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WO2009037325A2 - Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant - Google Patents

Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant Download PDF

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Publication number
WO2009037325A2
WO2009037325A2 PCT/EP2008/062479 EP2008062479W WO2009037325A2 WO 2009037325 A2 WO2009037325 A2 WO 2009037325A2 EP 2008062479 W EP2008062479 W EP 2008062479W WO 2009037325 A2 WO2009037325 A2 WO 2009037325A2
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alkyl
formula
group
optionally substituted
radical
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WO2009037325A3 (fr
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Andrew Greaves
Nicolas Daubresse
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LOreal SA
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LOreal SA
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    • 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
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
    • 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
    • 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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- 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
    • 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
    • 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
    • A61K2800/434—Luminescent, Fluorescent; Optical brighteners; Photosensitizers

Definitions

  • the invention relates to the dyeing of keratin materials using thiol and disulfide, indole-derived, styryl fluorescent dyes.
  • the direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridine dyes, or dyes of the azo, xanthene, acridine, azine or triarlymethane type.
  • a chemical bleaching process comprises treating the keratin fibers, such as the hair, with a strong oxidizing system, generally composed of hydrogen peroxide, possibly in combination with persalts, generally in an alkaline medium.
  • This bleaching system has the drawback of damaging the keratin fibers, in particular the hair, and of detrimentally affecting their cosmetic properties.
  • the fibers in fact have a tendency to become rough, more difficult to disentangle and more brittle.
  • the lightening or the bleaching of keratin fibers with oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in hair straightening treatments.
  • Another lightening technique comprises applying fluorescent direct dyes to dark hair. This technique, described in particular in documents WO 03/028685 and
  • disulfide dyes in particular azo-imidazolium chromophore dyes in patent applications WO 2005/097051 or EP 1647580, and pyridinium/indolizinium styryl chromophore dyes in patent applications WO 2006/134043 and WO 2006/136617.
  • Patent application WO 2007/039527 discloses particular styrylthiol dyes for dyeing hair bearing an indole moiety substituted on the 1,2- position of the indole group. None of those documents mentions the problem of lightening keratin fibers without the use of chemical oxidation agents.
  • the aim of the present invention is to provide new systems for dyeing keratin materials, in particular human keratin fibers, especially the hair, which do not have the drawbacks of the existing bleaching processes.
  • one of the aims of the present invention is to provide direct dyeing systems for obtaining lightening effects, especially on naturally or artificially dark keratin fibers, which are resistant to successive shampooing operations, which do not damage the keratin fibers and which do not detrimentally affect their cosmetic properties.
  • Another aim of the invention is to dye keratin materials chromatically and in a manner which is persistent with respect to outside attacks.
  • a subject of which is a process for dyeing keratin materials, in particular keratin fibers, especially human keratin fibers such as the hair, more particularly dark hair, comprising applying, to the keratin materials, a dye composition comprising, in a suitable cosmetic medium, at least one disulfide or thiol, indole derived sytryl fluorescent dye, chosen from the dyes of formulae (I) and (II) below:
  • n 1 or 2 ;
  • > p represents an integer between 1 and 4 inclusive;
  • ⁇ R 1 and R 3 which may be identical or different, represent a hydrogen atom or an optionally substituted (Ci-C 6 ) alkyl group; in particular, R 1 and R 3 represent a hydrogen atom or a methyl group;
  • R 2 which may be identical or different, represents a hydrogen or halogen atom, a (di) (Ci-C 6 ) (alkyl) amino, cyano, hydroxyl, (poly) halo (Ci-C 6 ) alkyl such as trifluoromethyl, acyl (Ci-C 4 ) (alkyl) amino, (Ci-C 6 ) alkoxy, (Ci-C 6 )- alkylthio, (poly) hydroxy (C 2 -C 6 ) alkoxy, (Ci-C 6 )- alkylcarbonyloxy, (Ci-C 6 ) alkoxycarbonyl, (Ci-C 6 )- alkylcarbonylamino, carbamoyl, (Ci-C 6 ) alkyl- sulfonyl (Ci-C 4 ) (alkyl) amino, (Ci-C 4 ) (di) (alkyl) - aminosulf
  • Het + represents a cationic heteroaryl radical chosen from those of formulae (A) , (B) , (C) and (D) below:
  • - Zi represents an oxygen, sulfur or selenium atom or a radical NR 7 ;
  • - Z 2 represents a nitrogen atom or a radical CR 8 ;
  • - Z 3 represents a nitrogen atom or a radical CR 9 ;
  • Z 4 represents a nitrogen atom or a radical CR 10 ; - it being understood that the two radicals Z 3 and Z 4 cannot simultaneously represent a nitrogen atom; and when Z 1 represents an oxygen, sulfur or selenium atom, then Z 2 represents a radical CR 8 ;
  • R 5 , R 6 , R 8 , R 9 and R 10 which may be identical or different, represent a hydrogen atom or a group chosen from: (Ci-C ⁇ ) alkyl, (Ci-C ⁇ ) alkoxy,
  • L represents an optionally substituted Ci-C 2 O divalent hydrocarbon-based chain, optionally interrupted i) with one or more divalent groups or combinations thereof chosen from: -NR-; -N + RR 0 -, An " ; -O-, -S-, -C(O)- and -S(O) 2 - with R, R 0 , which may be identical or different, chosen from a hydrogen, and a C 1 -C 4 alkyl, hydroxyalkyl or aminoalkyl radical, and An " representing an anionic counterion, or ii) with a cationic heterocycle or cationic heteroaryl Heti + , An " , with An " being an anionic counterion and Heti + representing a saturated or unsaturated heterocycle comprising from 5 to 10 members, or a heteroaryl comprising from 5 to 10 members, such as imidazolium, piperazinium, piperidinium, pyrrolidinium or benzoimidazolium; in
  • ⁇ Y represents: i) a hydrogen atom, ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + R ⁇ R R ⁇ R , An'' " or a phosphonium group: P + R ⁇ R ⁇ R ⁇ R ⁇ , An'' " with R ⁇ , R ⁇ , R ⁇ and R ⁇ , which may be identical or different, representing a hydrogen atom or a (Ci-C 4 ) alkyl group and An'' " an anionic counterion; or v) a thiol-function- protecting group; it being understood that, when n is 2, then m is zero, and when n is 1, then m is 1.
