FR3050379A1 - USE OF O-GLYCOSYL INDOLE OR INDOLINE DERIVATIVES IN THE PRESENCE OF GLYCOSIDASE FOR THE COLORING OF KERATIN FIBERS - Google Patents

Abstract

The invention relates to the use of i) hydroxyindol derivative (s) (s) glycosylated on at least one hydroxy group, in the presence of at least one (ii) an activity-active enzyme. glycosidase, in particular beta-glycosidase, more particularly glucosidase and even more particularly beta-glucosidase, for the treatment of keratinous fibers, in particular the coloration of human keratinous fibers such as the hair, preferably the coloration of said fibers. The subject of the invention is also a method for treating keratin fibers using i), ii) and a kit comprising ingredients i) and ii). The method according to the invention has the advantage of coloring human keratin fibers, with powerful or chromatic coloring results, resistant to washes, perspiration, sebum and light and more durable without alteration of said fibers. In addition, the colorations obtained from the process give homogeneous colors from the root to the tip of a fiber (low color selectivity). In addition, the compositions comprising the at least one hydroxyindol derivative (s) glycosylated on at least one of the hydroxy groups degrade very little in the air and remain stable on storage.

Description

The subject of the invention is the use of (i) hydroxyindol derivative (s) which are glycosylated (s) and are preferably used in the presence of glycosylated (Glycinate) ) on at least one hydroxyl group, in the presence of at least ii) an enzyme with glycosidase activity, in particular beta-glycosidase more particularly glucosidase and even more particularly beta-glucosidase, for the treatment of keratinous fibers, in particular the coloration of keratin fibers such as the hair, preferably the coloring of said fibers. The subject of the invention is also a method for treating keratin fibers using i), ii) and a kit comprising ingredients i) and ii).

It is known to obtain so-called "permanent" stains with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and compounds. heterocyclic. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. This oxidation dyeing process consists in applying to the keratinous fibers, bases or a mixture of bases and couplers with hydrogen peroxide (H 2 O 2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse, then to rinse the fibers. The resulting dyes are permanent, powerful, and resistant to external agents, including light, weather, washing, perspiration and friction,

However, commercial hair dyes that contain them may have disadvantages such as staining, odor problems, comfort and degradation of keratin fibers. This is particularly the case with oxidation stains.

It is also known to dye keratinous fibers with so-called autooxydisable dyes such as 5,6-dihydroxyindoles or 5,6-dihydroxyindolines i.e. which oxidize with oxygen in the air progressively, especially in a basic medium. However, the results obtained with this method are not always satisfactory, particularly in terms of color intensity and the risks of color homogeneity of the keratinous fibers are not negligible. In addition, these dyes being able to oxidize in the presence of oxygen in the air this reactivity represents a risk of degradation during storage and attenuates their colonel performance on keratin fibers. It should also be noted that auto-oxidizable dyes can stain clothing fabrics which can be problematic when we want to achieve the so-called "clean" coloring.

There is therefore a real need to develop coloring processes, and hair compositions which make it possible to obtain strong colorations from indole derivatives or indolines which are storage stable, especially in basic medium, easy to formulate and whose quantity can be optimized according to the target dye level, while limiting the discoloration of keratin fibers. In particular, there is a need to obtain colorings that are less aggressive for the hair and at the same time that resist external agents (light, bad weather, shampoo), which are stubborn and homogeneous while remaining powerful and / or chromatic.

This goal (s) is (are) achieved by the present invention whose first object is the use of (i) hydroxyindol derivative (s) on glycosylated (s) on at least one of the hydroxy groups, in the presence of at least ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase, more particularly glucosidase and preferably beta-glucosidase iii) preferably at a pH inclusive between 3 and 8 for the treatment of keratinous fibers, in particular the coloration of keratinous fibers, preferably human keratinous fibers such as the hair.

Another subject of the invention is a process for treating keratinous fibers, in particular a process for staining human keratin fibers such as the hair using i) one or more derivatives of hydroxyindol (in) e ( s) glycosylated on at least one of the hydroxy groups, ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase particularly glucosidase and even more particularly beta-glucosidase, at a pH iii) inclusive between 3 and 8.

Another object of the invention is a multi-compartment device comprising ingredients i) to iii) as defined above, it being understood that ingredients i) and ii) or ii) and iii) are in separate compartments.

The process according to the invention has the advantage of coloring keratinous fibers, in particular human keratinous fibers, with results of powerful and / or chromatic colorings, resistant to washes, perspiration, sebum and light and moreover durable without altering said fibers. In addition, the colorations obtained from the process give homogeneous colors from the root to the tip of a fiber (low color selectivity). In addition, the compositions comprising the at least one hydroxyindol derivative (s) glycosylated on at least one of the hydroxy groups degrade very little in the air and remain stable on storage. They are easier to formulate and we can optimize the quantity according to the target dyer level. (1) Hydrovin (I) derivatives derived from at least one hydroxyl group

According to a particular embodiment of the invention, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxyl group of the invention is (are) chosen (s). ) among the derivative (s) of hydroxyindole (s) glycosylated on at least one hydroxyl group, in particular from those of formula (Ia) below:

as well as their enantiomers, diastereoisomers, tautomers and their organic or inorganic acid or base salts, and / or their solvates such as hydrates;

Formula (la) in which: R 1 and R 3, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical; R2 represents a hydrogen atom, a C1-C4 alkyl, -C (O) -OH or -C (O) -OR4 radical with R4 representing a (CrC4) alkyl group; X and Y, which may be identical or different, denote a hydrogen atom, an -OH group or -O-sugar; and - Sugar represents a monosaccharide or polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3, and preferably from 2 saccharide units, it being understood that at least one of the groups X, or Y represents a group -O- Sugar.

For the purposes of the present invention, the term "S *" sugar also means a monosaccharide or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3, and preferably from 2 saccharide units.

According to a preferred embodiment, the sugar is attached to the oxygen atom of -O-Sucre by the carbon atom C 1 of the monosaccharide S *:

Ra representing a hydrogen atom, a (CrC4) alkyl group such as methyl or a (poly) hydroxy (CrC4) alkyl group such as hydroxymethyl or 1,2-dihydroxy-ethyl, the hydroxyl function (s) of the poly (hydroxyl) group; (C1-C4) alkyl being substituted with A as defined hereinafter; it being understood that the radical Ra is in position C5 if the sugar unit is in pyranose form or in C4 if it is in furanose form;

Rb representing a hydrogen atom or a (CrC4) alkyl group preferably hydrogen;

Rc representing a hydrogen atom, (CrC4) alkyl group or Rd-C (X ') -, which are identical in the case of several hydroxyl functions, with X' representing an oxygen or sulfur atom, in particular a hydrogen atom; oxygen and Rd representing a group (Cr C4) alkyl, preferably Rc representing an acetyl group CH3-C (O) -;

Re represents a hydrogen atom or a -CH 2 -O-A group; A representing a hydrogen atom, a (CrC6) alkyl group, or a hydroxy-protecting group such as Rd-C (X ') - as defined above and in particular acetyl CH3-C (O) -, or when n is greater than or equal to 2 and two A-O groups are contiguous, then two A groups may together form a straight or branched chain (Cr C6) alkylene; in particular all the protecting groups of A are identical, preferably A represents a hydrogen atom; n is 1, 2 or 3 and m is 0 or 1.

In particular, "sugar" represents a monosaccharide or polysaccharide, more particularly said sugar is chosen from mono or polysaccharides composed of the following sugars: pentoses (such as ribose, arabinose, xylose, lyxose, ribulose, or xylulose); hexoses (such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, or tagatose), hexosamines (such as glucosamine, galactosamine or mannosamine) and deoxy-hexoses ( such as fucose, or rhamnose). In particular, sugar represents a monosaccharide. Preferably, the monosaccharides may be of configuration D or L, preferably of configuration D.

According to a particular embodiment, said "sugar" represents a monosaccharide chosen from Glucose, Glucosamine, Rhamnose and Xylose, preferentially D-glucose, D-glucosamine, D-rhamnose, D-xylose and more preferably D-Glucose.

Preferably the group -Ο-Sugar or Sugar-O- represents a monosaccharide chosen from Si to S6:

particularly-Ο-Sugar represents Si, S3, S5, S6, more particularly Si: and preferentially -Ο-Sugar represents:

O-glycosylation is carried out by standard methods known to those skilled in the art, e.g. enzymatically or chemically.

According to another embodiment, the sugar radical S * represents a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3, and preferably from 2 saccharide units, linked together via an oxygen atom (oxy ) at 1-4 (C ·) of a saccharide unit C4 of the other saccharide unit) or 1-> 3 (Ci of a saccharide unit C3 of the other saccharide unit) or H 6 (Ci of one saccharide unit C6 of the other saccharide unit), each saccharide unit of which consists of a heterocycle comprising 4 or 5 carbon atoms, of the following formula:

Formula S * "in which p and q, represent integers inclusive between 0 and 4 with p + q inclusive between 1 and 4, particularly between 1 and 2, preferentially p + q = 1; Ra, identical or different, are as defined above for the monosaccharide, Rb, which are identical or different, are as defined previously for the monosaccharide, Rc, which may be identical or different, are as defined previously for the monosaccharide, Re, which may be identical or different. , are as defined above for the monosaccharide, A identical or different, are as defined previously for the monosaccharide, m, identical or different, are as defined previously for the monosaccharide, n, identical or different, are as defined above for the monosaccharide; it being understood that the two sugar units between the brackets q and p can be interchanged i.e. represent the following sequence:

According to this embodiment, the sugar radical S * or S * "represents a disaccharide chosen from: lactose, maltulose, palatinose, lactulose, tonsillosis, turanose, cellobiose, isomaltose, rutinose, maltose and more particularly lactose; said disaccharide radical being connected to the remainder of the molecule by a bond between the C1 carbon atom of the sugar or of one of the sugars and this link which may be anomeric α or β.

