4 is substituted with X' if p = 1 or Csat if p = 0.
Particularly, the chromophores (111-1 ) and (IV-1 ) are chosen from Basic Red 51 ,
Basic Yellow 87 and Basic Orange 31 or derivatives thereof:
Figure imgf000021_0002
Basic Red 51 Basic Orange 31 Basic Yellow 87 with Q' as defined previously, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesityl. According to another particular embodiment of the invention, the chromophore A is chosen from anionic chromophores, especially those derived from direct dyes known as "Acid dyes". More particularly, the anionic chromophore A is chosen from (poly)azo dyes such as anionic (di)azo, anthraquinone, naphthoquinone, triaryl methane and nitro dyes, xanthene derivatives, quinoline derivatives and indoles.
Mention may be made of the anionic chromophores of formulae (VI) to (XVII) below: a) the ani
Figure imgf000022_0001
in which formulae (VI) and (VII):
■ R7, R8, R9, R10, R'7, R'e, R'9 and R' 0, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
- (C C8)alkoxy, (C C8)alkylthio;
hydroxyl, mercapto;
nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or a group (CrC8)alkyl or aryl; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (CrC8)alkyl; (0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion;
- (O)CO"-, M+with M+ as defined previously;
R"-S(0)2-, with R" representing a hydrogen atom, an alkyl group, an aryl group, (di)(CrC8)(alkyl)amino, aryl(C C8) (alkyl)amino; preferentially a phenylamino or phenyl group;
- R'"-S(0)2-X'- with R'" representing a group (C C8)alkyl, optionally substituted aryl, X' as defined previously;
(di) (CrC8)(alkyl)amino;
aryl(CrC8)(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0")-, M+ and iv) alkoxy with M+ as defined previously;
optionally substituted heteroaryl; preferentially a benzothiazolyl group;
cycloalkyi; especially cyclohexyl,
- Ar-N=N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C8)alkyl, (0)2S(0 , M+ or phenylamino;
or alternatively two contiguous groups R7 with R8 or R8 with R9 or R9 with R 0 together form a fused benzo group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R' 0 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 , M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(C C8)(alkyl)amino; with M+, R°, X, X', X" and Ar as defined previously;
W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent radical i)
-NR- with R as defined previously, or ii) methylene -C(Ra)(Rb)- with Ra and R , which may be identical or different, representing a hydrogen atom or an aryl group, or alternatively Ra and R form, with the carbon atom that bears them, a spiro cycloalkyi; preferentially W represents a sulfur atom or Ra and R together form a cyclohexyl;
understood that: - the chromophore (VI) or (VII) comprises at least one sulfonate radical (0)2S(0")-, M+ or a carboxylate radical (O)CO"-, M+ on one of the rings A, B, or C; preferentially sodium sulfate;
- the chromophore (VI) or (VII) is linked to the rest of the molecule of formula (I) via one of the rings A, B, or C, in which case one of the substituents is absent and the carbon atom of one of the rings where the said substituent is absent is linked to X' if p = 1 or Csat if p = 0.
As examples of chromophores of formula (VI), derived from dyes, mention may be made of: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1 , Food Black 2;
and as examples of chromophores of formula (VII) derived from dyes, mention may be made of: Acid Red 11 1 , Acid Red 134, Acid yellow 38. b) the anionic pyrazolone azo chromophores of formula (VIII) or (IX):
Figure imgf000024_0001
in which formulae (VIII) and (IX):
■ Rii, Ri2 and R 3, which may be identical or different, represent a hydrogen or halogen atom, an alkyl group or -(0)2S(0"), M+ with M+ as defined previously;
■ Ri4 represents a hydrogen atom, a group (d-C8)alkyl or a group -C(0)0", M+ with M+ as defined previously;
■ Ri5 represents a hydrogen atom;
■ Ri6 represents an oxo group, in which case R'16 is absent, or alternatively R 5 with Ri6 together form a double bond;
■ R 7 and R 8, which may be identical or different, represent a hydrogen atom, or a group chosen from:
- (0)2S(0 , M+ with M+ as defined previously;
- Ar-0-S(0)2- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more groups (C C8)alkyl;
■ Ri9 and R2o, together form either a double bond, or a benzo group D, which is optionally substituted;
■ R'i6, R'i9 and R'2o, which may be identical or different, represent a hydrogen atom or a group (CrC8)alkyl, or hydroxyl;
■ R2i represents a hydrogen atom or a group (CrC8)alkyl or (CrC8)alkoxy;
■ Ra and Ra, which may be identical or different, are as defined previously, preferentially Ra represents a hydrogen atom and R represents an aryl group;
■ Y represents either a hydroxyl group or an oxo group;
■ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that:
- the chromophore (VIII) or (IX) comprises at least one sulfonate radical (0)2S(0")-, M+ or a carboxylate radical -C(0)0", M+ on one of the rings D or E; preferentially sodium sulfonate;
- the chromophore (VIII) or (IX) is linked to the rest of the molecule of formula (I) via one of the rings D, E, or F, in which case one of the substituents is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0. As examples of chromophores of formula (VIII) derived from dyes, mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of chromophores of formula (IX) derived from dyes, mention may be made of: Acid Yellow 17. c) the
Figure imgf000026_0001
in which formulae (X) and (XI):
■ R22, R23, R24, R25, R∑6 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- (CrC8)alkyl;
hydroxyl, mercapto;
- (C C8)alkoxy, (C C8)alkylthio;
- aryloxy or arylthio optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0")-, M+ with M+ as defined previously;
aryl(CrC8)(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0")-, M+ with M+ as defined previously; - (di) (C C8)(alkyl)amino;
(di)(hydroxy(Ci-C8)alkyl)amino
- (0)2S(0 , M+ with M+ as defined previously;
■ Z' represents a hydrogen atom or a group NR28R29 with R28 and R29, which may be identical or different, representing a hydrogen atom or a group chosen from: - (C C8)alkyl; polyhydroxy(CrC8)alkyl such as hydroxyethyl;
aryl optionally substituted with one or more groups, particularly i) (d-C8)alkyl such as methyl, n-dodecyl, n-butyl; ii) (0)2S(0 , M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously, preferentially R° represents a group (CrC8)alkyl; cycloakyl; especially cyclohexyl;
■ Z, represents a group chosen from hydroxyl and NR'28R'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously;
it being understood that:
- the chromophore (X) or (XI) comprises at least one sulfonate radical (0)2S(0 , M+ or a carboxylate radical -C(0)0", M+; preferentially sodium sulfonate;
- the chromophore (X) or (XI) is linked to the rest of the molecule of formula (I) via one of the benzo groups G, or H of anthraquinone, in which case one of the substituents R22 to R27, Z or Z' is absent and the carbon atom of one of the said benzo groups G, or H where the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0.
As examples of chromophores of formula (X) derived from dyes, mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3;
and as examples of chromophores of formula (XI) derived from dyes, mention may be made of: Acid Black 48; d) nitro chromophores of formula (XII) or (XIII):
Figure imgf000027_0001
Figure imgf000028_0001
hich formulae (XII) and (XIII):
■ R30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- (C C8)alkyl;
(CrC8)alkoxy optionally substituted with one or more hydroxyl groups, (C C8)alkylthio optionally substituted with one or more hydroxyl groups;
hydroxyl, mercapto;
nitro, nitroso;
- polyhalo(CrC8)alkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°; X, X' and X" as defined previously;
- (0)2S(0 , M+ with M+ as defined previously;
- (O)CO"-, M+with M+ as defined previously;
- (di)(C C8)(alkyl)amino;
(di)(hydroxy(Ci-C8)alkyl)amino;
heterocycloalkyl such as piperidino, piperazino or morpholino;
in particular, R30, R31 and R32 represent a hydrogen atom;
■ Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;
■ W is as defined previously; W particularly represents a group -NH-;
■ ALK represents a linear or branched divalent C C8 alkylene group; in particular, ALK represents a group -CH2-CH2-;
■ n is 1 or 2;
■ p represents an integer between 1 and 5 inclusive;
■ q represents an integer between 1 and 4 inclusive;
■ u is 0 or 1 ;
■ when n is 1 , J represents a nitro or nitroso group; particularly nitro; ■ when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S(0)m- with m representing an integer 1 or 2; preferentially J represents a radical -S02-;
■ M' represents a hydrogen atom or an organic or mineral cationic counterion;
■ may be present or absent, represents a benzo group optionally
Figure imgf000029_0001
substituted with one or more groups R30 as defined previously; it being understood that:
- the chromophore (XII) or (XIII) comprises at least one sulfonate radical (0)2S(0")-, M+ or a carboxylate radical -C(0)0", M+; preferentially sodium sulfonate;
- the chromophore (XII) or (XIII) is linked to the rest of the molecule of formula (I) via one of the rings L, U, L", L'" or L"", in which case one of the substituents is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0.
As examples of chromophores of formula (XII) derived from dyes, mention may be made of: Acid Brown 13; Acid Orange 3; as examples of chromophores of formula (XIII) derived from dyes, mention may be made of: Acid Yellow 1 , sodium salt of 2,4- dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitrobenzenesulfonic acid, 2(4'-N,N(2"- hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, 4-P-hydroxyethylamino-3- nitrobenzenesulfonic acid; e) the triarylmethane chromophores of formula (XIV):
Figure imgf000029_0002
in which formula (XIV): ■ R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from (d-C8)alkyl, optionally substituted aryl and optionally substituted aryl(CrC8)alkyl; particularly a group (CrC8)alkyl and benzyl optionally substituted with a group (0)mS(0 , M+ with M+ and m as defined previously;
■ R37, R38, R39, R40, R41 , R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
- (CrC8)alkoxy, (C C8)alkylthio;
- (di)(C C8)(alkyl)amino;
hydroxyl, mercapto;
nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or a group (CrC8)alkyl or aryl; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (CrC8)alkyl;
(0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion;
- (O)CO"-, M+with M+ as defined previously;
- or alternatively two contiguous groups R4 with R42 or R42 with R43 or R43 with
R44 together form a fused benzo group: Γ; with Γ optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0")-, M+; iv) hydroxyl; v) mercapto; vi) (di)(C C8)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'- C(X)-; ix) R°-X'-C(X)-X"-; with M+, R°, X, X', X" as defined previously;
particularly, R37 to R40 represent a hydrogen atom, and R41 to R44, which may be identical or different, represent a hydroxyl group or (0)2S(0")-, M+; and when R43 with R44 together form a benzo group, it is preferentially substituted with a group (0)2S(0")-; it being understood that:
- the chromophore (XIV) comprises at least one of the rings G', H', or Γ containing at least one sulfonate radical (0)2S(0 or a carboxylate radical -C(0)0"; preferentially sulfonate; - the chromophore (XIV) is linked to the rest of the molecule of formula (I) via one of the rings G', H', or Γ, in which case one of the substituents is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0;
As examples of chromophores of formula (XIV) derived from dyes, mention may be made of: Acid Blue 1 ; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 50; f) the anionic xanthen -based chromophores of formula (XV):
Figure imgf000031_0001
in which formula (XV):
■ R45, R46, R47 and R48, which may be identical or different, represent a hydrogen atom or a group chosen from:
■ R49, R50, R51 and R52, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
- (C C8)alkoxy, (C C8)alkylthio;
hydroxyl, mercapto;
- nitro, nitroso;
(0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion;
- (O)CO"-, M+with M+ as defined previously;
particularly 53 R54, R55 and R48represent a hydrogen or halogen atom;
■ G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom; ■ L represents an alkoxide O", M+; a thioalkoxide S", M+ or a group NRf, with Rf representing a hydrogen atom or a group (d-C8)alkyl, and M+ as defined previously; M+ is particularly sodium or potassium;
■ L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, which may be identical or different, representing a hydrogen atom, a group (CrC8)alkyl, optionally substituted aryl; U represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more groups (CrC8)alkyl or (0)mS(0 , M+ with m and M+ as defined previously;
■ Q and Q', which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
■ M+ is as defined previously;
it being understood that the chromophore (XV) is linked to the rest of the molecule of formula (I) via one of the rings, in which case one of the substituents R45, R46, R47, R48, R49, R50, R51 or R52 is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0;
As examples of chromophores of formula (XV) derived from dyes, mention may be made of: Acid Yellow 73; Acid Red 51 ; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9; g) the anionic indol -based chromophores of formula (XVI):
Figure imgf000032_0001
in which formula (XVI):
■ R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
- (CrC8)alkoxy, (C C8)alkylthio;
hydroxyl, mercapto;
nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or a group (d-C8)alkyl or aryl; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (CrC8)alkyl;
- (0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion;
- (0)C(0 , M+with M+ as defined previously;
■ G represents an oxygen or sulfur atom or a group NRe with Re as defined previously; particularly G represents an oxygen atom;
■ Rj and Rh, which may be identical or different, represent a hydrogen atom or a group (C C8)alkyl;
it being understood that:
- the chromophore (XVI) comprises at least one sulfonate radical (0)2S(0")-, M+ or a carboxylate radical -C(0)0", M+; preferentially sodium sulfonate;
- the chromophore (XVI) is linked to the rest of the molecule of formula (I) via one of the rings, in which case one of the substituents R53, R54, R55, R56, R57, R58, R59 or R6o is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0; As examples of dyes of formula (XVI), mention may be made of: Acid Blue 74. h) the anionic quinoline-
Figure imgf000033_0001
which formula (XVII):
■ R6i represents a hydrogen or halogen atom or a group (CrC8)alkyl;
■ R62, R63, and R64, which may be identical or different, represent a hydrogen atom or a group (0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion; ■ or alternatively R6i with R62, or R6i with R64, together form a benzo group optionally substituted with one or more groups (0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion; it being understood that:
- the chromophore (XVII) comprises at least one sulfonate radical (0)2S(0")-, M+ preferentially sodium sulfonate;
- the chromophore (XVII) is linked to the rest of the molecule of formula (I) via one of the rings, in which case one of the substituents R6i , R62, R63, or R64 is absent and the carbon atom of one of the rings in which the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0;
As examples of chromophores of formula (XVII) derived from dyes, mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.