  • Another subject of the invention is a dye composition for dyeing keratin materials such as dark hair, comprising, in a suitable cosmetic medium, at least one disulfide or thiol, indole-derived, styryl fluorescent dye (I) or (II) as defined above, and optionally a reducing agent.
  • a subject of the invention is also novel disulfide or thiol, indole-derived, styryl fluorescent dyes of formula (I) or (II) as defined above.
  • the dyeing process according to the invention makes it possible to visibly color dark keratin materials, in particular dark human keratin fibers, especially dark hair. Furthermore, the process of the invention makes it possible to obtain a coloring of the hair, without damaging it, which is persistent with respect to shampooing operations, common attacks (sunlight, perspiration) and other hair treatments. The process of the invention also makes it possible to obtain lightening of keratin materials such as keratin fibers, in particular dark keratin fibers, and more particularly dark hair.
  • the new dyes according to the invention are particularly photostable. This process also makes it possible to dye bleached keratin fibers in a powerful, relatively nonselective, homogenous and chromatic manner .
  • the lightening of the hair is evaluated by the variation in "tone height” before and after application of the compound of formula (I) or (II) .
  • tone is based on the classification of the natural shades, one tone separating each shade from the shade immediately following or preceding it. This definition and the classification of the natural shades are well known to hair styling professionals and are published in the book “Science des.s capillaires” [Hair Treatment Sciences], by Charles Zviak 1988, published by Masson, pp. 215 and 278.
  • the tone heights range from 1 (black) to 10 (very light blond), one unit corresponding to one tone; the higher the figure, the lighter the shade.
  • An artificially colored hair is a hair whose color has been modified by a dyeing treatment, for example dyeing with direct dyes or oxidation dyes.
  • the term "bleached hair” is intended to mean hair whose tone height is greater than 6 and preferably greater than 8.
  • 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 hair reflectance .
  • the composition should, after application to dark hair, lead to the results below.
  • Interest is focused on the hair reflectance performance levels when said hair is irradiated with visible light in the wavelength range from 400 to 700 nanometers.
  • the curve corresponding to the treated hair should show a reflectance in the wavelength range of from 500 to 700 nanometers which is higher than the curve corresponding to the untreated hair.
  • the reflectance curve corresponding to the treated hair is higher than the reflectance curve corresponding to the untreated hair.
  • the term "higher” is intended to mean a difference of at least 0.05% in reflectance, and preferably of at least 0.1%. All the same, there may be, in the wavelength range of from 540 to 700 nanometers, at least one range where the reflectance curve corresponding to the treated hair is superimposable on or lower than the reflectance curve corresponding to the untreated hair.
  • the wavelength where the difference is at a maximum between the reflectance curve of the treated hair and that of the untreated hair is within the wavelength range of from 500 to 650 nanometers, and preferably within the wavelength range of 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 chosen from:
  • Ci-Cs alkyl radical optionally substituted with one or more radicals chosen from the radicals: hydroxyl, C1-C2 alkoxy, C2-C4 (poly) hydroxyalkoxy, acylamino and amino substituted with two Ci-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 heterocycle comprising from 5 to 7 members, preferably 5 or 6 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises another heteroatom which may be identical or different from the nitrogen;
  • halogen atom such as chlorine, fluorine or bromine
  • hydroxyl group • a halogen atom such as chlorine, fluorine or bromine
  • an optionally cationic 5- or 6-membered heteroaryl radical preferably imidazolium, optionally substituted with a Ci-C 4 alkyl radical, preferably methyl
  • an amino radical substituted with one or two Ci-C ⁇ alkyl radicals which may be identical or different, optionally bearing at least: i) one hydroxyl group, ii) one amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen, • -NR-C(O)R' in which the R radical is a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical is a C1-C2 alkyl radical;
  • R' S (0) 2-NR- in which the R radical represents a hydrogen atom or a C1-C4 alkyl radical optionally bearing at least one hydroxyl group, and the R' radical represents a Ci-C 4 alkyl radical or a phenyl radical;
  • R 2 N-S(O) 2 - in which the R radicals, which may or may not be identical, represent a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group,
  • Ci-C 4 alkoxy • C 2 -C 4 (poly) hydroxyalkoxy;
  • R' radical is a hydrogen atom or a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group
  • R radical is a C1-C2 alkyl radical or an amino radical substituted with two Ci-C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group
  • .RC(O)-O- in which the R radical is a Ci-C 4 alkyl radical or an amino radical substituted with one or two Ci-C 4 alkyl groups, which may be identical or different, optionally bearing at least one hydroxyl group, said alkyl radicals possibly forming, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, which is saturated or unsaturated, which is optionally substituted, and which optionally comprises at least one other heteroatom which may or may not be different from nitrogen;
  • R radical is a Ci-C 4 alkyl radical optionally bearing at least one hydroxyl group; a cyclic or heterocyclic radical or a nonaromatic part of an aryl or heteroaryl radical may also be substituted with one or more oxo or thioxo groups;
  • an "aryl" radical represents a condensed or noncondensed, monocyclic or polycyclic group containing from 6 to 22 carbon atoms, and at least one ring of which is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl; a "diarylalkyl” radical represents a group comprising, on the same carbon atom of an alkyl group, two aryl groups, which may be identical or different, such as diphenylmethyl or 1,1- diphenylethyl ; a "heter
  • the disulfide or thiol, indole-derived, styryl fluorescent dyes of formula (I) or (II) as defined above are fluoresent dyes, i.e. capable of absorbing in the UV radiation or visible range at a wavelength ⁇ abs of between 250 and 800 nm and capable of re-emitting in the visible range at an emission wavelength ⁇ em of between 400 and 800 nm.