According to a particular embodiment of the invention, the compounds of formula (Ia) are such that X is on carbon atom 6 and Y is on carbon atom 5.

According to another embodiment of the invention, the hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group (i) is (are) chosen from those of formula (I '):

as well as their enantiomers, diastereoisomers, tautomers and their salts of organic or inorganic acid or base and / or their solvates such as hydrates; formula (Γ) wherein: • Ri represents a hydrogen atom, or a group selected from (CrC4) alkyl, -C (O) -OH and -C (O) -OR4 'with R4' representing a group (Ci -C4) alkyl such as methyl, or ethyl; particularly, R 1 represents a hydrogen atom, or a group selected from (C 1 -C 4) alkyl and -C (O) -OH, more particularly R 1 represents a hydrogen atom; • Sugar is as defined previously; • p is 1 or 2.; and q is 0 or 1; it being understood that the sum p + q is 2

According to a particular embodiment of the invention p is 1 and q is 1, and Sucre-O-is in position 5.

According to another particular embodiment of the invention p is 1 and q is 1, and Sucre-O- is in position 6.

According to another particular embodiment of the invention p is 2, and Sucre-O- is in position 5 and 6 and q is 0.

According to a preferred embodiment of the invention, the hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group (i) is (are) chosen from those of formula (Ia1), (Ia2) and (Ia3):

as well as their enantiomers, diastereoisomers, tautomers and their salts of organic or inorganic acid or base and / or their solvates such as hydrates;

Formulas (Ia1), (Ia2) and (Ia3) in which R1, R2 and R3 and Sugar are as defined for (la), in particular R2 and R3 represent a hydrogen atom or (C1-C6) alkyl, of preferably hydrogen.

When several sugar-O groups are present in the formulas (Ia), (Ia), (Ia1), (Ia2) and (Ia3) of the invention, then the sugar-O groups are preferably identical.

More particularly, the at least one hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group (i) is (are) chosen from among the hydroxyindole derivative (s). (s) glycosylated (s) on at least one hydroxyl group, in particular those of formula (Ia1) and (Ia2) as defined above.

According to another variant of the invention the derivatives (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one arouDe hvdroxv \) are chosen

In the following conriDosés H) to (15):

and their organic or mineral acid or base salts, and / or their solvates, with S * -O-representing a monosaccharide selected from Si to Se as defined above, and particularly S * -O- represents a chosen monosaccharide among Si, S3, S5, S6, more particularly Si and more preferably:

Preferably, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention are chosen from compounds (1), (2), and 3). According to a first variant, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention are chosen from the hydroxyindole derivatives (1), (2), and preferably (1) their acid or base salts, organic or mineral and / or solvated.

More particularly, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention are chosen from hydroxyindole derivatives (1), (2) , associated with S * -0- which represents Si and in particular

and preferably (1) associated with S * -0- which represents

their acid or base salts, organic or mineral, and / or their solvates.

The two groups S * of the compounds (3), (6), (9), (12) or (15) of the invention are preferably identical to each other.

Process for the preparation of hydroxylindol derivatives (in) glycosylated on at least one hydroxyl group i) in particular those of formula (I '):

The at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention may be prepared chemically or enzymatically.

According to one particular embodiment of the invention, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxyl group of the invention is (are) prepared (s). ) chemically, more particularly according to the following method:

With R 1, R 2, R 3, as defined previously for (la) and (Ib), - representing a single bond or double bond and Y "representing a hydrogen atom or a hydroxyl group, Sucre'-OP * represents a monosaccharide or oligosaccharide sugar, preferably monosaccharide, protected by protecting groups or GP conventionally used to protect the hydroxy and / or amino groups of sugars such as i) (hetero) aryl (Cr C4) alkyl such as benzyl, ii) RC ( Z) - with Z representing an oxygen or sulfur atom, R represents a) a hydrogen atom, b) a (CrC4) alkyl group such as methyl, c) (hetero) aryl such as phenyl, d) ( hetero) aryl (CrC4) alkyl such as benzyl, e) (hetero) cycloalkyl such as cyclohexyl, or iii) RaRbRcSi- with Ra, Rb and Rc, same or different, represent a) a (CrC4) alkyl, b) group ( hetero) aryl such as phenyl, c) (hetero) aryl (Ci-C4) alkyl such as benzyl, and P * represents a protecting group GP of the group hydroxy, preferably carried by the C1 carbon atom carrying the alpha or beta anomer, as defined for i) above; examples of hydroxyl protecting groups that may be mentioned more particularly are the acetyl, TH P, TMS, TBDMS, trityl, tosyl, tert-butyl, MOM, and benzoate groups;

A process which comprises reacting the indol (in) e derivative of formula [1] with one sugar-protected sugar equivalent Sucre'-OP * or 2 equivalents Sucre'-OP * to yield compounds (2) and (31 * the compounds (2) and (3) can then be deprotected by conventional methods to yield the compounds of the invention (12) and (13), with Ο-Sugar being as defined above, preferably sugar represents S * as defined above.

The steps of protecting and deprotecting the hydroxy and / or amino groups of the sugars are known to those skilled in the art. For example, the following scientific articles can be cited: Turkish J. Chem., D.P. Iga et al, 37, 299-307 (2013); Carbohydrate Research, C. Fernandez et al., 327, 353-365 (2000) and "Protective Groups in Organic Synthesis," T.W. Greene, John Willey & Sounds ed., NY, 1981, pp. 193-217; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.

According to another particular embodiment of the invention, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention is (are) prepared ( s) enzymatically, more particularly according to the following process:

Production of 5β-D-glucosylated 5-dihydroxyindole C 5 indole (Compound 1), 5,6-dihydroxyindole β-D-glucosylated C 6 indole (Compound 2), and 5,6-dihydroxyindole di-β-D-glucosyl dihydroxyindole (Compound 3) β-D-glucosylated on the carbon atoms in position 5 and 6 of the indole:

The process for producing 5-hydroxyindole, 6-hydroxyindole and 5,6-dihydroxyindole (or 5,6-DHI) glucosylated by a β-D-glucose is carried out from an in vitro reaction which comprises contacting 5,6-DHI with one or more UGT polypeptides, in the presence of one or more UDP-sugars.

By "UDP-glycosyltransferase", "glycosyltransferase," and "UGT" is meant any enzyme capable of transferring a sugar residue for example galactose, xylose, rhamnose, glucose, arabinose, glucuronic acid, and other amino sugars such as the N-glycosyltransferase. acetyl glucosamine) from MBHB Ref. No .: 15-1854-PRO9 to a recipient molecule. The recipient molecule here being 5,6-DHI.

Evolva has prepared the enzymatic means below to synthesize the mono- and di-glycosylated compounds of the 5,6-dihydroxyindole derivatives.

The compounds 1 to 3 below have been fully characterized by conventional spectrometric and spectroscopic methods:

Scheme 1 below illustrates an expression vector of E. coli used for the expression of UGT genes in vitro. The plasmid was synthesized by GeneArt ™ GeneSynthesis. It carries a T7 promoter and transcription terminator according to the following scheme 1:

Diagram 1

The stable glucosylated melanic precursors can be produced by UGTs isolated in vitro, such as 5,6-DHI glucosylated forms. The glucosylated forms of 5,6-DHI may be glucosylated forms alone, such as Compound 1 or Compound 2. In another embodiment, the glucosylated forms of 5,6-DHI obtained may be in the doubly glycosylated form. ie, the 5- and 6-hydroxyl groups of the indole are glucosylated (Compound 3).

Identification of UGTs capable of 5,6-DHI glycosylation in vitro

UGTs transformed with a melanin production yeast strain can spontaneously slow or stop the polymerization of melanin precursors by the formation of glycosylated Melanin Precursors (GLYMPs). Therefore, in this example, UGTs capable of glucosylating 5,6-DHI melanin precursors to form GLYMPs have been identified by systematic screening or in vitro screening.

The term "precursor of glucosylated melanin" or "glucosylated melanin precursor" or "GLYMP" is understood to mean any form of "melanin precursor" which has been glucosylated. GLYMPs are more specifically 5,6-DHI mono-glucosylated in position 5 ( Compound 1), mono-glucosylated at position 6 (Compound 2), and di-glucosyl at positions 5 and 6 (Compound 3 or "Di-GIc").

The term "melanin precursor" or "melanin precursor" is intended to mean any known molecule involved in the synthesis of melanin (see, for example, "Current Trends in the Chemistry of Permanent Hair Dyeing", Chem Rev., 2011, 111, 2537- 2561) including L-DOPA, DOPAquinone, LeucoDOPAchrome, DOPAchrome, 5,6-DHICA, 5,6-DHI, 5,6-indolequinone-CA, 5,6-indolequinone, and melanochrome.

