JP2014528401A - Dye composition comprising glycosyl iridoid compound and specific aldehyde or imine compound, dyeing method, and apparatus therefor - Google Patents

Abstract

The present invention relates to a composition for dyeing human keratin fibers, and includes the following in a cosmetically acceptable medium: * Iridoid family of the following formula (I): Extract: [where R1: hydrogen, methyl, hydroxymethyl, aldehyde; -CO2R4 (where R4: hydrogen, C1-C2 alkyl; sugar); R2: hydrogen atom, hydroxyl group, sugar group; R3: hydrogen , Hydroxyl, alkyloxy; R: a sugar group (aldose or derivative); an integer ranging from 1 to 5; a formula (I A compound of formula (i) and (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine compound, and further comprising at least one aldehyde or imine compound: [where n Is equal to 0 or 1; X: O, NR'1; A: COOH, optionally substituted Aryl, cationic or non-cationic, saturated or unsaturated, 5- or 6-membered heterocycle, optionally substituted with 1 or 2 heteroatoms, alkyl, Alkenyl; A2 divalent alkylene; the compound is probably in the form of an acetal or hemiacetal in the case of an aldehyde]. The invention also relates to methods of using such compositions and to multi-compartment devices.

Description

  The present invention relates to at least one compound from the glycosylidoid family extracted from plants and at least one particular aldehyde or optionally pre-glycosylated in a cosmetically acceptable medium. It relates to dye compositions containing imine compounds and also to dyeing methods using such compositions.

  In recent years, there has been an increasing interest in natural compounds that can be used as hair dyes.

  For example, European Patent No. , A composition comprising at least one compound of (seco) iridoid-glycosides or non-glycosyl (seco) ylidoids (also known as aglycones) extracted from plants such as Ericaceae, Loganiaceae, etc. Disclosed is a method for dyeing hair using an object.

  The problem encountered with such coloration is that they are not particularly strong and require repeated application of the composition over several days or weeks to obtain a satisfactory coloration.

  Furthermore, it is difficult to achieve the desired natural shading as an advantage. Moreover, it is not uncommon for substantial color changes to be observed over time when such shades are realized.

European Patent No. 440494 French Patent No. 2842200 French Patent No. 2854161

E. Fredon et al., “Hydrophobic films from maize bran hemicelluloses”, Carbohydrate Polymers 49, 2002, 1-12 R. E. Wing, J. L. Willet, `` Water soluble oxidized starches by peroxide reaction extrusion '', Industrial Crops and Products 75 (1997), 45-52

  The object of the present invention is therefore to overcome the above-mentioned drawbacks.

  In particular, surprisingly, the color fixability using non-glycosylidoid compounds and their derivatives, and in general any natural extract with the same, indicates that this compound is a specific aldehyde or It has been discovered that when combined with an imine compound, it can be substantially improved.

  It has also been found that the structure of the treated fiber is not impaired by the coloring according to the invention.

Thus, one subject of the present invention is
* The following compounds of the iridoid family of formula (I), optical or geometric isomers thereof, inorganic or organic acid salts thereof, solvates thereof, or plant extracts containing the same compounds:

[Where
R ₁ is a hydroxymethyl group, -CO ₂ R ₄ group (wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl group); a sugar group;
R ₂ represents a hydrogen atom, a hydroxyl group or a sugar group;
R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl group, a (C ₁ -C ₄ ) alkoxy group; the number of hydroxyl groups does not exceed 2;
R represents a sugar group;
N is an integer between 1 and 5;
The sugar group is a derivative obtained from aldose or an aldose derivative;
The compound of formula (I) optionally undergoes a first step performed by an enzyme, replacing the R group with a hydrogen atom];
** At least one aldehyde or imine compound selected from the following formulas (i) and (ii), its optical or geometric isomer, its organic acid salt or inorganic acid salt, its solvate, and at least one aldehyde Or an oxidized oligosaccharide or polysaccharide containing an imine functional group:

[In the formulas (i) and (ii),
M is an integer equal to 0 or 1,
· X represents an oxygen _{atom, NR '' 1 (R '} ' 1 represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group);
When X represents an oxygen atom, the compound is:
〇 additional primary monoalcohol (R _'3 OH) (wherein, R' ₃ is C ₁ -C ₅ alkyl group or symmetrical 1,2 or 1 containing C ₂ -C ₃ alkyl chain, May be in the form of a 5- or 6-membered cyclic or acyclic acetal produced from the condensation of
If A or A ₁ represents an alkyl group and n is equal to 0, it may be in the form of a hemiacetal formed from the condensation of hydroxyl groups present in A or A ₁ ;
The R ′ ₁ and R ′ ₂ groups, independently of each other, represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl group;
The monovalent group A and the divalent group A ₁ represent a group selected from the following groups:
* Hydroxycarbonyl group (-CO-OH):
* C ₆ aryl group optionally substituted with at least the following groups:
-Hydroxyl group,
- C ₁ -C ₄ alkyl group,
An aryl-ethylenyl group (the aryl group is C ₆ and is optionally substituted with at least one C ₁ -C ₂ alkyl group or C ₁ -C ₂ alkoxy group),
- -CO-OR _'4 group or -O-COR' ₄ (wherein, R _'4 represents a C ₁ -C ₂ alkyl group or a phenyl group);
-COOH groups in acid or salified form,
-OR ' ₅ group, wherein R' ₅ represents a C _{1 to} C ₈ alkyl group optionally substituted with at least one hydroxyl group, an ammonium group -N ⁺ R '' ₆ (R '' _6, which may be the same or different and represent a C ₁ -C ₂ alkyl group), - SiR _'7 group (R' _7, which may be identical or different, C ₁ -C represents ₂ alkyl group); a benzyl group _{(-CH 2 -C 6 H 6)} ,
-According to one particular variant, two --OR ' ₅ groups that are ortho to the C ₆ aryl group form a 5-membered or 6-membered heterocycle with two R' ₅ groups Well,
--N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and is optionally substituted with a C ₁ -C ₆ alkyl group, acid form optionally substituted with a hydroxyl group Or a carboxylic acid group in the salified form (—COOH), or a sulfonic acid group in the acid form or the salified form (—SO ₃ H); the R ′ ₈ group together with the nitrogen atom that carries them , O, N, and NR ′ ₉ (wherein R ′ ₉ represents a C ₁ -C ₂ alkyl group) optionally containing another heteroatom, a saturated or unsaturated 5- or 6-membered May form a heterocycle; the heterocycle is optionally substituted with a hydroxyl group},
--COR ′ ₁₀ group, wherein R ′ ₁₀ represents a C ₆ aryl group fused to a 6-membered hydrocarbon ring optionally substituted with at least one C ₁ -C ₂ alkyl group ),
- -SR _'11 (wherein, R' ₁₁ represents C ₁ -C ₂ alkyl group),
A halogen atom, preferably selected from chlorine and bromine,
--O-SO ₂ -C ₆ H ₆ group,
--SO ₃ H group,
- O, 'of ₁₂ (wherein, R' N and NR ₁₂ is a saturated or unsaturated, aromatic or C ₁ -C ₂ alkyl fused optionally 5-membered or 6-membered ring nonaromatic An unsaturated cationic or non-cationic 5-membered or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from the group consisting of 2 one of may be included in a ring; heterocyclic or fused ring is possibly substituted with at least one C ₁ -C ₂ alkoxy group, a heterocyclic ring,
The aryl group is optionally fused to a 5- or 6-membered heterocyclic group, from O, N and NR ′ ₁₃ , wherein R ′ ₁₃ represents a C ₁ -C ₄ alkyl group Containing 1 or 2 heteroatoms of choice, the heterocycle is optionally fused to a C ₆ aryl group;
- said aryl group is fused optionally to C ₆ aryl group which is optionally substituted with at least one C ₁ -C ₂ alkoxy group;
* O, N and NR ′ ₁₄ (R ′ ₁₄ is a hydrogen atom, a C ₁ -C ₆ alkyl group or a (R ′ ₁₅ ) ₂ NCO-group or a (R ′ ₁₅ ) CO-NH- group (where R _'15 may be different even in the same, C ₁ -C ₂ 1 piece preferably from representing a C ₆ aryl group which is optionally substituted} alkyl represents a group) is selected, or the same Or a cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group containing two different heteroatoms;
- the heterocyclic group may itself be fused with optionally at least one C ₁ -C ₂ alkyl, aryl group having 6 membered optionally substituted with C ₁ -C ₄ alkoxy or phenoxy group Cage;
The heterocyclic group is optionally substituted with at least the following groups:
〇 hydroxyl group,
C ₁ -C ₂ alkyl group which is optionally substituted with 〇 hydroxyl group;
Amino group -N (R _{'16) 2} {wherein, R' 〇 _16, which may be the same or different and represent C ₁ -C ₄ alkyl group optionally substituted with a hydroxyl group , R ′ ₁₆ group, together with the nitrogen atom holding them, any other heteroatom selected from O, N and NR ′ ₁₇ (wherein R ′ ₁₇ represents a C ₁ -C ₂ alkyl group) May optionally form a saturated or unsaturated 5-membered or 6-membered heterocyclic ring};
A C ₆ aryl group optionally substituted with at least one —COOH group, R ′ ₁₈ CONH— group (R ′ ₁₈ represents a C ₁ -C ₂ alkyl group), and a nitrogen of the heterocyclic group A C ₆ aryl group, optionally bonded to an atom, wherein the carbon atom is replaced with a hydrogen atom when the aryl group is not substituted with the group described above;
* One or more conjugated or non-conjugated carbon - carbon double bond, straight or branched, a C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group, at least one hydroxyl C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group optionally substituted with a group;
The divalent group A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two A ₁ groups via a carbon, oxygen or nitrogen atom];
In a cosmetically acceptable medium,
The compounds of formulas (i) and (ii) comprise, where appropriate, a cosmetically acceptable anion, or a mixture of anions An, which ensures the electrical neutrality of the formulation;
A composition for dyeing human keratin fibers.

  Another subject of the present invention is represented by a method for dyeing human keratin fibers, in which such a composition is used.

  Another subject of the invention consists of a multi-compartment device, said device comprising a first compartment containing at least one compound of formula (I), or a plant extract containing said compound, said compound comprising: An oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group A second compartment containing:

  Another subject also consists of a multi-compartment device, said device comprising a first compartment containing at least one compound of formula (I), or a botanical extract comprising said compound; and formula (i) Or at least one compound of (ii), an oxidized oligosaccharide or polysaccharide containing at least one aldehyde or imine functional group, and an enzyme to replace the R group of formula (I) with a hydrogen atom A second compartment is provided.

  Finally, the final subject matter of the present invention is represented by a multi-compartment device, the device comprising a first compartment containing at least one compound of formula (I) or a plant extract comprising said compound; And a second compartment containing an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group; and R of formula (I) A third compartment containing an enzyme for replacing the group with a hydrogen atom is provided.

  The composition according to the invention makes it possible to obtain a variety of shampoo-resistant colorings that do not damage the hair.

  Other features and advantages of the present invention will emerge more clearly upon reading the following description and examples.

  It should be noted that the upper and lower limits of the range of values given in the description are included within the range unless otherwise indicated.

  The human keratin fibers to be treated via the method according to the invention are preferably hair.

  In the text herein, the terms “at least one” and “one or more” are considered synonymous hereinafter.

  Inorganic acid salts are more specifically hydrochlorides, hydrobromides, sulfates and phosphates; organic acid salts are more specifically citrate, succinate, tartrate, lactate, Tosyl hydrochloride, benzene sulfonate and acetate.

  Solvates are more particularly hydrates.

A compound of formula (I) or a botanical extract comprising the same compound, as indicated above, the composition comprises at least one compound of formula (I) as defined above or the same compound in a cosmetically acceptable medium. Containing botanical extracts.

Preferably, R ₁ represents a hydrogen atom, a hydroxymethyl group, a hydroxycarbonyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

Preferably, R ₂ represents a hydrogen atom or a hydroxyl group.

Preferably, R ₂ may be the same or different and represents a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group or an n-butyloxy group.

Preferably, R represents a group derived from C ₆ aldose, such as a group derived from allulose, altrose, galactose, glucose, growth, idose, mannose or talose, preferably a group derived from glucose. With respect to aldose derivatives, deoxy derivatives are preferred, such as rhamnose, and diholoside, especially maltose, is also preferred.

  According to an even more specific embodiment of the invention, R represents a group derived from glucose, rhamnose or maltose, preferably a group derived from glucose.

According to a particularly advantageous embodiment of the invention, the compound of formula (I) is geniposide (R ₁ represents a methoxycarbonyl group), or geniposide acid or a salt thereof (R ₁ is in the acid form or salified. Represents a hydroxycarbonyl group in the form).