  • the fluorescent compounds of formula (I) or (II) of the invention are dyes capable of absorbing in the visible range ⁇ abs of between 400 and 800 nm and of re-emitting in the visible range ⁇ em of between 400 and 800 nm. More preferably, the dyes of formula (I) or (II) are dyes capable of absorbing at a ⁇ abs of between 420 and 550 nm and of re-emitting in the visible range at a ⁇ em of between 470 and 600 nm.
  • the compounds of the invention of formula (I) or (II) where n and m are 1 contain an SY function which may be in the covalent form -S-Y or ionic form -S ⁇ Y + depending on the nature of Y and on the pH of the medium.
  • a specific embodiment relates to the disulfide or thiol, indole-derived, styryl fluorescent dyes of formula (I) or (II) with n and m equal to 1 and where Y represents a hydrogen atom or an alkali metal.
  • Y represents a hydrogen atom.
  • Y as protective group cannot represent a group directly linked to the sulphur atom of formula (I) and (II) via another non oxidized sulphur atom.
  • Y represents a thiol-function- protecting group
  • Y is chosen from the following radicals :
  • arylcarbonyl such as phenylcarbonyl
  • aryl (Ci-C 4 ) alkoxycarbonyl ⁇ (di) (Ci-C 4 ) (alkyl) aminocarbonyl such as dimethylaminocarbonyl ;
  • aryl such as phenyl, dibenzosuberyl or 1, 3, 5-cycloheptatrienyl
  • heteroaryl including in particular the cationic or noncationic heteroaryl comprising from 1 to 4 heteroatoms below: i) monocyclic comprising 5, 6 or 7 members, such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium, thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1, 2, 4-triazolyl, 1,2,4- triazolium, 1, 2, 3-triazolyl, 1,2,3- triazolium, 1, 2, 4-oxazolyl, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolyl, 1, 2, 4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl, pyrazin
  • heterocycloalkyl group represents in particular a saturated or partially saturated, 5-, 6- or 7-membered monocyclic group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as di/tetrahydrofuranyl, di/tetrahydrothiophenyl, di/tetrahydropyrrolyl, di/tetrahydropyranyl, di/tetra/hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di/tetra/hexahydroazepinyl or di/tetrahydropyrimidinyl, these groups being optionally substituted with one or more groups such as (Ci-C
  • R' c , R' d , R' e , R' f , R' g and R' h which may be identical or different, represent a hydrogen atom or a (Ci-C 4 ) alkyl group, or else two groups R' g with R' h , and/or R' e with R' f , form an oxo or thioxo group, or else R' g with R' e together form a cycloalkyl; and v represents an integer between 1 and 3 inclusive; preferably, R' c to R' h represent a hydrogen atom; and An' ' ' represents a counterion;
  • R' c R' d N + R' e R' f ;
  • R' c , R' d , R' e and R' f which may be identical or different, represent a hydrogen atom or a (Ci-C 4 ) alkyl group; preferably, R' c to R' f represent a hydrogen atom; and
  • An''' " represents a counterion;
  • aryl (Ci-C 4 ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted with one or more groups in particular chosen from (Ci-C 4 ) alkyl, (Ci-C 4 ) alkoxy such as methoxy, hydroxyl, alkylcarbonyl and (di) (Ci-C 4 ) (alkyl) amino such as dimethylamino;
  • heteroaryl (Ci-C 4 ) alkyl optionally substituted (di) heteroaryl (Ci-C 4 ) alkyl
  • the heteroaryl group is in particular cationic or noncationic, and monocyclic, comprising 5 or 6 members and from 1 to 4 heteroatoms chosen from nitrogen, oxygen and sulfur, such as the groups pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl N-oxide, pyrylium, pyridinium or triazinyl, optionally substituted with one or more groups such as alkyl, particularly methyl, advantageously the
  • heteroaryl (Ci-C 4 ) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl;
  • R 1 , R 2 and R 3 which may be identical or different, representing a halogen atom or a group chosen from:
  • alkoxyalkyl such as methoxymethyl (MOM) , ethoxyethyl (EOM) or isobutoxymethyl .