In vitro collection of purified UGT enzymes from plants was used by high throughput screening (HT) to identify enzymes capable of transferring the sugar (s) to the 5,6-DHI provided from of UDP-glucose acting as a sugar donor. Methods In vitro reaction of glucosylation

A sample lot of 50 μι was prepared by mixing the following components:

Enzymes: The UGT genes were cloned into an appropriate E. coli expression vector (synthesized by GeneArt ™, Gene Synthesis (see Scheme 1 above) and were transformed and expressed in an E. coli system ( 100 μl of cultures), purified by conventional methods, and eluted in 300 μl of elution buffer (via 6XHis-tag purification, see Hochuli et al., "Genetic Approach to Facilitate Purification of Recombinant Proteins with a Novel Metal Chelate Adsorbent" , Nature Biotechnology, 1321-1325, Nov. 1988) A fixed volume of enzyme preparations was added to each reaction (5 μι).

The UDP-sugar donor sugar was added to each reaction to reach a final concentration of 0.6 mM.

Reaction buffer: 100 mM Tris-base, 5.1 mM MgCl 2 of 1 mM KCl, pH 8.0.

The substrate: 5,6-DHI dissolved in DMSO was added to each reaction to reach a final concentration of 0.2 mM (3: 1 sugar donor molar ratio: 5,6-DHI). Reactions were incubated overnight at 30 ° C with gentle shaking and directly injected for LC-MS analysis. GLYMPs analysis: An analytical method for GLYMP analysis was developed on a Waters UPLC (Ultra Performance Liquid Chromatography) system equipped with a Waters 2777 sample manager, and a PDA detector. The system has also been coupled to a Waters® SQD (Single Quadrupole) mass spectrometer.

Column: Acquity BEH C18, 2.1 x 100 mm, 1.7 μηι particle size (part no 186002352). The column was held at 35 ° C for the duration of the analysis.

Mobile phases: A: Demineralised water + 0.1% formic acid; B: Acetonitrile + 0.1% formic acid. Flow rate: 0.4 ml / min. The mobile phase gradient is as follows: time (min.) /% B: 0/1%; 5/50%; 5.5 / 100%; 7/100%; 7.1 / 1% and 10/1%.

In particular, the enzymes are glucosyltransferases chosen from Arabidopsis thaliana: UDP-glucosyl transferase 71C1, Arabidopsis thaliana UDP-glucosyl transferase 71C5, Arabidopsis thaliana UDP-glycosyltransferase 72B1, Arabidopsis thaliana UDPglycosyltransferase 72B2, Arabidopsis thaliana UDP-glycosyltransferase 74F1, Arabidopsis thaliana UDP-glycosyltransferase 75C1 , Arabidopsis thaliana UDP-glucosyl transferase 76D1, Arabidopsis thaliana UDP-glucosyl transferase 76E1, Arabidopsis thaliana UDP-glucosyltransferase 76E11, Arabidopsis thaliana UDP-glucosyl transferase 85A2 and Stevia rebaudiana UDP-glycosyltransferase 71E1.

* available at Life Sciences

Relative Protein Concentration: Calculated as a percentage of 1 μg of standard BSA loaded in SDS gel. BLQ: below the limit of quantitation.

This shows that UGTs can glucosylate especially at 5 and 6 hydroxy groups of 5,6-DHI. As UGTs capable of glycosylating 5,6-DHI, mention may be made of the UGTs 71C125571E1 chosen for the in vitro production of mono- and di-glucosylated 5,6-DHI respectively Compound 1, Compound 2 and Compound 3.

The derivative (s) of hydroxyindol (s) glycosylated on at least one hydroxy group i) of the invention may have a natural occurrence. One can then realize the invention by implementing one or more natural extracts of animal origin, plant such as certain extracts of beet (Beta vulgaris), or of bacterial or fungal origin comprising one or more derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one hydroxyl group i) of the invention, optionally followed by O-glycosylation enzymatically or chemically known to those skilled in the art.

According to the invention, the at least one hydroxyindol derivative (s) glycosylated on at least one hydroxy group i) of the invention as defined above are preferably present in a concentration ranging from from 0.0005 to 10% by weight relative to the total weight of the dye composition containing them. Even more preferentially, this concentration varies from 0.005 to 5% by weight, better still from 0.01 to 4% by weight relative to the total weight of the dyeing composition containing them.

Preferably the concentration i) of hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group of the invention is between 0.1 and 1% by weight of the total weight. of the composition which contains it, such as 0.5%.

For the purposes of the present invention, and unless a different indication is given:

The saturated or unsaturated cycles, optionally condensed, may also be optionally substituted.

Pr "hydroxyindol (in) e (s) glycosylated (s) on at least one hydroxy group" means a compound comprising at least one indole or indoline unit which comprises one or more hydroxyl groups, on the benzo part of the indole or indoline, wherein at least one of the hydroxy groups is O-glycosylated by a sugar group to yield a -O-sugar group.

By "-O-sugar" is meant a hydroxyl group which has been O-glycosylated by a sugar, said sugar being a monosaccharide (ose) or oligosaccharide (2 to 5 saccharide units), in particular a disaccharide (diholoside) which may be found in the form of furanose, pyranose, dextrorotatory (D), levogyre (L), in anomeric form alpha (a), and / or beta (β), said mono or polysaccharide radical being connected to the rest of the molecule by a bond between the an oxygen atom bonded to the carbon atom Ci of one of the sugars of said mono or polysaccharide radical, this bond possibly being anomeric to a or β. Said sugar may have a hydroxy group which has been substituted by a group selected from i) (di) (CrC6) (alkyl) amino, ii) aryl (CrC4) alkylamino such as benzylamino, iii) RC (X) -N (R) with R, R ', identical or different, representing a hydrogen atom or a group (CrC4) alkyl, andX representing an oxygen or sulfur atom, preferably the hydroxyl group of the sugar is substituted by a group amino NH2. Said sugar may have one or more O-protected hydroxyl groups, for example by a Rd-C (X ') - group, which are identical in the case of several protected hydroxyl functions, with X' representing an oxygen or sulfur atom, in particularly an oxygen atom and Rd representing a (CrC4) alkyl group, preferably Rd-C (X ') - represents an acetyl group CH3-C (O) -.

By "protecting group" or "PG" of the "hydroxyl" or "amino" function are meant those known to those skilled in the art, mention may be made of the two books "Protective Groups in Organic Synthesis", TW Greene, John Willey &; Sounds ed., NY, 1981, pp.193-217; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.

In particular, the protective group is chosen from: (C 1 -C 6) alkyl (thio) carbonyl such as formyl, acetyl or t-butylcarbonyl; (di) (tri) halo (C1-C6) alkyl (thio) carbonyl such as trifluoroacethyl (TFA); (C1-C6) alkoxy (thio) carbonyl such as methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, t-butyloxycarbonyl (BOC), vinyloxycarbonyl, allyloxycarbonyl; (diXtrohalogenoCrCo) alkoxyethio-arbonyl such as 2,2,2-trichloroethylcarbonyl (CrC6) alkylthiothiocarbonyl; (di) (tri) halo (C1-C6) alkylthiothiocarbonyl; (di) (C1-C6) (alkyl) aminocarbonyl; (di) (C 1 -C 6) (alkyl) aminothiocarbonyl; arylcarbonyl optionally substituted phenylcarbonyl, 2,4,6-trimethylphenylcarbonyl; optionally substituted aryloxycarbonyl such as p-nitrophenoxycarbonyl; optionally substituted aryl (C 1 -C 6) alkoxycarbonyl; substituted such as benzyloxycarbonyl or Cbz, p-methoxy-benzyloxycarbonyl, 3,4-dimethoxybenzyl-oxycarbonyl, o-nitrobenzyloxycarbonyl, p-nitrobenzyl-oxycarbonyl, 2-bromobenzyloxycarbonyl (2-bromo-Z) and 2-chlorobenzyl-oxycarbonyl (2-bromo-benzyloxycarbonyl). chloro-Z), 4-nitrobenzyloxycarbonyl (nitro-Z), heteroarylCI-C6alkoxycarbonyl such as 9-fluorenylmethoxycarbonyl (FMOC) or nicotinoyl; (diXCrCeXalkyl) aminocarbonyl as dimethylaminocarbonyl; (CrCeXalkyl) arylaminocarbonyl, carboxy; optionally substituted aryl l that phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl; optionally substituted heteroaryl; including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 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 pyrazinium pyridazinyl pyridazinium triazinyl triazinium tetrazinyl tetrazinium azepine azepinium, oxazepinyl, oxazepinium, thiepinyl, thiepinium, imidazolyl, imidazolium; ii) 8 to 11-membered bicyclic compounds such as indolyl, indolinium, benzoimidazolyl, benzoimidazolium, benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl, benzothiazolyl, benzothiazolium, pyridoimidazolyl, pyridoimidazolium, thienocycloheptadienyl, these mono or bicyclic groups being optionally substituted by one or more groups such as CrC4) alkyl as methyl, or polyhalo (CrC4) alkyl as trifluoromethyl; iii) or tricyclic ABC following:

wherein the two rings A, Ç optionally comprise a heteroatom, and the ring B is a 5-, 6- or 7-membered, particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl; optionally substituted heterocycloalkyl, optionally cationic, the heterocycloalkyl group represents in particular a saturated or partially saturated monocyclic group with 5, 6 or 7 members comprising 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, di / tetrahydropyrimidinyl these groups being optionally substituted with one or more groups such as CrC4) alkyl, oxo or thioxo preferably tetrahydropyranyl TH P; or the heterocycle represents the following group:

in which R'c, R'd, R'e, R'f, R'9 and R'h, which are identical or different, represent a hydrogen atom or a (CrC4) alkyl group, or else two R'9 groups with R'h, and / or R'e with R'f form an oxo or thioxo group, or else R'9 with R'e together form a cycloalkyl; and v represents an integer inclusive of between 1 and 3; preferentially R'c to R'h represent a hydrogen atom; and An 'represents a counterion; isothiouronium -C (NR'cR'd) = N + R'eR'f; An 'with R'c, R'd, R'e and R'f, identical or different, represent a hydrogen atom or a (CrC4) alkyl group; preferentially R'c to R'f represent a hydrogen atom; and An 'represents a counterion; isothiourea -C (NR'cR'd) = NR'e; with R'c, R'd and R'e as defined above; (DiJaryKCrC) alkyl or optionally substituted triarylC1-4alkyl such as 9-anthracenyl-methyl, phenylmethyl (benzyl), diphenylmethyl or triphenylmethyl optionally substituted with one or more groups chosen in particular from halogen, (CrC4) alkyl, (CrC4) alkoxy, and methoxy, hydroxy, (CrC4) alkylcarbonyl, (di) (CrC4) (alkyl) amino such as dimethylamino, nitro; (di) heteroaryl (CrC4) alkyl or triheteroaryl (CrC4) alkyl optionally substituted, the heteroaryl group is, in particular, cationic or not, monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide groups such as 4- pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted with one or more groups such as alkyl particularly methyl, advantageously (di) heteroaryl (Ci-C4) alkyl is (di) heteroarylmethyl o u (di) heteroarylethyl; CR1R2R3 with R1, R2 and R3 same or different, representing a halogen atom such as (tri) (di) halo (CrC4) alkyl such as 2,2,2-trichloroethyl or a group selected from : - (CrC4) alkyl such as methyl; - (CrC4) alkoxy; optionally substituted aryl such as phenyl optionally substituted by one or more groups such as (CrC4) alkyl, (CrC4) alkoxy, hydroxy; - optionally substituted heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted with a (CrC4) alkyl group; P (Z1) R'1R'2R'3 with R'1, and R'2 which are identical or different, represent a hydroxyl, (CrC4) alkoxy or alkyl group, R'3 represents a hydroxyl or (Cr C4) alkoxy group, and Z1 represents an oxygen or sulfur atom; (C2-C6) alkylene in particular allyl H2C = CH-CH2-; optionally substituted arylsulfonyl such as p-toluenesulfonyl (Tos); sterically hindered cycloalkyl such as adamantyl group; sterically hindered cycloalkyloxy (thio) carbonyl such as 1-adamantyl-oxycarbonyl (Adoc) or 1- (adamantyl) -1-methylethoxy-carbonyl (Adpoc); (CrC4) optionally substituted alkoxy (CrC4) alkyl such as methoxymethyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl; (tri) (di) halo (CrC4) alkyl such as 2,2,2-trichloroethyl;

ReRfRgSi-with Re, Rf, and Rg, identical or different, representing a group (Cr C6) alkyl, optionally substituted aryl, (di) aryl (CrC4) alkyl optionally substituted, triaryKCrCalkyl optionally substituted, such as benzyl, in particular selected from trimethylsilyl or TMS, triethylsilyl, isopropyldimethylsilyl, terbutyldimethylsilyl or TBDMS, (triphenylmethyl) dimethylsilyl, t-butyldiphenylsilyl, methyldiisopropylsilyl, methyl (di-t-butyl) silyl, tribenzylsilyl, tri-p-xylylsilyl, triisopropylsilyl, triphenylsilyl; or two contiguous hydroxy groups may be protected by an alkylene group -C (R ') (Rm) - (C (Rk) (Rj)) q- * as shown below:

with Rj, Rk, R1, and Rm, which may be identical or different, representing a hydrogen atom or a (CrC4) alkyl, (poly) halo (CrC4) alkyl, optionally substituted aryl group such as phenyl or aryl (CrC4) alkyl group; benzyl, (poly) halo (Cr C4) alkoxy, (CrC4) alkoxy, halogen, (di) (C1-C4) (alkyl) amino, hydroxy, or both R1 and Rk and / or R1, and Rm form together with the carbon atom carrying them an oxo group or a (hetero) cycloalkyl such as cyclohexyl or cyclopropyl; q is 0, 1, 2 or 3, preferably -C (R ') (Rm) - (C (Rk) (Rj)) q- * represents methylene, ethylene, propylene, dimethylmethylene, -C (CH3) ) 2- * or diphenylmethylene * -C (Ph) 2- *, cyclopentylidene, cyclohexylidene, cycloheptylidene, benzylidene, p-methoxybenzylidene, 2,4-dimethoxybenzylidene, methoxymethylene and ethoxymethylene As examples of protecting groups, mention may be made more particularly the groups acetyl, THP, TMS, TBDMS, trityl, tosyl, tert-butyl, MOM, and benzoate. The "alkyl" radicals are saturated, linear or branched hydrocarbon radicals, generally CrC20, particularly CrCiO, preferably radicals. C1-C6 alkyls, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl.

The "aryl" radicals are mono- or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl, more preferably a phenyl radical.

The "alkoxy" radicals are alkyl-oxy radicals with alkyl as defined above, preferably C1-C10, such as methoxy, ethoxy, propoxy and butoxy.

"Alkoxyalkyl" radicals are preferably alkoxy (CrC2o) alkyl (Cr C20) radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like.

"Cycloalkyl" radicals are in general C 4 -C 8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals. The cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups.

The "alkyl" radicals, when they are optionally substituted, may be substituted with at least one substituent carried by at least one carbon atom, chosen from: a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a quaternary ammonium group -N + R'R "R '", M' for which R ', R ", R'", which may be identical or different, represent a hydrogen atom, or a C 1 -C 4 alkyl group; and Me represents the counter-ion of the organic acid, mineral or corresponding halide; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a hydroxyl group; an amino group optionally substituted by one or two optionally substituted C 3 -C 3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle comprising optionally at least one other heteroatom different or different from nitrogen; a quaternary ammonium group -N + R'R "R" \ M as defined previously; or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (CrC4) alkyl radical, preferably methyl; an acylamino radical (-NR-C (O) R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R' radical is an alkyl radical; in CrC2; a carbamoyl radical ((R) 2 N-CO-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group; an alkylsulphonylamino radical (R'S (O) 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents an alkyl radical; C1-C4, a phenyl radical; an aminosulphonyl radical ((R) 2 N -S (O) 2-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; carboxylic radical in acid or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); a cyano group; a nitro group; a carboxy or glycosylcarbonyl group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy group; and a phenyl group optionally substituted by one or more hydroxyl groups.

The "aryl", "heteroaryl" or "heterocyclic" or "aryl", "heteroaryl" or "heterocyclic" radical radicals when they are optionally substituted may be substituted by at least one substituent borne by at least one carbon atom, chosen from: a C1-C10 alkyl radical, preferably a C1-C8 alkyl radical, optionally substituted with one or more radicals chosen from hydroxyl, C1-C6 alkoxy and (C2-C4) poly (-hydroxyalkoxy) acylamino radicals; amino substituted with two identical or different C 1 -C 4 alkyl radicals, optionally carrying at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated ring optionally comprising another heteroatom identical to or different from nitrogen; a halogen atom; a hydroxyl group; a C 1 -C 2 alkoxy radical; a C1-C10 alkoxycarbonyl radical; a C2-C4 (poly) -hydroxyalkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different C1-C6 alkyl radicals optionally bearing at least: a hydroxyl group; an amino group optionally substituted by one or two optionally substituted C 3 -C 3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered optionally substituted saturated or unsaturated heterocycle comprising optionally at least one other heteroatom different or different from nitrogen; a quaternary ammonium group -N + R'R "R '", M' for which R ', R ", R'", which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group; and M 'represents the counter-ion of the organic acid, mineral or corresponding halide; or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (CrC4) alkyl radical, preferably methyl; an acylamino radical (-NR-C (O) R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C 1 -C 2 alkyl radical; a carbamoyl radical ((R) 2 N-CO-) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; an alkylsulphonylamino radical (R'-S (O) 2-NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C1-C4 alkyl radical, a phenyl radical; an aminosulphonyl radical ((R) 2 N -S (O) 2 -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; a nitro group; a polyhaloalkyl group, preferentially trifluoromethyl; a carboxy group; a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; a glycosyloxy or O-sugar group; and a phenyl group optionally substituted by one or more hydroxyl groups.

By "glycosylated" is meant a radical derived from a mono or an oligosaccharide having from 2 to 5 units, preferably derived from a mono or a disaccharide.

The radicals containing one or more silicon atoms are preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane, stearoxydimethicone radicals.

"Heterocyclic" radicals are cyclic radicals in general, saturated or unsaturated, containing from 3 to 22 members, comprising in at least one ring one or more heteroatoms chosen from O, N and S, preferably O or N, optionally substituted by in particular one or more alkyl, alkoxy, carboxylic acid, hydroxy, amine or ketone groups. These rings may contain one or more oxo moieties on the carbon atoms of the heterocycle of the non-aromatic moiety. The heterocycles include heteroaryl, heterocycloalkyl or heterocycloacenyl groups.