  The compounds of formula (I) are the following plants: Abelia grandiflora, Adenorandia kalbreyeri, Adina polycephala, Aeginetia indica var. , Canthium schimperianum, Castilleja wightii, Chaenorhinum minus, Clerodendrum serratum, Coprosma sp, Cornus officinalis, Craibiodendron henryi, Cremaspora triflora, Crucianella sp, Daphniphyllum calycinum, Daphniphyllum humile humifusum, Galium verum, Gardenia jasminoides, Garrya elliptica, Globulularia dumulosa, Hedyotis corymbosa, Hygrophila difformis, Ixeris chinensis, Lamiastrum galeobdolon (Lamium galeobdolon), Lamiophlomis rotata, Phlomisono rotata (Phlomisono rotata) cilicia, Nepeta nuda ssp., Albiflora, Odeontites verna, Oldenlandia corymbosa, Paederia scandens, Pedicularis chinensis, Pedicularis condensata, Pedicularis dolichocyagota, Penstemon confertus, Penstemon deutus, Penstemon richardsonii, Penstemon serrulatus, Pithecoctenium crucrumrum, Pithecoctenium crucrum , Randia dumetorum, Rhododendron latoucheae, Rothmannia withfieldii, Rubia peregrina, Rubia tinctorum, Saprosma scortechinii, Scrophularia korainensis, Scrophularia lepidota, Scrophularia ningpoensis, Scyphiphora hydrophyllacea, Sida Commonly found in plant extracts derived from laxum, Verbascum nigrum, Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vitex nigrum, Wendlandia formosana That.

  Preferably, the plant extract used is Gardenia jasminoides.

  The term “extract” refers to a liquid or powder, obtained from one or more extraction, enrichment or concentration operations, optionally obtained via drying, starting from natural plant material. It should be noted.

  These compounds of formula (I) are extracted from plants in a manner known per se.

  Thus, in the case of the aerial part, the aerial part is optionally ground, then softened by dipping in a suitable solvent, more particularly ethanol or water, then filtered, concentrated and optionally Dried at option.

  In the more specific fruit case, the fruit is optionally frozen and washed with water to remove any impurities present. The fruit may optionally be sterilized, more specifically sterilized with a solution containing ethanol and chlorine.

  In actual extraction, the fruit is thawed and pressed as needed, eg, using a specially adopted hydraulic press.

  The recovered liquid is then subjected to a concentration and drying step, if appropriate.

  In the case of Gardenia jasminoides, there are commercial extracts with various contents of the compound of formula (I).

  The content of the compound of formula (I) in the dry extract ranges from 0.1% to 70% by weight.

  The content of the compound of formula (I) in the composition is between 0.001% by mass and 10% by mass with respect to the mass of the composition.

  It should be noted that the compound of formula (I) has undergone a step of replacing the R group with a hydrogen atom prior to or simultaneously with the dyeing step.

  This reaction may be carried out by any means known to those skilled in the art, in particular using an enzyme selected from isoalase and β-glucosidase, for example from sweet almond (EEC 3.2. 1.21).

  Thus, in cases where the operation is performed simultaneously with the dyeing process, the enzyme is added to the composition just prior to applying the composition to the fiber.

  In cases where the procedure is performed prior to applying the composition to the fiber, the enzyme is added to a buffered (acetate with a pH between 5.5 and 6) aqueous solution of formula (I). Preferably, the concentration of the compound of formula (I) is in the range of 10 to 30 mM. Enzymes are generally used at concentrations ranging from 5 to 100 units / ml (1 unit of enzyme is generally defined by the number of micromoles of substrate hydrolyzed per minute).

  The operation is usually performed at a temperature close to room temperature (between 20 and 45 ° C.) for a range of 1 to 5 hours.

  The reaction product may be used directly or, alternatively, the compound may be obtained by extraction by utilizing a solvent such as, for example, ethyl acetate.

Additional dye The dye composition may have an additional dye in addition to the compound of formula (I) above.

  Among these additional dyes may be mentioned natural or synthetic direct dyes, oxidation dyes with a base optionally combined with couplers, and combinations thereof.

  These direct dyes are, for example, neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinones, especially anthraquinones It can be selected from dyes, azine direct dyes, triarylmethane direct dyes, indamine direct dyes, and natural direct dyes.

  Among natural direct dyes, Lawson, Yuglon, Alizarin, Purpurin, Carminic acid, Kermesic acid, Purprogalin, Anthragalol protocatechualdehyde, Indigo, Isatin, Curcumin, Spinulosin, Apigenin, Chlorophyll, Chlorophylline , Orcein, hematin, hematoxylin, bradylin, brazilein, safflower colorants (e.g. in cartamine), flavonoids (e.g. in morin, apigenin and sandalwood), anthocyan (e.g. apigenin), carotenoids, tannins, sorghum and cochineal carmine, or It is a mixture. It is also possible to use extracts or leachates with these natural dyes, in particular henna poultices or extracts.

  Among the oxidation bases, mention may be made of para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol, bis-para-aminophenol, ortho-aminophenol and heterocyclic bases and their additions Salt.

  Among these couplers, mention may be made in particular of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene couplers and heterocyclic couplers, and addition salts thereof.

  The oxidation base present in the dye composition is each in an amount between 0.001% and 10% by weight, preferably in an amount between 0.005% and 6% by weight, relative to the total weight of the dye composition. Generally present.

  Each coupler is generally present in an amount between 0.001% and 10% by weight, preferably between 0.005% and 6% by weight, based on the total weight of the dye composition.

  In general, oxidation bases and coupler addition salts which can be used in connection with the present invention are in particular addition salts with acids, such as hydrochloride, hydrobromide, sulfate, citrate, succinate, Selected from tartrate, lactate, tosylate, benzenesulfonate, phosphate and acetate.

Aldehyde / imine compound As noted above, the composition also comprises at least one aldehyde or imine compound selected from formulas (i) and (ii) above, and an oxidized containing at least one aldehyde or imine functional group. Also includes oligosaccharides or polysaccharides.

  According to a first variant of the invention, the compounds of the formulas (i) and (ii) are those in which X represents an oxygen atom.

The compounds of (i) and (ii) have an additional primary monoalcohol (R ′ ₃ OH) where R ′ ₃ has a C ₁ -C ₅ alkyl group, or a C ₂ -C ₃ alkyl chain It can also be in the form of a 5- or 6-membered cyclic or acyclic acetal produced from the condensation of a symmetric 1,2- or 1,3-diol).

These compounds can be A or A ₁ is the time equal to n 0 represents an alkyl group, there is also in the form of hemiacetal that is produced from the condensation of the hydroxyl groups present in A or A _1.

Note that the electrical neutrality of formulas (i) and (ii) is demonstrated as needed by organic or inorganic anions, or mixtures of anions, that can equilibrate the charge of the compound. They should be, for example, halide ions such as chloride, bromide, fluoride or iodide ions; hydroxide ions; sulfide ions; hydrogen sulfate ions; methyl sulfate or ethyl sulfate ions, etc. alkylsulfate ion (straight or branched is there the alkyl moiety is C ₁ -C _6); carbonate ion and bicarbonate ion; formate ion, acetate ion, citrate ion, such as tartrate and oxalate carboxylic acid in; alkylsulfonate ion (alkyl moiety of wherein the linear or branched is C ₁ -C _6), such as methyl sulfonate ion; example Arylsulfonate ion (aryl moiety therein, preferably phenyl is optionally substituted with one or more C ₁ -C ₄ alkyl group), such as 4 birds sulfonate ion; and alkylsulfonic such mesylate Selected from acid ions.

  The non-ionic or anionic oxidized polysaccharide contains one or more aldehyde groups and optionally contains one or more anionic groups. These anionic groups are preferably carboxylic acid groups or carboxylate groups.

The nonionic or anionic oxidized polysaccharide used may be represented by the following formula (II):
P- (CHO) m (COOX) n (II)
[Where
P represents a polysaccharide chain consisting of monosaccharides containing 5 carbon atoms or more than 5 carbon atoms, preferably 6 or more carbon atoms, more particularly 6 carbon atoms;
X is a hydrogen atom, an alkali metal or an alkaline earth metal such as sodium or potassium, ammonia, an organic amine such as monoethanolamine, diethanolamine, triethanolamine and 3-amino-1,2-propanediol, and lysine, arginine Selected from ions derived from basic amino acids such as sarcosine, ornithine and citrulline,
m + n is 1 or more,
M is one in which the degree of substitution of the polysaccharide with one or more aldehyde groups (DS (CHO)) is in the range of 0.001 to 2, preferably in the range of 0.005 to 1.5,
n is such that the degree of substitution of the polysaccharide with one or more carboxylic acid groups (DS (COOX)) is in the range of 0 to 2, preferably in the range of 0.001 to 1.5. ]

  The term “degree of substitution of polysaccharides with DS (CHO) or DS (COOX) according to the invention” refers to the number of carbons oxidized as aldehyde or carboxylic acid groups for all repeating units and the polysaccharide. It means the ratio between the number of basic monosaccharides that make up (and that are opened by preoxidation).

  The groups CHO and COOX may be obtained during the oxidation of certain carbon atoms, for example at the C2, C3 or C6 position of a sugar unit having 6 carbon atoms. Preferably, the oxidation may be carried out at C2 and C3, more particularly at a ring that is probably opened from 0.01% to 75%, preferably from 0.1% to 50%. Also good.

  The polysaccharide chain represented by P is preferably selected from inulin, cellulose, starch, pectin, guar gum, xanthan gum, pullulan gum, alginate gum, agar gum, carrageenan gum, gellan gum, gum arabic, xylose and tragacanth gum, and their derivatives. It is.

  The term “derivative” means a compound obtained by chemical modification of a listed compound. They may be esters, amides or ethers of said compounds.

  Oxidation is a process known in the art, e.g., French Patent No. 2842200, French Patent No. 2854161 or the article "Hydrophobic films from maize bran hemicelluloses" by E. Fredon et al., Carbohydrate Polymers Vol. 49, 2002. 1 to 12 pages. Another oxidation process is described in "Water soluble oxidized starches by peroxide reaction extrusion", Industrial Crops and Products Vol. 75 (1997), pages 45-52, R. E. Wing, J. L. Willet. These oxidation steps are easy to perform, effective, and produce no toxic or difficult to remove by-products.

  The peroxide may be an alkali metal or alkaline earth metal percarbonate or perborate, alkyl peroxide, peracetic acid or hydrogen peroxide. The amount of peroxide in the reaction medium is generally between 0.05 and 1 molar equivalent per polysaccharide glucose unit.

  A single phthalocyanine or a mixture of phthalocyanines, such as a mixture of cobalt phthalocyanine and iron phthalocyanine, can also be used as a catalyst. The amount of catalyst depends on the desired degree of substitution. In general, small amounts are suitable for use, for example an amount corresponding to 0.003 to 0.016 molar equivalents per 100 glucose units of the polysaccharide.

  This step can also be carried out by bringing the polysaccharide in powder form into contact with a solvent dissolved in a small amount of water and with a peroxide. This process is referred to as a “semi-drying” process.

  More preferentially, polysaccharides are inulin, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, starch acetate, hydroxyethyl starch, hydroxypropyl starch, guar gum, carboxymethyl guar gum, carboxymethyl hydroxy Obtained by oxidation of propyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, xylose, xanthan gum or carrageenan gum, or mixtures thereof.

  The most particularly preferred polysaccharides in the present invention are those of formula (II) where P represents a polymer chain derived from inulin and starch; m is one or more aldehyde groups (DS (CHO)) The degree of substitution of the polysaccharide is within the range of 0.005 to 2.5; n is the degree of substitution of the polysaccharide with one or more carboxylic acid groups (DS (COOX)) within the range of 0.001 to 2 ).

  Mention may be made, by way of example, of compounds of the formulas (i) and (ii), oxidized oligosaccharides and polysaccharides comprising at least one aldehyde or imine function, which are particularly suitable for carrying out the present invention. The following compounds, their salts, their isomers and their solvates, these compounds are single or mixed:

  Preferably, the composition comprises at least one compound of formula (i).