The anionic dyes that are most particularly preferred are the dyes designated in the Color Index under the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9, 10- anthraquinone-3-sulfonic acid), C.I. 60730 (monosodium salt of 2-[(9,10-dihydro-4- hydroxy-9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-2,7-naphthalenedisulfonic acid), C.I. 20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8- hydroxy-3,6-naphthalenedisulfonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4- [ethyl[3-sulfophenyl)methyl]amino]phenyl](2-sulfophenyl)methylene]-2,5-cyclohexadien- 1-ylidene]-3-sulfobenzenemethanaminium hydroxide, inner salt), C.I. 61570 (disodium salt of 2,2'-[(9, 10-dihydro-9, 10-dioxo-1 ,4-anthracenediyl)diimino]bis[5-methyl]benzene- sulfonic acid. It is also possible to use the chromophores corresponding to the mesomeric or tautomeric forms of structures (III) to (XVII).
According to one particular embodiment of the invention, the anionic chromophore A is chosen from anionic (poly)azo dyes such as (di)azo dyes, anthraquinones, naphthoquinones, triarylmethanes, nitro dyes, and quinoline and indole derivatives, i.e. it does not contain any xanthene derivatives. Particularly, A is not an anionic fluorescein-based chromophore, more particularly A is not an anionic chromophore obtained from a xanthene derivative of formula (XV) as defined previously.
The radical A of formula (I) may contain one or more identical or different fluorescent coloured chromophores.
1.2. Fluorescent coloured chromophore A:
According to one particular embodiment of the invention, A is is a coloured and fluorescent chromophore.
The term "coloured and fluorescent chromophore" does not mean "optical brightener" chromophores, or any other fluorescent but colourless compounds, i.e. which do not absorb in the visible spectrum (see Ullmann's Encyclopedia of Industrial Chemistry, in the chapters "Fluorescent Dyes" and "Optical Brighteners", 2005, Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/143560007.a18_153; and 2005, Wiley-VCH Verlag GmbH & co. KGaA, Weinheim 10.1002/143560007.a1 1_279).
As fluorescent coloured chromophores that are useful in the present invention, mention may be made of radicals derived from the following dyes: acridines, acridones, azlactones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2/-/-pyrrol-2- ylidene-kN)methyl]-1 H-pyrrolato-kN}bores (BODIPY ®), dipyrinones, diketopyrrolopyrroles, fluorindines, (poly)methines (especially cyanins and styryls/hemicyanins), naphthalimides, naphthanilides, naphthylamine (such as dansyls), naphtholactams, oxadiazoles, oxazines, perilones, perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes, xanthenes, thioxanthenes, and thiazines.
Mention may also be made of the fluorescent dyes described in documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144, EP 714 954 and those listed in the encyclopaedia The chemistry of synthetic dyes by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in Kirk Othmer's encyclopaedia Chemical Technology, in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of Ullmann's Encyclopedia of Industrial Chemistry 7th edition, Wley and Sons, especially in Ullmann's Encyclopedia of Industrial Chemistry in the chapter "Fluorescent Dyes", 2005, Wley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/143560007.a1 1_279; in The Handbook— A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/I nvitrogen - Oregon 2005 circulated by Internet or in the preceding printed editions.
Preferably, the chromophores are chosen from those derived from dyes of coumarin type, of (poly)methine type, especially cyanins and styryl/hemicyanin dyes, and of naphthalimide type.
According to one variant, radical A of formula (I) contains at least one cationic radical borne by, or included in, at least one of the chromophores.
Preferably, the cationic radical is a quaternary ammonium; more preferentially, the cationic charge is endocyclic.
These cationic radicals are, for example, a cationic (di/tri)(CrC8)alkylammonium radical bearing an exocyclic charge, or a cationic acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium radical bearing an endocyclic charge. According to one preferred variant of the invention, the fluorescent coloured chromophore is cationic, comprising at least one quaternary ammonium radical such as the polymethines of formulae (XVIII) and (XIX) below:
W+-[C(Rc)=C(Rd)]m.-Ar'-(*) Q" (XVIII) or
Ar-[C(Rd)=C(Rc)]m-W'+-(*) Q" (XIX),
formulae (XVIII) or (XIX) with:
• W+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (d-C8)alkyl optionally substituted especially with one or more hydroxyl groups;
• W'+ representing a divalent heterocyclic or heteroaryl radical as defined for W+;
• Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more groups (CrC8)alkyl, preferably of C C4 such as methyl; iii) one or more groups hydroxyl; iv) one or more groups (C C8)alkoxy such as methoxy; v) one or more groups hydroxy(CrC8)alkyl such as hydroxyethyl, vi) one or more groups amino or (di)(CrC8)alkylamino, preferably with the C C4 alkyl part optionally substituted with one or more hydroxyl groups, such as (di)hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as pyrrolidinyl, pyridyl and imidazolinyl;
• Ar' is a divalent aryl radical as defined for Ar;
• m' represents an integer between 1 and 4 inclusive, particularly m is 1 or 2; more preferentially 1 ;
• Rc and Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted group (CrC8)alkyl, preferentially of C C4, or alternatively Rc contiguous with W or W and/or Rd contiguous with Ar or Ar' form, with the atoms that bear them, a (hetero)cycloalkyl, particularly Rc is contiguous with W+ or W'+ and forms a (hetero)cycloalkyl such as cyclohexyl;
• Q" is an organic or mineral anionic counterion as defined previously;
• (*) represents the part of the chromophore linked to the residue of formula (I) via X' if p = 1 or Csat if p = 0. According to one preferred embodiment of the invention, the dyes of formula (I) contain a chromophore A that is not an anionic fluorescein-based chromophore, and more particularly A is not an anionic chromophore based on a xanthene derivative of formula (XV) as defined previously.
According to another variant, the dye of formula (I) is a quaternized or quaternizable fluorescent dye such that, in formula (I), A represents a naphthalimidyl radical optionally bearing an exocyclic cationic charge, of formula (XX) or (XXI):
Figure imgf000038_0001
(XX) (XXI) in which formulae (XX) and (XXI):
• G' represents an amino group -NRfRe or ammonium group -N+RfReRh, M";
• G" represents a divalent amino group -N(Rh)- or ammonium group -N+(Rh)(Rj)-, M";
• Re, Rf, R9, Rh and Rj, which may be identical or different, represent a hydrogen atom or a C C6 alkyl group optionally substituted preferentially with a hydroxyl, amino, di(CrC6)alkylamino or tri(CrC6)alkylammonium group, such as trimethylammonium, M"; with M" with M" representing an organic or mineral counterion,
Figure imgf000038_0002
representing the bond linking the naphthalimidyl radical to the rest of the molecule by X, if p = 1 or alternatively by Csat if p = 0;
R1, which may be identical or different, represents a hydrogen atom, a halogen atom, a (di)(CrC4)(alkyl)amino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2-C6)alkoxy, (C C4)alkylcarbonyloxy, (C C4)alkoxycarbonyl or (Ci-C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (Ci-C4)alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (CrCi6)alkyl optionally substituted with a group chosen from (CrC6)alkoxy, hydroxyl, cyano, carboxyl and (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another heteroatom that is identical to or different from a nitrogen atom;
• v represents an integer between 1 and 5 inclusive;
preferentially v is 5, G' represents an amino group -NRfRe and G" represents a divalent amino group -N(Rh)-, R1 represents a hydrogen atom; Re and R9 represent a Ci-C6 alkyl group substituted with a group di(CrC6)alkylamino or tri(C C6)alkylammonium, M"; Rf, Rh represent a hydrogen atom or a C C6 alkyl group; and the amino group RfReN- or -N(Rh)- is in position 4 or 5 of the naphthalimidyl radical.
Preferably, W+ or W'+ is an imidazolium, pyridinium, benzimidazolium, pyrazolium, benzothiazolium or quinolinium optionally substituted with one or more identical or different C C4 alkyl radicals. According to one particularly preferred embodiment of the invention, A represents the chromophore (XIX) as defined previously with m' = 1 , Ar representing a phenyl group substituted para to the styryl group -C(Rd)=C(Rc)- with a group (di)(hydroxy)(C C6)(alkyl)amino such as dihydroxy(C C4)alkylamino, and W'+ representing an imidazolium or pyridinium group, preferentially ortho- or para-pyridinium.
1.2. C«at.
As indicated previously, in formula (I), Csat, represents a linear or branched, optionally substituted, optionally cyclic divalent C Ci8 alkylene chain. Substituents that may be mentioned include amino, (C C4)alkylamino and di(C C4)alkylamino groups, or the group Ra-Za-C(Zb)- (in which Za, Zb, which may be identical or different, represent an oxygen or sulfur atom, or a group NRa', and Ra represents an alkali metal, a hydrogen atom or a group C C4 alkyl and Ra' represents a hydrogen atom or a group Ci-C4 alkyl) preferably present in the beta or gamma position of the ascorbic acid- based radical of formula (11-1 ) to (M-4) as defined previously or of formula (Ι -1 ) to (Ι -4) as defined in point 1.4 below. Preferably, in the case of formula (I), Csat represents a chain -(CR1 R2)k- with k representing an integer between 1 and 10 inclusive, R1 and R2, which may be identical or different, representing a hydrogen atom or a group (C C4)alkyl, (C Ci2)alkoxy, hydroxyl, cyano, carboxyl or (di)(C C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; preferentially, and R2, are hydrogen atoms or an amino group; more preferentially, and R2 represent a hydrogen atom, thus forming an alkylene chain -(CH2)k— with k' being an integer between 1 and 8 inclusive. More particularly, k' is 1 , 2 or 3.
1.3. X and X':
In accordance with one particular embodiment of the invention, in the abovementioned formula (I), when p and/or p', is equal to 1 , the radical(s) X and X', which may be identical or different, represent the following sequence:
-(T)t-(Z)Z-(TV
the said sequence being linked in formula (I), as follows:
- Csat-(T'MZ)Z-(T),-(A or Asc);
in which sequence:
> T and T', which may be identical or different, represent one or more radicals or combinations thereof chosen from: -S(0)2-; -0-; -S-; -N(R)-; -N+(R)(R°)-, Q";
-C(O)-; with R, R°, which may be identical or different, representing a hydrogen atom, a C C4 alkyl, C C4 hydroxyalkyl or aryl(C C4)alkyl radical and Q" representing an organic or mineral anionic counterion; and a cationic or non- cationic, preferentially monocyclic heterocycloalkyl or heteroaryl radical, preferentially containing two heteroatoms (more preferentially two nitrogen atoms) and preferentially being 5- to 7-membered, more preferentially imidazolium, piperazinyl or piperidyl;
preferentially T and T represent one or more radicals or combinations thereof chosen from -0-, -N(R)-, -C(O)-, with R chosen from a hydrogen atom and a (C C4)alkyl radical;
> the indices t and t', which may be identical or different, are equal to 0 or 1 ;
> Z represents:
o -(CRi R2)m- with m being an integer between 1 and 8 inclusive and and R2, which may be identical or different, represent a hydrogen atom or a group (C C4)alkyl, (C C4)alkoxy, hydroxyl, cyano, carboxyl or (di)(C C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen, such as morpholino or piperidino; and R2 particularly represent a hydrogen atom;
o -(CH2CH20)q- or -(OCH2CH2)q- in which q is an integer between 1 and 15 inclusive, preferentially between 1 and 6, or
o a divalent arylene, (C C4)alkylaryl or aryl(C C4)alkyl radical such as benzyl whose aryl radical is preferably C6, being optionally substituted with at least one group S03M with M representing a hydrogen atom, an alkali metal or an ammonium group, the ammonium being substituted with one or more identical or different, linear or branched (C C4)alkyl radicals, optionally substituted with one or more hydroxyl groups;
> z is O or l
According to one particular embodiment of the invention, Z represents divalent group chosen from:
Figure imgf000041_0001
with q representing an integer between 1 and 6 inclusive, and M representing organic or mineral cationic counterion.
1.4. Asc - ascorbic acid-based radical:
The ascorbic acid-based radical Asc of the dye of formula (I) represents an ascorbyl or dehydroascorbyl radical chosen from formulae (11-1 ) to (M-4) as defined previously.