The "heterocycloalkyl" radicals represent mono- or polycyclic saturated groups, fused or otherwise, optionally cationic, comprising from 3 to 22 members, preferably from 3 to 7 members, such as morpholinyl thiomoropholinye, piperidinyl, piperazinyl, pyrrolidinyl, tetrahydrofuranyl azepanyl preferentially pirrolidinyl and morpholino;

The "heterocycloacenyl" radicals represent unsaturated or optionally cationic mono or polycyclic unsaturated groups, comprising from 3 to 22 ring members, preferably from 5 to 7 ring members, which contain from 1 to 3 double bonds, conjugated or otherwise, particularly heterocycloacenyls. are pyperenzenyl such as pyperazin-2-en-4-yl optionally substituted in particular by two carboxy groups at the 2-position and 6-position of said heterocycloacenyl;

The "heteroaryl" radicals represent mono- or polycyclic groups, condensed or not, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium, and wherein at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyl, oxazolyl, oxazolopyridyl phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyryl, triazolyl, xanthyl and its ammonium salt;

Among the "heterocyclic" radicals that can be used, mention may be made of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl and thienyl groups.

More preferably, the "heterocyclic" groups are fused groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromannyl, isochromannyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl, these groups may be substituted, particularly by one or more OH groups.

By "organic or inorganic acid salt" is meant a salt derived for example i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4, iv) alkylsulphonic acids: Alk- S (O) 20H such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 20H such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-O-S (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid P (O) (OH) 3; xiii) acetic acid CH3C (O) OH; xiv) triflic acid CF3S (0) 20H and xv) tetrafluoroboric acid HBF4.

And "organic or inorganic base salt" is understood for example a salt derived from inorganic bases such as i) sodium NaOH, ii) potash KOH, or organic bases such as iii) ammonia; iv) amines and hydroxyamines such as (tri) (Cr C6) alkylamine (tri) hydroxy (C1-C6) alkylamine; or (v) salts of the alkali or alkaline earth metals;

The "solvates" within the meaning of the present invention comprise conventional solvates such as those formed during the last step of preparation of said compounds due to the presence of solvents. By way of example, mention may be made of solvates due to the presence of water (hydrates) or of linear or branched alcohols, such as ethanol or isopropanol. ii) glycosidase enzymes

The glycosidases of the invention are glycoside hydrolase enzymes which catalyze the hydrolysis of glycosidic linkages by releasing at least one osidic compound.

Glycosidases within the meaning of the present invention may be in powder form, in solution or immobilized on a solid support i.e. a support bearing ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase.

By "support" carrying one or more enzyme (s) is meant a "matrix" on which has been immobilized one or more enzymes; said enzymes have retained their catalytic functions. Said enzymes are immobilized on support by chemical or physical immobilization methods, and remain in a defined space in which they can be used several times or continuously. Examples of methods for immobilizing said enzymes are conventional methods known to those skilled in the art (see, for example, "Enzyme immobilization: an overview on techniques and support materials, 3 Biotech"; 3 (1): 1-9 (2013). Feb), Ph.D. thesis, Ecole Supérieure Chimie Montpellier, H. Jarrar, "Enzymatic bioelectrodes for applications in biosensors and biopiles" (16/12/2011) in particular chapter 1.7), such as adsorption crosslinking, covalent grafting, encapsulation, affinity / bioaffinity recognition such as antigen / antibody recognition. The matrices used are those known to those skilled in the art, mention may in particular be made of: i) organic polymers such as agarose, cellulose, dextrans, polymers such as polyvinyl chloride, acrylates, nylons, polystyrene ii) inorganic materials: silica in the form of microporous glass beads and silica gel and iii) hybrids of the two preceding matrices i) and ii) such as agarose-acryl amide and polymer-coated silica .

In particular, the matrix used to immobilize, by encapsulation or otherwise, the enzyme or enzymes of the invention is alginate. Alginate is an algae extract composed of alternating chains of alpha-L-guluronic acid and beta-D-mannuronic acid residues. The alginate supports are preferably prepared by crosslinking the carboxylic group of alpha-L-guluronic acid with a cationic ligand such as calcium chloride, barium chloride, or poly- (L-lysine). (see, e.g., Carbohydrate Polymers 56 (4), 483-488 (2004), Journal of Applied Polymer Science 132 (26), 42125 / 1-42125 / 15 (2015), Chitosan-Based Hydrogels 339-406 (2012). Shiyou Huagong 39 (1), 7-12 (2010); Surface Science, 648, 53-59 (2016); Bioorganic and Medicinal Chemistry Letters, 18 (6), 1922-1925 (2008); Enzyme Research Vol 2011 (2011), Article ID 642460 and FR2393810):

The glycosidases ii) are chosen according to the nature of the glycosyl radical carried by the derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one hydroxy group i) in order to be adapted to the hydrolysis of the bond between the glycosylated radical S * and the hydroxyindol radical (in) e (s) as defined above.

The at least one hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group as defined above is (are) used in the presence of one or more ii) enzyme (s) with glycosidase activity and in particular beta-glycosidase more particularly glucosidase and preferentially beta-glucosidase.

The enzyme (s) with glycosidase activity may be of plant, animal, fungal or bacterial origin

Preferentially, the glycosidases of the invention are glucosidases and in particular beta-glucosidases.

The latter carry out a -O-glucoside binding hydrolysis to beta-glucoside of a monosaccharide or oligosaccharide having a glucose portion.

These enzymes are known under the names of gentiobiase, cellobiase, emulsin, elaterase, arylbeta-glucosidase, beta-D-glucosidase, beta-glucoside glucohydrolase, arbutinase, amygdalinase, p-nitrophenyl beta-glucosidase, primeverosidase, amygdalase, linamarase, salicilinase, and beta-1,6-glucosidase (EC number 3.2.1.21 - Locus Chr 4, p15.31). these are also known as Amygdalin beta-glucosidase, Prunasin beta-glucosidase, Vicianin beta-glucosidase, Glucosylceramidase, and cellulase-type enzymes produced primarily by fungi, bacteria, and protozoa that catalyze the hydrolysis of cellulose.

According to a preferred embodiment of the invention, the glycosidase or glycosidases used represent from 0.0001% to 10% by weight approximately of the total weight of the composition (s) containing this or glycosidases and even more preferentially of 0.0005%. at about 0.1% by weight. By way of examples of glycosidases, mention may be made, for example, of O-Glycan-peptide hydrolase marketed by Sigma-Aldrich under the name Ο-Glycosidase (EC 3.2.1.97). Examples of glucosidases that may be mentioned include, for example those chosen from: beta-primeverosidase, marketed by Amano under the name Aromase®; Cellulase marketed by Amano under the name Cellulase DS®; and beta-glucosidases marketed by DuPont under the names MULTIFECT® CX 15L and Optimase® CX 15L. iii) dH of the composition (s)

The pH of the compositions of the invention can be adjusted to the desired value by means of acidifying or alkalinizing agents usually used for dyeing keratinous fibers or else using conventional buffer systems. Among the acidifying agents of the compositions used in the invention, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Among the alkalizing agents include those mentioned in point iv) below.

When speaking of pH for the use of the invention, it is understood that the ingredients i) and / or ii) are in an aqueous cosmetic composition, iii) at the pH in question ie at pH inclusive between 3 and 8 ; more particularly at a pH ranging between 4 and 7 and preferably between 4.5 and 6.

According to a particular embodiment, the pH of the cosmetic composition comprising ingredient i) as defined above is between 3 and 8 inclusive; more particularly at a pH ranging between 4 and 7 and preferably between 4.5 and 6.

According to another particular embodiment of the invention, the pH of the cosmetic composition comprising ingredient ii) as defined above is between 3 and 8 inclusive; more particularly at a pH ranging between 4 and 7 and preferably between 4.5 and 6.

Especially the pH of the so-called "final" composition comprising ingredients i) and ii) is at pH inclusive between 3 and 8; more particularly at a pH inclusive of between 4 and 7 and preferably between 4.5 and 6

Particularly i) the hydroxyindol derivative (s) (s) glycosylated on at least one hydroxy group i) of the invention is (are) used with (ii) one or more glycosidases (s) as (s) previously defined in an aqueous cosmetic composition, iii) a pH inclusive between 3 and 8; more particularly at a pH ranging between 4 and 7 and preferably between 4.5 and 6.

According to one particular embodiment of the invention, the pH of the cosmetic composition containing ii) the glycosidase (s) and (i) at least one hydroxyindol derivative (s) glycosylated on at least one group hydroxy as defined above is included between 4 and 7 and preferably between 4.5 and 6.

After the implementation of the dyeing process according to the invention involving the ingredients i) ii) and iii), the dyeing process of the invention can implement the application of an aqueous alkaline cosmetic composition comprising one or more alkalizing agents, especially those as defined in point iv).

After the use of ingredients i) ii) and iii) for the treatment in particular the coloration of keratinous fibers, especially human fibers such as the hair, it may be used an aqueous alkaline cosmetic composition comprising one or more alkalinizing agents, especially those such as defined in point iv).

The pH of the alkaline composition is greater than 7, in particular between 8 and 11 inclusive, preferably between 8.5 and 10. iv) basifying agents

The basifying agent (s) may be inorganic or organic.