  • the protected thiol dyes of formula (I) or (II) for which m and n are 1, comprising a group Y i) which is a cationic, aromatic 5- or 6-membered monocyclic heteroaryl group comprising from 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1, 2, 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1, 2, 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium or imidazolium; ii) cationic 8- to 11-membered bicyclic heteroaryl group, such as indolinium, benzo
  • R' c and R' d which may be identical or different, represent a hydrogen atom or a (Ci-C 4 ) alkyl group; preferably, R' c to R' d represent a (Ci-C 4 ) alkyl group such as methyl; and An''' represents an anionic counterion .
  • Y represents a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1, 2, 4-triazolium, 1, 2, 3-triazolium, 1, 2, 4-oxazolium, 1 , 2 , 4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted with one or more (Ci-C 4 ) alkyl groups, in particular methyl.
  • Y represents an alkali metal or a protecting group such as: > (Ci-C 4 ) alkylcarbonyl, such as methylcarbonyl or ethylcarbonyl ;
  • arylcarbonyl such as phenylcarbonyl
  • aryl such as phenyl
  • 5- or 6-membered monocyclic heteroaryl such as imidazolyl or pyridyl
  • cationic monocyclic heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium or imidazolium; these groups being optionally substituted with one or more identical or different (Ci-C 4 ) alkyl groups, such as methyl;
  • M + with M + representing an alkali metal such as sodium or potassium, or else Q ⁇ or An' ⁇ of formula (I) or (II) and M + are absent.
  • An which may be identical or different, representing an anionic counterion.
  • the protected thiol dyes of formula (I—Y) or (II—Y) for which m and n are 1 can be synthesized in two stages.
  • the first stage consists in preparing the nonprotected thiol dye (I-H) or (II-H) according to the methods known to those skilled in the art, for instance "Thiols and organic sulfides", “Thiocyanates and isothiocyanates, organic", Ullmann' s Encyclopedia, Wiley-VCH, Weinheim, 2005.
  • the second step consists in protecting the thiol function according to the conventional methods known to those skilled in the art in order to produce the protected thiol dyes of formula (I-Y) or (II-Y) .
  • This method can be illustrated by means of the method consisting i) in generating thiol, indole-derived, styryl fluorescent dyes of formula (I-H) or (II-H) by reduction of an indole-derived, styryl, two-chromophore fluorescent dye bearing a disulfide function -S-S- such as (I-S) or (II-S) and ii) in protecting said thiol function of (I-H) or (II-Y) , according to the conventional methods, with the reactant 7 Y' R in order to obtain the protected thiol, indole-derived, styryl fluorescent dyes of formula (I—Y) or (II—Y) .
  • the thiol compound (I-H) or (II-H) may also be metallated with an alkali metal or alkaline earth metal Met* so as to produce the thiolate dye of formula (I-Met) or (II- Met) .
  • Y' representing a thiol-function-protecting group
  • Met* representing an alkali metal or an alkaline earth metal, particularly sodium or potassium, it being understood that, when the metal is an alkaline earth metal, 2 chromophores comprising a thiolate -S ⁇ function can be associated with 1 Metal 2+ ; and with R 1 to R 3 , Het + , L and Q ⁇ being as defined above; Y' represents a thiol-function-protecting group; and R represents a nucelofuge leaving group, for instance mesylate, tosylate, triflate or halide.
  • a protected thiol compound (b) protected with a protecting group Y' as defined above, prepared according to one of the procedures described in the books described above, said protected thiol compound comprising at least one nucleophilic function, can be reacted with a sufficient, preferably equimolar, amount of an indole- derived, styryl fluorescent chromophore (a) or (ai) , and which comprises an electrophilic function, so as to form a ⁇ covalent bond; see below, the preparation of dyes of formula (l ' -Y) and (Il ' -Y) :
  • R 1 to R 3 Het + and Q as defined above; m' and n' being integers between 1 and 6 inclusive, with the sum m' + n' being an integer between 2 and 6; Nu representing a nucleophilic group; E representing an electrophilic group; and ⁇ representing the link generated after attack by the nucleophile on the electrophile .
  • ⁇ covalent bonds that can be generated are listed in the table below based on condensation of electrophiles with nucleophiles :
  • **the acyl nitrides may rearrange to give isocyanates .
  • a thiol reactant ( ⁇ ) Y' -SH comprising a Y' group as defined above, the nucleophilic SH function of which can react with the carbon atom of the radical L in the ⁇ -position with respect to the halogen atom borne by an indole-derived, styryl fluorescent chromophore (a' ) or (a' i) , so as to give the protected thiol dye of formula (I-Y) or (II-Y) as defined above:
  • R 1 to R 3 Het ⁇ L, p and Q " (I-Y) and (H-Y) as defined above, and Hal representing a nucleofuge halogen atom such as bromine, iodine or chlorine.
  • Another variant may make it possible to obtain the compound (I''—Y) or (II''—Y) from the cyclic thiourea derivative of imidazoline type (b ⁇ _) , followed by alkylation of said imidazoline using R' d -Lg, with Lg being a leaving group such as chloride, bromide, tosylate or mesylate:
  • a variant is to use, in place of the halide comprising the indole-derived, styryl fluorescent chromophore (a' ) or (a' 1) , a chromophore comprising another type of nucleofuge such as tosylate or mesylate.