Particularly, the ascorbic acid-based radical is chosen from formulae (11-1 ) to (II- 3) such that:
- R5 is absent and Asc is linked to the rest of the molecule via the carbon atom bearing R6 and R7; - R6, R7 and R8 represent a hydrogen atom
- R10 represents a hydrogen atom or a (C C4)alkyl, particularly hydrogen;
- R9 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously; preferentially:
a) (CrC8)alkyl such as isobutyl (i-butyl) or tert-butyl (t-butyl),
b) (poly)halo(CrC8)alkyl such as trifluoromethyl or trichloroethyl, c) (C2-C8)alkenyl such as allyl (CH2-CH=CH2-),
d) aryl, for instance halophenyl such as para-chlorophenyl,
f) aryl(CrC8)alkyl, such as benzyl, s) R-C(O)-, with R representing 1) a hydrogen atom, or 2) a group (CrC8)alkyl such as methyl, 3) (poly)halo(aryl)(CrC8)alkyl such as chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl or chlorodiphenylmethyl, 4) (CrC8)alkoxy such as methoxy, ethoxy or isobutoxy, 5) (aryl)(C2-C8)alkenyloxy such as vinyloxy, allyloxy or cinnamyloxy, 6) (poly)halo(CrC8)alkoxy such as trichloroethoxy, 7) (C2-C8)alkenyl, 6) (C C8)alkoxy(CrC8)alkyl such as methoxymethyl, 8) (poly)aryl(Ci-C8)alkoxy(Cr C8)alkyl such as triphenylmethoxymethyl, 9) (C2-C8)alkenyloxy such as vinyloxy, 10) aryl such as 2,4,6-trimethylphenyl or mesityl, 1 1) aryl(CrC8)alkoxy such as para-methoxybenzoxy, 3,4-dimethoxybenzoxy, ortho-nitrobenzoxy, para- nitrobenzoxy, 12) (poly)aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl such as benzyl or 2,4,6- trimethylbenzyl, triphenylmethyl or phenylethyl, 13) aryloxy such as para- nitrophenoxy or phenoxy, 14) aryloxy(CrC8)alkyl such as phenoxymethyl or halophenoxymethyl such as para-chlorophenoxymethyl or 2,6-dichloro-4- methylphenoxymethyl, 15) cycloalkyl such as adamantyl, 16) heterocycloalkyl, 17) heteroaryl such as imidazolyl, especially imidazolo, 18) (di)(C C8)(alkyl)amino, 19) aryl(C C8)alkylamino(C C8)alkyl 20) (di)aryl(d- C8)alkylamino, such as phenylamino; t) R'R"P(0)-, with R' and R", which may be identical or different, representing 1) a hydrogen atom, or 2) a hydroxyl group, 3) (CrC8)alkoxy, 4) (C2-C8)alkenyloxy such as vinyloxy, 6) aryl such as 2,4,6- trimethylphenyl or mesityl, 7) aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl such as benzyl or 2,4,6-trimethylbenzyl, 8) aryloxy such as phenoxy, 9) aryloxy(CrC8)alkyl such as phenoxymethyl, 10) cycloalkyl such as adamantyl, 11) heterocycloalkyl, 12) heteroaryl, or 13) (di)(CrC8)(alkyl)amino such as dimethylamino;
more particularly, R9 represents a hydroxyl group or the same -O-protected with a protecting group chosen from:
■ aryl(C C8)alkyl,
■ benzyl, and
■ R-C(O)-, with R representing 1) a hydrogen atom, or 2) a group (C C8)alkyl such as methyl.
According to another particular embodiment of the invention, the dye of formula (I) comprises a group Asc of formula (11-1 ) to (M-3) as defined previously with R9 absent and Asc linked to the rest of the molecule via the carbon atom bearing R8;
- R6, R7 and R9 represent a hydrogen atom;
- R-io represents a hydrogen atom or a (C C4)alkyl, particularly hydrogen;
- R5 represents a hydroxyl group or the same -O-protected with a protecting group as defined previously.
More articularly, Asc is chosen from the groups of formulae (Ι -1 ) to (Ι -3):
Figure imgf000043_0001
(ΙΓ-1 ) (ΙΓ-2) (ΙΓ-3)
with R'9 representing a hydrogen atom or a protecting group as defined previously; preferentially, R'9 represents a hydrogen atom, Rn and R 2 being as defined previously, and •^ /^ - representing the point of attachment of Asc to the rest of the molecule of formula (I).
According to another preferred variant of the invention, the dye of formula (I) comprises a group Asc of formula (M-4) as defined previously with R9 absent and Asc linked to the rest of the molecule via the carbon atom bearing Y and R 0 represents a hydrogen atom or a (C C4)alkyl, particularly hydrogen, in which case Asc is of formula (M'-4) below:
Figure imgf000044_0001
(ΙΓ-4)
with Y as defined previously, particularly Y is an oxygen atom. 1.5. Preferred dyes of formula (I):
According to one preferred variant, the dyes of formula (I) are such that they correspond to formula (Ι'):
A- (Ta CR^)™- (Tb)t - Csat - (To),- - Asc' (Ι') in which formula (Ι'):
- Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly (M'-1 ) to (M'-4);
- Csat is as defined previously, particularly Csat represents a (d-C8)alkylene chain, such as -(CH2)k- with k being an integer between 1 and 8 inclusive; preferentially, k is 1 , 2 or 3;
- m represents an integer between 1 and 8 and and R2, are as defined previously, particularly represent a hydrogen atom or a group (CrC4)alkyl;
- A represents:
a) either a cationic chromophore chosen from the following formulae:
Figure imgf000044_0002
with formulae (III), (III'), (IV), (IV), (XVIII) and (XIX) as defined previously;
b) or an anionic chromophore chosen from following formulae: with formulae (VI) and (X) as defined previously;
- z is 0 or 1 ;
- 1, t' and t", which may be identical or different, are equal to 0 or 1 , and
- Ta, Tb, and Tc, which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0)2- -0-, -S-, -N(R)-, -N+(R)(R°)- M" and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom or a radical (C C4)alkyl or hydroxy(C C4)alkyl; or an aryl(C C4)alkyl such as benzyl, and M" represents an organic or mineral anionic counterion such as a halide;
preferentially, t and t" are equal to 1 , t' is 0, Ta represents a group -N(R)- and Tc represents a group chosen from a radical -0-, -C(O)- or -N(R)-, or a combination thereof with R, representing a hydrogen atom or a group (C C4)alkyl such as methyl; and
more particularly Ta iS in the para position on Ar or Ar' relative to the hydrazono part of (III) or (III'), or the polymethine part -[C(Rc)=C(Rd)]m- of (IV), (XVIII) or (XIX), is in the para position on rings A or B relative to the azo part of (VI), or alternatively is in the place of Z or Z' on the chromophore (X);
c) or a neutral or cationic naphtalimide chromophore chosen from the following formulae:
Figure imgf000045_0001
According to one particularly advantageous mode of the invention, the radical Het+, W+, or W'+, is a group chosen from imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, indolinium and pyrazolium, optionally substituted preferentially with one or more identical or different C C4 alkyl radicals. More particularly, Het+, W+ or W'+, is chosen from pyridinium, imidazolium and indolinium groups optionally substituted with one or more identical or different (C C4)alkyl radicals, such as methyl.
According to one particularly advantageous mode of the invention, Ar is an optionally substituted phenyl, Ar' is an optionally substituted phenylene and Ar+ is an optionally substituted phenyl or naphthyl bearing an exocyclic tri(CrC8)alkylammonium cationic charge, M- with M- representing an organic or mineral anionic counterion, such as trimethylammonium.
More preferentially, the dye bearing an ascorbic acid-based group is a dye chosen from the compounds of formulae (la) to (ln) below:
Figure imgf000046_0001
Figure imgf000047_0001
Fy— [Tb]— (CR3R4)n Tc AsC (1)
Figure imgf000048_0001
(CR^J-UJ— (CR3R4)n— T— AsC (Ij)
Figure imgf000048_0002
(CR^^^FJ— (CR3R4)n— T— AsC
(CR.R,)— [TJ— (CR3R4)n— T— AsC (I and also the organic or mineral acid salts, optical isomers, geometrical isomers, tautomers and solvates thereof such as hydrates;
in which formulae (la) to (ln):
• Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined previously, particularly (Ι -1 ) to (Ι -4);
• G represents a group -NRcRd, or (d-C6)alkoxy; preferentially G represents a group -NRcRd, which is preferentially in the para position relative to the styryl, azo or hydrazono group;
• Ra and R'a, which may be identical or different, represent an optionally substituted group (CrC6)alkyl; preferentially, Ra represents a group (CrC3)alkyl optionally substituted with a hydroxyl group, preferentially unsubstituted, such as methyl;
• Rb represents a hydrogen atom or an optionally substituted C C6 alkyl group; preferentially unsubstituted, such as methyl;
· Rc and Rd, which may be identical or different, represent a hydrogen atom, a group aryl(CrC4)alkyl, (CrC6)alkoxy or an optionally substituted group (C
C6)alkyl; Rc and Rd preferentially represent a hydrogen atom or a group (C
C3)alkyl optionally substituted with i) a hydroxyl group, ii) amino, iii) (di)(C
+
C3)alkylamino, or iv) quaternary ammonium (R")(R"')(R"")N -, Q" with Q" being an organic or mineral anionic counterion;
or alternatively two adjacent radicals Rc and Rd, borne by the same nitrogen atom together form a heterocyclic or heteroaryl group; preferentially, the heterocycle or heteroaryl is monocyclic and 5- to 7-membered; more preferentially, the groups are chosen from imidazolyl and pyrrolidinyl;
particularly, Rc and Rd represent identical groups; preferentially Rc and Rd represent a (CrC3)alkyl optionally substituted with a hydroxyl group, such as methyl, hydroxyethyl and 2-hydroxypropyl;
• Rg, R'g, Rh and R'h, which may be identical or different, represent a hydrogen atom, a halogen atom, a group (di)(C C4)(alkyl)amino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2-
C6)alkoxy, (C C4)alkylcarbonyloxy (C C4)alkoxycarbonyl or (C C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (C C4)alkylsulfonylamino radical, an aminosulfonyl radical or a radical (CrCi6)alkyl optionally substituted with a group chosen from (CrC6)alkoxy, hydroxyl, cyano, carboxyl and (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom form a 5- to 7-membered heterocycle optionally comprising another heteroatom which is identical to or different from a nitrogen atom; preferentially, Rg, R'g, Rh and R'h, represent a hydrogen or halogen atom or a group (CrC3)alkyl; more preferentially Rg, R'g, Rh and R'h, represent a hydrogen atom;
or alternatively two groups Rg and R'g; Rh and R'h; borne by two adjacent carbon atoms, together form a benzo or indeno group, a fused heterocycloalkyl or heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl group being optionally substituted with a halogen atom, a (di)(CrC4)(alkyl)amino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2-C4)alkoxy, (C C4)alkylcarbonyloxy (C C4)alkoxycarbonyl or (Ci-C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (C C4)alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (Ci-Ci6)alkyl optionally substituted with: a group chosen from (d-C6)alkoxy, hydroxyl, cyano, carboxyl, (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocyde optionally comprising another heteroatom identical to or different from a nitrogen atom; preferentially, Rg and R'g; together form a benzo group;
or alternatively when G represents -NRcRd two groups Rc and R'g; Rd and Rg; together form a saturated heteroaryl or heterocyde, optionally substituted with one or more groups (CrC6)alkyl, preferentially a 5- to 7-membered heterocyde containing one or two heteroatoms chosen from nitrogen and oxygen; more preferentially the heterocyde is chosen from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl groups;
Ri, Rj, R'j and R'j, which may be identical or different, represent a hydrogen atom, or a group C C4 alkyl; more preferentially, R, Rj, R'j and R'j represent a hydrogen atom;
or alternatively R with Rg, R'j with Rh borne by two adjacent atoms, together form a (hetero)cycloalkyl group, particularly, for (la) and (lb), R with Rg or R'j with Rh form a cycloalkyl such as cyclohexyl;
Rs represents a sulfonate radical (0)2S(0")-, M+ or a carboxylate radical -C(0)0", M+ with M+ representing an organic or mineral cationic counterion; preferentially sulfonate such as sodium sulfonate;
Ri , R∑, R3 and R4, which may be identical or different, represent a hydrogen atom or a group (C C4)alkyl, (CrCi2)alkoxy, hydroxyl, cyano, carboxyl or (di)(Ci-C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocyde, optionally comprising another heteroatom identical to or different from nitrogen; preferentially, R2, R3 and R4, are hydrogen atoms or an amino group; more preferentially, R^ R2, R3 and R4, represent a hydrogen atom;
• Re, Rf, R9, and Rh, which may be identical or different, represent a hydrogen atom or an alkyl C C6 group optionally substituted preferentially with a group di(CrC6)alkylamino or tri(CrC6)alkylammonium, M" with M" representing an organic or mineral anionic counterion, such as trimethylammonium, M";
Preferably, Re and R9 represent an alkyl C C6 group substituted with a group di(CrC6)alkylamino or tri(CrC6)alkylammonium, M" and Rf, Rh represent a hydrogen atom or a C C6 alkyl group; and the amino group RfReN- or -N(Rh)- is in position 4 of the naphthalimidyl radical;
• t and t', which may be identical or different, are equal to 0 or 1 ; preferentially, t' is 0:
• Ta, Tb and Tc, which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0)2-, -0-, -S-, -N(R)-, -N+(R)(R°)- M" and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom, a radical (C C4)alkyl or hydroxy(C C4)alkyl; or an aryl(Ci-C4)alkyl, and M" represents an organic or mineral anionic counterion such as halide, preferentially, t' is zero and Tc represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C C4)alkyl such as methyl; more particularly, Tc represents a group -C(0)-0-, -O- or -N(R)-C(0)-;
• """^j represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring; when the ring is present, the ring is preferentially a benzo; more preferentially, the ring is absent;
• m and n, which may be identical or different, represent an integer between 0 and 10 inclusive with m+n representing an integer between 1 and 10, particularly between 1 and 6, more particularly m+n = 1 , 2 or 3; and
• M' representing an organic or mineral anionic counterion.