Among the organic alkalinizing agents that may be mentioned are organic amines and in particular alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, amino acids, in particular basic amino acids such as lysine and arginine, optionally substituted alkylene diamines of formula (V):

wherein W is a linear or branched (C -C 6) alkylene group optionally substituted by one or more hydroxy groups or a C 1 -C 4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical; as the diamine compounds such as diaminopropane.

Preferably, the organic basifying agent (s) are chosen from basic amino acids. More preferentially, the organic alkalinizing agent is arginine.

Among the alkalizing inorganic agents include ammonia, alkali metal or alkaline earth metal hydroxides, phosphates, monohydrogenphosphates, (bi) carbonates.

According to the invention, the alkalinizing agent (s) used preferably represent from 0.001% to 10% by weight of the total weight of the composition, still more preferably from 0.005% to 5% by weight.

The pH of the alkaline composition is greater than 7, in particular between 8 and 11, preferably between 8.5 and 10.

The essays

Another subject of the invention relates to especially cosmetic compositions in particular aqueous (C1) for the dyeing of human keratinous fibers such as the hair which contain at least one hydroxyindole derivative glycosylated on at least one hydroxy group of formula (la ), (Ia1), (Ia2), (Ia3), as defined above, in particular those for which the sugar S * denotes a monosaccharide and in particular a monosaccharide of structure Si to S6 as defined above, it being understood that the compounds of formula (Ia), (Ia1), (Ia2), (la3), are different from the following compound (1 '):

More particularly, the compositions (C1) contain at least one compound of structure (1) to (15) defined above, in particular those for which the sugar S * denotes a monosaccharide and in particular a monosaccharide of structures Si to S6, in particular Si , as defined above being understood that (1) can not represent (1 ').

Even more particularly, the compositions (C1) contain at least one compound chosen from the compound of structure (1) with S * representing S2, S3, S4, S5 and S6, the compounds (2), and (3), for which the sugar S * denotes a monosaccharide of structures Si to S6, in particular Si, as defined previously.

Another subject of the invention relates to a particularly cosmetic composition, in particular an aqueous composition (C2) for the dyeing of human keratinous fibers, such as the hair, containing i) at least one hydroxyindole derivative (in) glycosylated on at least one hydroxyl group (s) as defined above and ii) at least one enzyme with glycosidase activity and in particular beta-glycosidase, more particularly glucosidase and preferentially beta-glucosidase.

In particular, the compositions (C2) contain ii) at least one enzyme having beta glycosidase activity and i) at least one compound of formula (Ia), (Ia1), (Ia2), (Ia3), as defined above, in particular those for which the sugar S * denotes a monosaccharide of structures Si to S6 as defined above. More particularly, the compositions (C2) contain ii) at least one beta-glycosidase active enzyme and at least one compound of structures (1) to (15) as defined above, in particular those for which the sugar S * denotes a monosaccharide of S structures! at S6, in particular Si, as defined above. Even more particularly, the compositions (C2) contain ii) at least one enzyme with beta glycosidase activity and i) at least one compound chosen from the compounds of structure (1), (2), (3), for which the sugar S * denotes a monosaccharide and in particular a monosaccharide of structure Si to S6, in particular Si, as defined above.

Another subject of the invention relates to a particularly cosmetic composition, in particular an aqueous composition (C3), for the dyeing of human keratin fibers, such as the hair, containing i) at least one hydroxyindole derivative (in) glycosylated on at least one hydroxyl group of formula (I), iii) at a pH between 0 and 3 limits not included and 8 and 12 limits not included and not containing enzyme beta glycosidase activity.

Another subject of the invention relates to a particularly cosmetic composition, in particular an aqueous composition (C4) containing the compound the compound of structure (1) with S * representing Si (corresponds to the compound (1 ') as defined above) and at least one cosmetic adjuvant chosen from anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or their mixtures, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or their mixtures, mineral or organic thickeners, and in particular, anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, sequestering agents, perfumes, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preservatives, opacifying agents.

In the compositions of the invention in particular (C1), (C2), (C3) and (C4), the concentration i) of hydroxyindol derivative (s) glycosylated on at least one hydroxyl group of the invention is preferably from 0.0005 to 10% by weight relative to the total weight of the composition containing them. Even more preferentially, this concentration varies from 0.005 to 5% by weight, better still from 0.01 to 4% by weight relative to the total weight of the composition containing them.

Preferably the concentration i) of hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group of the invention is between 0.1 and 1% by weight of the total weight. of the composition which contains it, such as 0.5%.

The compositions of the invention are cosmetics which are cosmetically acceptable i.e. they comprise a staining medium which generally contains water or a mixture of water and one or more organic solvents or a mixture of organic solvents.

By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.

Preferably, all the compositions of the invention are cosmetic and aqueous, more preferably they contain between 10% and 99.9% of water.

Organic Solvents: As an organic solvent, mention may be made, for example, of 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 monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol.

The organic solvents are present in proportions preferably of 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 additives:

The composition or compositions of the dyeing method according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof. anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners.

The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the coloring process according to the invention are not not, or not substantially, impaired by the addition or additions envisaged.

Additional dyes:

The method and the composition implementing the ingredients i) to iii) as defined above, together or sequentially, can further implement or include one or more additional direct dyes. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes other than orthodiphenols, direct quinone dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine, triarylmethane, indoamine, methines, styryls, porphyrins, metalloporphyrins, direct dyes, phthalocyanines, methine cyanines, and fluorescent dyes. All these additional dyes are different from orthodiphenol derivatives according to the invention.

Among the natural direct dyes that may be mentioned are lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins and polyphenols. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

The additional direct dye (s) used in the composition (s) preferably represent from 0.001% to 10% by weight approximately of the total weight of the composition (s) containing them and even more preferentially from 0.05% to 5% by weight approximately.

The compositions of the process implementing ingredients i) to iii) as defined above as defined above may also implement or comprise one or more oxidation bases and / or one or more couplers conventionally used for dyeing fibers. keratin.

Among the oxidation bases that may be mentioned are para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

The oxidation base (s) present in the composition (s) are in general present each in an amount of between 0.001% and 10% by weight relative to the total weight of the corresponding composition (s).

The composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form that is suitable for dyeing keratinous fibers. . They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. vi) Coloring processes

Another subject of the invention is a process for staining keratinous fibers of the invention, comprising the application to the fibers of a composition comprising one or more derivatives of hydroxyindol (in) and (s) glycosylated ( s) on at least one of the hydroxyl groups as defined above.

According to a particular embodiment of the invention, the method uses i) one or more hydroxyindole derivative (s) glycosylated on at least one of the hydroxyl groups such that defined above and ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined previously.

According to a more particular embodiment of the invention, the process for treating keratinous fibers, in particular a process for staining human keratinous fibers such as the hair, involves i) one or more hydroxyindol derivative (s) glycosylated on at least one of the hydroxyl groups as defined previously, ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase in particular with glucosidase activity and more particularly beta-glucosidase, iii) preferentially at a pH of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6.

According to a particular embodiment of the invention the process is a dyeing process in which the more particularly human keratinous fibers such as the hair are treated with: a composition (A) comprising: i) one or more derivative (s) hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxyl groups as defined previously (s); iii) optionally at a pH inclusive of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6; and then by a composition (B) comprising ii), one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase optionally in aqueous solution, preferably at a pH of between 3 and 8, it being understood that at least one of the compositions is at a pH inclusive of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6.

The pause time, after the composition (A) has been brought into contact with the composition (B), is set at a duration of between 5 minutes and 1 hour, preferably between 15 and 45 minutes and more particularly between 20 and 40 minutes. minutes

According to another particular embodiment of the invention, the process is a dyeing process in which the more particularly human keratinous fibers such as the hair are treated: by a composition (B) comprising ii), one or more enzyme (s) ) with glycosidase activity and in particular beta-glycosidase optionally in aqueous solution, preferably at a pH of between 3 and 8, then with a composition (A) comprising: i) one or more derivatives of hydroxyindol (in) e ( s) glycosylated on at least one of the hydroxyl groups as defined previously; iii) optionally at a pH inclusive of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6; then, it being understood that at least one of the compositions is at a pH of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6.

The pause time after the composition (B) has been brought into contact with the composition (A) is set at a duration of between 5 minutes and 1 hour, preferably between 15 and 45 minutes and more particularly between 20 and 40 minutes.

According to a preferred embodiment of the invention the process is a dyeing process in which the more particularly human keratinous fibers such as the hair are treated with: a composition (A) comprising: i) one or more derivative (s) hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxyl groups as (s) previously defined iii) at a pH between 3 and 8, more particularly between 4 and 6, preferably between 4.5 and 6; and simultaneously with a composition (B) comprising ii), one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase optionally in aqueous solution, preferably at a pH of between 3 and 8, it being understood that the pH of the composition resulting (A) + (B) is included between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6.

The pause time, after the composition (A) has been brought into contact with the composition (B), is set at a duration of between 5 minutes and 1 hour, preferably between 15 and 45 minutes and more particularly between 20 and 40 minutes. minutes

According to an advantageous variant of the method for dyeing keratinous fibers, said fibers are treated with a cosmetic composition comprising: i) one or more derivatives of hydroxyindol (in) and (s) glycosylated on at least one of hydroxy groups as defined previously; ii), one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase, and iii) at a pH ranging between 3 and 8, more particularly between 4 and 6, preferably between 4.5 and 6.