  • certain protected thiol dyes (I' -Y) or (II' -Y) can be obtained by reacting a protected thiol compound with a compound bearing two carboxylic acid functions that are activated, according to the conventional methods (for example, reaction with a carbodiimide or with thionyl chloride) .
  • the resulting product (d) or (dl) is subsequently reacted with an indole-derived, styryl fluorescent chromophore (c) or (cl) , bearing a nucleophilic function (c) , for example of primary or secondary amine type, or of aliphatic alcohol type.
  • Another variant is to use a thiolactone derivative based on specific nucleophilic chromophores (c' ) and (c' i) so as to give the derivatives (I' -H) or (II' -H) comprising a linker L interrupted with an amide function as represented by the scheme below:
  • G' representing an oxygen or sulfur atom or an NR' group with R' representing a hydrogen atom or a alkyl radical, and R representing a hydrogen atom, a Ci-C 4 alkyl radical, a C1-C4 hydroxyalkyl radical or an aryl (Ci-C 4 ) alkyl .
  • the protected thiol dyes of formula (1'''-Y) and (11'''-Y) can be obtained by reaction of a compound (d' ) comprising a thiol group protected with a Y' group, and a nucleofuge leaving group Lg, for instance mesylate, tosylate, triflate or halide, with an indole-derived, styryl fluorescent chromophore (c' ) or (c' ' '
  • the activating group Z' is conventionally used by those skilled in the art to activate a nitrogen atom contained in a heteroaryl such as indole.
  • Z' representing an alkali metal such as sodium, lithium or potassium, or a magnesium compound MgX, with X representing a halogen atom such as bromine; it being understood that the use of reactants comprising Li, K, Na or MgX is carried out once the other functions capable of reacting with these same reactants have been pre-protected according to the methods as described in "Protective Groups in Organic Synthesis", T. W. Greene, John Willey & Sons ed., NY, 1981, or "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.
  • compounds containing a protected thiol group (1'''-Y) or (11'''-Y) contain a nucleofuge leaving group R, for instance mesylate, tosylate or triflate, which can undergo nucleophilic attack from the amine of the indole-derived styryl fluorescent chromophore (c' ) or (c' ' ) as follows:
  • the indole- derived, styryl thiol dyes of formula (I) or (II) according to the invention can be obtained by reaction of a compound comprising a thiol group possibly protected with Y' as defined above and an electophilic group (f) or (f' ) , with an indole-derived compound comprising a nucleophilic group.
  • the starting reactants are commercially available or accessible by the conventional methods known to those skilled in the art.
  • the reactant (II—S) using 2 equivalents of indole derivative 1. optionally activated on the nitrogen atom of the indole Z', and one equivalent of disulfide reactant comprising two leaving groups Lg, so as to give the derivative bearing two -C(G')- disulfide functions 3_ j _ which can in turn be condensed with two equivalents of cationic heteroaryl compound Het + comprising an activated methyl group 4_, so as to give (H-S) .
  • R 1 , R 2 , R 3 , p, L, Het + and Q as defined above
  • Z' representing a hydrogen atom or a group which activates the nucleophilicity of the nitrogen atom of the indole
  • Lg representing a nucleofuge leaving group, for instance mesylate, tosylate, triflate, alkoxy or halide .
  • Het representing a group chosen from (A' ) , (B' ) , (C ) and (D ' ) : where Z 1 , Z 2 , Z 3 and Z 4 are as defined above, a or b represents the bond which links the groups (A' ) to (D' ) to the methyl group of the reactant Het-CH 3 ; R 1 , R 2 , R 3 , p, L and Het + are as defined above; and Lg " represents the counterion subsequent to the departure of Lg such as mesylate, tosylate, triflate alk-O ⁇ , or halide.
  • the counterions Lg " of the compounds of the invention, above, can be replaced with counterions Q ⁇ of other types, using methods known to those skilled in the art, in particular by ion-exchange resin.
  • the thiol, indole-derived, styryl fluorescent dyes formed can be converted to -S Y' protected thiol fluorescent dyes by protection of the -SH thiol using the conventional protecting groups.
  • the thiol, indole- derived, styryl dyes are metallated by also using the conventional methods known to those skilled in the art, such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4th Ed., John Willey & Sons, NY, 1992.
  • the protected thiol, indole-derived, styryl fluorescent dyes can be deprotected by conventional pathways such as those described in the books "Protective Groups in
  • composition of the invention contains at least one disulfide, thiol or protected thiol, indole-derived styryl fluorescent dye of formula (I) or (II) .
  • composition of the invention may also contain at least one reducing agent.
  • This reducing agent may be chosen from thiols, for example cysteine, homocysteine or thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulfites, thioglycolic acid, and also its esters, in particular glyceryl monothioglycolate, and thioglycerol .
  • This reducing agent may also be chosen from borohydrides and derivatives thereof, for instance the salts of borohydride, of cyanoborohydride, of triacetoxyborohydride or of trimethoxyborohydride : sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammonium) salts; and catechol borane.