According to one preferred embodiment of the invention, the direct dyes are chosen from those of formulae (la), (lb), (lc), (lf), (lg), (1), (lj), (lk), (L) and (ln).
More particularly, the dyes according to the invention are chosen from the direct dyes of formulae (I'.), (I'b), (l'c), (l'f), (l'g), (Ι',), (I'j), (l'k), (l'm) and (l'n) below:
Figure imgf000052_0001
Figure imgf000053_0001
in which formulae (I'.), (I'b), (l'c), (l'f), (l'g), (ΙΊ), (I'j), (l'k), (l'm) and (l'n):
Figure imgf000053_0002
(ΙΓ-3) (ΙΓ-4)
(ll"-1) (||M-2)
with •^ /^ - representing the point of attachment of Asc to the rest of the molecule by Tc;
Ra, Rj and R'j represent a group (d-C4)alkyl such as methyl; Rb represents a hydrogen atom or a group (C C4)alkyl such as methyl; preferentially, R is a hydrogen atom;
Rg and R'g are as defined previously and preferentially represent a hydrogen atom;
Rs represents a sulfonate radical (0)2S(0")-, M+ such as sodium sulfonate;
preferentially, Rs is ortho to the group RcRdN- of (I'j)
Ri with Rg, R'j with Rh borne by two adjacent atoms, together form a group cycloalkyl, particularly for (l'a) and (l'b), form a cycloalkyl such as cyclohexyl; Tc represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C
C4)alkyl such as methyl, and more particularly Tc represents a group -C(0)-0- or -N(R)-C(0)-;
< m' is 1 , 2 or 3;
n' is an integer between 1 and 10 inclusive, and more particularly between 3 and 6 such as 5;
Rc and Rd represent identical groups (CrC3)alkyl optionally substituted with a hydroxyl group, such as methyl or hydroxyethyl;
Re and R9 represent a C C6 alkyl group substituted with a group di(C C6)alkylamino or tri(CrC6)alkylammonium, M";
Rf and Rh represent a hydrogen atom or a C C6 alkyl group; preferably the amino group RfReN- or -N(Rh)- is in position 4 of the naphthalimidyl radical; and M' representing an organic or mineral anionic counterion;
it being understood that the styryl, hydrozono or azo function is in position 2 (ortho) or 4 (para) relative to the phenyl, preferentially in position 4 and that the styryl or hydrazono function is in position 2' (ortho) or 4' (para) relative to the pyridinium, or 2' (ortho) or 4' (para) relative to the phenyl for (l'k), preferentially in position 4'.
According to an even more preferred embodiment of the invention, the direct dyes are chosen from those of formulae (lb), and (lm) and more particularly (l'b), and
As examples of dyes bearing an ascorbic acid-based group, mention may be made especially of the following compounds:
Figure imgf000055_0001
55
Figure imgf000056_0001

Figure imgf000057_0001

Figure imgf000058_0001
Figure imgf000059_0001
with An" representing an organic or mineral anionic counterion, especially halide such as chloride and M+ representing an organic or mineral cationic counterion such as sodium or potassium. The dyes of formula (la) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2). This reaction is well known to those skilled in the art. It is known as the Knoevenagel reaction and consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemi -471-60180-2). This reaction is illustrated in the scheme below:
Figure imgf000059_0002
with Ri to R4, Ra, Rb, G, m, n, Tb, t' Tc, Rg, R'g, Ri, R'i, Rh, R'h and M' as defined previously.
Compounds (a1 ) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Compounds (a2) may be synthesized via a nucleophilic substitution reaction between a compound (a3) and a compound (a4). This reaction is known to those skilled in the art and is described in the literature. By way of example, reference may be made to the book Advanced Organic Chemistry (ISBN 0-471-60180-2). This reaction is illus
Figure imgf000060_0001
with R to R4, Ra, Rb, G, m, n, Tb, t' Tc, R,, R',, Rh, R'h as defined previously and Hal representing a halogen atom such as fluorine.
The fluorobenzaldehydes, compounds (a3), are known to those skilled in the art and/or are commercially available.
Compounds (a4) may be synthesized via a reaction between a compound (a5) and a compound (a6). This reaction is illustrated in the scheme below:
Figure imgf000060_0002
with R† to R4, R , m, n, Tb, t' as defined previously; Nu representing a nucleophilic group; Έ representing an electrophilic group; and Tc the bond generated after attack of the nucleophile on the electrophile.
By way of example, the covalent bonds Tc that may be generated are listed in Table A below, starting with condensation of electrophiles with nucleophiles:
Table A
Electrophiles Έ Nucleophiles Wa Covalent bonds Tc
Activated esters* Amines Carboxamides
Acyl azides** Amines Carboxamides
Acyl halides Amines Carboxamides
Acyl halides Alcohols Esters
Acyl cyanides Alcohols Esters
Acyl cyanides Amines Carboxamides Alkyl halides Amines Alkylamines
Alkyl halides Carboxylic acids Esters
Alkyl halides Thiols Thioesters
Alkyl halides Alcohols Ethers
Sulfonic acids and salts thereof Thiols Thioethers
Sulfonic acids and salts thereof Carboxylic acids Esters
Sulfonic acids and salts thereof Alcohols Ethers
Anhydrides Alcohols Esters
Anhydrides Amines Carboxamides
Aryl halides Thiols Thioethers
Aryl halides Amines Arylamines
Aziridines Thiols Thioethers
Carboxylic acids Amines Carboxamides
Carboxylic acids Alcohols Esters
Carbodiimides Carboxylic acids N-Acylureas or anhydrides
Diazoalkanes Carboxylic acids Esters
Epoxides Thiols Thioethers
Haloacetamides Thiols Thioethers
Imide esters Amines Amidines
Isocyanates Amines Ureas
Isocyanates Alcohols Urethanes
Isothiocyanates Amines Thioureas
Maleimides Thiols Thioethers
Sulfonic esters Amines Alkylamines
Sulfonic esters Thiols Thioethers
Sulfonic esters Carboxylic acids Esters
Sulfonic esters Alcohols Ethers
Sulfonyl halides Amines Sulfonamides
*the activated esters of general formula -CO-Part with Part representing a leaving group such as optionally substituted oxysuccinimidyl, oxybenzotriazolyl or aryloxy;
the acyl halides may rearrange to give isocyanates. These reactions are known to those skilled in the art and are described in the literature. Reference may be made to the book Advanced Organic Chemistry (ISBN 0- 471 -60180-2).
One variant to this process is to use a fluorescent chromophore containing an electrophilic acrylate function (-OCO-C=C-) on which is performed an addition reaction that will generate a bond T .
In certain cases, it is necessary to protect the amine bearing the group R before the reaction, and then to deprotect it after the reaction between compounds (a5) and (a6). Amine protecting groups are well known to those skilled in the art, including the reaction conditions necessary for the protection and deprotection step. Reference may be made to the book Protecting groups in Organic Chemistry (ISBN 0-471 -05764- 9) for the protection and deprotection conditions.
Compounds (a5) are known to those skilled in the art and are commercially available.
Compounds (a6) are known to those skilled in the art, and their syntheses are described in Comprehensive Heterocyclic Chemistry I I I, 2008, Chapter 4.1 1 , Pages 893-954 and Comprehensive Heterocyclic Chemistry I II , 2008, Chapter 13.10, Pages 299-319. Some compounds are commercially available.
Alternatively, compounds (a4) may be synthesized via a reaction between a compound (a7) and a compound (a8). This reaction is illustrated in the scheme below:
UN— (CR1R2)m (CR3R4)-<E (a8) HN-(CR1R2)m (CR3R4)n-T0— Asc' Rb (a7) Rb
(a4)
with R to R4, Ra, Rb, m, n, Tb, t' Tc, Έ, Nu as defined previously;
Compounds (a7) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Compounds (a8) are known to those skilled in the art and their synthesis is described in Comprehensive Heterocyclic Chemistry I II , 2008, Chapter 4.1 1 , Pages 893-954 and Pages 299-319. Some compounds are commercially available.
In certain cases, it is necessary to protect the amine bearing the group Rb before the reaction, and then to deprotect it after the reaction between compounds (a7) and (a8). Amine protecting groups are well known to those skilled in the art, including the reaction conditions necessary for the protection and deprotection step. Reference may be made to the book Protecting groups in Organic Chemistry (ISBN 0- 471-05764-9) for the protection and deprotection conditions.
Alternatively, compounds (a2) may be synthesized via a reaction between a compound (a9) and a compound (a10). This reaction is illustrated in the scheme below:
Figure imgf000063_0001
with R† to R4, Ra, Rb, m, n, Tb, t' Tc, R,, R',, Rh, R'h as defined previously; Nu representing a nucleophilic group; <E representing an electrophilic group; and Ta the bond generated after attack of the nucleophile on the electrophile. By way of example, the covalent bonds T that may be generated are such as those listed in Table A for Tc starting from the condensation of electrophiles with nucleophiles (see Table A above):
Compounds (a10) are known to those skilled in the art and are described in the literature. Mention may be made of the publications Comprehensive Heterocyclic Chemistry III, 2008, Chapter 4.11 , Pages 893-954 and Chapter 13.10, Pages 299-319. Certain compounds are commercially available.
Compounds (a9) are known to those skilled in the art and are described in the literature. Some compounds are commercially available. Their synthesis consists in reacting a primary or secondary amine (compounds (a11 )) with a fluorobenzaldehyde (compounds (a3)). This reaction is illustrated in the scheme below:
Figure imgf000063_0002
(a3) (a9)
with RL R2, Rb, m, Nu, Rh, R'h R'i, are as defined previously and Hal represents a halogen atom such as fluorine;
Compounds (a3) and (a11 ) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Another synthetic variant consists in reacting a compound (a12) with a heterocyclic compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000064_0001
with R† to R4, Ra, Rb, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g,
Figure imgf000064_0002
Rh, R'h and M' as defined previously;
Compounds (a8) are known to those skilled in the art and their syntheses are described in Comprehensive Heterocyclic Chemistry III, 2008, Chapter 4.11 , Pages 893-954 and Chapter 13.10, Pages 299-319. Some compounds are also commercially available.
The dyes of formula (lb) may be synthesized via a condensation reaction between a compound (a1) and a compound (a2). This reaction is well known to those skilled in the art, and is known as the Knoevenagel reaction, which consists in condensing an aldehyde with a nucleophile of activated methyl type. This reaction is illustrated in the scheme below:
Figure imgf000064_0003
with R† to R4, Ra, Rb, G, m, n, Tb, t' Tc, Έ, N < u, Rg, R'g, Ri, R'i, Rh, R'h and M' as defined previously;
Compounds (a23) are known to those skilled in the art and are described in the literature. Some of them are commercially available. Compounds (a24) may be synthesized via a quaternization reaction between an electrophilic compound (a25) and a pyridine compound (a26). This reaction is well known to those skilled in the art.
Figure imgf000065_0001
(a25) (a24)
with R to R4, Ra, Rb, m, n, Tb, t' Tc, Έ, Nu, R,, R', and M' as defined previously;
The group Gp' represents a leaving group, which, once it has left, generates an anionic counterion. Mention may be made of halides such as iodide, bromide, chloride or the mesylate, sulfate, phosphate, triflate or tosylate group.
Compounds (a26) are known to those skilled in the art and are commercially available.
The compounds (a25) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below:
Figure imgf000065_0002
Q ' (CRi¾m ScRjF -T-Asc1
(a27) (a25)
with R to R4, Ra, Rb, m, n, Tb, t' Tc, Έ, Nu as defined previously;
Compounds (a5) and (a27) are known to those skilled in the art and are commercially available.
Alternatively, compounds (a28) may be synthesized via a reaction between a compound (a26) and a compound (a6). This reaction is illustrated in the scheme below:
Figure imgf000065_0003
Asc'
(a28) (a25)
with R to R4, Ra, Rb, m, n, Gp', Tb, t' Tc, Έ, Nu, as defined previously;
Compounds (a28) are known to those skilled in the art and are described in the literature. Some compounds are commercially available. Compounds (a8) are described above. Alternatively, compounds (1 d) may be synthesized via a reaction between a compound (a29) and a compound (a6). This reaction is illustrated in the scheme below:
Figure imgf000066_0001
with R† to R4, Ra, Rb, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g,
Figure imgf000066_0002
Rh, R'h and M' as defined previously; and compounds (a6) are as described previously.
Compounds (a29) may be synthesized via a reaction between a compound (a30) and a compound (a23). This reaction is illustrated in the scheme below:
Figure imgf000066_0003
with R-i to R4, Ra, Rb, G, m, n, Ta, £, 3Vu, Rg, R'g, Ri, R'i, Rh, R'h, M' as defined previously; compounds (a23) are as defined previously.
