KR102071728B1 - Dye composition comprising a glycosyl iridoid compound and a particular aldehyde or imine, dyeing process and devices therefor - Google Patents

Abstract

(식 중, R₁: 수소, 메틸, 히드록시메틸, 알데히드; -CO₂R₄ (여기서, R₄: 수소, C₁-C₂ 알킬); 당; R₂: 수소 원자, 히드록실 라디칼, 당 라디칼; R₃: 수소, 히드록실, 알킬옥시; R: 당 라디칼 (알도오스 또는 유도체); 정수 범위 1 내지 5; 식 (I) 의 화합물(들) 은 임의로는 효소를 사용해 수행되는, 라디칼 R 을 수소 원자로 대체시키는 것으로 이루어진 예비 단계를 겪음);
** 화학식 (i) 및 (ii) 의 하나 이상의 알데히드 또는 이민 화합물, 및 또한 하나 이상의 알데히드 또는 이민 관능기를 포함하는 산화 올리고당 또는 다당류:

(식 중, n 은 0 또는 1; X: O, NR'₁; A: COOH, 임의로 치환된 아릴, 1 또는 2 개의 헤테로원자를 포함하는 양이온성 또는 비양이온성, 포화 또는 불포화 5- 또는 6-원 헤테로사이클, 알킬, 알케닐 (임의로 치환됨); A₂: 2가 알킬렌; 알데히드의 경우, 상기 화합물은 아세탈 또는 헤미아세탈 형태일 수 있음).
본 발명은 또한 상기와 같은 조성물 및 또한 다구획 장치를 사용하는 방법에 관한 것이다.The present invention relates to a composition for human keratinous fiber, comprising in a cosmetically acceptable medium:
Iridoid family compounds of the following formula (I), or a plant extract comprising the above:

Wherein R ₁ : hydrogen, methyl, hydroxymethyl, aldehyde; -CO ₂ R ₄ (where R ₄ : hydrogen, C ₁ -C ₂ alkyl); sugar; R ₂ : hydrogen atom, hydroxyl radical, Sugar radicals; R ₃ : hydrogen, hydroxyl, alkyloxy; R: sugar radicals (aldoses or derivatives); integer range 1 to 5; compound (s) of formula (I) are radicals, optionally carried out using enzymes Undergoing a preliminary step consisting of replacing R with a hydrogen atom;
** Oxidized oligosaccharides or polysaccharides comprising at least one aldehyde or imine compound of formulas (i) and (ii), and also at least one aldehyde or imine function:

Wherein n is 0 or 1; X: O, NR '₁; A: COOH, optionally substituted aryl, cationic or noncationic, saturated or unsaturated 5- or 6 comprising 1 or 2 heteroatoms -Membered heterocycle, alkyl, alkenyl (optionally substituted); A ₂ : divalent alkylene; for aldehydes, the compound may be in acetal or hemiacetal form).
The invention also relates to such compositions and also methods of using multicompartment devices.

Description

DYE COMPOSITION COMPRISING A GLYCOSYL IRIDOID COMPOUND AND A PARTICULAR ALDEHYDE OR IMINE, DYEING PROCESS AND DEVICES THEREFOR

The present invention relates to a dye composition comprising, in a cosmetically acceptable medium, at least one compound of the glycosyl iridoid family extracted from a plant (optionally deglycosylated), and at least one specific aldehyde or imine compound, and It also relates to a dyeing method using such a composition.

There is an increasing interest in natural compounds that can be used as hair dyes in recent years.

For example, patent application EP 440 494 includes Rubiaceae, Euphorbiaceae, Valalerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, One of (seco) iridoid-glycoside or non-glycosyl (seco) iridoid (also known as aglycone), extracted from plants such as Ericaceae, Loganiaceae, etc. A hair dyeing method using the composition containing the above compound is disclosed.

The problem with such coloring is that they are not particularly strong or require repeated application of the compositions over days or weeks in order to obtain satisfactory coloring.