  • borohydrides and derivatives thereof for instance the salts of borohydride, of cyanoborohydride, of triacetoxyborohydride or of trimethoxyborohydride : sodium salts, lithium salts, potassium salts, calcium salts, quaternary ammonium (tetramethylammonium, tetraethylammonium, tetra-n-butylammonium or benzyltriethylammoni
  • the dye composition that can be used in the invention generally contains an amount of fluorescent dye of formula (I) or (II) of between 0.001% and 50% relative to the total weight of the composition. Preferably, this amount is between 0.005% and 20% by weight, and even more preferably between 0.01% and 5% by weight, relative to the total weight of the composition.
  • the dye composition may also contain additional direct dyes.
  • These direct dyes are, for example, chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone, in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
  • Extracts or decoctions containing these natural dyes, and in particular poultices or henna-based extracts, may also be used.
  • the dye composition may contain one or more oxidation bases and/or one or more couplers conventionally used for dyeing keratin fibers.
  • oxidation bases mention may be made of para- phenylenediamines, bisphenylalkylenediamines, para- aminophenols, bis-para-aminophenols, ortho- aminophenols, heterocyclic bases, and addition salts thereof.
  • couplers mention may in particular be made of meta-phenylenediamines, meta-aminophenols, meta- diphenols, naphthalene couplers, heterocyclic couplers, and addition salts thereof.
  • the coupler (s) is (are) each generally present in an amount of between 0.001% and 10% by weight of the total weight of the dye composition, preferably between 0.005% and 6%.
  • the oxidation base(s) present in the dye composition is
  • addition salts of the oxidation bases and of the couplers that can be used in the context of - A A - the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates, and addition salts with a base, such as hydroxides of an alkali metal such as sodium or potassium, aqueous ammonia, amines or alkanolamines .
  • an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates
  • a base such as hydroxides of an alkali metal such as sodium or potassium, aqueous ammonia, amines or alkanolamines .
  • the medium suitable for dyeing is a cosmetic medium generally constituted of water or of a mixture of water and at least one organic solvent.
  • organic solvent mention may, for example, be made of Ci-C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
  • the solvents when they are present, are preferably present in proportions of preferably between 1% and 40% by weight approximately, relative to the total weight of the dye composition, and even more preferably between 5% and 30% by weight approximately.
  • the dye composition may also contain various adjuvants conventionally used in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or blends thereof, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric associative polymer thickeners, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents such as, for example, modified or unmodified, volatile or nonvolatile silicones, such as amino silicones, film-forming agents, ceramides, preservatives, opacifiers or conductive polymers.
  • adjuvants conventionally used in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cati
  • the above adjuvants are in general present in an amount, for each of them, of between 0.01% and 20% by weight relative to the weight of the composition.
  • the pH of the dye composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It may be adjusted to the desired value by means of acidifying or basifying agents normally used in the dyeing of keratin fibers or else by means of conventional buffer systems.
  • acidifying agents mention may, by way of example, be made of mineral or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.
  • basifying agents mention may, by way of example, be made of aqueous ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, and also derivatives thereof, sodium hydroxide or potassium hydroxide and the compounds of formula ( ⁇ ) below:
  • W a is a propylene residue optionally substituted with a hydroxyl group or a Ci-C 4 alkyl radical
  • R a i, R a 2, Ra3 and R a4 which may be identical or different, represent a hydrogen atom, a Ci-C 4 alkyl radical or a Ci-C 4 hydroxyalkyl radical.
  • the dye composition may be in various forms, such as in the form of a liquid, a cream or a gel, or in any other form suitable for dyeing keratin fibers, and in particular the hair.
  • a subject of the invention is also a process for dyeing keratin materials, in particular keratin fibers, more particularly dark hair, consisting in applying thereto a dye composition comprising, in a cosmetic medium, at least one indole-derived, disulfide or thiol styryl fluorescent dye chosen from the fluorescent dyes of formulae (I) and (II) as defined above.
  • a reducing agent may also be applied as a pretreatment before the application of the composition containing at least one indole-derived, styryl fluorescent dye of formula (I) or (II) .
  • This pretreatment may be of short duration, in particular from 1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as mentioned above.
  • the composition comprising at least one indole-derived, styryl fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
  • the process of the invention may be preceded by a deprotection step aimed at restoring the SH function in situ.
  • the deprotection step can also be carried out during a hair pretreatment step, for instance reducing pretreatment of the hair.
  • the reducing agent is added to the dye composition containing at least one indole- derived, styryl fluorescent dye of formula (I) or (II) at the time of use.
  • the composition comprising at least one indole-derived, styryl fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
  • the reducing agent is applied as a post-treatment, after the application of the composition containing at least one indole-derived, styryl fluorescent dye of formula (I) or (II) .
  • the duration of the post-treatment with the reducing agent may be short, for example from 1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above.
  • the reducing agent is an agent of thiol or borohydride type as described above.
  • a specific embodiment of the invention relates to a process in which the indole-derived, styryl fluorescent dye of formula (I) or (II) can be applied directly to the hair without reducing agents, free of reducing pretreatment or reducing post-treatment.
  • a treatment with an oxidizing agent may optionally be combined.
  • the process of the invention comprises an additional step consisting in applying an oxidizing agent to the keratin fibers.
  • oxidizing agent conventional 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.
  • peroxidases 2-electron oxidoreductases
  • 4-electron oxygenases such as laccases.
  • the use of hydrogen peroxide is particularly preferred.
  • the duration of the possible post-treatment with an oxidizing agent is between 1 second and 10 minutes.