Advantageously, formula (i) is:
* m is 0 or 1;
* R ′ ₁ group and R ′ ₂ group independently of each other represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl group;
* X represents an oxygen atom;
A represents the following:
* At least one C ₅ -C ₁₀ alkyl group linear optionally substituted with a hydroxyl group or branched;
* Carbon - C ₂ -C ₈ alkenyl group containing a carbon double bond;
* Hydroxycarbonyl group (-COOH);
* C ₆ aryl group optionally substituted with at least the following groups:
〇 hydroxyl group,
〇 C ₁ -C ₄ alkyl group,
〇 -CO-OR _'4 group or -O-COR' ₄ group (wherein, R _'4 represents a C ₁ -C ₂ alkyl group),
〇 -OR _'5 group (wherein, R' ₅ represents a C ₁ -C ₆ alkyl group),
An aryl-ethylenyl group (the aryl group is C ₆ and is optionally substituted with at least one C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy group),
O, N and NR ′ _{12 where} R ′ ₁₂ is a C ₁ -C ₂ alkyl optionally fused to a saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered ring An unsaturated cationic or non-cationic 5-membered or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from the group consisting of 2 one of may be included in a ring; heterocyclic or fused ring is substituted with at least one C ₁ -C ₂ alkoxy group, a heterocyclic ring,
The aryl group is optionally fused to a 5- or 6-membered heterocyclic group, from O, N and NR ′ ₁₃ , wherein R ′ ₁₃ represents a C ₁ -C ₄ alkyl group Containing 1 or 2 selected heteroatoms;
* O, N and NR ′ ₁₄ (R ′ ₁₄ is a (R ′ ₁₅ ) ₂ NCO-group or (R ′ ₁₅ ) CO—NH- group (where R ′ ₁₅ is a C ₁ -C ₂ alkyl group) is optionally substituted with a representative), hydrogen atom, C ₁ -C ₆ alkyl preferably from representing] group or a C ₆ aryl group is selected, one, or the same or different two hetero atoms A cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group containing
- the heterocyclic group is itself is fused optionally to at least one C ₁ -C ₂ alkyl or C ₁ -C ₄ optional 6-membered substituted with an alkoxy group an aryl group;
-The heterocyclic group is optionally substituted with at least the following groups:
〇 hydroxyl group,
C ₁ -C ₂ alkyl group which is optionally substituted with 〇 hydroxyl groups,
Amino group N (R _{'16) 2} {wherein, R' 〇 _16, which may be the same or different and represent C ₁ -C ₄ alkyl group optionally substituted with a hydroxyl group, R ′ ₁₆ group is optionally another heteroatom selected from O, N and NR ′ ₁₇ (where R ′ ₁₇ represents a C ₁ -C ₂ alkyl group), together with the nitrogen atom holding them. Which may form a saturated or unsaturated 5- or 6-membered heterocyclic ring containing};
* The compound of formula (i) contains, where appropriate, a cosmetically acceptable anion, or a mixture of anions An that ensures the electrical neutrality of the formulation;
* The compound of formula (i) is probably in the form of an acetal or a hemiacetal as described above.

  As examples of preferred compounds (i), the following compounds, their isomers, their salts or their solvates can be mentioned, these compounds being a single substance or a mixture:

  More specifically, the content of the compound of formula (i) or (ii) or the oxidized oligosaccharide or polysaccharide containing at least one aldehyde or imine functional group is from 0.001% by weight, based on the weight of the composition. Between 30% by weight.

Examples of preferred oxidized oligosaccharides or polysaccharides that may be mentioned are the following compounds:
-Oxidized starch (Rn 9047-50-1), starch known under the following trade names: Caldas 10; Caldas 5; Caldas 5H; Caldas 5S; Caldas C 5; Caldas C 5GP; Caldas C 5GT; Caldas No. 5; DAS 100; Dialdehyde starch; Dialdehydostarch; Formamyl; Periodate starch; Polyaldehyde starch; Starch dialdehyde; Sumstar; Sumstar 150; Sumstar 190;
-Oxidized cellulose (Rn 9032-52-4), cellulose known by the following names: 2,3-dialdehydecellulose; 2,3-dialdehydecellulose; aldehyde cellulose; cellulose 2,3- Dialdehyde; cellulose dialdehyde; dialdehyde cellulose;
-Oxidized inulin (Rn 82446-43-3);
-Dextran dialdehyde (Rn 37317-99-0).

Amine According to one embodiment of the invention, the composition may comprise at least one primary or secondary amine, or addition salts thereof, ammonia or hydroxylamine, or mixtures thereof.

  In general, addition salts of these amine compounds that can be used in connection with the present invention are in particular addition salts with acids such as hydrochloride, hydrobromide, sulfate, citrate, succinate, Selected from tartrate, lactate, tosylate, benzenesulfonate, dodecylbenzenesulfonate, phosphate and acetate, preferably hydrochloride, citrate, succinate, tartrate, phosphoric acid Selected from salts and lactates.

  Specifically, primary or secondary amines that may be used in connection with the present invention are selected from amines of formula (III), aminopolymers, purine bases described in detail below, and Of addition salts as well as combinations thereof.

Specifically, formula (III) is as follows:
R ' ₇ R' ₈ NH (III)
[In the formula (III), R ′ ₇ and R ′ ₈ independently of one another represent the following:
-Hydrogen atom;
- linear, branched, and / or cyclic, saturated and / or unsaturated, of an aromatic or C ₁ -C ₂₀ hydrocarbon group non-aromatic, five from 1 carbon - Optionally having a carbon double bond and / or containing one or more heteroatoms and / or containing at least one heteroatom or containing at least one heteroatom, Optionally substituted with one or more groups (preferably selected from oxygen, nitrogen, sulfur, C═O, C═S, SO and SO ₂ or combinations thereof), optionally interrupted Optionally hydrocarbon groups; the hydrocarbon groups R ′ ₇ and R ′ ₈ together with the nitrogen atom to which they are attached form a saturated or unsaturated 5- or 7-membered heterocycle It is optionally substituted, optionally aromatic, and optionally Optionally fused to a 6-membered aromatic or heteroaromatic nucleus and optionally containing another heteroatom, nitrogen or not; the hydrocarbon group may be nitro, nitroso, peroxo or diazo Contains no functional groups. ]

  The compound of formula (III) is advantageously neither an oxidation base nor an oxidation coupler used to dye keratin fibers.

Among the groups present as substituents on heterocyclic hydrocarbon groups are the following groups:
Carboxyl, sulfone, phosphone, in acid or salified form
Hydroxyl, C ₁ -C ₄ alkoxy, (C ₁ ~C ₈₎ alkoxycarbonyl,
(C ₁ ~C ₄₎ alkyl sulfonates, (C ₁ ~C ₈₎ alkyl phosphonate,
Tri (C ₁ ~C ₄₎ alkylsilyl, tri (C ₁ ~C ₄₎ alkoxy silanyl,
Amino, (di) (C ₁ ~C ₄₎ alkylamino, tri (C ₁ -C ₄₎ alkylammonium,
Thiol, (C ₁ ~C ₄₎ alkylthio,
Aminosulfonyl, (di) (C ₁ ~C ₄₎ alkylaminosulfonyl,
Aminocarbonyl, (di) (C ₁ ~C ₄₎ alkylaminocarbonyl,
(C ₁ ~C ₄₎ alkylcarbonylamino,
Guanidine,
Ureido (N (R) ₂ -CO-NR′-) (wherein the R group and the R ′ group independently of one another are a hydrogen atom or C ₁ -C ₄ alkyl or (C ₁ -C ₄ ) alkylsulfonyl) Represents an amino group);
Phenyl, indolyl, pyrrolyl, imidazolyl, optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

Preferably, group present as a substituent, the following groups: acid form or carboxyl in form chloride; hydroxyl: C ₁ -C ₄ alkoxy; (C ₁ ~C ₈₎ alkoxycarbonyl; thiol; (C ₁ -C ₄₎ alkylthio; amino; mono- and di (C ₁ -C ₄₎ alkylamino; aminocarbonyl; mono- and di (C ₁ -C ₂₎ alkylaminocarbonyl; (C ₁ -C ₄₎ alkylcarbonylamino; 1 Selected from phenyl, indolyl, pyrrolinyl, imidazolyl, optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

  Specifically, the amines of formula (III) may be the same or different and contain 1 to 5 primary and / or secondary amine functional groups; Not included. Furthermore, the amine of formula (III) does not contain more than two heteroatoms bonded together.

Preferably, the amine is a compound of the formula (III), more specifically selected from the following compounds of the formulas (IIIa) to (IIIi), (IIIi ′) and also from their addition salts.
O Amino acids and / or derivatives of the general formula (IIIa):

[In the formula (IIIa)
- R ₉ represents a hydrogen atom, a linear or branched C ₁ -C ₆ alkyl group (one or more hydroxyl, hydroxycarbonyl, thiol, (C ₁ -C ₄₎ alkylthio, amido, amino or guanidine group A phenyl group (optionally substituted with one or more hydroxyls), an indolyl group (optionally substituted with one or more hydroxyls), an imidazolyl group, It represents or unsubstituted phenyl group; pyrrolinyl (which is optionally substituted with C ₁ -C ₂ alkyl group) groups;
- R '' ₉ represents hydrogen, a C ₁ -C ₄ alkyl group or an unsubstituted phenyl group;
- R ₁₀ represents hydrogen or C ₁ -C ₄ alkyl group;
-R ″ ₉ and R ₉ together with the nitrogen atom to which they are attached may form a saturated 5- or 6-membered heterocycle. ]

  Most particularly possible examples of compounds of formula (IIIa) are asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolidine, serine, threonine, tryptophan and tyrosine, and their addition salts. is there.

  According to another variant, the compound of formula (IIIa) is advantageously 2-amino-2-methylpropenoic acid; α-methyl-D, L-phenylalanine; D, L-α- (hydroxymethyl) Alanine; D, L-α-methyl-meta-tyrosine; α-methyl-D, L-tryptophan; D, L-α-methylhistidine dihydrochloride; L-2-methylserine; (S) -2-methylcysteine Dihydrochloride; selected from (S) -2-methyl-2-pyrrolidine carboxylic acid.

〇 Esters derived from amino acids and / or derivatives of general formula (IIIb):

[In the formula (IIIb),
R ₉ is a hydrogen atom, a linear or branched C ₁ -C ₆ alkyl group {one or more hydroxyl, hydroxycarbonyl, (C ₁ -C ₄ ) alkoxycarbonyl, thiol, (C ₁ -C ₄ ) preferably substituted with alkylthio, amido, amino or guanidine groups}, phenyl group (optionally substituted with one or more hydroxyls), indolyl group (optionally substituted with one or more hydroxyls) in is substituted), an imidazolyl group, which is optionally substituted with a pyrrolinyl group (C ₁ -C ₂ alkyl group); represents or unsubstituted phenyl group;
- R '' ₉ represents hydrogen, a C ₁ -C ₄ alkyl group or an unsubstituted phenyl group;
- R ₁₀ represents hydrogen or C ₁ -C ₄ alkyl group;
-R '' ₉ and R ₉ together with the nitrogen atom to which they are attached may form a saturated 5- or 6-membered heterocycle;
-R ₁₁ represents:
- linear or branched, saturated or C ₁ -C ₁₈ 5 one conjugated or non-conjugated carbon from hydrocarbon groups (1 unsaturated - include optionally carbon double bond, optionally as previously indicated At least one heteroatom, preferably selected from one or more heteroatoms and / or oxygen, nitrogen, sulfur, C═O, C═S, SO and SO ₂ or combinations thereof One or more groups containing atoms are optionally interrupted); alkyl groups do not contain any nitro, nitroso, peroxo or diazo functional groups;
-Unsubstituted benzyl group. ]

According to one particular variation, R ₉ and R ₁₁ can optionally form a saturated 5-membered carbocyclic ring.

Preferably, R ₁₁ is a linear or branched, optionally substituted C ₁ -C ₁₀ alkyl group; a benzyl group; even more preferably at least one hydroxyl group, preferably 1 to 2 optionally substituted with hydroxyl groups, linear or branched C ₁ -C ₄ alkyl radical; a benzyl group.

  Examples of formula (IIIb) are methoxytyrosine, 2-ethylpiperidinecarboxylate; D, L-phenylalanine methyl ester; L-cystine dimethyl ester dihydrochloride; L-leucine methyl ester; 2-amino Methyl-3-methylbutyrate; L-phenylalanine ethyl ester hydrochloride; L-glutamic acid diethyl ester hydrochloride; (S) -2-amino-3-methylbutanoic acid ethyl hydrochloride; D, L-serine methyl ester hydrochloride; tyrosine Methyl ester hydrochloride; L-cysteine ethyl ester hydrochloride; L-histidine methyl ester hydrochloride; (S) -pyrrolidine-2-carboxylic acid methyl hydrochloride; 2-aminoacetic acid methyl hydrobromide; ethyl glycine; HD , L-alanine ethyl ester hydrochloride; D, L-tyrosine ethyl ester hydrochloride; 2- (phenylamino) acetic acid methyl hydrochloride; ethyl glutamate; D, L-aspartate bis (α, β -tert-butyl) hydrochloride; L-α-aminoisocaproic acid ethyl hydrochloride; glycylic acid benzyl para-toluenesulfonate; D, L-alanine ethyl ester hydrochloride; 5-hydroxy-D, L-tryptophan methyl ester D, L-threonine methyl ester hydrochloride; D, L-proline tert-butyl ester; D, L-phenylalanine methyl ester hydrochloride.