The pause time of the composition comprising i) to iii) is set between 5 minutes and 1 hour, preferably between 15 and 45 minutes and more particularly between 20 and 40 minutes.

According to a preferred method of the invention, the keratinous fibers are treated with a composition resulting from the mixture of the two compositions (A) and (B) in which: the composition (A) comprises: i) one or more derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxyl groups as defined above; and the composition (B) comprises: ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined previously and; or else a support bearing ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined previously; it being understood that at least one of the compositions (A) and / or (B) is an aqueous solution and that the pH of the mixture (A) + (B) is between 3 and 8 inclusive, more particularly between 4 and 6, preferably between 4.5 and 6.

According to another preferred embodiment of the invention the process is a dyeing process in which the more particularly human keratinous fibers such as the hair are treated with a composition resulting from the mixture of the two compositions (A) and (B) in which: the composition (A) comprises: i) one or more derivatives of hydroxyindol (in) glycosylated on at least one of the hydroxyl groups as defined previously optionally in aqueous solution; and iii) optionally at a pH of from 3 to 8, more preferably from 4 to 6, preferably from 4.5 to 6, and the composition (B) comprises: ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase optionally in aqueous solution and optionally at a pH ranging between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6, or a support bearing ii) one or more enzymes ( s) with glycosidase activity and in particular beta-glycosidase optionally in an aqueous solution, at a pH of between 3 and 8, more preferably between 4 and 6, preferably between 4.5 and 6; at least one of the compositions (A) and / or (B) is an aqueous solution and the pH of the mixture (A) + (B) is between 3 and 8 inclusive, more preferably between 4 and 6, preferably between 4, 5 and 6.

In particular, the composition resulting from the mixture of (A) + (B) is left on the keratinous fibers for a period ranging from 5 minutes and 1 hour, more particularly from 15 to 45 minutes and preferably from 20 to 40 minutes.

According to a particular embodiment of the above process, the composition resulting from the mixture of (A) + (B) is obtained after mixing the ingredients i), ii), and whose pH of said mixture (A) + (B) is included inclusive between 3 and 8, for a duration (D) of between 5 minutes and 1 hour, more particularly between 15 to 45 minutes and preferably between 20 and 40 minutes and then applied to the keratinous fibers for a period (D) as defined above ..

In particular, the composition resulting from the mixture of (A) + (B) can be obtained in the absence of air. According to one variant, this composition resulting from the mixture of (A) + (B) is applied to the dry or moist keratinous fibers immediately after the time (D) as defined previously.

According to an advantageous variant, the composition resulting from the mixture (A) + (B) after the time (D) is separated from the enzymes ii) for example by filtration and then applied to the particular human keratinous fibers such as the hair, for a duration ranging from 5 minutes and 1 hour, more particularly 15 to 45 minutes and preferably 20 and 40 minutes.

According to a particularly preferred embodiment of the invention, said method comprises a step of separating the enzymes as defined above before application to the keratinous fibers.

According to a particular embodiment of the invention, the process after implementation of i), ii) and iii) comprises the application iv) of an alkaline composition at a pH greater than 7, in particular between 8 inclusive. and 11, preferably included between 8 and 10, more preferably between 8.5 and 10 as defined above.

The pause time of the alkaline composition iv) is set between 5 minutes and 1 hour, preferably between 15 and 45 minutes and more particularly between 20 and 40 minutes.

The keratinous fibers may or may not be previously moistened.

According to a particular dyeing process of the invention, said process may be followed by post-treatment steps such as shampooing with conventional shampoo, rinsing for example with water and or drying the keratinous fibers in air or by heat treatment as defined below.

Whatever the mode of application, the application temperature is generally between ambient temperature (25 ° C.) and 60 ° C. and particularly preferably between 15 ° and 50 ° C., more particularly between 20 ° and 40 ° C., preferably 25 and 35 ° C.

Thus, it is advantageous, after application of the composition according to the invention, to subject the hair to a heat treatment by heating at a temperature of between 30 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices.

As a means for heating and smoothing the hair, it is possible to use a heating iron at a temperature of between 60 and 220 ° C. and preferably between 120 and 200 ° C., preferably after the application of the composition. alkaline iv) as defined above.

A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C).

In all the particular modes and variants of the processes previously described, the compositions (A) and (B) mentioned are ready-to-use compositions which may result from the extemporaneous mixing of two or more compositions and in particular of compositions present in dyeing kits. . vii) Dyeing device or "kit":

Another object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed ingredients i) to iii) as defined above, it being understood that ingredients i) and ii) are in separate compartments ; and optionally in another separate compartment is an alkaline composition iv) which contains one or more alkaline agents as defined above, preferably comprising ammonia.

According to a particularly advantageous embodiment, the device further comprises a separate compartment which comprises an alkaline composition iv) which comprises one or more alkaline agents as defined above, preferably comprising ammonia.

The compositions of the device according to the invention are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges.

The device mentioned above can also be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in the patent FR 2,586,913.

EXAMPLES OF COLORING

Preparation of solutions • Preparation of the citrate / phosphate buffer solution pH 5: Introduce 24.3 mL of solution A and 25.7 mL of solution B into a 100 mL flask and make up with distilled water. The pH is 5.01.

Solution A: 0.1 M citric acid solution (19.21 g / L);

Solution B: 0.2 M dibasic sodium phosphate solution (53.65 g / L Na 2 HPO 4, 7H 2 O); • Solution of 5,6-dihydroxyindole in pH 5 buffer (12.0 g / L, 80 mM); C5 glycosylated 5,6-dihydroxyindole solution (Compound 1) * in pH 5 buffer (25 g / L, 80 mM); • Optimase® CX15L solution (DuPont) in pH 5 buffer (25 g / L); • Ammonia solution at 2%. * compound accessible through the extraction, separation and synthesis methods described in the literature: Shipin Gongye Keji 34 (7), 300-304 (2013); Rapid Common. Mass Spectrum., 19, 2603-2616 (2005); Zeitschrift fur Naturforschung, C: Journal of Biosciences, 56 (5/6), 343-348 (2001); and Helvetica Chimica Acta, 67 (5), 1348-55 (1984) or enzymatically according to the method described above.

The same solutions in pH 5 buffer were prepared with C6 glycosylated 5,6-dihydroxyindole and C5 and C6 di-glycosylated 5,6-dihydroxyindole. Deglycosylation kinetics carried out in the presence of Optimase® enzyme on the three molecules - C5 glycosylated 5,6-dihydroxyindole (compound 1), C6-glycosylated 5,6-dihydroxyindole (compound 2) ** and 5,6-dihydroxyindole di-glycosylated C5 and C6 (compound 3) ** - have well shown the gradual release of 5,6-dihydroxyindole.

'' Enzymatically accessible especially according to the method described above.

Example 1 (comparative)

The wicks used weigh 0.25 g and are treated with 2.5 mL of solution (bath ratio (RB) of 10/1) 1 / ATo, introduce into a flask 1.05 mL of solution of 5,6-dihydroxyindole + 1.05 mL of buffer solution at pH 5, then maintain magnetic stirring at 30 ° C 2 / A T30, (30 minutes after T0) spread the solution on a lock of Caucasian white hair (90%) permed (sensitized) . Then apply 0.4 mL of 2% ammonia solution and leave for 30 minutes at 32 ° C. 3 / A T60, (60 min after T0) rinse, shampoo, rinse and dry the wick in the open air 4 / A T6h, measure the L, a, b values of the wick

Example 2 (invention)

The locks used weigh 0.25 g and are treated with 2.5 mL of 10/1 solution (RB) 1 / A T0, put in a vial 1.05 mL of solution of Compound 1 + 1.05 mL Optimase® CX15L, then maintain magnetic stirring at 30 ° C 2 / A T30, (30 minutes after T0) spread the solution on a lock of white hair (90%) Caucasian permed (sensitized). Then apply 0.4 mL of 2% ammonia solution and leave for 30 minutes at 32 ° C. 3 / A T60, (60 min after T0) rinse, shampoo, rinse and dry the wicks 4 / A T6h, measure the values of L, a, b wicks

Hair color is read on a Minolta spectrophotometer (CM3600d, D65 illuminant, 10 ° angle, SCI values) for L *, a *, b * colorimetric measurements. In this system L * a * b *, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The higher the value of a * the higher the shade is red and the higher the value of b * the hue is yellow.

Chromaticity C ':

The chromaticity in the CIE system L *, a *, b * is calculated according to the following equation:

The higher the value of C *, the more chromatic coloration is obtained

The composition of Example 2 of the invention is very stable to oxygen in the air whereas the comparative composition is not stable to oxygen in the air (see Example 3 below). Moreover, it has not been noted on the cloths used with the composition of the invention stains on white towels, while with the comparative composition it is worth noting some brown spots that appear after a few minutes. Moreover, it appears from the colorimetric measurements that the results obtained in particular in terms of chromaticity are identical to those obtained with the comparative composition.