Furthermore, it is difficult to achieve a natural tone, which is the desired advantage. Moreover, it is not unusual for significant color changes to be observed over time when such hue is achieved.

It is therefore an object of the present invention to overcome the disadvantages described above.

In particular, surprisingly, by combining the compound with a particular aldehyde or imine compound, the color build-up is used with a compound of the aglycosyl iridoid type and its derivatives and generally any natural extracts containing the above, It has been found that it can be substantially improved.

It was also confirmed that the structure of the treated fibers was not damaged by the coloring according to the invention.

Accordingly, one subject of the present invention is a composition for dyeing human keratin fibers comprising, in a cosmetically acceptable medium:

Iridoid family compounds of formula (I) , optical or geometrical isomers thereof, inorganic or organic acid salts thereof, solvates thereof, or plant extracts comprising the following:

[In meals:

R ₁ represents a hydroxymethyl radical, a group —CO ₂ R ₄ , wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; Represents sugar radicals;

R ₂ represents a hydrogen atom, a hydroxyl radical or a sugar radical;

R ₃ , which may be the same or different, represents a hydrogen atom, a hydroxyl radical, a (C ₁ -C ₄ ) alkyloxy radical; The number of hydroxyl groups does not exceed 2;

R represents a sugar radical;

N is an integer from 1 to 5;

Sugar radicals are derivatives obtained from aldose or aldose derivatives:

The compound (s) of formula (I) undergo a preliminary step consisting in replacing the radicals R with hydrogen atoms, optionally carried out by enzymes;

** Oxidized oligosaccharides comprising at least one aldehyde or imine compound selected from formulas (i) and (ii), optical or geometric isomers thereof, organic or inorganic acid salts thereof, solvates thereof, and also at least one aldehyde or imine functional group Or polysaccharides:

[Formula (i) and (ii),

M is an integer of 0 or 1,

X represents an oxygen atom, NR ″ ₁ , wherein R ″ ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl radical;

When X represents an oxygen atom, the compound may also be of the form:

o additional primary monoalcohols (R ′ ₃ OH), wherein R ′ ₃ represents a symmetric 1,2- or 1,3-diol containing C ₁ -C ₅ alkyl radicals or C ₂ -C ₃ alkyl chains; In the form of 5- or 6-membered cyclic or noncyclic acetals obtained by condensation of

о A or A ₁ represents an alkyl radical, when n is 0, the form of a hemiacetal obtained by condensation of the hydroxyl groups existing on the A or A _1;

The radicals R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;

Monovalent radical A and divalent radical A ₁ represent a group selected from:

* Hydroxycarbonyl group ( -CO - OH ) :

* C ₆ optionally substituted by at least Aryl group :

-Hydroxyl group,

C ₁ -C ₄ alkyl radicals,

Aryl-ethylenyl radicals (where said aryl groups are C ₆ and optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals),

-CO-OR ' ₄ or -O-COR' ₄ groups, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group;

-COOH groups in acidic or chlorided form,

—OR ′ ₅ group, wherein R ′ ₅ represents a C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups, —N ⁺ R ″ ₆ ammonium group, where R ″ ₆ is the same or Which may be different and represent a C ₁ -C ₂ alkyl radical, a —SiR ′ ₇ group wherein R ′ ₇ may be the same or different and represent a C ₁ -C ₂ alkyl radical; Benzyl radical (-CH ₂ -C ₆ H ₆ ),

-According to one particular variant, two radicals -OR ' ₅ in the ortho position relative to the C ₆ aryl group can form a 5- or 6-membered heterocycle by two radicals R' ₅ ,

—N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and may be a hydroxyl group, an acidic or chlorinated carboxyl group (—COOH), or an acidic or chlorinated sulfone group A C ₁ -C ₆ alkyl radical optionally substituted with (-SO ₃ H); said radical R ' ₈ together with the nitrogen atom containing it optionally contains O, N and NR' ₉ , wherein R ' ₉ is C A saturated or unsaturated 5- or 6-membered heterocycle comprising another heteroatom selected from ₁ -C ₂ alkyl radical; wherein said heterocycle is optionally substituted with a hydroxyl group),