O Amides and thioesters derived from amino acids and / or derivatives of general formula (IIIc):

[In the formula (IIIc),
R ₉ is a hydrogen atom, a linear or branched C ₁ -C ₆ alkyl group (one or more, hydroxyl, (C ₁ -C ₄ ) alkoxycarbonyl, hydroxycarbonyl, thiol, (C _1- C ₄₎ alkylthio, amide, preferably at an amino or guanidine groups are substituted), optionally substituted with a phenyl group (one or more hydroxyl), optionally indolyl group (one or more hydroxyl selection is substituted with), it represents an imidazolyl group, a pyrrolinyl group (C ₁ -C ₂ is substituted with an alkyl group optionally);
- R '' ₉ represents a C ₁ -C ₄ alkyl radical hydrogen or hydroxy sulfonyl group, is optionally substituted;
- R ₁₀ represents hydrogen or C ₁ -C ₄ alkyl group;
-R '' ₉ and R ₉ together with the nitrogen atom to which they are attached may form a saturated 5-membered heterocycle;
-R ₁₂ represents:
* Hydrogen atom;
* C ₁ -C ₆ alkyl group (one or more hydroxyl, thiol, (C ₁ -C ₄₎ alkylthio, preferably an amide or amino is substituted), optionally a phenyl group (one or more hydroxyl substituted with selection), and is optionally substituted with indolyl group (one or more hydroxyl), an imidazolyl group, which is optionally substituted with a pyrrolinyl group (C ₁ -C ₂ alkyl group);
-X represents a sulfur or nitrogen atom. ]

According to one particular variation, R ₉ and R ₁₂ can optionally form a saturated 5-, 6- or 7-membered carbonaceous ring.

As previously defined, X represents a nitrogen atom and R ₁₂ represents an alkyl group, and most particularly amino acid residues and / or their corresponding methyl or ethyl esters (alanine, arginine, asparagine, aspartate, In the case of cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pyrrolidine, serine, threonine, tryptophan, tyrosine, valine, leucine or isoleucine), the compound of formula (IIIc) is Represents a dipeptide or oligopeptide.

  As examples of compounds of formula (IIIc), mention may be made of 3-aminodihydrothiophen-2-one hydrochloride; D, L-homocysteine thiolactone; D, L-leucyl-D, L-alanine, aspartame ; (S) -pyrrolidine-2-carboxamide; [N-(-acetamido)]-2-aminoethanesulfonic acid; D, L-alanyl-D, L-phenylalanine; 2- (2-aminoacetamido) -3- (4-hydroxyphenyl) propanoic acid; 2- (2-aminoacetylamino) acetic acid; (R) -3-aminoazepan-2-one; glycinamide hydrochloride; L-leucinamide hydrochloride; 2-aminopropanediamide; 2- (2-Amino-3-methylbutanamide) propanoic acid; L-tyrosyl-L-alanine; L-valyl-L-phenylalanine; sarkosyl-L-phenylalanine; L-tyroyl-β-alanine; glycyl-L- Proline; glycyl-D, L-valine; 2-aminomalonamide; L-methionamide hydrochloride; 2-amino-3-methylbutane Amide; D-alanine amide hydrochloride; L-tyrosine amide; aspartic acid amide hydrobromide; L-tyrosine amide hydrochloride; L-arginine amide dihydrochloride; lysine amide dihydrochloride; threonine amide hydrochloride; Histidineamide dihydrochloride; D, L-alaninamide hydrochloride; 2-amino-3- (4-hydroxyphenyl) propionamide; D, L-tryptophanamide hydrochloride; N-hydroxy-L-arginine acetic acid Salt (H-ARG-NH2 2AcOH); Asparagine amide hydrochloride; L-glutamic acid α, γ-diamide hydrochloride; D-phanylalanine amide; D-leucine amide hydrochloride; L-glutamic acid α-amide; L-methionine amide L-cystine bisamide hydrochloride; glycinamide acetate; D-lysine amide dihydrochloride; glycinamide; L-isoglutamine γ-methyl ester hydrochloride; D-arginine amide dihydrochloride; (S) -pyrrolidine-2 cal Boxamide; prolyl histamine hydrochloride.

〇 Amino compounds of general formula (IIId)

[In the formula (IIId),
-R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ independently of one another represent the following:
* Hydrogen atom;
* Linear or branched and / or cyclic, saturated and / or aromatic carbon by C ₁ -C ₂₀ 5 one optional hydrocarbon group (1 unsaturated - have a carbon-carbon double bond Well, optionally substituted as indicated above, preferably on one or more heteroatoms and / or from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof one or more groups containing at least one heteroatom selected has been interrupted optionally, holds at least one hydroxyl or C ₁ -C ₂ alkoxy group optionally said R ₁₃ And R ₁₄ , or R ₁₄ and R ₁₅ , or R ₁₅ and R ₁₆ , together with the carbon atom to which they are attached, may form a saturated or unsaturated 5- or 7-membered heterocycle, Optionally substituted as shown above, and Is optionally aromatic and optionally contains another identical heteroatom, nitrogen or non-nitrogen; the alkyl group does not contain any nitro, nitroso, peroxo or diazo functionality; more specific Then it is C ₁ -C ₁₀ alkyl group which is optionally substituted; preferably, at least one hydroxyl group, preferably 1 to 2 hydroxyl groups, a hydroxycarbonyl group, a ureido group, (C ₁ -C ₄₎ A linear or branched alkyl group optionally substituted with an alkoxycarbonyl group; an unsubstituted phenyl group);
-X represents a nitrogen, oxygen or sulfur atom;
-R ₁₇ represents:
* Hydrogen atom;
* Linear or branched, saturated or a C ₁ -C ₁₈ hydrocarbon group (1 unsaturated five conjugated or non-conjugated carbon - include optionally carbon double bond, optionally as previously indicated One or more heteroatoms and / or at least one heteroatom preferably selected from oxygen, nitrogen, sulfur, CO, C═S, SO and SO ₂ or combinations thereof One or more groups are optionally interrupted; the alkyl group does not contain any nitro, nitroso, peroxo or diazo functional groups; more particularly, R ₁₇ is optionally substituted with hydrogen, A straight-chain or branched C ₁ -C ₁₀ alkyl group; preferably hydrogen, straight-chain, or optionally substituted with at least one hydroxyl group, preferably with one to two hydroxyl groups branched C ₁ -C ₄ alkyl group It represents);
-R ₁₈ represents:
* Hydrogen atom;
* Is optionally substituted as indicated for the straight chain or branched C ₁ -C ₈ alkyl group (before, in one or more hetero atoms, and / or oxygen, nitrogen, sulfur, CO, C = S, in one or more groups containing at least one heteroatom preferably from SO and SO2, or combinations thereof are chosen, they are interrupted optionally, at least one hydroxyl or C ₁ -C ₂ alkoxy Optionally retaining the group; the alkyl group does not contain any nitro, nitroso, peroxo or diazo functionality);
-o is an integer between 0 and 5. ]

According to another variant of the invention, the radicals R ₁₆ and R ₁₇ are saturated or unsaturated, together with the carbon atom for R ₁₆ and the atom X for R ₁₇ , respectively, attached thereto. A 5- or 6-membered heterocycle of may optionally be formed, optionally substituted as indicated above, optionally aromatic, nitrogenous or not nitrogen Optionally containing one heteroatom.

According to another variant of the invention, the radicals R ₁₈ and R ₁₅ are saturated or unsaturated, together with the nitrogen atom for R ₁₈ and the carbon atom for R ₁₅ , respectively, attached thereto. A 5-membered or 6-membered heterocycle may optionally be formed, optionally substituted as indicated above, optionally aromatic, nitrogenous or not nitrogen Hetero atoms are optionally included.

  As examples of compounds of formula (IIId), mention may be made of L-2-aminohexanoic acid amide hydrochloride; L-phenylalaninamide; (S)-(+)-aminosuccinic acid; (R) -2- ( Methylamino) succinic acid; ethyl nipecoate; 3-piperidinecarboxylic acid; 3-phenyl-β-alanine; ethyl 3-aminobutyrate; 2-carboethylamine; D, L-β-aminoadipic acid; β-alanine ethyl ester Hydrochloride; ethyl 3-amino-3-ureido-N-butyrate; (S) -dimethyl succinate amino acid; β-L-alanine methyl ester hydrochloride; 4-carboxyethoxypiperidine; 4-aminobutyric acid; D, L -β-aminoadipic acid; 4- (methylamino) butyric acid hydrochloride; ethyl γ-aminobutyric acid hydrochloride; hexahydronicotinamide; piperidine-4-carboxamide; 3-carbamoyl-2,2,5,5-tetramethyl Pyrrolidine.

〇 Amino compounds of general formula (IIIe):

[In the formula (IIIe),
-R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as before,
-R ₁₉ represents:
* Hydrogen atom;
* Is optionally substituted as indicated for the straight chain or branched C ₁ -C ₈ alkyl group (before, in one or more hetero atoms, and / or oxygen, nitrogen, sulfur, CO, C = S, in one or more groups containing at least one heteroatom preferably from SO and SO2, or combinations thereof are chosen, they are interrupted optionally, at least one hydroxyl or C ₁ -C ₂ alkoxy Optionally retaining the group; the alkyl group does not contain any nitro, nitroso, peroxo or diazo functionality);
-p is an integer between 0 and 7;
-u is an integer equal to 1 or 2. When u is equal to 2, R ₁₈ represents hydrogen. ]

According to another variant of the invention, the groups R ₁₃ and R ₁₄ together with a carbon for R ₁₃ and R ₁₄ to which the substituents are attached, together with a saturated 5- or 6-membered Heterocycles can be optionally formed.

  Examples of compound (IIIe) are the following acids, their enantiomers (if present), their salts, and their hydrates: (Aminoethyl) phosphonic acid, (aminomethyl) phosphonic acid, (1-aminoethyl-1-cyclohexyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (1-aminobutyl) phosphonic acid, iminobis (methylphosphonic acid), (1-amino-2-methylpropyl) phosphonic acid, (1-amino-2-phenylethyl) phosphonic acid, (1-amino-1-methylethyl) phosphonic acid, (1-amino-3-methylbutyl) phosphonic acid 1-aminobenzylphosphonic acid, 1-aminohexylphosphonic acid, diethyl (aminoethyl) phosphonic acid (especially oxalate), tetraethyl (aminomethylene) bisphosphonic acid (especially its salt), (1-amino-2,2 -Dimethylpropyl) phosphone N-methylaminomethylphosphonic acid, (1-aminopentyl) phosphonic acid, (1-amino-2-methylbutyl) phosphonic acid, (1-aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) phosphonic acid (1-amino-1,2-dimethylpropyl) phosphonic acid, (1-amino-1,3-dimethylbutyl) phosphonic acid, (1-amino-1-methylbutyl) phosphonic acid, (1-amino-1- Cyclopentyl) phosphonic acid, (1-aminohydroxycarbonyl) propylphosphonic acid, (1-amino-1-methylethyl) phosphonic acid, 1-amino-2-methylbutylphosphonic acid, 1-phosphono-2-phenylethylamine, (Aminomethyl) phosphonic acid, 3-aminopropylphosphonic acid, 2-amino-2-methyl-4-phosphonobutanoic acid, and their ethyl esters, (diethyl (3-aminopropyl) phosphonic acid (especially oxalate), 3 -(N-hydroxyamino) propyl Sphonic acid, 2-amino-2-methyl-4-phosphonobutyric acid, diethyl (3-aminopropyl) phosphonate, 2-amino-4-phosphonobutyric acid, 2-aminoethylphosphonic acid, 2-amino-3-phosphonopropion Acid, diethyl (2-aminoethyl) phosphonate, diethyl (2-aminoethyl) phosphonic acid, (2-((2-pyrrolidinylcarbonyl) amino) ethyl) phosphonic acid, diethyl (2-amino-1-methyl- 2-phenyl) ethyl phosphonate, diethyl (2-amino-2-phenyl) ethyl phosphonate, and / or mixtures thereof.

〇 Amino compounds of general formula (IIIf):

[In the formula (IIIf),
-R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as before. In addition, the groups R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are, independently of one another, a hydroxyalkyl group, a (C ₁ -C ₄ ) alkoxycarbonyl group, a carboxaldehyde group, (C ₁ -C ₃ ) alkoxy May represent;
-q is an integer between 1 and 18;
-X represents an oxygen atom, an SH or OH group, or a methylene group, optionally substituted with a hydroxyl group;
-When X represents an oxygen atom, R ₁₈ forms a 5 or 6 membered ring optionally substituted with one or more hydroxyl (methyl), preferably 1 to 4 hydroxyl (methyl) groups To do. ]

According to another variant of the invention, the R ₁₆ and R ₁₈ groups, or the R ₁₃ and R ₁₈ groups, are each bound to the carbon for R ₁₆ (or for R ₁₃ ). Together with the atom, and the nitrogen atom for R ₁₈ , a saturated or unsaturated 5- or 6-membered heterocycle may be optionally formed, optionally substituted as indicated above, and optionally It optionally contains another identical heteroatom that is aromatic and is or is not nitrogen.

  According to another variant of the invention, the amine of the formula (IIIf) reduces the acid or ester function to one alcohol of the 20 esterified or non-esterified amino acids. It can be a β-aminoalcohol originating from that.