Compounds (a30) may be synthesized via a reaction between a compound (a27) and a pyridine derivative (a26). This reaction is illustrated by the scheme below: Gp'- (CR, R2)m
Figure imgf000067_0001
(a27) (a30) with R† to R4, m, n, Ta, Έ, Nu, Rg, R'g, R,, R',, Rh, R'h, M' as defined previously;
Compounds (a27) and (a26) are as defined previously. They are known to those skilled in the art and are described in the literature. Some compounds are commercially available.
Another synthetic variant consists in reacting a compound (a31) with compounds (a8)
Figure imgf000067_0002
with R† to R4, Ra, Rb, G, m, n, Tb, t', Tc, Έ, Nu, Rg, R'g, Ri, R'i, Rh, R'h, M' as defined previously; compounds (a8) are as described previously.
Compounds (a31 ) may be synthesized via a reaction between a compound (a32) and a compound (a23). This reaction is illustrated in the scheme below:
Figure imgf000068_0001
with Ri to R4, Ra, Rb, G, m, n, Tb, <E, Rg, R'g, R,, R',, Rh, R'h, M as defined previously; compounds (a23) are as defined previously.
Compounds (a32) may be synthesized via a reaction between a compound
(a28) and a compound (a26). This reaction is illustrated by the scheme below:
Figure imgf000068_0002
(a28) (a32)
with R to R4, Ra, Rb, m, n, Ta, Έ, R,, R',, Rh, R'h, M', Gp' as defined previously; compounds (a28) and (a26) are described above. They are known to those skilled in the art and are described in the literature. Some compounds are commercially available.
The dyes of formula (lc) may be synthesized via the synthetic routes described previously for the dyes of formula (la). The main difference is that compounds (a14), compounds bearing an indolinium unit, are used instead of compounds (a1 ), compounds bearing a pyridinium unit. The reaction with compounds (a14) is illustrated in the scheme below:
Figure imgf000069_0001
with R† to R4, Ra, Rb, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Ri, R'i, Rn, R'n, Rj, R'j, and M' as defined previously;
Compounds (a14) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Alternatively, compounds (lb) may be synthesized via a condensation reaction between a compound (a15) and a compound (a8). The reaction with compounds (a14) is illustrated in the scheme below:
Figure imgf000069_0002
with R† to R4, Ra, Rb, m, n, Tb, f Tc, Έ, Nu, Rg, R'g, Ri, R'i, Rn, R'n, Rj, R'j and M' as defined previously;
One variant of this synthesis is a condensation reaction between a compound (a15') and a compound (a6). The reaction with compounds (a15') is illustrated in the scheme below:
Figure imgf000069_0003
with R† to R4, Ra, Rb, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Ri, R'i, Rh, R'h, Rj, R'j and M' as defined previously; Compounds (ld) may be synthesized via a reaction between a compound (a33) and a compo
Figure imgf000070_0001
with R† to R4, Ra, Rb, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, R R'i, Rj, R'j, Rh, R'h and M' as defined previously; compounds (a8) are described above.
Compounds (a33) may be synthesized via a reaction between a compound trated in the scheme below: £
Figure imgf000070_0002
with R3, R4, Ra, Rb, G, m, n, Ta, Έ, Nu, Rg, R'g, R R'i, Rj, R'j and M' as defined previously; compounds (a34) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Compounds (a34) may be synthesized via a reaction between a compound
(a35) and a compound (a23). This reaction is illustrated by the scheme below:
Figure imgf000070_0003
with (le), Ra, G, m, n, WM, Rg, R'g, R,, R',, Rj, R'j and M' as defined previously; Compounds (a35) are known to those skilled in the art and are described in the literature. Some of them are commercially available; compounds (a23) are as defined previously.
Alternatively, compounds (ld) may be synthesized via a reaction between a compound (a36) and a compound (a6). This reaction is illustrated by the scheme below:
Figure imgf000071_0001
with (ld), R3, R4, Ra, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Ri, R'j, Rj, R'j, Rh, R'h and M' as defined previously; compounds (a6) are as described previously.
Compounds (a36) may be synthesized via a reaction between a compound
Figure imgf000071_0002
with R3, R4, Ra, G, m, n, T , Έ, Nu, Rg, R'g, R,, R'j, Rj, R'j and M' as defined previously;
Compounds (a38) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
Compounds (a37) may be synthesized via a reaction between an indolinium derivative (a38) and a compound bearing a carbonyl group (a23). This reaction is illustrated in the scheme below:
Figure imgf000072_0001
with Ra, G, m, n, <E, Rg, R'g, Ri, R'i, Rj, R'j, Rh, R'h and M' as defined previously;
Compounds (a38) are known to those skilled in the art and are described in the literature. Some of them are commercially available and compounds (a23) are as described previously.
Compounds (le) may also be synthesized via a reaction between a compound bearing a carbonyl group (a23) and a compound (a39). This reaction is illustrated by the scheme below:
Figure imgf000072_0002
with (le), R3, R4, Ra, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Ri, R'i, Rj, R'j, Rh, R'h and M' as defined previously; compounds (a23) are described previously.
Compounds (a39) may be synthesized via a reaction between a compound (a4
Figure imgf000072_0003
with R3, R4, Ra, G, m, n, Tb, t' Tc, Έ, jfu, Rg, R'g, Ri, R'i, Rj, R'j, Rh, R'h and M' as defined previously; Compounds (a35) are known to those skilled in the art and are described in the literature. Some of them are commercially available.
1/2 £-(CR3R4)-£
(a34)
Nu—Asc £-(CR3R4)-T- — Asc
(a8) (a40)
with R3, R4, n, Tc, <E, svh as defined previously;
Compounds (a8) and (a34) are known to those skilled in the art and some are commercially available.
Alternatively, compounds (a39) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
Figure imgf000073_0001
with R3, R4, Ra, n, Tb, t' Tc, Έ, Nu, R , R' , Rj, R'j, M' as defined previously;
Compounds (a38) are known to those skilled in the art and are commercially available.
Compounds (a41 ) may be synthesized via a reaction between a compound (a41 ) and a compound (a38). This reaction is illustrated in the scheme below:
1/2 £— Asc
(a6)
3Vi/— (CRaFg— 3VK - W«-(CR3R4)-TC— Asc
(a38) (a41)
with R3, R4, n, Tc, Έ, Nu and M' as defined previously;
Compounds (a6) are described previously. Compounds (a38) are known to those skilled in the art and are commercially available.
Compounds (le) may be synthesized via a reaction between a compound (a33) and a compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000074_0001
(a42)
with R† to R4, G, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, R,, R'j, Rh R'j, M' as defined previously. Compounds
-(CRiRz)
Figure imgf000074_0002
(a42)
(a25)
with R† to R4, Ra, Rb, G, m, n, Tb, t' Tc, Έ, N < u, Ri, R'i, Rj, R'j, M' as defined previously;
The group Gp' represents a leaving group, which, once it has been removed, generates an anionic counterion M'. Mention may be made of halides such as iodide, bromide, chloride or the triflate, sulfate, phosphate, mesylate or tosylate group.
Compounds (a43) are known to those skilled in the art and are commercially available. Compounds (a25) are as described above.
Alternatively, compounds (1 g) may be synthesized via a reaction between a compound ( heme below:
Figure imgf000074_0003
with R† to R4, G, m, n, Tb, t' Tc, Έ, N < u, Rg, R'g, Ri, R'i, Rj, R'j, Rh, R'h, M' as defined previously; compounds (a6) are as described previously.
Compounds (a44) may be synthesized via a reaction between a compound (a45) and a compound (a23). This reaction is illustrated in the scheme below:
Figure imgf000075_0001
with R† to R4, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g,
Figure imgf000075_0002
R'i, Rj, R'j, Rh, R'h, M as defined previously; compounds (a23) are as described previously.
Compounds (a45) may be synthesized via a reaction between a compound (a46) and a compound (a27). This reaction is illustrated in the scheme below:
Figure imgf000075_0003
(a27) (a45) with R† to R4, Gp', m, n, Tb, t' Nu, R,, R'j, Rj, R'j, and M' as defined previously; compounds (a27) are as described previously. Compounds (a46) are known to those skilled in the art and are described in the literature.
Alternatively, compounds (lg) may be synthesized via a reaction between a compound ( eme below:
Figure imgf000075_0004
with R† to R4, G, m, n, Tb, t' Tc, Έ, N < u, Rg, R'g, Ri, R'i, Rj, R'j, M' as defined previously; compounds (a8) are as described previously.
Compounds (a44') may be synthesized via a reaction between a compound
(a45') and a compound (a23). This reaction is illustrated in the scheme below:
Figure imgf000076_0001
with Ri to R4, G, m, n, Tb, t' Tc, <E, Rg, R'g, Ri, R'i, Rj, R'j and M' as defined previously; compounds (a23) are as described previously.
Compounds (a45') may be synthesized via a reaction between a compound (a46) an
Figure imgf000076_0002
(a28) (a45') with R† to R4, Gp', m, n, Ta, Έ, R,, R'j, Rj, R'j and M' as defined previously;
Compounds (a28) and (a46) are as described previously.
Compounds (lf) may be synthesized via a reaction between a compound (a46) and a compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000076_0003
(a46) (If) with R-i to R4, Ra, G, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h and M' as defined previously. Compounds (a8) are as described previously. Compounds (a46) may be synthesized in two steps via a reaction between a compound (a47) and a compound (a48), followed by a quaternization reaction. These reactions are illustrated in the scheme below:
Figure imgf000077_0001
(a46)
with to R4, Ra, G, m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Rh, R'h and M' as defined previously;
The first step, to form compound (a49), is a reaction that is well known to those skilled in the art. It is known as a "diazotization" reaction. This reaction is described in the literature. It consists in diazotizing an aromatic amine (compounds (a48)) and in condensing it with an electron-rich aromatic molecule to form a diazo bond. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471- 60180-2). Compounds (a48) are known to those skilled in the art and are described in the literature.
The second step, to form compound (a46), is a reaction that is well known to those skilled in the art. It is known as a "quaternization" reaction. This reaction is described in the literature. Reference may be made, for example, to the book Advanced Organic Chemistry (ISBN 0-471 -60180-2).
One variant to this synthesis is a condensation reaction between a compound (a50) and a compound (a6). The reaction is illustrated in the scheme below:
Figure imgf000078_0001
(aSO) (If) with Ri to R4, Ra, G, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h and M' as defined previously. Compounds (a6) are as described previously.
Compounds (lg) may be synthesized via a reaction between a compound (a51) and a compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000078_0002
with R! to R4, Ra, R'a, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h and M' as defined previously. Compounds (a8) are as described previously.
One variant of this synthesis is a condensation reaction between a compound (a50) and a compound (a6). The reaction is illustrated in the scheme below:
Figure imgf000078_0003
with R† to R4, Ra, R'a, m, n, Tb, t' Tc, £, Nu, Rg, R'g, Rh, R'h and M' as defined previously. Compounds (a6) are as described previously. The general syntheses of azo dyes are known to those skilled in the art and are described in the literature. Reference may be made to the book Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments 3rd, Revised Edition (ISBN: 3-906390-23-3)
Compounds (lh) may be synthesized via a reaction between a compound (a53)
Figure imgf000079_0001
with R† to R4, Ra, m, n, Tb, t' Tc, £, Nu, Rg, R'g, Rh, R'h and M' as defined previously. Compounds (a6) are as described previously.
One variant of this synthesis is a condensation reaction between a compound (a54) and a compound (a8). The reaction is illustrated in the scheme below:
Figure imgf000079_0002
with R† to R4, Ra, m, n, Tb, t' Tc, £, Nu, Rg, R'g, Rh, R'h, Ri, R'i, and M' as defined previously. Compounds (a8) are as described previously.
Compounds (lj) may be synthesized via a reaction between a compound (a55) and a compound (a6). This reaction is illustrated in the scheme below:
Figure imgf000080_0001
(a55)
(li)
with R-i to R4, Ra, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h, R,, R',, and M' as defined previously. Compounds (a6) are as described previously.
The general synthesis of diazahemicyanin dyes are known to those skilled in the art and are described in the literature. Reference may be made to the book Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments 3rd, Revised Edition (ISBN: 3-906390-23-3)
One variant of this synthesis is a condensation reaction between a compound (a54) and a com below:
Figure imgf000080_0002
(a54)
with R-i to R4, Ra, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h, R,, R',, and M' as defined previously. Compounds (a8) are as described previously.
Compounds (1j) may be synthesized via a reaction between a compound (a56) and a compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000081_0001
with R† to R4, R , m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h as defined previously. Rs represents a sulfonate group (S03 " M+) with M+ as defined previously, such as sodium or potassium. Compounds (a8) are as described previously.
One variant of this synthesis is a condensation reaction between a compound (a57) and a compound (a6). The reaction is illustrated in the scheme below:
Figure imgf000081_0002
with R† to R4, R , Rs, m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h as defined previously. Compounds (a6) are as described previously.
The general syntheses of anthraquinone dyes are known to those skilled in the art and are described in the literature. Reference may be made to the book Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments 3rd, Revised Edition (ISBN: 3-906390-23-3).