- -COR _'10 group (where, R' ₁₀ represents an optionally substituted 6-membered hydrocarbon ring fused to a C ₆ aryl substituted with one or more C ₁ -C ₂ alkyl radical),

- -SR _'11 group (where, R' ₁₁ represents a C ₁ -C ₂ alkyl radical),

Halogen atoms, preferably selected from chlorine and bromine,

-O-SO ₂ -C ₆ H ₆ group,

-SO ₃ H group,

One or two selected from O, N and NR _'12 , wherein R' ₁₂ represents a C ₁ -C ₂ alkyl group optionally fused to a saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered ring; Unsaturated cationic or non-cationic 5- or 6-membered heterocycles comprising heteroatoms (one of the heteroatoms may be included in two rings; the heterocycle or fused ring is one or more C ₁ -C ₂ May be substituted with an alkoxy radical),

- the aryl group O, N and NR _'13 (wherein, R' ₁₃ is C ₁ -C ₄ represents an alkyl radical), 1 or 2 cyclic 5-or 6-membered heterocycloalkyl containing heteroatoms selected from the groups Optionally fused, said heterocycle is optionally fused to a C ₆ aryl group,

Said aryl group is optionally fused to a C ₆ aryl group optionally substituted with one or more C ₁ -C ₂ alkoxy groups;

* Preferably from O, N and NR _'14 (wherein, R' ₁₄ represents a hydrogen atom, C ₁ -C ₆ alkyl radical or a C ₆ aryl radical ((R _{'15) 2} NCO- or (R' ₁₅₎ CO- NH—group, where R ′ ₁₅ may be the same or different and optionally substituted with C ₁ -C ₂ alkyl radicals), or one or two identical or different heteroatoms selected from Cationic or noncationic , saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic groups ;

Said heterocyclic group is optionally fused itself to a 6-membered aryl group optionally substituted with one or more C ₁ -C ₂ alkyl, C ₁ -C ₄ alkoxy or phenoxy groups;

Said heterocyclic group is optionally substituted with at least:

о hydroxyl group,

o C ₁ -C ₂ alkyl radicals optionally substituted with hydroxyl radicals;

o the amino radical —N (R ′ ₁₆ ) ₂ , wherein R ′ ₁₆ represents a C ₁ -C ₄ alkyl radical which may be the same or different and optionally substituted with a hydroxyl group, said radical R ′ ₁₆ together with the nitrogen atom-containing, and optionally O, N and NR _'17 (wherein, R' ₁₇ is C ₁ -C ₂ alkyl refers to the radical) or other heteroatoms, saturated or unsaturated 5-or 6-containing selected from Can form a heterocycle),

о one or more -COOH, R _'18 CONH- group (wherein, R' ₁₈ is C ₁ -C ₂ alkyl radical represents a) an optionally substituted C ₆ aryl radicals (wherein the C ₆ aryl radical to the nitrogen of the heterocyclic group Optionally linked to an atom, when the aryl radical is not substituted with the abovementioned radicals, the carbon atom is substituted with a hydrogen atom);

* Linear or branched C ₁ - C ₁₀ Alkyl Radical, or one or more conjugated or non-conjugated carbon - C ₁₀ - C ₂ containing a carbon-carbon double bond Alkenyl Radicals (the alkyl or alkenyl radicals are optionally substituted with one or more hydroxyl groups);

Divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ via a carbon, oxygen or nitrogen atom;

Where appropriate, the compounds of formulas (i) and (ii) comprise cosmetically acceptable anions or mixtures of anions An, which ensure the electrical neutrality of the formulation.

Another subject of the invention is presented as a method of dyeing human keratin fibres, in which such compositions are used.

Another subject of the invention is a first compartment comprising at least one compound of formula (I) or a plant extract comprising said compound, wherein said compound undergoes a preliminary step consisting in replacing radical R with a hydrogen atom; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidative oligosaccharide or a polysaccharide comprising at least one aldehyde or imine function.