  Examples of compound (IIIf) include the following compounds, their enantiomers (if present), their salts, and their hydrates: isopropanolamine , Isopropylamine, methylethanolamine, methylglucamine, stearamine, tromethamine, promethazine, 1,3-dimethylpentylamine, octodrine, spermidine, theanine, octamilamine, 2-amino-1-phenylpropane-1,3-diol 1,3-dihydroxy-2-amino-2-methylpropane, 2-amino-2- (hydroxymethyl) propane-1,3-diol tris, 2-amino-1,3-dihydroxy-2-ethylpropane, 2-Amino-3-methylbutan-1-ol, 2-amino-2-methylpropan-1-ol, phenylglycinol, 2-aminopropanol, 2-hydroxyethylamine 2-aminohexane-1-ol, 1-amino-1-cyclopentanemethanol, histidinol, 2-amino-3- (3-indolyl) propanol, 3- (4-hydroxyphenyl) -2-amino-1-propanol , Β-aminoisobutanol, 2-amino-1-propanol, 2-amino-1,3-propanediol, 2-amino-4-methyl-1-pentanol, 2-amino-3-methyl-1-butanol , Β-aminobenzenepropanol, 2-aminopropan-1-ol, 2-amino-1-butanol, 2-amino-4-methylpetan-1-ol, 3-aminopropanethiol, 2-amino-4-mercaptobutane Ethyl acetate, 6-hydroxyhexylamine, β-D-galactopyranosylamine, β-D-glucopyranosylamine, 1-amino-2,5-anhydro-D-mannitol, 1-amino-1-deoxy-D -Fructose, D-glucosamine, 2-pyrrolidinemethanol, 1-amino-2 , 3-Dihydroxypropane, 3-propanolamine, 3-[(2-hydroxyethyl) amino] propan-1-ol, di-β-hydroethylamine, bis (3-hydroxypropyl) amine, N-2'-amino Ethyl-N-propanolamine, 4-amino-N-butanol, methyl 3-amino-3-deoxy-α-D-mannopyranoside, N-butyl-4-hydroxybutylamine, 4-amino-4- (3-hydroxypropyl ) -1,7-heptanediol, 1-hexylamine, 1-octylamine, 1-nonylamine, 1-decylamine, laurylamine, 1-tetradecylamine, 1-hexadecylamine, 3-amino-2-hydroxypropion Acids, 3-amino-2-hydroxy-4-phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, ethyl ethyl 4-hydroxy-2-pyrrolidinecarboxylate, and mixtures thereof.

〇 Amino compounds of general formula (IIIg):

[In the formula (IIIg)
-R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as before;
-R ₂₀
* Linear C ₁ -C ₄ alkyl group,
* Represents a straight-chain C ₁ -C ₄ alkoxy group,
-o is an integer between 0 and 5,
-v is an integer equal to 1 or 2. When v is equal to 2, R ₁₈ represents hydrogen. ]

  Examples of compound (IIIg) include aminopropyltriethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan-1-amine, 4- (triethoxy (Silyl) butan-1-amine, N- [3- (trimethoxysilyl) propyl] ethylenediamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine and (3-methylaminopropyl) Trimethoxysilane, as well as mixtures thereof.

〇 Amino compounds of general formula (IIIh):

[In the formula (IIIh),
-R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as before. In addition, R ₁₃ group, R ₁₄ group, R ₁₅ group and R ₁₆ group are independently of each other a hydroxyl group, (C ₁ -C ₄ ) alkoxycarbonyl group, carboxyl aldehyde group, (C ₁ -C ₃ ) May represent alkoxy;
-R ₂₁ and R ₂₂ independently of one another represent:
* Hydrogen atom;
* Linear, branched and / or cyclic, saturated and / or C ₁ unsaturated -C ₂₀ hydrocarbon group (1 to 5 carbon - may have a carbon-carbon double bond, previously indicated Optionally substituted and at least one heteroatom and / or preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO2 or combinations thereof one or more groups containing a hetero atom, are interrupted optionally, at least one hydroxyl or C ₁ -C ₂ alkoxy group, C ₁ -C ₁₀ alkyl group that is optionally substituted and more particularly A linear or branched C ₁ -C ₄ alkyl optionally substituted with at least one hydroxyl group, preferably with 1 to 2 hydroxyl groups Group;
-R ₂₁ and R ₂₂ together with the nitrogen atom to which they are attached may form a saturated or unsaturated, 5- or 7-membered heterocycle, optionally as indicated above Substituted, optionally aromatic, optionally containing another identical heteroatom, nitrogen or non-nitrogen; alkyl group does not contain any nitro, nitroso, peroxo or diazo functionality ;
-w is an integer between 1 and 10. ]

According to another variant of the invention, the alkyl groups R ₁₆ and R ₂₁ are saturated or unsaturated, together with the carbon atom for R ₁₆ and the nitrogen atom for R ₂₁ , respectively, attached thereto. A 5- or 6-membered heterocycle may be formed, optionally substituted as indicated above, optionally aromatic, nitrogen, or non-nitrogen, with another heteroatom Optionally included.

According to another variant of the invention, the alkyl groups R ₁₈ and R ₂₁ , together with the first nitrogen atom for R ₁₈ and the last nitrogen atom for the R ₂₁ group, respectively bonded thereto, A saturated or unsaturated, 5- to 14-membered heterocyclic ring may be formed, optionally substituted as indicated above, optionally aromatic, nitrogenous or not nitrogenous, Another heteroatom is optionally included.

  Among the compounds of formula (IIIh) that may be mentioned in particular are the following amines, their enantiomers (if present), their salts as well as their hydrates: gelontin, N -[3-Aminopropyl] -1,4-butanediamine, 1,4-butanediamine, 4- (ethylamino) -N-butylamine, 2- [3- (2-hydroxy-1,1-bis-hydroxy Methylethylamino) propylamino] -2-hydroxymethylpropane-1,3-diol, 1,4,8,11-tetraazacyclotetradecane, 1,4-diazacycloheptane, 1,3-diamino-2- Hydroxypropane, N, N'-bis (2-aminoethyl) propane-1,3-diamine, 3-methylaminopropylamine, 1,3-diaminopropane, N, N'-dimethyltrimethylenediamine, 2,2 -Dimethyltrimethylenediamine, 2,2-dimethyl-1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropa , N- (2-hydroxyethyl) -1,3-diaminopropane, cystamine, 1,5 diaminopentane, 1,6-diaminohexane, rauraminopropylamine, 2-methylheptylamine (2- (N-methyl ) Heptylamine), ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, 3-aminoalanine, piperazine-2-carboxylic acid, β-N-methylaminoalanine, methylpiperazine-2-carboxylate, ethyl 3 -Aminoprolinate, 2,4-diamino-N-butyric acid, N- [3- (trimethoxysilyl) propyl] ethylenediamine, or mixtures thereof.

O Amino compounds of general formula (IIIi) and / or (IIIi '):

[In the general formula (IIIi) and / or (IIIi ′),
-R ₂₃ and R ₂₄ , independently of one another, represent:
* To C ₁ -C ₆ alkyl group (one or more heteroatoms which is optionally substituted, and or at least one oxygen, nitrogen, sulfur, CO, preferably from SO and SO _2, or a combination thereof is selected One or more groups containing 1 heteroatom are optionally interrupted; the alkyl group does not contain any nitro, nitroso, peroxo or diazo functionality);
* Alkylcarbonyl group (R-CO -) (wherein, R represents a C ₁ -C ₄ alkyl group);
* Alkylsulfonyl group (RSO ₂ -) (wherein, R represents a C ₁ -C ₄ alkyl group);
* (Di) (alkyl) aminosulfonyl group _{((R) 2 N-SO} 2 -) ( wherein, R groups are independently hydrogen or C ₁ -C ₄ alkyl group);
* (Di) (alkyl) aminocarbonyl group _{((R) 2 N-CO} 2 -) ( wherein, R groups are independently hydrogen or C ₁ -C ₄ alkyl group);
* A halogen atom, preferably selected from bromine, chlorine and fluorine;
* C ₁ -C ₄ alkoxy groups;
C ₂ -C ₄ (poly) hydroxyalkoxy group;
* Hydroxycarbonyl group (HO-CO-);
* An alkoxycarbonyl group (RO-CO -) (wherein, R represents a C ₁ -C ₄ alkyl group);
* Alkylcarbonylamino group (RCO-NR '-) (wherein, R groups represents a C ₁ -C ₄ alkyl group, a group R' represents a hydrogen atom or a C ₁ -C ₄ alkyl group);
* Alkylsulfonyl group (RSO ₂ -) (wherein, R groups represents C ₁ -C ₄ alkyl group);
-Y represents a carbon or nitrogen atom;
-z, z 'and z'', independently of one another, represent a carbon atom, a nitrogen atom or a nitrogen atom substituted with hydrogen;
-x is an integer between 0 and 2; when x is less than 2, an unsubstituted carbon atom retains a hydrogen atom;
-x is an integer equal to 0 or 1; when x is less than 1, an unsubstituted carbon atom retains a hydrogen atom. ]

  Among the compounds of formula (IIIi) and / or (IIIi ′), mention may be made in particular of the compounds listed below, their enantiomers (if present), and their salts, These hydrates can also be mentioned: α-pyridylamine, 2-amino-3-hydroxypyridine, 2-aminonicotinic acid, 2-amino-3-methylpyridine, 6-methoxy-3-pyridylamine, 3-aminopyridine 3-amino-4-pyridinylamine, 2,5-aminopyridine, γ-pyridylamine, 2,3-dimethylpyridin-4-amine, 4-aminosalicylic acid, methyl para-aminobenzoate, benzocaine, aminobenzoic acid, 4-amino-m-anisic acid, 4-amino-3-hydroxybenzoic acid, methyl 3,4-diaminobenzoate, methyl-4-amino-3-methoxybenzenecarboxylic acid, 2-aminoanisole-4-carboxylic acid 3-amino-4-hydroxybenzoic acid, 3-amino Ethyl benzoate, 1-amino-3-carboxybenzene, methyl 2-aminobenzoate, ethyl anthranilate, 1H-pyrazol-3-ylamine, 3-amino-4-carboethoxy-1H-pyrazole, 5-amino- 1-ethylpyrazole, 1H-benzimidazol-2-amine, 2-imidazolamine, 1-methylbenzimidazol-2-amine, and mixtures thereof.

  The following amines may also be used, which may or may not be in salt form: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, 2-amino -4,5-dimethylthiazole, hexetidine, mecamylamine, tranylcypromine, triamterene, methyl [2- (3-trimethoxysilylpropylamino) ethylamine], bis (triethoxysilylpropyl) amine, N1- (3- (tri Methoxysilyl) propyl) hexane-1,6-diamine, diethylenetriaminopropyltrimethoxysilane, N- (3-triethoxysilylpropyl) ethylenediamine, N- (3-trimethoxysilylethyl) ethylenediamine.

  According to another variant of the invention, the amine is selected from aminopolymers and also from their addition salts. The term “aminopolymer” means a macromolecule with a higher or lower molecular weight, having primary or secondary amine functionality. The term “polymer” means a compound comprising at least 5 repeating units joined in sequence via a covalent bond.

Aminopolymer is
-Via radical reaction (polyacrylate, polymethacrylate, polyvinyl, etc.),
-Via a concentration reaction (polyester, potassium ether, polyamide, polyurethane, polydimethylsiloxane, polypeptide, etc.)
-Via a ring-opening reaction (such as polyester),
It may be synthesized.

  The aminopolymers may be of natural origin and may be optionally chemically modified, such as polysaccharides (cellulose, dextran, chitosan, guar) and their amino or thiol derivatives.

  The polymer may be of any topology: linear, branched, star chain or hyperbranched (eg dendrimer), block chain, random chain or alternating chain.

  The chemical group may be naturally occurring on the polymer chain, grafted to the end of the chain along the main chain or side chain, or on a branch of a star or hyperbranched polymer , May exist naturally.

The following are most particularly preferred:
Polyamino acids having 1 / OH or NH ₂ or SH or COOH radicals, such as polylysine,
2 / natural or modified polysaccharides with NH ₂ or SH functional groups,
3 / amino silicone,
4 / Synthetic polymers with NH ₂ or SH functional groups are, among other things, polyvinyl vinyl substituted with amine functional groups, polymers made with the following commercially available monomers:

And in particular polylysine; chitosan; polyethoxylated amines such as carboxy PEG-8 amine, carboxy PEG-12 amine or carboxy PEG-24 amine; or combinations thereof.

  According to another variant of the invention, the amine is a purine base, in particular adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, their addition salts, and their Selected from the combinations.

  Combining some of these variations does not depart in the context of the present invention.

Preferably, when the composition comprises one or more amines, they are selected from ammonia, especially when R ₂₀ represents a linear C ₁ -C ₄ alkoxy group, formula (IIIa), (IIIb) , (IIIc), (IIIe) and (IIIg) and selected from (IIIi ′) alone or as a mixture.

  When the composition contains one or more primary or secondary amines, ammonia or hydroxylamine, their content in the composition is from 0.001% by weight, based on the weight of the composition. It represents between 65% by weight, preferably between 0.001% and 30% by weight.