Compounds (lk) may be synthesized via a reaction between a compound (a58) and a compound (a8). This reaction is illustrated in the scheme below:
Figure imgf000082_0001
with to R4, R , m, n, Tb, t' Tc, <E, Nu, Rg, R'g, Rh, R'h as defined previously. Compounds (a8) are as described previously. One variant to this synthesis is a condensation reaction between a compound
(a59) and a compound (a6). The reaction is illustrated in the scheme below:
Figure imgf000082_0002
with R! to R4, R , m, n, Tb, t' Tc, Έ, Nu, Rg, R'g, Rh, R'h as defined previously. Compounds (a6) are as described previously.
The general syntheses of azo dyes are known to those skilled in the art and are described in the literature. Reference may be made to the book Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments 3rd, Revised Edition (ISBN: 3-906390-23-3).
Compounds (lm) may be synthesized via a reaction between a compound (a60) and a compound (a61 ), to give the intermediate (Α'), which may itself react with a nucleophilic group G'H to give (C). The latter group is capable of reacting, for example via esterification, with a hydroxyl group of an ascorbic derivative Asc-OH. This reaction is illustrated in the scheme below:
Figure imgf000083_0001
with G', Asc, R† to R4, R , R', m, n, v, T , t' Tc as defined previously, and Hal represents a halogen atom such as chlorine, bromine or iodine.
The general syntheses of naphthalimide dyes are known to those skilled in the art and are described in the literature. Reference may be made to the book Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments 3rd, Revised Edition (ISBN: 3-906390-23-3).
//. Composition comprising the dye of formula (I) or (l')
Another subject of the invention is a dye composition comprising, in a cosmetically suitable medium, at least one fluorescent dye bearing a group derived from ascorbic acid of formula (I) or (Γ) as defined previously.
Besides the presence of at least one fluorescent dye of formula (I), the composition of the invention may also contain a reducing agent.
Preferentially, the composition does not contain any reducing agent. According to one particularly advantageous mode of the invention, the cosmetic composition comprising one or more dyes of formula (I) or (Γ) does not contain any chemical oxidizing agent. The term "chemical oxidizing agent" means any chemical or enzymatic oxidizing agent other than atmospheric oxygen.
The dye composition that is useful in the invention generally contains an amount of dye of formula (I) or (Γ) of between 0.001 % and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005% and 20% by weight and even more preferentially between 0.01 % and 5% by weight relative to the total weight of the composition.
The dye composition may also contain additional direct dyes. These direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
Among the natural direct dyes, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. Extracts or decoctions containing these natural dyes and especially henna-based poultices or extracts, may also be used.
The dye composition may contain one or more oxidation bases and/or one or more couplers conventionally used for the dyeing of keratin fibres.
Among the oxidation bases, mention may be made of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.
Among these couplers, mention may be made especially of meta- phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and the addition salts thereof.
The coupler(s) are each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition. The oxidation base(s) present in the dye composition is (are) each generally present in an amount of between 0.001 % and 10% by weight and preferably between 0.005% and 6% by weight relative to the total weight of the dye composition.
In general, the addition salts of the oxidation bases and couplers used in the context of the invention are especially chosen from the salts of addition with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and the salts of addition with a base, such as alkali metal hydroxides, for instance sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
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 C4 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. Preferentially, the composition contains an aromatic alcohol such as benzyl alcohol.
When they are present, the solvents are preferably 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, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic 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, conditioning agents, for instance volatile or non-volatile, modified or unmodified silicones such as amino silicones, film-forming agents, ceramides, preserving agents, opacifiers and conductive polymers.
The above adjuvants are generally present in an amount for each of them of between 0.01 % 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 is generally between 3 and 14 approximately and preferably between 4 and 11 approximately, and more particularly the pH is such that 3 < pH < 9. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, or alternatively using standard buffer systems. According to one preferred embodiment of the invention, the pH of the composition comprising at least one dye of formula (I) is an acidic pH (i.e. 3 < pH < 7) and in particular the pH is 4. According to another embodiment, the pH is basic (i.e. 7 < pH < 11), more particularly 7 < pH < 9.
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, examples that may be mentioned include 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 (γ) below:
/ Ra2
N Wa-N
Ra4 XRa3 (γ)
in which formula (γ):
Wa is a divalent group (d-C6)alkylene optionally interrupted with one or more heteroatoms such as O or N and/or optionally substituted with one or more hydroxyl groups or a C C4 alkyl radical; particularly, Wa represents a propylene group;
Rai , a2, Ra3 and Ra4, which may be identical or different, represent a hydrogen atom or a C C4 alkyl or C C4 hydroxyalkyl radical.
The dye composition may be in various forms, such as in the form of a liquid, a cream or gel, or in any other form that is suitable for dyeing keratin fibres, and especially the hair. ///. Dyeing and/or lightening process using a dye of formula (I) or (l')
Another subject of the invention is a process for dyeing and/or lightening keratin material, especially dark keratin material, which consists in applying to the said materials a composition comprising at least one dye of formula (I) or (Ι') as defined previously.
The process of optical lightening of dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 involves fluorescent dyes of formula (I) or (Ι'), i.e. dyes in which A represents a fluorescent coloured chromophore. Mention may be made particularly of those defined in point 1.2 above. More particularly, the chromophore A is chosen from those of formulae (XVIII), (XIX), (XX) and (XXI) as defined previously.
According to one preferred mode of the invention, the process for lightening dark keratin fibres such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 uses fluorescent dyes of formula (I) or (Ι') chosen from those of formulae (la), (lb), (U), (Id), ( ), (L) and (ln). Advantageously, the fluorescent dyes are chosen from (l'a), (I'b), (l'c), (I'm) and (l'n).
Preferentially, the fluorescent dyes used for lightening dark keratin materials such as keratin fibres with a tone depth of less than or equal to 6 and more particularly less than or equal to 4 are within the orange range.
According to one particular embodiment, in the process of the invention, a reducing agent may be applied before, at the same time as or after application of the composition containing at least one dye of formula (I).
Preferentially, no reducing agent is used in the process according to the invention.
According to one variant, once the composition containing at least one dye of formula (I) has been applied to the keratin materials, the composition is left on for a certain time, and the keratin materials are then rinsed, and/or drained dry and/or undergo a heat treatment and/or are exposed to ultraviolet (UV) light. Preferentially, the fibres undergo a heat treatment, especially at a temperature of between 50 and 200°C and preferentially between 80 and 180°C.
The duration of the treatment after application of the composition containing may be short, for example from 0.1 second to 1 hour, particularly between 5 minutes and 50 minutes and more particularly between 10 and 45 minutes, and preferentially the leave-on time is 30 minutes.
The duration of the post-treatment with heat may be short, for example from 0.1 to 30 minutes. The temperature is between 40°C and 250°C, more particularly between 50°C and 200°C and preferentially from 80°C to 180°C. According to one particular embodiment, the heat treatment of the keratin fibres is performed using an iron for smoothing keratin fibres or using a hairstyling hood, a hairdryer or an infrared ray dispenser.
According to one preferred variant of the invention, the dyeing and/or lightening process according to the invention consists in applying the composition according to the invention to keratin materials and then in draining them dry and/or subjecting them to a heat treatment particularly at a temperature of between 50 and 200°C and more preferentially between 80 and 180°C, with, for example, a smoothing iron. Optionally, in this process variant, the heat treatment is followed by rinsing.
The duration of the post-treatment with UV is between 1 second and 2 hours, preferentially 30 minutes.
One particular embodiment of the invention concerns a process in which the compound of formula (I) may be applied directly to the hair without reducing agents, free of pretreatment or post-treatment reducing agents.
A treatment with a chemical oxidizing agent may optionally be combined. Any type of chemical oxidizing agent that is standard in the field may be used. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and also enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases such as laccases. The use of hydrogen peroxide is particularly preferred.
This oxidizing agent may be applied to the fibres before or after applying the composition containing at least one compound of formula (I).
According to a particularly advantageous embodiment of the invention, the dyeing or optical lightening process does not involve any chemical oxidizing agent.
The examples that follow serve to illustrate the invention without, however, being limiting in nature. The thiol-based fluorescent dyes in the examples hereinbelow were fully characterized by the standard spectroscopic and spectrometric methods. I- EXAMPLES OF SYNTHESIS Example 1 :
5
Procedure for synthesizing a dye comprising an ascorbic acid unit of formula (I) according to the invention:
Figure imgf000089_0001
^ Q Dye 3 belonging to formula (I) according to the invention step i):
The alcohols of the side chain of ascorbic acid (1 ,2-dihydroxyethyl) are protected in acetonide form in acetone with one equivalent of acetyl chloride to give compound (A). 15 step ii): Compound (A) thus obtained is reacted again to protect the vicinal alcohols of ascorbic acid (furanone ring) in A/,A/-dimethylformamide (DMF) in the presence of two equivalents of potassium carbonate and two equivalents of benzyl bromide, to give compound (B).
step Hi):
The alcohols of the 1 ,2-hydroxyethyl chain are then deprotected in refluxing acetic acid/methanol medium to give compound (C).
ROUTE 1 - steps iv), v) and vi):
Compound (C) is reacted in dichloromethane in the presence of triethylamine and 1.2 equivalents of 4-bromobutyryl chloride to give compound (D) (step iv), followed by a standard deprotection by debenzylation (for example via catalytic hydrogenation such as H2 with palladium on graphite or charcoal) (step v).
Compound (D) is reacted in refluxing acetonitrile in the presence of a large excess of the dye to be grafted (5 equivalents) for at least 12 hours (step iv). Compound (F) = commercial compound sold by Sigma-Aldrich.
The expected product, dye 3, is thus obtained after purification on a column of silica gel.
Figure imgf000090_0001
Figure imgf000091_0001
Compound (J) is obtained by reacting the commercial compound (F) with one equivalent of the ethyl ester of bromobutyric acid in refluxing toluene (step viii), followed by saponification of the ester and purification on an ion-exchange column in water (step ix).
Compound (J) is then reacted in DMF in the presence of one equivalent of N- hydroxysuccinimide (NHS) and dicyclohexylcarbodiimide (DCC), at low temperature, followed by the addition of compound (C) (step vii). The expected product, dye 3, is thus obtained after deprotection by debenzylation and purification on a column of silica.
Example 2:
Procedure for synthesizing a dye comprising an ascorbic acid unit of formula (I) according to the invention:
Generaj 1 synthetic sdieme: First route:
Figure imgf000092_0001
First route:
4-Chloro-1 ,8-naphthalic anhydride is reacted in refluxing ethanol in the presence of one equivalent of amine reagent to give compound (Α'). This compound is then reacted with a very large excess of amine (Β') at a temperature close to 1 10°C to give the derivative (C). This derivative is then reacted in 98% sulfuric acid solution in the presence of a slight excess of ascorbic acid to give, after removal of the salts and purification, dye 15. Second route:
Compound (C) obtained according to the first route, is reacted in DMF in the presence of one equivalent of /V-hydroxysuccinimide (NHS) and dicyclohexylcarbodiimide (DCC), at low temperature, followed by addition of the prepared ascorbic derivative. The expected product, dye 15, is thus obtained after deprotection by debenzylation and purification on a column of silica.

Claims

1. Dye bearing an ascorbic acid-based unit of formula (I) below:
A- (X)p - Csat - (X'V - Asc (I)
organic or mineral acid salts, optical isomers, geometrical isomers, tautomers and solvates thereof such as hydrates;
in which formula (I):
> A represents a coloured chromophore;
> Asc represents a radical derived from ascorbic acid chosen from ascorbyl and dehydroascorbyl radicals, chosen from formulae (11-1 ) to (II-4), and which is linked to the rest of the molecule via one of the substituents R5, Re, R7, Re or Rg, or alternatively the said radical is linked to the rest of the molecule directly via one of the carbon atoms bearing the substituents R5, R6, R , R8 or R9, in which case one of these substituents is absent:
Figure imgf000094_0001
(11-1 ) (II-2) (||_3) (II- ) in which formulae (11-1 ) to (II-4):
■ R5, R6, R7, Re, R9 and R 0, which may be identical or different, represent a hydrogen atom or a group chosen from i) (d-C8)alkyl, N) hydroxyl, iii) carboxyl, iv) and -O-protected with a protecting group;
or alternatively R5, and R9 together form a divalent group -0-(CRaRb)n-0- with Ra and R , which may be identical or different, representing a hydrogen atom or a group (CrC8)alkyl such as methyl or t-butyl, (C C8)alkoxy, aryl or (poly)halo(CrC8)alkyl, and n is equal to 1 , 2, or 3;
■ Rn and R 2, which may be identical or different, represent a hydrogen atom, an alkali metal, an alkaline-earth metal or a protecting group;
or alternatively Rn and R 2 together form a divalent group -(CRaRb)n- with
Ra and R , and n as defined previously;
■ Y represents an oxygen or sulfur atom; > X and Χ', which may be identical or different, represent:
a linear or branched, saturated or unsaturated divalent CrC30 hydrocarbon- based chain, optionally interrupted and/or optionally terminated at one or both of its ends with one or more divalent groups or combinations thereof chosen from:
o -N(R)-; -N+(R)(R')-, Q"; -0-; -S-; -C(O)-; -S(0)2- with R, R\ which may be identical or different, chosen from a hydrogen atom and a C C4 alkyl, hydroxyalkyl or amino(CrC8)alkyl radical and Q" represents an organic or mineral anionic counterion;
o an aromatic or non-aromatic, saturated or unsaturated, fused or non-fused (hetero)cyclic radical optionally comprising one or more identical or different, optionally substituted heteroatoms;
a divalent group or a combination chosen from: -N(R)-; -N+(R)(R')-, Q"; -0-; -S-; -C(O)-; -S(0)2- with R, R' and Q" as defined previously;
preferentially, the divalent group(s) or combinations thereof are chosen from -0-;
-N(R)-; -C(O)- with R chosen from a hydrogen atom and a C C4 alkyl radical;
> p and p', which may be identical or different, represent an integer equal to 0 or 1 ; and
> CSat represents a linear or branched, optionally cyclic C Ci8 alkylene chain.