Another subject is also a first compartment comprising at least one compound of formula (I) or a plant extract comprising said; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidative oligosaccharide or polysaccharide comprising at least one aldehyde or imine function and an enzyme for replacing the radical R of formula (I) with a hydrogen atom It consists of a multi-compartment device.

Finally, a final subject matter of the present invention comprises a first compartment comprising at least one compound of formula (I) or a plant extract comprising said; And a second partition comprising at least one compound of formula (i) or (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine function; And a third compartment comprising an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

The composition according to the invention makes it possible to obtain various, shampoo-fast colorings that do not damage the hair.

Other features and advantages of the present invention will become more apparent from the following detailed description and examples.

Unless stated otherwise, it should be noted that the limits of the range of values given in the detailed description are included within the range.

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

In the following text, the terms "at least one" and "one or more" are considered synonymous.

Inorganic acid salts are more particularly hydrochlorides, hydrobromide, sulfates and phosphates; Organic acid salts are more particularly citrate, succinate, tartrate, lactate, tosylate, benzenesulfonate and acetate.

Solvates are more particularly hydrates.

Compounds of formula (I) or plant extracts comprising the above

As set forth above, the composition comprises, in a cosmetically acceptable medium, at least one compound of formula (I) mentioned above or a plant extract comprising the same.

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

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

Preferably, R ₃ 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 radical derived from a C ₆ aldose such as allose, altrose, galactose, glucose, gulose, iodos, mannose or talos, preferably glucose. Regarding the aldose derivatives, deoxy derivatives such as rhamnose and also diholoxide, in particular maltose, are preferred.