Enzymes Compositions according to the present invention include, for example, isolases such as β-glucosidase from sweet almond (EC 3.2.1.21), alcohol oxidase (EC 1.1.3.13), alcohol dehydrogenase EC 1.1.1.1, alcohol dehydrogenase EC 1.1.1.2, Alcohol dehydrogenase EC 1.1.1.71, aromatic alcohol dehydrogenase EC 1.1.1.90 (also known as aryl alcohol dehydrogenase), aromatic alcohol dehydrogenase EC 1.1.1.97, 3-hydroxybenzyl alcohol dehydrogenase EC 1.1.1.97, coniferyl alcohol dehydrogenase EC 1.1.1.194, cinnamyl alcohol dehydrogenase EC 1.1.1.195, methanol dehydrogenase EC 1.1.1.244, aromatic alcohol oxidase EC 1.1.3.7 (also known as aryl alcohol oxidase), alcohol oxidase EC 1.1.3.13, 4-hydroxymandelate oxidase EC 1.1.3.19, hydrocarbon long chain alcohol oxidase EC 1.1.3.20, methanol oxidase EC 1.1.3.31, alcohol dehydrogenase EC 1.1.99.20, methyl glutamate dehydrogenase EC 1.5.99.5, 2- Optionally comprising at least one enzyme selected from oxoacid decarboxylase EC 4.1.1.1, benzoylformate decarboxylase EC 4.1.1.7, phenylpyruvate decarboxylase EC 4.1.1.43 and threonine aldolase EC 4.1.2.5 it can.

  When an enzyme is present, the concentration of enzyme used in the dye composition is between 0.005% and 40% by weight, preferably relative to the weight of the composition, relative to the total weight of the composition. And between 0.05 mass% and 10 mass%.

Salts Compositions comprising compounds of formula (I) and / or (II) may optionally contain one or more salts.

  When present, these salts are generally selected from organic solvents and / or inorganic salts and / or selected from combinations thereof.

  Specifically, the anions forming these salts are inorganic ions (chloride ions, carbonate ions, hydrogen carbonate ions, sulfide ions, hydrogen sulfate ions, silicate ions, phosphate ions, hydrogen phosphate ions. Ions, hydroxide ions, etc.) or organic ions (aspartate, formate, acetate, lactate, citrate, gluconate, succinate, malate, fumarate, orotate, etc.) ) Can be either.

  The cations constituting these salts related to the above anions are alkali metals (preferably lithium, sodium or potassium), alkaline earth metals (preferably magnesium or calcium), or transition metals (scandium, Titanium, vanadium, manganese, molybdenum, iron, cobalt, nickel, copper, zinc, silver or gold). Other cations can form salts, for example ammonium. Preferably, the cation is selected from alkali metals (lithium, sodium or potassium), alkaline earth metals (magnesium or calcium), ammonium, and transition metals: manganese, molybdenum, iron, copper, zinc, silver and gold. become.

  When they are present, their content represents from 0.001% to 40% by weight relative to the weight of the composition, and even more preferentially from 0.001% to 20% relative to the weight of the composition. Between mass%.

Other Materials Cosmetically acceptable media generally include at least water or a mixture of water and at least one organic solvent. Mention may be made, as examples of the organic solvent, C ₁ -C ₄ lower alkanols such as ethanol and isopropanol; polyols such as 1,3-propanediol or 1,6-hexanediol and polyol ethers, such as 2- There are butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

  When they are present, the solvent is preferably in a proportion between 1% and 99% by weight relative to the weight of the composition, and even more preferentially 5% relative to the weight of the composition. Present in a proportion between mass% and 95 mass%.

  The compositions used in the method according to the invention are various adjuvants conventionally used in hair dye compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic. Surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and especially anionic, cationic, Nonionic and amphoteric associative polymer thickeners, antioxidants, penetrants, sequestering agents, fragrances, buffers, dispersants, conditioning agents such as volatile or non-volatile modified or non-modified silicones, For example, you may have amino silicone, a film formation agent, ceramide, antiseptic | preservative, opacifier, and a conductive polymer.

  In the above adjuvants, each adjuvant is generally present in an amount of between 0.01% and 20% by weight relative to the weight of the composition.

  It goes without saying that the person skilled in the art knows this or any of these so that the advantageous properties inherently associated with the dye composition according to the invention are not adversely affected or substantially unaffected by the envisaged addition. The additional compounds of choice will be carefully selected.

  The pH of the composition is generally between about 3 and 14, preferably between about 4 and 11, more preferentially between 6 and 11. The pH may be adjusted to the desired value by acidifying or basifying agents commonly used to dye keratin fibers, and alternatively using standard buffer systems.

  Among the acidifying agents, mention may be made, for example, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.

  Among the basifying agents, mention may be made of aqueous ammonia, the alkali metal carboxylates mentioned above and amines.

  The composition may be in various forms, for example in the form of a liquid, cream or gel, in the form of a powder mixed before use to obtain a poultice, in the form of an infusion, or keratin fibers, in particular hair. It may be in any other form suitable for dyeing.

  The materials of the above composition are advantageously stored separately.

  In particular, a compound of formula (I), or a plant extract containing the same compound (the compound has been or has not been previously degraded); if compound (I) has not been previously degraded In some cases, the enzyme to replace the R group with hydrogen; and the aldehyde or imine compound or the oxidized oligosaccharide or polysaccharide having an aldehyde or imine functional group are stored separately.

  When one or more amine compounds are present, these compounds are also stored separately from compound (I) or from plant extracts containing the same compound, whether or not they are degraded. It should be noted.

  It may also be advantageous to store at least the compound of formula (I), or a degraded or undegraded plant extract containing the same compound in an airtight container.

  The composition used in the method according to the invention may comprise one or more oxidizing agents. In this case it is referred to as a ready-to-use composition.

Oxidizing agent In particular, when an oxidizing agent is present, a ready-to-use composition advantageously advantageously mixes the aforementioned composition with at least one composition comprising one or more oxidizing agents without preparation prior to application. Can be obtained.

  The oxidizing agent is preferably hydrogen peroxide, urea peroxide, alkali metal bromate or ferricyanide, peroxide salts such as persulfates, alkali metal or alkaline earth metal perborates and percarbonates. For example, sodium, potassium and magnesium.

  Further oxidizing agents suitable for use are of the enzyme type, for example 4-electron oxidoreductase (eg laccase), 2-electron redox in the presence of the respective donor or its cofactor where appropriate. Enzymes (eg uricase), and peroxidase.

  It is particularly preferred to use hydrogen peroxide.

  This oxidant is advantageously formed by hydrogen peroxide in an aqueous solution (aqueous hydrogen peroxide solution), the titer of which is more particularly 1 to 40 volumes, more preferentially 5 to 40 volumes. May be the range.

  Thus, it should be noted that the composition used in the present invention can be produced by mixing several compositions without preparation.

  The composition described so far is applied in this way to human keratin fibres, in particular to the hair.

Dyeing Method According to the first embodiment, the applied composition does not contain any oxidizing agent.

  In this case, the material (compound of formula (I), or a decomposed or undegraded extract; an enzyme, aldehyde or imine compound, or an aldehyde or Oxidized oligosaccharides or polysaccharides having imine functional groups) are stored separately.

  This embodiment is particularly suitable in cases where the composition does not contain an oxidative dye (base or coupler).

  According to the second embodiment, the ready-to-use composition, which has been described in detail up to this point and obtained by mixing without preparation prior to application, has been described as not containing an oxidizing agent in the oxidizing composition, Applied to fiber.

  This embodiment is particularly suitable in cases where the composition comprises one or more oxidative dyes (base or coupler) or when it is desired to obtain a lightening effect.

  According to a second variant of this embodiment, a composition that does not contain an oxidizing agent and an oxidizing composition is successfully applied without intermediate rinsing.

  The oxidizing composition used comprises one or more oxidizing agents as defined above.

  With respect to the organic solvents that may be present in the oxidizing composition, reference may be made to the list given earlier in connection with the description of the composition according to the invention.

  Usually, the pH of the oxidizing composition is less than 7.

  The oxidizing composition may take the form of a solution, emulsion or gel.

  It can optionally include one or more additives conventionally used in the field of dyeing human keratin fibers as a function of the desired herbal form. Here again, reference can be made to the list of additives given above.

  Regardless of the selected embodiment (with or without oxidant, whether the composition and oxidant are mixed without preparation or applied continuously), the mixture applied to the fiber is Generally, it is left for about 1 minute to 5 hours, preferably 10 minutes to 3 hours.

  With respect to the temperature at which the composition is applied, it is between 20 and 200 ° C., preferably between 20 and 55 ° C.

  This operation can therefore be carried out using, for example, a heated hood, an infrared lamp or a straightening or curling iron.

  The method according to the invention can advantageously be carried out in the presence of a light stimulus.

This is more particularly because keratin fibers treated in this way have UVA irradiation (specifically, the irradiance emitted by a continuous spectrum lamp or a line spectrum lamp is between 0.01 and 0.40 milliwatts / cm ² , Preferably between 0.1 and 0.2 milliwatts / cm ² ) and / or UVB irradiation (specifically, the irradiance emitted by a continuous or linear spectral lamp is 0.01 to 0.20 milliwatts / cm ² And preferably between 0.01 and 0.1 milliwatt / cm ² .

  Preferably, these compounds are alkali metals, alkaline earth metals, or ammonium, carboxylates, bicarbonates, chlorides, sulfates, silicates, monobasic phosphates or acetates.

  According to one preferred variant of the invention, this irritation occurs in a cosmetically acceptable medium in lithium, sodium, potassium, calcium carbonate or ammonium carbonate; sodium hydrogen carbonate or potassium hydrogen carbonate; calcium chloride, lithium chloride. Or sodium chloride; ammonium sulfate, sodium sulfate or magnesium sulfate; sodium silicate; monobasic sodium phosphate or monobasic potassium phosphate; and a composition containing at least one salt selected from sodium acetate.

  The composition advantageously has a salt content in the range of 0.001% to 40% by weight relative to the weight of the composition, even more preferentially 0.001% by weight relative to the weight of the composition. With a content between% and 20% by weight.

  It is not deviating in the context of the present invention to carry out several successive steps combining different stimuli.

  After the standing time, the keratin fibers may be rinsed with water, optionally washed with shampoo, rinsed with water, dried or left to dry.

  Another subject of the invention consists of a multi-compartment device, said device comprising a first compartment containing at least one compound of formula (I), or a plant extract containing said compound, said compound comprising: An oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group A second compartment containing:

  Another subject also consists of a multi-compartment device, said device comprising a first compartment containing at least one compound of formula (I), or a botanical extract comprising said compound; and formula (i) or A second agent comprising at least one compound of (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine functional group, and an enzyme for replacing the R group of formula (I) with a hydrogen atom. Has two compartments.

  Finally, the final subject matter of the invention is represented by a multi-compartment device, which device comprises a first compartment containing at least one compound of formula (I), or a plant extract containing the same compound. And a second compartment containing an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group; and of formula (I) A third compartment containing an enzyme for replacing the R group with a hydrogen atom is provided.

  Preferably, the decomposed or undecomposed compound of formula (I) is stored, advantageously under an inert atmosphere, so as to protect it from the air.

  The device can optionally include additional compartments containing one or more amines, or one or more salts.

  The following examples illustrate it without limiting the scope of the invention.

  The extract of Gardenia jasminoides enriched to some extent in geniposide is first dissolved in the presence of β-glucosidase. Genipin from this extract is then separated by crystallization by 100 kD ultrafiltration. The extract thus obtained is enriched 99% in genipin.

Gardenia jasminoides extract 5 × 10 ^-3 mol% enriched in genipin 99% in aqueous solution buffered to pH 9 by treatment with sonicator for 30 minutes, and vanillin 5 × 10 ^-3 mol % Or 25 × 10 ⁻³ mol% is dissolved to obtain a dye composition.

  Each composition is applied to natural gray hair with 90% gray hair (1 g of hair bundles per 2 g of solution) and the hair bundles are placed under different application conditions (hot plate, see table below) .

  The hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

Degraded Gardenia jasminoides extract 5 × 10 ⁻³ mol% enriched in genipin in a solution buffered to pH 9 by treatment for 30 minutes with sonicator, and oxidized starch 2.5 The dye composition is obtained by dissolving ^10-2 mol%.

  The composition is applied to natural gray hair with 90% gray hair (1 g of hair bundle per 2 g of solution) and left at 100 ° C. (hot plate) for 5 minutes.

  After this time to leave on, the hair bundle is rinsed, washed with a shampoo and dried with a hair dryer.

  A green-black coloration is obtained.

Degraded Gardenia jasminoides extract 5 x 10 ^-3 mol% enriched in genipin 99% in solution buffered to pH 9 by treatment with sonicator for 30 min, and vanillin 10 x 10 ⁻³ mol% is dissolved in the presence of a salt or amine to obtain a dye composition.