2. Dye of formula (I) according to the preceding claim, in which the radical A is a chromophore derived from the following dyes: acridines; acridones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanins; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines such as dimethines of stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, especially nitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; stilbenestyryls; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes; in particular, A is derived from (poly)azo, hydrazono, (poly)methine or anthraquinone dyes.
3. Dye of formula (I) according to any one of the preceding claims, the chromophore A of which is cationic; particularly chosen from the hydrazono chromophores of formulae (III) and (ΙΙΓ), the azo chromophores of formulae (IV) and (IV), and the diazo chromophores of formula (V) below:
Het+-C(Ra)=N-N(Rb)-Ar, Q" (III),
Het+-C(Ra)=N-N(Rb)-Ar, Q" (III),
Het+-N=N-Ar, Q" (IV)
Ar+-N=N-Ar", Q" (IV) and
Het+-N=N-Ar'-N=N-Ar, Q" (V) formulae (III), (III'), (IV), (IV) and (V) with:
Het+ representing a cationic heteroaryl radical;
- Ar+ representing an aryl radical bearing an exocyclic cationic charge;
- Ar represents an aryl group, optionally substituted, or alternatively Ar represents a julolidine group;
- Ar' is an optionally substituted divalent (hetero)arylene group;
- Ar" is an optionally substituted (hetero)aryl group;
Ra and Rb, which may be identical or different, representing a hydrogen atom or an optionally substituted group (d-C8)alkyl;
or alternatively the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form, together with the atoms that bear them, a (hetero)cycloalkyl; Q" represents an organic or mineral anionic counterion;
it being understood that the chromophore (III), (ΙΙΓ), (IV), (IV) or (V) is linked to the rest of the molecule of formula (I) via Het+, Ar+, Ar or Ar".
4. Fluorescent dye of formula (I) according to any one of the preceding claims, in which the radical: - A represents cationic fluorescent coloured chromophore comprising at least one quaternary ammonium radical, such as the polymethines of formulae (XVIII) and (XIX) below:
W+-[C(Rc)=C(Rd)]m -Ar'-(*) Q" (XVIII)
Ar-[C(Rd)=C(Rc)]m-W'+-(*) Q" (XIX),
formulae (XVIII) and (XIX) with:
• W+ representing a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (d-C8)alkyl optionally substituted especially with one or more hydroxyl groups;
• W'+ representing a divalent heterocyclic or heteroaryl radical as defined for W+;
• Ar representing an optionally substituted aryl group;
• Ar' representing a divalent aryl radical as defined for Ar;
• m' representing an integer between 1 and 4 inclusive;
• Rc, Rd, which may be identical or different, representing a hydrogen atom or an optionally substituted group (CrC8)alkyl, or alternatively Rc contiguous with W or W and/or Rd contiguous with Ar or Ar' form, with the atoms that bear them, a (hetero)cycloalkyl, particularly Rc is contiguous with W+ or W'+ and forms a (hetero)cycloalkyl such as cyclohexyl;
• Q" representing an organic or mineral anionic counterion;
• (*) representing the part of the chromophore linked to the residue of formula (I) by X' if p = 1 or Csat if p = 0; or alternatively
- A represents a fluorescent coloured naphthalimidyl chromophore optionally bearing an exocyclic cationic charge of formula (XX) or (XXI):
Figure imgf000097_0001
(XX) (XXI) in which formulae (XX) and (XXI):
G' represents an amino group -NRfRe or ammonium group -N+RTReRn, M"; G" represents a divalent amino group -N(Rh)- or ammonium group -N+(Rh)(Rj)-, M";
Re, Rf, R9, Rh and Rj, which may be identical or different, represent a hydrogen atom or a C C6 alkyl group optionally substituted preferentially with a hydroxyl, amino, di(CrC6)alkylamino or tri(CrC6)alkylammonium group, such as trimethylammonium, M"; with M" with M" representing an organic or mineral counterion,
Figure imgf000098_0001
representing the bond linking the naphthalimidyl radical to the rest of the molecule by X, if p = 1 or alternatively by Csat if p = 0;
• R, which may be identical or different, represents a hydrogen atom, a halogen atom, a (di)(CrC4)(alkyl)amino, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2-C6)alkoxy, (C C4)alkylcarbonyloxy (C C4)alkoxycarbonyl or (Ci-C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (Ci-C4)alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (CrCi6)alkyl optionally substituted with a group chosen from (CrC6)alkoxy, hydroxyl, cyano, carboxyl and (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another heteroatom that is identical to or different from a nitrogen atom;
• v represents an integer between 1 and 5 inclusive;
preferentially, v is 5, G' represents an amino group -NRfRe and G" represents a divalent amino group -N(Rh)-, R represents a hydrogen atom; Re and R9 represent a Ci-C6 alkyl group substituted with a group di(CrC6)alkylamino or tri(C C6)alkylammonium, M"; Rf, Rh represent a hydrogen atom or a C C6 alkyl group; and the amino group RfReN- or -N(Rh)- is in position 4 or 5 of the naphthalimidyl radical.
5. Dye of formula (I) according to any one of the preceding claims, in which the radical Csat represents a chain -(CR1R2)k- with k representing an integer between 1 and 10 inclusive, R1 and R2, which may be identical or different, representing a hydrogen atom or a group (C C4)alkyl, (CrCi2)alkoxy, hydroxyl, cyano, carboxyl, (di)(Ci-C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; preferentially, and R2, represent a hydrogen atom, thus forming an alkylene chain -(CH2)k— with k' being an integer between 1 and 8 inclusive.
6. Dye of formula (I) according to any one of the preceding claims, in which, when p and/or p', are equal to 1 , the radical X and/or X', which may be identical or different, represent the following sequence:
-(T),-(Z)z-(T')t.- the said sequence being linked in formula (I), as follows:
- Csat-(T')t.-(Z)z-(T)t-(A or Asc);
in which sequence:
> T and T', which may be identical or different, represent one or more radicals or combinations thereof chosen from: -S(0)2-; -0-; -S-; -N(R)-; -N+(R)(R°)-, Q"; -C(O)-; with R, R°, which may be identical or different, representing a hydrogen atom, a C C4 alkyl, C C4 hydroxyalkyl or aryl(C C4)alkyl radical and Q" representing an organic or mineral anionic counterion; and a cationic or non- cationic heterocycloalkyi or heteroaryl radical; preferentially, T and T' represent one or more radicals or combinations thereof chosen from -0-, -N(R)-, -C(O)-, with R chosen from a hydrogen atom, and a radical (C C4)alkyl;
> the indices t and t', which may be identical or different, are equal to 0 or 1 ;
> Z represents:
o -(CRi R2)m- with m an integer between 1 and 8 and and R2, which may be identical or different, represent a hydrogen atom or a group (C C4)alkyl, (Ci-C4)alkoxy, hydroxyl, cyano, carboxyl or (di)(C C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen, such as morpholino or piperidino; particularly, and R2 represent a hydrogen atom; o -(CH2CH20)q- or -(OCH2CH2)q- in which q is an integer between 1 and 15 and preferentially between 1 and 6, or
o a divalent arylene radical, (C C4)alkylaryl or aryl(C C4)alkyl, being optionally substituted with at least one group S03M with M representing a hydrogen atom, an alkali metal or an ammonium group, the ammonium being substituted with one or more identical or different, linear or branched (CrC4)alkyl radicals, optionally substituted with one or more hydroxyl groups;
> z is O or l
7. Dye of formula (I) according to any one of the preceding claims, in which the ascorbyl and dehydroascorbyl radicals Asc chosen from formulae (11-1 ) to (M-3) are such that:
- R5 is absent and Asc is linked to the rest of the molecule via the carbon atom bearing R6 and R7;
- R6, R7 and R8 represent a hydrogen atom;
- R-io represents a hydrogen atom or a group (C C4)alkyl, particularly hydrogen;
- R9 represents a hydroxyl group or the same -O-protected with a protecting group particularly chosen from:
a) (CrC8)alkyl,
b) (poly)halo(C C8)alkyl,
c) (C2-C8)alkenyl,
d) aryl,
f) aryl(C C8)alkyl,
s) R-C(O)-, with R representing 1) a hydrogen atom, or 2) a group (CrC8)alkyl, 3) (poly)halo(aryl)(C C8)alkyl, 4) (C C8)alkoxy, 5) (aryl)(C2-C8)alkenyloxy, 6) (poly)halo(C C8)alkoxy, 7) (C2-C8)alkenyl, 6) (C C8)alkoxy(C C8)alkyl, 8) (poly)aryl(C C8)alkoxy(C C8)alkyl, 9) (C2-C8)alkenyloxy, 10) aryl, 1 1) aryl(C C8)alkoxy, 12) (poly)aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl, 13) aryloxy, 14) aryloxy(C C8)alkyl, 15) cycloalkyl, 16) heterocycloalkyl, 17) heteroaryl, 18) (di)(C C8)(alkyl)amino, 19) aryl(C C8)alkylamino(C C8)alkyl 20) (di)aryl(d- C8)alkylamino; and
t) R'R"P(0)-, with R' and R", which may be identical or different, representing 1) a hydrogen atom, or 2) a hydroxyl group, 3) (CrC8)alkoxy, 4) (C2- C8)alkenyloxy, 6) aryl, 7) aryl(CrC8)alkyl, the aryl group being optionally substituted with one or more groups (CrC8)alkyl, 8) aryloxy, 9) aryloxy(C C8)alkyl, 10) cycloalkyl, 11) heterocycloalkyl, 12) heteroaryl, or 13) (di)(C C8)(alkyl)amino.
8. Dye of formula (I) according to the preceding claim, in which the ascorbyl and dehydroascorbyl radicals Asc are chosen from the groups of formulae (Ι -1 ) to (Ι -3) below:
Figure imgf000101_0001
(ΙΓ-1 ) (ΙΓ-2) (ΙΓ-3)
with R'9 representing a hydrogen atom or a protecting group as defined in Claim 1 or 7, preferentially, R'9 representing a hydrogen atom, Rn and R 2 being as defined in Claim
1 , and •^ /^ - representing the point of attachment of Asc to the rest of the molecule of formula (I).
9. Dye of formula (I) according to any one of Claims 1 to 6, in which the ascorbyl or dehydroascorbyl radical Asc is of formula (II-4) as defined in Claim 1 with R9 absent and Asc being linked to the rest of the molecule via the carbon atom bearing Y and R 0 representing a hydrogen atom or a (C C4)alkyl; particularly, Asc is of formula (Ι -4) below:
Figure imgf000101_0002
(ΙΓ-4)
with Y as defined in Claim 1 , and preferentially Y is an oxygen atom.