  • the application of the dye composition according to the invention is generally carried out at ambient temperature. It may, however, be carried out at temperatures ranging from 20 to 180 0 C.
  • a subject of the invention is also a multicompartment dyeing device or dyeing "kit” in which a first compartment contains a dye composition comprising at least one indole-derived, styryl fluorescent dye of formula (I) or (II) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin materials and/or of the indole- derived, styryl disulfide fluorescent dye of formula (I) or (II) .
  • One of these compartments may also contain one or more other dyes of direct dye or oxidation dye type.
  • the invention also relates to a multicompartment device in which a first compartment contains a dye composition comprising at least one indole-derived, styryl fluorescent dye of formula (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of keratin materials and/or of the indole-derived, styryl disulfide fluorescent dye of formula (I) or (II) ; and a third compartment contains an oxidizing agent.
  • the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol, indole-derived, styryl fluorescent dye of formula (I) or (II) where m and n are 1 and a second compartment containing an agent capable of deprotecting the protected thiol so as to free the thiol, and optionally a third compartment comprising an oxidizing agent.
  • Each of the devices mentioned above may be equipped with a means for delivering the desired mixture to the hair, for example such as the devices described in patent FR 2 586 913.
  • Example 1 Synthesis of 1, 1 ' - (disulfanediyldiethane- 2,l-diyl)bis ⁇ 4-[2-(l-methyl-lH-indol-3-yl)vinyl]- pyridinium ⁇ dimethane sulfonate [1]
  • the precipitate is filtered off and washed with 3 times 50 ml of ethyl acetate.
  • the organic phases are extracted with 100 ml of ice-cold water, 100 ml of water, 3 times 50 ml of a saturated solution of sodium hydrogen carbonate (NaHCOs) and with 2 times 20 ml of a saturated solution of sodium chloride (NaCl), and are then dried over anhydrous sodium sulfate (Na2SO 4 ) .
  • the reaction mixture is poured into 55 ml of ethyl acetate, it is filtered and washed with 50 ml of ethyl acetate and then dried. 2.4 g of dark green powder are recovered. The analyses indicate that the product is in conformity and pure.
  • Stage 2 Synthesis of 4, 4 ' - ⁇ disulfanediylbis [ethane- 2, 1-diylimino (2-oxoethane-2, 1-diyl) (2-methyl-lH-indole- 1, 3-diyl)ethene-2, 1-diyl] ⁇ bis (1-methylpyridinium) bis tosylate
  • compositions A (9 ml) and B (1 ml) are mixed, then the formulations are applied to locks of natural white hair containing 90% white hairs (NW) , permanent-waved white hair (PW) or chestnut-brown hair having a tone height of 4 (TH4) .
  • the leave-in time is 20 minutes at ambient temperature (AT) .
  • a fixer (Dulcia Vital II®) diluted 10-fold with water is applied for 5 minutes at AT. After rinsing with running water and shampooing, the locks are air-dried. During the shampooing operations, there is no visible bleeding of the color; the shampoo foam and the rinsing water are uncolored.
  • compositions in accordance with the invention were also expressed as a function of the reflectance of the hair. These reflectances are compared with the reflectance of a lock of untreated hair of tone height TH4.
  • the reflectance is measured by means of a KONIKA- MINOLTA ® , CM 360Od spectrophotocolorimeter apparatus and after irradiation of the hair with visible light in the wavelength range of from 400 to 700 nanometers.
  • NW white hair and permanent-waved (PW) white hair are colored bright orange.
  • the locks treated are divided into two, half are subjected to 5 successive shampooing operations according to a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water, followed by drying.

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Abstract

L'invention concerne la coloration de matériaux à base de kératine au moyen de colorants fluorescents styryles dérivés d'indole, thiol et disulfure. L'invention concerne une composition colorante comprenant des colorants fluorescents styryles dérivés d'indole, thiol et disulfure et un procédé de coloration produisant un effet éclaircissant sur des matériaux à base de kératine, en particulier des fibres de kératine, spécifiquement des fibres de kératine humaines, par exemple les cheveux, au moyen de ladite composition. L'invention concerne également des nouveaux colorants fluorescents styryles dérivés d'indole, thiol et disulfure et leurs utilisations dans l'éclaircissement de matériaux à base de kératine. Cette composition permet d'obtenir un effet éclaircissant qui est particulièrement résistant et visible sur des fibres de kératine foncées.