  Each composition is applied to natural gray hair with 90% gray hair (bath ratio (BR): 1 g of hair bundle per 10 g of solution) and the hair bundle is placed under cellophane at 40 ° C. for 2 hours.

  Each hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

Aqueous solution (79% by weight) buffered to benzoic acid (1% by weight), benzyl alcohol (5% by weight), ethanol (15% by weight), and pH 9 by treatment in a sonicator for 30 minutes in a medium containing, was 93% enriched in genipin, Gardenia jasminoides extract 5 × 10 ^-3 mol% being decomposed, by dissolving the materials 10 × 10 ^-3 mol%, to obtain a dye composition .

  Each composition is applied to a natural gray hair bundle in which 90% is gray hair (bath ratio (BR): 1 g of hair bundle per 10 g of solution) and the hair bundle is placed under cellophane for 30 minutes at 50 ° C. .

  The hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

Degraded Gardenia jasminoides extract 5 x 10 ^-3 mol% enriched in 99% genipin in aqueous solution buffered to pH 9 by treatment with sonicator for 30 minutes, and vanillin 10 × 10 ⁻³ mol% is dissolved in the presence of a salt (saturated solution) to obtain a dye composition.

  Each composition is applied to natural and / or permanent waved gray hair, 90% gray (bath ratio (BR): 1 g of hair bundle per 5 g of solution), And put under cellophane for 2 hours.

  The hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

In a medium containing an aqueous solution (79% by weight) buffered to 1% by weight of benzoic acid, 5% by weight of benzyl alcohol, 15% by weight of ethanol, and pH 9 by treatment in a sonicator for 30 minutes, was 93% enriched in genipin, Gardenia jasminoides extract 5 × 10 ^-3 mol% being decomposed, by dissolving the materials 10 × 10 ^-3 mol%, to obtain a dye composition.

  Each composition is applied to a natural gray hair bundle in which 90% is gray hair (bath ratio (BR): 1 g of hair bundle per 10 g of solution) and the hair bundle is placed under cellophane for 30 minutes at 50 ° C. .

  The hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

By treatment in a sonicator for 20 minutes, at (added KHCO ₃₎ an aqueous solution of pH 8, was 93% enriched in genipin, Gardenia jasminoides extract 1.13 g% being decomposed, and vanillin Dissolve (1.56 g% if present) to obtain each dye composition.

  Each composition is applied to a natural gray hair bundle that is 90% gray hair (1 g of hair bundle per 5 g of solution) and the hair bundle is placed at 30 ° C. for 60 minutes (hot plate).

  The hair bundle is then rinsed, washed with shampoo and dried with a hair dryer.

  The result is as follows:

  From the above results, it is clear that the color is more intense with vanillin.

Preparation of imine type compound Vanillin (0.4g%) is reacted with 3-aminopropanol (0.2g%) in water (5ml) / ethanol (1ml) mixture in the presence of acetic acid for 30 minutes at room temperature To prepare the imine.

  The resulting imine is then added to 1.13 g% of degraded Gardenia jasminoides extract enriched 93% in genepin plus vanillin (1.56 g% if present).

The pH of the composition is then adjusted to 8 by addition of KHCO ₃ and then placed in a sonicator for 20 minutes.

  The composition is applied to a natural gray tress that is 90% gray hair (1 gram of tress per 6 g of solution) and the tress is placed at 40 ° C. for 60 minutes (hot plate).

  The color of the hair is dark green blue.

Degraded Gardenia jasminoides extract 1.13 g% enriched in genipin and oxidized inulin (1.13 g%) in an aqueous solution at pH 8 (with KHCO ₃ addition) in a sonicator Each dye composition is obtained by dissolving for 20 minutes.

  Each composition is applied to a natural gray hair bundle which is 90% gray hair (1 g of hair bundle per 5 g of solution) and the hair bundle is placed for 60 minutes at 40 ° C. (hot plate).

  The hair is colored golden yellow.

Claims (15)

* The following compounds of the iridoid family of formula (I), optical or geometric isomers thereof, inorganic or organic acid salts thereof, solvates thereof, or plant extracts containing the same compounds:

[Where
R ₁ is a hydroxymethyl group, -CO ₂ R ₄ group (wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl group); a sugar group;
R ₂ represents a hydrogen atom, a hydroxyl group or a sugar group;
R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl group, a (C ₁ -C ₄ ) alkoxy group; the number of hydroxyl groups does not exceed 2;
R represents a sugar group;
N is an integer between 1 and 5;
Sugar groups are obtained from aldoses or aldose derivatives:
The compound of formula (I) has undergone a step of replacing the R group with a hydrogen atom prior to or simultaneously with the dyeing step];
** At least one aldehyde or imine compound selected from the following formulas (i) and (ii), optical or geometric isomers thereof, organic acid salts or inorganic acid salts thereof, solvates thereof, and further, at least one Oxidized oligosaccharides or polysaccharides containing two aldehyde or imine functional groups:

[In the formulas (i) and (ii),
M is an integer equal to 0 or 1,
· X represents an oxygen _{atom, NR '' 1 (R '} ' 1 represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group) represents;
When X represents an oxygen atom, the compound is:
'In ₍₃ OH (wherein, R 〇 additional primary monoalcohol R)' ₃ is C ₁ -C ₅ alkyl or C ₂ -C ₃ symmetry containing alkyl chain 1,2- or 1,3 In the form of a 5- or 6-membered cyclic or acyclic acetal produced from the condensation of
If A or A ₁ represents an alkyl group and n is equal to 0, it may be in the form of a hemiacetal formed from the condensation of hydroxyl groups present in A or A ₁ ;
R ′ ₁ group and R ′ ₂ group independently of each other represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl group;
The monovalent group A and the divalent group A ₁ represent a group selected from the following groups:
* Hydroxycarbonyl group (-CO-OH):
* C ₆ aryl group optionally substituted with at least the following groups:
-Hydroxyl group,
- C ₁ -C ₄ alkyl group,
An aryl-ethylenyl group (the aryl group is C ₆ and is optionally substituted with at least one C ₁ -C ₂ alkyl group or C ₁ -C ₂ alkoxy group),
- -CO-OR _'4 group or -O-COR' ₄ group (wherein, R _'4 represents a C ₁ -C ₂ alkyl group or a phenyl group);
-COOH groups, in acid form or in salified form,
- -OR _'5 group {R' ₅ is at least one C ₁ -C ₈ alkyl group which is optionally substituted with hydroxyl group, an ammonium group _{^{-N + R '' 6 (R}} '' 6 are identical may be differ also represent C ₁ -C ₂ alkyl group), - SiR _'7 group (R' _7, which may be independently identical or different, C ₁ -C ₂ alkyl group Represents a benzyl group (—CH ₂ —C ₆ H ₆ )},
-According to one particular variant, two --OR ' ₅ groups that are ortho to the C ₆ aryl group form a 5-membered or 6-membered heterocycle with two R' ₅ groups Often,
--N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and is optionally substituted with a C ₁ -C ₆ alkyl group, acid form optionally substituted with a hydroxyl group or carboxylic acid groups in the salified form (-COOH), or an acid form or sulfone groups in the chloride form _{(-SO 3 H); R '} 8 group, together with the nitrogen atom carrying them, It may form a saturated or unsaturated 5- or 6-membered heterocycle, optionally O, N and NR ′ ₉ (where R ′ ₉ represents a C ₁ -C ₂ alkyl group) Optionally containing another heteroatom selected from: the heterocycle is optionally substituted with a hydroxyl group},
--COR ′ ₁₀ group, wherein R ′ ₁₀ represents a C ₆ aryl group fused to a 6-membered hydrocarbon ring optionally substituted with at least one C ₁ -C ₂ alkyl group ),
- -SR _'11 (wherein, R' ₁₁ represents a C ₁ -C ₂ alkyl group),
A halogen atom, preferably selected from chlorine and bromine,
--O-SO ₂ -C ₆ H ₆ group _,
--SO ₃ H group,
- O, 'of ₁₂ (wherein, R' N and NR ₁₂ is a saturated or unsaturated, aromatic or non-aromatic, 5-membered or C ₁ fused optionally in 6-membered rings -C ₂ An unsaturated cationic or non-cationic 5-membered or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from the group (wherein the alkyl group represents one). may be contained in the heterocyclic or fused ring may optionally be possibly substituted with at least one C ₁ -C ₂ alkoxy group, a heterocyclic ring,
The aryl group is optionally fused to a 5 or 6 membered heterocyclic group, O, N and NR ′ _{13 where} R ′ ₁₃ represents a C ₁ -C ₄ alkyl group; Comprising 1 or 2 heteroatoms selected from wherein the heterocycle is optionally fused to a C ₆ aryl group;
- said aryl group is fused optionally in C ₆ aryl group which is optionally substituted with at least one C ₁ -C ₂ alkoxy group;
* O, N and NR ′ ₁₄ (R ′ ₁₄ is a hydrogen atom, a C _{1 to} C ₆ alkyl group or (R ′ ₁₅ ) ₂ NCO- or (R ′ ₁₅ ) CO—NH— (where R ′ ₁₅ May be the same or different and represents a C ₁ -C ₂ alkyl group) and optionally represents a C ₆ aryl group} selected from one or the same Or a cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic, 5- or 6-membered heterocyclic group containing two different heteroatoms;
- the heterocyclic group is itself is fused optionally at least one C ₁ -C ₂ alkyl, the 6-membered aryl group which is optionally substituted with C ₁ -C ₄ alkoxy or phenoxy group;
-The heterocyclic group is optionally substituted with at least the following groups:
〇 hydroxyl group,
C ₁ -C ₂ alkyl group which is optionally substituted with 〇 hydroxyl group;
Amino group -N (R _{'16) 2} {wherein, R' 〇 _16, which may be the same or different and represent C ₁ -C ₄ alkyl group optionally substituted with a hydroxyl group , R ′ ₁₆ , together with the nitrogen atom holding them, optionally another heterogeneous selected from O, N and NR ′ _{17 where} R ′ ₁₇ represents a C ₁ -C ₂ alkyl group May form a saturated or unsaturated 5- or 6-membered heterocycle optionally containing atoms},
A C ₆ aryl group optionally substituted with at least one —COOH group, R ′ ₁₈ CONH-group (R ′ ₁₈ represents a C ₁ -C ₂ alkyl group), are bonded optionally a nitrogen atom, when the aryl group is not substituted with the groups described above, the carbon atoms is substituted with a hydrogen atom, C ₆ aryl group;
* One or more conjugated or non-conjugated carbon - carbon double bond, a linear or branched C ₁ of -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group, at least one hydroxyl group optionally substituted with, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group in;
The divalent group A ₂ represents a linear C ₁ -C ₁₀ alkylene chain bonded to _two groups A ₁ via a carbon, oxygen or nitrogen atom]
In a cosmetically acceptable medium,
Where appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion, or a mixture of anions An that ensures the electrical neutrality of the formulation.
A method for dyeing human keratin fibers, wherein the composition is applied.   Plant extracts are derived from the following plants: Abelia grandiflora, Adenorandia kalbreyeri, Adina polycephala, Aeginetia indica var. , Canthium schimperianum, Castilleja wightii, Chaenorhinum minus, Clerodendrum serratum, Coprosma sp, Cornus officinalis, Craibiodendron henryi, Cremaspora triflora, Crucianella sp, Daphniphyllum calycinum, Daphniphyllum humile humifusum, Galium verum, Gardenia jasminoides, Garrya elliptica, Globulularia dumulosa, Hedyotis corymbosa, Hygrophila difformis, Ixeris chinensis, Lamiastrum galeobdolon (Lamium galeobdolon), Lamiophlomis rotata, Phlomisono rotata (Phlomisono rotata) cilicia, Nepeta nuda ssp., Alb iflora, Odeontites verna, Oldenlandia corymbosa, Paederia scandens, Pedicularis chinensis, Pedicularis condensata, Pedicularis dolichocymba, Penstemon confertus, Penstemon deutus, Penstemon richardsonii, Penstemon serrulatus, Pithecrumen Premna barbata, Randia dumetorum, Rhododendron latoucheae, Rothmannia withfieldii, Rubia peregrina, Rubia tinctorum, Saprosma scortechinii, Scrophularia korainensis, Scrophularia lepidota, Scrophularia ningpoensis, Scyphiphora hydrophyllacea, Swida controversa, Syringa vulgaris, Tarenna kotoensis, Tecoma heptaphylla, Thevetia gaumeri, Thevetia peruviana , Verbascum laxum, Verbascum nigrum, Verbascum phlomoides, Verbascum salviifolium, Verbascum sinuatum, Verbascum thapsus, Verbascum undulatum, Veronica derwentiana, Vitex nigrum, Wendlandia formosana, preferably Gardenia jasminoides, claim Item 2. The method according to Item 1.   The method according to claim 1 or 2, wherein the content of the compound of formula (I) in the composition is between 0.001% by mass and 10% by mass with respect to the mass of the composition.   The method according to any one of claims 1 to 3, wherein the compound of the formula (i) or (ii) is a compound in which X represents an oxygen atom. The compound is a compound of formula (i),
* n is 0 or 1;
* Groups R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl group;
* X represents an oxygen atom;
A represents the following:
* At least one C ₅ -C ₁₀ alkyl group linear optionally substituted with a hydroxyl group or branched;
* Carbon - C ₂ -C ₈ alkenyl group containing a carbon double bond;
* Hydroxycarbonyl group (-COOH);
* C ₆ aryl group optionally substituted with at least the following groups:
-Hydroxyl group,
- C ₁ -C ₄ alkyl group,
- -CO-OR _'4 group or -O-COR' ₄ group (wherein, R _'4 represents a C ₁ -C ₂ alkyl group),
- -OR _'5 group (wherein, R' ₅ represents a C ₁ -C ₆ alkyl group),
An aryl-ethylenyl group (the aryl group is C ₆ and is optionally substituted with at least one C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy group),
- O, 'of ₁₂ (wherein, R' N and NR ₁₂ is a saturated or unsaturated, aromatic or non-aromatic, 5-membered or C ₁ fused optionally in 6-membered rings -C ₂ An unsaturated cationic or non-cationic 5-membered or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from (which represents an alkyl group), one of the heteroatoms being may be included in the two rings; heterocyclic rings or fused rings are substituted with at least one C ₁ -C ₂ alkoxy group, a heterocyclic ring,
The aryl group is optionally fused to a 5- or 6-membered heterocyclic group, O, N and NR ′ _{13 wherein} R ′ ₁₃ represents a C ₁ -C ₄ alkyl group; Containing 1 or 2 heteroatoms selected from;
* O, N and NR ′ ₁₄ (R ′ ₁₄ is a hydrogen atom, a C ₁ -C ₆ alkyl group or a (R ′ ₁₅ ) ₂ NCO-group or a (R ′ ₁₅ ) CO-NH- group (where R _'15, preferably from representing a C ₆ aryl group which is optionally substituted with representing the C ₁ -C ₂ alkyl group)} is selected, the one, or the same or different two hetero atoms Including a cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic, 5- or 6-membered heterocyclic group;
- the heterocyclic group may itself is fused optionally to at least one C ₁ -C ₂ alkyl or C ₁ -C ₄ aryl group having 6 membered optionally substituted with an alkoxy group;
-The heterocyclic group is optionally substituted with at least the following groups:
〇 hydroxyl group,
C ₁ -C ₂ alkyl group which is optionally substituted with 〇 hydroxyl groups,
Amino group -N (R _{'16) 2} {wherein, R' 〇 _16, which may be the same or different and represent C ₁ -C ₄ alkyl group optionally substituted with a hydroxyl group The group R ′ ₁₆ can optionally be another heteroatom selected from O, N, and NR ′ ₁₇ (where R ′ ₁₇ represents a C ₁ -C ₂ alkyl group), together with the nitrogen atom that holds them. May optionally form a saturated or unsaturated, 5- or 6-membered heterocyclic ring},
* Where appropriate, the compound of formula (i) comprises a cosmetically acceptable anion, or a mixture of anions An that ensures the electrical neutrality of the formulation,
* The compound of formula (i) may be in the form of an acetal or hemiacetal,
5. A method according to any one of claims 1 to 4.   The content of the compound of formula (i) or (ii), or the oxidized oligosaccharide or polysaccharide containing at least one aldehyde or imine functional group, is 0.001% to 30% by weight relative to the weight of the composition 6. The method according to any one of claims 1 to 5, wherein the method is between. * Chloride ion, carbonate ion, bicarbonate ion, sulfide ion, hydrogen sulfide ion, silicate ion, phosphate ion, hydrogen phosphate ion, hydroxide ion, aspartate ion, formate ion, acetate ion, lactic acid Organic anions selected from ions, citrate ions, gluconate ions, succinate ions, malate ions, fumarate ions, orotic acid ions,
* 1 type selected from alkali metals, alkaline earth metals, transition metals such as scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold, or a combination of ammonium 7. The method according to any one of claims 1 to 6, comprising a plurality of organic or inorganic salts.   The salt content is in the range of 0.001% to 40% by weight relative to the weight of the composition, and even more preferentially in the range of 0.001% to 20% by weight relative to the weight of the composition. The method according to any one of claims 1 to 7, wherein:   9. The method according to any one of claims 1 to 8, wherein the step of replacing the group R with a hydrogen atom is carried out using an enzyme selected from isolase and β-glucosidase (EC 3.2.1.21).   10. A method according to any one of claims 1 to 9, wherein a temperature between 30 and 200 <0> C is applied. UVA radiation, irradiance between 0.01 and in particular 0.40 milliwatts / cm ^2, and / or UVB radiation, against which the irradiance between 0.01 and 0.20 milliwatts / cm ² in particular, of claims 1 to 10 The method according to any one of the above.   First compartment containing at least one compound of formula (I) or a plant extract comprising said compound according to claim 1 and 2, which has undergone a first step of replacing the R group with a hydrogen atom And an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group according to any one of claims 1, 4 and 5. A multi-compartment device comprising a second compartment containing:   A first compartment containing at least one compound of formula (I) according to claim 1 or 2, or a botanical extract comprising said compound, and any one of claims 1, 4 and 5. At least one compound of formula (i) or (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine functional group, and of formula (I) according to claim 9 A multi-compartment device comprising a second compartment containing an enzyme for replacing the R group with a hydrogen atom.   A first compartment containing at least one compound of formula (I), or a plant extract containing said compound, as defined in claims 1 and 2, and at least one of formula (i) or (ii) A second compartment containing one compound, an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine functional group according to any one of claims 1, 4 and 5, and claim 9 A multi-compartment device comprising a third compartment containing an enzyme for replacing the R group of formula (I) with a hydrogen atom as described in 1 above. * Botanical extracts containing compounds of the iridoid family of formula (I), optical or geometric isomers thereof, inorganic or organic acid salts thereof, solvates thereof or compositions thereof:

[Where
R ₁ is a hydroxymethyl group, -CO ₂ R ₄ group (wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl group); a sugar group;
R ₂ represents a hydrogen atom, a hydroxyl group or a sugar group;
R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl group, a (C ₁ -C ₄ ) alkoxy group; the number of hydroxyl groups does not exceed 2;
R represents a sugar group;
N is an integer between 1 and 5;
The sugar group is obtained from an aldose or aldose derivative;
The compound of formula (I) is optionally subjected to a preliminary step performed by the enzyme to replace the R group with a hydrogen atom];
** At least one aldehyde or imine compound selected from the following formulas (i) and (ii), optical or geometric isomers thereof, organic acid salts or inorganic acid salts thereof, solvates thereof, and at least one more Oxidized oligosaccharides or polysaccharides containing aldehyde or imine functional groups:

[In the formulas (i) and (ii),
M is an integer equal to 0 or 1,
· X represents an oxygen _{atom, NR '' 1 (R '} ' 1 represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group) represents;
When X represents an oxygen atom, the compound is:
An additional primary monoalcohol (R ′ ₃ OH), wherein R ′ ₃ is a symmetric 1,2- or 1, having a C ₁ -C ₅ alkyl group, or a C ₂ -C ₃ alkyl chain It may be in the form of a 5- or 6-membered cyclic or acyclic acetal produced from the condensation of 3-
O If A or A ₁ represents an alkyl group and n is equal to 0, it may be in the form of a hemiacetal produced from condensation of the hydroxyl group present in A or A ₁ ;
R ′ ₁ group and R ′ ₂ group independently of each other represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl group;
The monovalent group A and the divalent group A ₁ represent a group selected from the following groups:
* Hydroxycarbonyl group (-CO-OH):
* C ₆ aryl group optionally substituted with at least the following groups:
-Hydroxyl group,
- C ₁ -C ₄ alkyl group,
An aryl-ethylenyl group (the aryl group is C ₆ and is optionally substituted with at least one C ₁ -C ₂ alkyl group or C ₁ -C ₂ alkoxy group),
- -CO-OR _'4 group or -O-COR' ₄ (wherein, R _'4 represents a C ₁ -C ₂ alkyl group or a phenyl group);
-COOH groups in acid or salified form,
- -OR'5 group (wherein, R _'5 represents a C ₁ -C ₈ alkyl group which is optionally substituted with at least one hydroxyl group), an ammonium group -N ⁺ R'_'6 (R '' _6, which may be the same or different and represent a C ₁ -C ₂ alkyl group), - SiR _'7 group (R' _7, which may be identical or different, C ₁ -C represents ₂ alkyl group); a benzyl group _{(-CH 2 -C 6 H 6)} ,
-According to one particular variant, two --OR ' ₅ groups that are ortho to the C ₆ aryl group may form a 5- or 6-membered heterocycle with the two R' ₅ groups. Often,
--N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and is optionally substituted with a C ₁ -C ₆ alkyl group, acid form optionally substituted with a hydroxyl group or carboxylic acid groups in the salified form (-COOH), or an acid form or sulfone groups in the chloride form _{(-SO 3 H); R '} 8 group, together with the nitrogen atom carrying them, Saturated or unsaturated, 5- or 6-membered optionally containing another heteroatom selected from O, N and NR ′ _{9 wherein} R ′ ₉ represents a C ₁ -C ₂ alkyl group A heterocycle may be formed; the heterocycle is optionally substituted with a hydroxyl group},
--COR ′ ₁₀ group, wherein R ′ ₁₀ represents a C ₆ aryl group fused to a 6-membered hydrocarbon ring optionally substituted with at least one C ₁ -C ₂ alkyl group ),
- -SR _'11 (wherein, R' ₁₁ represents a C ₁ -C ₂ alkyl group),
A halogen atom, preferably selected from chlorine and bromine,
--O-SO ₂ -C ₆ H ₆ group _,
--SO ₃ H group,
- O, 'of ₁₂ (wherein, R' N and NR ₁₂ is a saturated or unsaturated, aromatic or non-aromatic, C ₁ -C ₂ are fused optionally 5-membered or 6-membered ring An unsaturated cationic or non-cationic 5-membered or 6-membered heterocyclic ring containing 1 or 2 heteroatoms selected from (which represents an alkyl group), one of the heteroatoms being 2 one of may be included in a ring; heterocyclic or fused ring is substituted with at least one C ₁ -C ₂ alkoxy group, a heterocyclic ring,
The aryl group comprises 1 or 2 heteroatoms selected from O, N and NR ′ ₃ (wherein R ′ ₁₃ represents a C ₁ -C ₄ alkyl group), 5-membered or 6-membered Optionally fused to a heterocyclic group, wherein the heterocyclic ring is optionally fused to a C ₆ aryl group,
- said aryl group is fused optionally in C ₆ aryl group which is optionally substituted with at least one C ₁ -C ₂ alkoxy group;
* O, N and NR ′ ₁₄ (R ′ ₁₄ is a hydrogen atom, or (R ′ ₁₅ ) ₂ NCO-group or (R ′ ₁₅ ) CO-NH- group (wherein R ′ ₁₅ is the same 1 or 2 preferably selected from a C ₁ -C ₆ alkyl group or a C ₆ aryl group optionally substituted with a C ₁ -C ₂ alkyl group optionally substituted) A cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic, 5- or 6-membered heterocycle containing the same or different heteroatoms;
- the heterocyclic group may itself be fused with optionally at least one C ₁ -C ₂ alkyl, aryl group having 6 membered optionally substituted with C ₁ -C ₄ alkoxy or phenoxy group Cage;
-The heterocyclic group is optionally substituted with at least the following groups:
〇 hydroxyl group,
C ₁ -C ₂ alkyl group which is optionally substituted with 〇 hydroxyl groups,
Amino group -N (R _{'16) 2} {wherein, R' 〇 _16, which may be the same or different and represent C ₁ -C ₄ alkyl group optionally substituted with a hydroxyl group , R ′ ₁₆ group, together with the nitrogen atom holding them, any other heteroatom selected from O, N and NR ′ ₁₇ (wherein R ′ ₁₇ represents a C ₁ -C ₂ alkyl group) May optionally form a saturated or unsaturated, 5- or 6-membered heterocyclic ring},
A C ₆ aryl group optionally substituted with at least one —COOH group, R ′ ₁₈ CONH-group (R ′ ₁₈ represents a C ₁ -C ₂ alkyl group), Optionally bonded to a nitrogen atom,
When the aryl group is not substituted with the aforementioned groups, the carbon atom is substituted with a hydrogen atom, a C ₆ aryl group;
* One or more conjugated or non-conjugated carbon - carbon double bond, a linear or branched C ₁ of -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group, at least one hydroxyl group C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl group substituted in optionally;
The divalent group A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two groups A ₁ via a carbon, oxygen or nitrogen atom]
In a cosmetically acceptable medium,
The compounds of formulas (i) and (ii) comprise, where appropriate, a cosmetically acceptable anion, or a mixture of anions An that ensures the electrical neutrality of the formulation.
A composition for dyeing human keratin fibers.