10. Dye of formula (I) according to any one of the preceding claims, of formula (Ι') below:
A- (Ta)t-(CR1R2)m- (Tb),.- Csat - (To),- - Asc' (Ι') which formula (Ι'):
- Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined in any one of Claims 1 and 7 to 9;
- CSat is as defined in Claim 1 or 5;
- m represents an integer between 1 and 8 and and R2, are as defined in Claim 5, particularly representing a hydrogen atom or a group (C C4)alkyl;
- A represents:
a) either a cationic chromophore chosen from the following formulae:
Figure imgf000102_0002
with formulae (III), (III'), (IV), (IV), (XVIII) and (XIX) as defined in Claim 3 or 4; b) or an anionic chromophore chosen from the following formulae:
Figure imgf000102_0001
in which (VI) and (X) formulae;
■ R7, R8, R9, R10, R'7, R'e, R'9 and R' 0, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
- (C C8)alkoxy, (C C8)alkylthio;
hydroxyl, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom or a group (CrC8)alkyl or aryl; X, X' and X", which may be identical or different, representing an oxygen or sulfur atom, or NR with R representing a hydrogen atom or a group (d-C8)alkyl;
(0)2S(0")-, M+ with M+ representing a hydrogen atom or an organic or mineral cationic counterion;
- (O)CO"-, M+with M+ as defined previously;
R"-S(0)2-, with R" representing a hydrogen atom, an alkyl group, an aryl group, (di)(CrC8)(alkyl)amino, aryl(CrC8)(alkyl)amino; preferentially a phenylamino or phenyl group;
- R'"-S(0)2-X'- with R'" representing a group (C C8)alkyl, optionally substituted aryl, X' as defined previously;
(di) (CrC8)(alkyl)amino;
aryl(CrC8)(alkyl)amino optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0")-, M+ and iv) alkoxy with M+ as defined previously;
optionally substituted heteroaryl;
cycloalkyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group
or alternatively two contiguous groups R7 with R8 or R8 with R9 or R9 with R 0 together form a fused benzo group A'; and R'7 with R'8 or R'8 with R'9 or R'9 with R' 0 together form a fused benzo group B'; with A' and B' optionally substituted with one or more groups chosen from i) nitro; ii) nitroso; iii) (0)2S(0 , M+; iv) hydroxyl; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) optionally substituted aryl(C C8)(alkyl)amino; with M+, R°, X, X', X" and Ar as defined previously;
R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- (CrC8)alkyl;
hydroxyl, mercapto;
- (CrC8)alkoxy, (C C8)alkylthio;
aryloxy or arylthio optionally substituted, preferentially substituted with one or more groups chosen from alkyl and (0)2S(0 , M+ with M+ as defined previously; aryl(CrC8)(alkyl)amino optionally substituted with one or more groups chosen from alkyl and (0)2S(0")-, M+ with M+ as defined previously;
(di) (CrC8)(alkyl)amino;
(di)(hydroxy(Ci-C8)alkyl)amino
- (0)2S(0")-, M+ with M+ as defined previously;
Z' represents a hydrogen atom or a group NR28 29 with
R2e and R29, which may be identical or different, represent a hydrogen atom or a group chosen from:
- (CrC8)alkyl;
polyhydroxy(CrC8)alkyl;
aryl optionally substituted with one or more groups, particularly i) (C C8)alkyl; ii) (0)2S(0 , M+ with M+ as defined previously; iii) R°-C(X)-X'-, R°- X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined previously;
cycloakyl;
Z, represents a group chosen from hydroxyl and NR'28R'29 with R'28 and R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined previously;
it being understood that:
- the chromophore (VI) or (X) comprises at least one sulfonate radical (0)2S(0)-, M+ or a carboxylate radical (O)CO"-, M+ on one of the rings A, B, G or H; preferentially sodium sulfonate;
- the chromophore (VI) or (X) is linked to the rest of the molecule of formula (I) via one of the rings A or B, or via one of the benzo groups G, or H of anthraquinone; in which case one of the substituents is absent and the carbon atom of one of the rings or benzo where the said substituent is absent, is linked to X' if p = 1 or Csat if p = 0;
t, t' and t", which may be identical or different, are equal to 0 or 1 , and
Ta, Tb, and Tc, which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0)2- -0-, -S-, -N(R)-, -N+(R)(R°)- M", -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom, a radical (C C4)alkyl or hydroxy(C C4)alkyl; or an aryl(Ci-C4)alkyl, and M" represents an organic or mineral anionic counterion t; preferentially, t and t" are equal to 1 , t' is 0, Ta represents a group -N(R)- and Tc represents a group chosen from a radical -0-, -C(O)-, -N(R)-, or a combination thereof with R, representing a hydrogen atom or a group (C C4)alkyl such as methyl; and particularly Ta is in the para position on Ar or Ar' relative to the hydrazono part of (III) or (ΙΙΓ) or the polymethine part -[C(Rc)=C(Rd)]m- of (IV), (XVIII), or (XIX), Ta is in the para position on ring A or B relative to the azo part of (VI) or alternatively is in the place of Z or Z' on the chromophore (X); c) or a neutral or cationic naphtalimide chromophore chosen from the following formulae:
Figure imgf000105_0001
■ with G\ G" and R as defined in Claim 4.
11. Dye of formula (I) or (Ι') according to any one of Claims 3 to 10, in which the radical Het+, W+ or W'+ is a group chosen from imidazolium, pyridinium, benzopyridinium, benzimidazolium, quinolinium, indolinium and pyrazolium, optionally substituted preferentially with one or more identical or different C C4 alkyl radicals; Ar is an optionally substituted phenyl, Ar' is an optionally substituted phenylene and Ar+ is an optionally substituted phenyl or naphthyl bearing an exocyclic tri(C C8)alkylammonium cationic charge, M" with M" representing an organic or mineral anionic counterion, such as trimethylammonium, M".
12. Dye of formula (I) or (Ι') according to any one of the preceding claims, chosen from the dyes of formulae (la) to (ln) below: 105
Figure imgf000106_0001
Figure imgf000106_0002
Figure imgf000107_0001
Figure imgf000108_0001
and also the organic or mineral acid salts, optical isomers, geometrical isomers, tautomers and solvates thereof such as hydrates;
in which formulae (la) to (ln):
• Asc' represents an ascorbic acid-based radical of formulae (11-1 ) to (M-4) as defined in Claims 7 to 9;
• G represents a group -NRcRd, or (d-C6)alkoxy;
• Ra and R'a, which may be identical or different, represent an optionally substituted group (CrC6)alkyl;
• Rb represents a hydrogen atom or an optionally substituted group C C6 alkyl;
• Rc and Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted group aryl(CrC4)alkyl, (CrC6)alkoxy or (CrC6)alkyl;
or alternatively two adjacent radicals Rc and Rd, borne by the same nitrogen atom together form a heterocyclic or heteroaryl group;
• Rg, R'g, Rh and R'h, which may be identical or different, represent a hydrogen atom, a halogen atom, a group (di)(C C4)(alkyl)amino, cyano, carboxyl, hydroxyl, trifluoromethyl, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2- C6)alkoxy, (C C4)alkylcarbonyloxy (C C4)alkoxycarbonyl or (C C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (C C4)alkylsulfonylamino radical, an aminosulfonyl radical or a radical (CrCi6)alkyl optionally substituted with a group chosen from (d-C6)alkoxy, hydroxyl, cyano, carboxyl and (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom of an amino group form a 5- to 7-membered heterocyde optionally comprising another heteroatom identical to or different from a nitrogen atom;
or alternatively two groups Rg and R'g; Rh and R'h; borne by two adjacent carbon atoms, together form a benzo or indeno group, a fused heterocycloalkyl or heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl group being optionally substituted with a halogen atom, a (di)(C C4)(alkyl)amino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C C4)alkoxy, (poly)hydroxy(C2-C4)alkoxy, (C C4)alkylcarbonyloxy (C C4)alkoxycarbonyl or (Ci-C4)alkylcarbonylamino radical, an acylamino, carbamoyl or (C C4)alkylsulfonylamino radical, an aminosulfonyl radical, or a radical (CrCi6)alkyl optionally substituted with: a group chosen from (CrC6)alkoxy, hydroxyl, cyano, carboxyl, (di)(C C4)(alkyl)amino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocyde optionally comprising another heteroatom identical to or different from a nitrogen atom;
or alternatively, when G represents -NRcRd, two groups Rc and R'g; Rd and Rg; together form a saturated heteroaryl or heterocyde, optionally substituted with one or more groups (CrC6)alkyl;
Ri, Rj, R'j and R'j, which may be identical or different, represent a hydrogen atom, or a group C C4 alkyl;
or alternatively R, with Rg, R'j with Rh borne by two adjacent atoms, together form a (hetero)cycloalkyl group, particularly, for (la) and (lb), R, with Rg or R'j with Rh form a cycloalkyl such as cyclohexyl;
Rs represents a sulfonate radical (0)2S(0")-, M+ or a carboxylate radical -C(0)0", M+ with M+ representing an organic or mineral cationic counterion;
Ri , R∑, R3 and R4, which may be identical or different, represent a hydrogen atom or a group (C C4)alkyl, (CrCi2)alkoxy, hydroxyl, cyano, carboxyl or (di)(Ci-C4)(alkyl)amino, the said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another heteroatom identical to or different from nitrogen; particularly, R2, R3 and R4 represent a hydrogen atom;
Re, Rf, R9, and Rh, which may be identical or different, represent a hydrogen atom or an alkyl C C6 group optionally substituted preferentially with a group di(CrC6)alkylamino or tri(CrC6)alkylammonium, M" with M" representing an organic or mineral anionic counterion, such as trimethylammonium, M";
preferably, Re and R9 represent a C C6 alkyl group substituted with a group di(CrC6)alkylamino or tri(CrC6)alkylammonium, M" and Rf, Rh represent a hydrogen atom or a C C6 alkyl group; and the amino group RfReN- or -N(Rh)- is in position 4 of the naphthalimidyl radical; t and t', which may be identical or different, are equal to 0 or 1 ; preferentially, t' is 0:
Ta, Tb and Tc, which may be identical or different, represent one or more radicals or combinations thereof chosen from -S(0)2-, -0-, -S-, -N(R)-, -N+(R)(R°)- M" and -C(O)-, with R, R°, which may be identical or different, representing a hydrogen atom or a radical (C C4)alkyl or hydroxy(C C4)alkyl; or an aryl(C C4)alkyl, and M" represents an organic or mineral anionic counterion such as halide, preferentially, t' is zero and Tc represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C C4)alkyl such as methyl; more particularly, Tc represents a group -C(0)-0-, -O- or -N(R)-C(0)-; represent an aryl or heteroaryl group fused to the phenyl ring; or
Figure imgf000110_0001
alternatively is absent from the phenyl ring; preferentially, the ring is absent; m and n, which may be identical or different, represent an integer between 0 and 10 inclusive with m+n representing an integer between 1 and 10;
M' representing an organic or mineral anionic counterion.
13. Dye of formula (I) or (Ι') according to any one of the preceding claims, chosen from the dyes of formulae (I'.), (I'b), (l'c), (l'f), (l'g), (I'i), (I'j), (l'k), (l'm) and (l'n) below:
Figure imgf000111_0001
Figure imgf000112_0001
in which formulae (l'a), (l'b), (l'c), (l'f), (l'g), (I'i), (I'j), (l'k), (l'm) and (l'n):
Figure imgf000112_0002
(ll"-3) (ΙΓ-4)
(ll"-1) (||M-2)
with •^ /^ - representing the point of attachment of Asc' to the rest of the molecule by Tc;
Ra, Rj and R'j represent a group (d-C4)alkyl; Rb represents a hydrogen atom or a group (C C4)alkyl; preferentially, R is a hydrogen atom;
Rg and R'g are as defined in the preceding claim, and preferentially represent a hydrogen atom;
Rs represents a sulfonate radical (0)2S(0")-, M+with M+ representing an organic or mineral cationic counterion; such as sodium sulfonate;
preferentially, Rs is ortho to the group RcRdN- of (I'j)
Ri with Rg, R'j with Rh borne by two adjacent atoms, together form a cycloalkyl group, particularly for (I'a) and (I'b), form a cycloalkyl such as cyclohexyl;
Tc represents a group chosen from a radical -0-, -C(O)-, -N(R)- or a combination thereof with R, representing a hydrogen atom or a group (C
C4)alkyl such as methyl; particularly, Tc represents a group -C(0)-0- or -N(R)-
C(O)-;
m' is 1 , 2 or 3;
n' is an integer between 1 and 10 inclusive, and more particularly between 3 and 6, such as 5;
Rc and Rd represent identical groups (CrC3)alkyl optionally substituted with a hydroxyl group, and
Re and R9 represent a C C6 alkyl group substituted with a group di(C
C6)alkylamino or tri(CrC6)alkylammonium, M";
Rf and Rh represent a hydrogen atom or a C C6 alkyl group; preferably the amino group RfReN- or -N(Rh)- is in position 4 of the naphthalimidyl radical; and M' representing an organic or mineral anionic counterion;
it being understood that the styryl, hydrozono or azo function is in position 2 (ortho) or 4 (para) relative to the phenyl, preferentially in position 4 and that the styryl or hydrazono function is in position 2' (ortho) or 4' (para) relative to the pyridinium, or 2' (ortho) or 4' (para) relative to the phenyl for (I'k), preferentially in position 4'.
14. Dye of formula (I) or (Ι') according to any one of the preceding claims, chosen from the dyes below:
Figure imgf000114_0001
114
Figure imgf000115_0001
115
Figure imgf000116_0001
116
Figure imgf000117_0001
Figure imgf000118_0001
organic or mineral cationic counterion.
15. Dye composition comprising, in a suitable cosmetic medium, one or more dyes of formula (I) or (Γ) as defined in any one of the preceding claims; in particular, the composition is at acidic pH and comprises an aromatic alcohol such as benzyl alcohol.
16. Process for dyeing and/or lightening keratin materials, in which a suitable dye composition as defined in the preceding claim is applied to the said materials.
17. Process for dyeing and/or lightening keratin materials according to the preceding claim, in which the composition comprising the compound(s) of formula (I) or (Γ) is left on, and the keratin materials are then rinsed and/or drained dry and/or undergo a heat treatment and/or are exposed to ultraviolet (UV) light; preferentially, the materials are keratin fibres and undergo a heat treatment especially at a temperature of between 50 and 200°C.
18. Process according to Claim 16 or 17, not using a chemical oxidizing agent and/or not using a reducing agent.
19. Dyeing and/or lightening process according to any one of Claims 16 to 18, in which the keratin materials are dark keratin fibres with a tone depth of less than or equal to 6 and particularly less than or equal to 4.
20. Use of the dyes of formula (I) or (Γ) as defined in Claims 1 to 14, for the dyeing and/or lightening of human keratin materials such as human keratin fibres, especially dark fibres with a tone depth of less than 6 and preferentially less than or equal to 4.
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