Example 3: stability test

Preparation of the citrate / phosphate buffer solution pH 5.2:

Introduce 24.3 ml of solution A and 25.7 ml of solution B into a 100 ml vial and make up with distilled water. The pH is 5.2. Solution A: 0.1 M citric acid solution (19.21 g / L); Solution B: 0.2 M Dibasic Sodium Phosphate Solution (53.65 g / L Na 2 HPO 4, 7H 2 O)

Preparation of stock solutions (MS): - Compound 1: 50.12 mg qs 2 mL of citrate / phosphate buffer pH 5.2 (SM1) - 5,6-dihydroxyindole: 22.44 mg qs 2 mL of citrate / phosphate buffer pH 5 , 2 (SM2)

Preparation of the daughter solutions: 1 / Test A: introduce into a vial 0.8 mL of the SM1 solution. Add 0.8 mL of buffer, 0.3 mL of 2% ammonia solution and then stir with magnetic stirring at room temperature. The pH of the solution is 9.2. 2 / Test B: introduce into a vial 0.8 mL of the SM2 solution. Add 0.8 mL of buffer, 0.3 mL of 2% ammonia solution and then stir with magnetic stirring at room temperature. The pH of the solution is 9.2.

Each test is taken at t = 5 min, t = 6 h and t = 24 h, diluted by a factor of 20 in water and then the percentage of residual compound is determined by UPLC / UV (297 nm).

UPLC / UV material and method The analysis of the samples is performed on an ACQUITY UPLC H -Class (Waters) chain comprising a diode array detector:

Acquity column BEH C18

Length: 50 mm

Internal diameter: 2.6 mm

Vcolonne .0,18 mL

Diameter of the particles: 1.7 μηι

Mobile phase A = H 2 O at 0.1% HC (O) OH

B = CH3CN at 0.1% HC (0) OH

Gradient 1 T (min)% A% B P (psi) 0 99 1 6750 3 90 10 4 0 100 4.7 0 100 5 99 1 7 99 1 Flow rate 0.6 mL / min

Temperature T column - 35 O T sample - 25 O Diode Barette Detection (DAD)

The chromatogram is recorded in MaxPlot over the wavelength range included between 191 nm and 700 nm.

The percentage values in the graphs correspond to the residual values of the compounds.

% is the residual percentage of the compounds after a time T

Thus, the results of tests A and B demonstrate the greater stability of the glycosylated 5,6-dihydroxyindoles according to the invention. unglycosylated 5,6-dihydroxyindole.

Claims (17)

1. Use of i) hydroxyindol derivative (s) glycosylated on at least one of the hydroxy groups, in the presence of at least ii) a glycosidase-active enzyme for staining fibers keratin. 2. Use according to the preceding claim wherein i) the derivative (s) of hydroxyindol (in) (s) glycosylated (s) on at least one hydroxyl group is (are) chosen from those of formula (the next one : as well as their enantiomers, diastereoisomers, tautomers and their organic or inorganic acid or base salts, and / or their solvates; Formula (la) in which: R 1 and R 3, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical; R2 represents a hydrogen atom, a C1-C4 alkyl, -C (O) OH or -C (O) -OR4 radical with R4 representing a (CrC4) alkyl group; X and Y, which are identical or different, denote a hydrogen atom, a hydroxyl group or -O-Sugar; Sugar represents a monosaccharide or polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3, and preferably from 2 saccharide units, it being understood that at least one of the X groups, or Y represents a -O-Sucre group . 3. Use according to the preceding claim wherein i) the derivative (s) of hydroxyindol (in) (s) glycosylated (s) on at least one hydroxyl group is (are) chosen from those of formula (Γ) following: as well as their enantiomers, diastereoisomers, tautomers and their salts of organic or inorganic acid or base and / or their solvates such as hydrates; formula (P) in which: R | represents a hydrogen atom, or a group selected from (CrC4) alkyl, -C (O) -OH and -C (O) -OR4 'with R4' representing a (CrC4) alkyl group such as methyl, or ethyl; particularly, R 1 represents a hydrogen atom, or a group selected from (C 1 -C 4) alkyl and -C (O) -OH, more particularly R 1 represents a hydrogen atom; • Sugar is as defined previously; • p is 1 or 2.; and q is 0 or 1; it being understood that the sum p + q is equal to 2; especially, p is 1 and q is 1, and Sugar-O- is at position 5 where p is 1 and q is 1, and Sugar-O- is at position 6 or p is 2, and Sugar-O- is in position 5 and 6 and q is 0. 4. Use according to any preceding claim wherein the derivative (s) of hydroxyindol (in) (s) glycosylated (s) on at least one hydroxyl group i) is (are) chosen (s) from those of formula (Ia1), (Ia2) and (Ia3): as well as their enantiomers, diastereoisomers, tautomers and their salts of organic or inorganic acid or base and / or their solvates Formulas (Ia1), (Ia2) and (Ia3) in which, Ri, R2, R3 and Sugar are such that defined for (la) in claim 3, in particular R 1, R 2 and R 3 represent a hydrogen atom or (CrC 4) alkyl, preferably hydrogen; the at least one hydroxyindol derivative (s) (s) glycosylated on at least one hydroxyl group (i) is (are) chosen from among the hydroxyindole derivative (s) ( s) glycosylated on at least one hydroxyl group, in particular those of formula (Ia1) and (Ia2) as defined above. 5. Use according to any one of the preceding claims wherein the sugar is attached to the oxygen atom of -O-sugar by the carbon atom of the sugar, which sugar is selected from mono or polysaccharides composed of the following sugars: pentoses; hexoses, hexosamines and deoxy-hexoses; these saccharides may be of D or L configuration, preferably of D configuration; preferably, said "sugar" represents a group chosen from Glucose, Glucosamine, Rhamnose and Xylose, preferentially D-glucose, D-glucosamine, D-rhamnose, D-xylose and more preferably D-Glucose. 6. Use according to any one of claims 2 to 5 wherein the Sugar-O- represents a monosaccharide selected from Si to S6: particularly Si and preferably -Ο-Sugar represents: 7. Use according to any one of the preceding claims wherein the hydroxyindol derivative (s) (s) glycosylated on at least one of the hydroxy groups is (are) selected in the following terms: and their organic or mineral acid or base salts, and / or their solvates, with S * -O-representing a monosaccharide selected from Si to S6 as defined in the preceding claim, and particularly S * -O- represents a monosaccharide chosen from Si, S3, S5, S6, more particularly Si and preferentially more preferably the derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxy groups is (are) chosen (s) from among the following compounds: 8. Use according to any one of the preceding claims wherein ii) the enzyme (s) with glycosidase activity are selected from gentiobiase, cellobiase, emulsin, elaterase, aryl-beta-glucosidase, beta-D-glucosidase, beta-glucoside glucohydrolase, arbutinase, amygdalinase, p-nitrophenyl beta-glucosidase, primeverosidase, amygdalase, linamarase, salicilinase, and beta-1,6-glucosidase (EC number 3.2.1.21 - Locus Chr. 4 p15.31). Amygdalin beta-glucosidase, Prunasin beta-glucosidase, Vicianin beta-glucosidase, Glucosylceramidase, and enzymes produced mainly by fungi, bacteria, and protozoa that catalyze the hydrolysis of cellulose. 9. Use according to any one of the preceding claims wherein the ingredients i) and / or ii) are used at the pH inclusive between 3 and 8, particularly at pH is included between 4 and 7 inclusive and more particularly between 4.5 and 6 A method of dyeing keratinous fibers comprising applying to the fibers a composition comprising one or more hydroxyindol derivative (s) glycosylated on at least one of the hydroxy groups such as s) as defined in any one of claims 1 to 7. 11. Method according to the preceding claim which implements i) one or more derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxyl groups as defined (s) in any one of claims 1 to 7 and ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined in one of claims 1 or 8. The method of any one of claims 10 or 11 comprising applying to the fibers a composition which comprises: i) one or more hydroxyindol derivative (s) glycosylated on at least one of the hydroxy groups as defined in any one of claims 1 to 8; ii) one or more enzyme (s) with glucosidase activity and in particular beta-glucosidase as defined in any one of claims 1 or 8; iii) at a pH inclusive of between 3 and 8 as defined in claim 9. 13. The method of claim 10 wherein said fibers are treated with a composition derived from the mixture of the two compositions (A) and (B) wherein: the composition (A) comprises: i) one or more derivative (s) of hydroxyindol (in) e (s) glycosylated (s) on at least one of the hydroxyl groups as defined (s) 1 to 7; and the composition (B) comprises: ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined in any one of claims 1 or 9 and; or a support bearing ii) one or more enzyme (s) with glycosidase activity and in particular beta-glycosidase as defined in any one of claims 1 or 9; it being understood that at least one of the compositions (A) and / or (B) is an aqueous solution and that the pH of the mixture (A) + (B) is between 3 and 8 inclusive, more particularly between 4 and 6, preferably between 4.5 and 6. 14. Method according to the preceding claim wherein the composition resulting from the mixture of (A) + (B) is left on the keratinous fibers for a period ranging from 5 minutes and 1 hour, more particularly from 15 to 45 minutes and preferably from 20 to 15 minutes. and 40 minutes. 15. Method according to the preceding claim comprising a step of separating the enzymes before application to the keratinous fibers. 16. The process as claimed in any one of claims 10 to 15, wherein after application of the cosmetic composition to said fibers, iv) is applied an alkaline composition at a pH greater than 7, in particular between 8 and 11, preferably inclusive between 8 and 10, more preferably between 8.5 and 10. 17. Multi-compartment dyeing device or kit which comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed ingredients i) to iii) as defined in any one of claims 1 to 9, it being understood that the ingredients i) and ii) are in separate compartments; and optionally in another separate compartment is an alkaline composition iv) which contains one or more alkaline agents as defined in the preceding claim, preferably comprising ammonia.