PCT/EP2008/062479 2007-09-21 2008-09-18 Colorant styryle dérivé d'indole thiol/disulfure, composition colorante comprenant ledit colorant, procédé d'éclaircissement de matériaux à base de kératine au moyen de ce colorant Ceased WO2009037325A2 (fr)

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FR0757767 2007-09-21
FR0757767A FR2921379B1 (fr) 2007-09-21 2007-09-21 Colorant derive d'indole styryle thiol/disulfure, composition tinctoriale comprenant ce colorant, procede d'eclaircissement des matieres keratiniques a partir de ce colorant
US96063007P 2007-10-09 2007-10-09
US60/960,630 2007-10-09

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WO2013174871A1 (fr) 2012-05-23 2013-11-28 L'oreal Procédé de teinture de fibres kératiniques comprenant une teinture/un pigment, un composé photoactif et une source lumineuse
CN104840461A (zh) * 2015-04-21 2015-08-19 中国科学院上海药物研究所 一类反式-1-(吲哚-3-基)-2-(喹啉-4-基)-乙烯衍生物的用途及组合物
CN106317018A (zh) * 2016-07-21 2017-01-11 湖南大学 一种肿瘤靶向性亲脂性阳离子‑苯丁酸氮芥化合物及制备方法和在白蛋白纳米药物中的应用
KR20180087412A (ko) * 2015-12-01 2018-08-01 디쉬맨 파마슈티컬스 앤드 케미컬스 리미티드 개선된 인디고 카르민의 제조방법
CN110407731A (zh) * 2019-06-28 2019-11-05 广东药科大学 一种小分子荧光剂及其制备方法
US10494527B2 (en) 2015-03-19 2019-12-03 Basf Se Cationic direct dyes
CN110621293A (zh) * 2017-05-10 2019-12-27 莱雅公司 用于染色角蛋白材料的带有脂族链和二硫化物/硫醇/受保护硫醇官能团的荧光直接染料
WO2020150103A1 (fr) * 2019-01-15 2020-07-23 The Board Of Trustees Of The Leland Stanford Junior University Composés cationiques lipophiles délocalisés et procédés d'utilisation associés
US11096880B2 (en) 2017-06-16 2021-08-24 L'oreal Process for dyeing keratin fibres using at least one direct dye and at least one disulfide, thiol or protected-thiol fluorescent dye
US11278482B2 (en) 2017-06-16 2022-03-22 L'oreal Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye

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GB1155404A (en) * 1966-05-09 1969-06-18 Agfa Gevaert Nv Improved Direct Positive Emulsions
FR1523626A (fr) * 1966-05-09 1968-05-03 Agfa Gevaert Nv éléments photographiques positifs directs
BRPI9806716B1 (pt) * 1997-10-22 2015-08-25 Oreal Composição pronta para o uso, processo de tintura das fibras queratínicas e dispositivo com vários compartimentos
EP1940966B1 (fr) * 2005-10-06 2012-12-05 Basf Se Colorants thiol
FR2921380B1 (fr) * 2007-09-21 2009-12-04 Oreal Colorant derive de pyridocycloalkyle styryle thiol/disulfure, composition tinctoriale comprenant ce colorant, procede d'eclaircissement des matieres keratiniques a partir de ce colorant
FR2921374A1 (fr) * 2007-09-21 2009-03-27 Oreal Colorant derive d'indolinium thiol/disulfure, composition tinctoriale comprenant ce colorant, procede d'eclaircissement des matieres keratiniques a partir de ce colorant

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US9730876B2 (en) 2012-05-23 2017-08-15 L'oreal Process for dyeing keratin fibres comprising a dye-pigment, a photoactive compound and a light source
WO2013174871A1 (fr) 2012-05-23 2013-11-28 L'oreal Procédé de teinture de fibres kératiniques comprenant une teinture/un pigment, un composé photoactif et une source lumineuse
US10494527B2 (en) 2015-03-19 2019-12-03 Basf Se Cationic direct dyes
CN104840461A (zh) * 2015-04-21 2015-08-19 中国科学院上海药物研究所 一类反式-1-(吲哚-3-基)-2-(喹啉-4-基)-乙烯衍生物的用途及组合物
KR20180087412A (ko) * 2015-12-01 2018-08-01 디쉬맨 파마슈티컬스 앤드 케미컬스 리미티드 개선된 인디고 카르민의 제조방법
KR102794967B1 (ko) 2015-12-01 2025-04-10 디쉬맨 카보젠 아믹스 리미티드 개선된 인디고 카르민의 제조방법
CN106317018A (zh) * 2016-07-21 2017-01-11 湖南大学 一种肿瘤靶向性亲脂性阳离子‑苯丁酸氮芥化合物及制备方法和在白蛋白纳米药物中的应用
CN110621293A (zh) * 2017-05-10 2019-12-27 莱雅公司 用于染色角蛋白材料的带有脂族链和二硫化物/硫醇/受保护硫醇官能团的荧光直接染料
US11096880B2 (en) 2017-06-16 2021-08-24 L'oreal Process for dyeing keratin fibres using at least one direct dye and at least one disulfide, thiol or protected-thiol fluorescent dye
US11278482B2 (en) 2017-06-16 2022-03-22 L'oreal Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye
WO2020150103A1 (fr) * 2019-01-15 2020-07-23 The Board Of Trustees Of The Leland Stanford Junior University Composés cationiques lipophiles délocalisés et procédés d'utilisation associés
JP2022522977A (ja) * 2019-01-15 2022-04-21 ザ ボード オブ トラスティーズ オブ ザ リーランド スタンフォード ジュニア ユニバーシティー 非局在化親油性カチオン化合物及びその使用方法
JP7227656B2 (ja) 2019-01-15 2023-02-22 ザ ボード オブ トラスティーズ オブ ザ リーランド スタンフォード ジュニア ユニバーシティー 非局在化親油性カチオン化合物及びその使用方法
US12172976B2 (en) 2019-01-15 2024-12-24 The Board Of Trustees Of The Leland Stanford Junior University Delocalized lipophilic cation compounds and methods of use thereof
WO2020258510A1 (fr) * 2019-06-28 2020-12-30 广东药科大学 Agent fluorescent à petites molécules et son procédé de préparation
CN110407731A (zh) * 2019-06-28 2019-11-05 广东药科大学 一种小分子荧光剂及其制备方法

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