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

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

Compounds of formula (I) are generally found in plant extracts of the following plant origin: Cauliflower (Abelia grandiflora), Adenolandia Calbray (Adenorandia kalbreyeri), Adina Polycepala (Adina polycephala), Aeginetia Indica Mutant Glacilis (Aeginetia indica var . gracilis), Asperula species (Asperula sp), Astasia Bella (Asystasia bella), Tree (Aucuba japonica), Abysenia Marina (Avicennia marina), Barthsia Trick Accident (Bartsia trixago), Buddleza Americana (Buddja Americana), Buddleja Crispa (Buddja crispa), Buddleja Japonica (Buddja japonica), Cantumium Schemperianum (Canthium schimperianum), Castilleja Witti (Castilleja wightii), Caenorinum Minus (Chaenorhinum minus), Clarodendum Ceratum (Clerodendrum serratum), Cyprus species (Coprosma sp), Cornus (Cornus officinalis), Krybiodendron Henry (Craibiodendron henryi), Cremaspora tripleola (Cremaspora triflora), Crocianella species (Crucianella sp), Daphnipilum Calicinum (Daphniphyllum calycinum), Daphnipilum Humilé (Daphniphyllum humile), Oyster Tree (Daphniphyllum macropodum), Eremotakis Glabra (Eremostachys glabra), Escalonia species (Escalonia sp), Tofu (Eucommia ulmoides), Peretia Apodantera (Feretia apodanthera), Gallium Fumifusum (Galium humifusum), Gallium BerumGalium verum), Gardenia (Gardenia jasminoides), Maria Elyutika (Garrya elliptica), Globularia Dumulosa (Globularia dumulosa), Hetiotis Corimbosa (Hedyotis corymbosa), Higrofila deformis (Hygrophila difformis), Exeris Chinensis (Ixeris chinensis), Lamiastrum Galleodollon (Lamiastrum galeobdolon(Laminum Galleodollon (Lamium galeobdolon)), Ramio Flomis Rotata (Lamiophlomis rotata(Flomis Rotata (Phlomis rotata)), Leonotis nepetaefolia (Leonotis nepetaefolia), Linaria species (Linaria sp), Morinda Correa (Morinda coreia), Musenda Pubessen (Mussaenda pubescens), Nefeta Silysia (Nepeta cilicia), Nefeta Nuda subspecies Albiflora (Nepeta nuda ssp . Albiflora), Odeontites Verna (Odeontites verna), Oldenlandia Kolimbosa (Oldenlandia corymbosa), Paederia Scandens (Paederia scandens), Pedicularis Chinensis (Pedicularis chinensis), Pediculis condensata (Pedicularis condensata), Pedicularis Dolly Simba (Pedicularis dolichocymba), Penstemon FERPERUS (Penstemon confertus), Penstemon Deutus (Penstemon deutus), Phenstemon richardsoni (Penstemon richardsonii), Penstemon cerulatus (Penstemon serrulatus), Pitecoquentium Crucige Room (Pithecoctenium crucigerum), Plantago Alpina (Plantago alpina), Plantago Carinata (Plantago carinata), Plantago Lagopus (Plantago lagopus), Plantago Lanceolata (Plantago lanceolata), Plantago Subulata (Plantago subulata), Premna Barbata (Premna barbata), Randia Dumetorum (Randia dumetorum), Rhododendron Latoukea (Rhododendron latoucheae), Rottmannia Whitpiedee (Rothmannia withfieldii), Ruby Peregrina (Rubia peregrina), Western marionette (Rubia tinctorum), Saprosma Skortekinini (Saprosma scortechinii), Scropularia Corinensis (Scrophularia korainensis), Scropularia Lepidodo (Scrophularia lepidota), Wonsam (Scrophularia ningpoensis), Scipiophora hydrophilaea (Scyphiphora hydrophyllacea), Swiss Controversa (Swida controversa), Syringa Bulgari (Syringa vulgaris), Tarenna Cotoensis (Tarenna kotoensis), Tecoma heftafila (Tecoma heptaphylla), Thebestia Gaumeri (Thevetia gaumeri), Thebestia Peruviana (Thevetia peruviana), Verbascum Laksum (Verbascum laxum), Verbascum Nigrum (Verbascum nigrum), Verbascum Flomoides (Verbascum phlomoides), Verbascum Salvifolium (Verbascum salviifolium), Verba Scum Sinuatum (Verbascum sinuatum), Verbascum TapusVerbascum thapsus), Verbascum Undullatum (Verbascum undulatum), Veronica Derwentiana (Veronica derwentiana), Bitex Nigrum (Vitex nigrum), Wendlandia Formosanas (Wendlandia formosana).

Preferably, the plant extract used is gardenia.

It should be noted that the term "extract" means juice or powder, starting from natural plant material, obtained through one or more of the operations of extraction, enrichment or concentration and optionally drying.

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

Thus, in the case of the aerial part, it is washed and, if desired, after grinding, after being macerated in a suitable solvent, in particular ethanol or water, followed by filtration, concentration and optionally drying.

For more specific fruits, they are optionally frozen and washed with water to remove the impurities present. It may optionally be sterilized, in particular with a solution comprising ethanol and chlorine.

For substantial extraction, the fruits are thawed and, if desired, compressed, for example using a particularly suitable hydraulic press.

Then, where appropriate, recovered juice may be subjected to steps of concentration and drying.

In the case of gardenia, there is a commercial extract having a variable content 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 from 0.001% to 10% by weight, in proportion to the weight of the composition.

It should be noted that the compound (s) of formula (I) undergo a step consisting of replacing a radical R with a hydrogen atom before or at the same time as the dyeing process.

The reaction can be carried out in any manner known to the person skilled in the art and in particular using an enzyme selected from, for example, isolase and β-glucosidase (EEC 3.2.1.21) from sweet almonds.

Thus, if the operation takes place simultaneously with the dyeing method, the enzyme is added to the composition just before its application to the fiber.

If the operation takes place prior to application to the fiber, the enzyme is added to a buffered aqueous solution of the compound of formula (I) (acetate, pH 5.5 to 6). Preferably, the concentration of compound of formula (I) is in the range of 10 to 30 mM. Enzymes are generally used at concentrations ranging from 5-100 units / ml (one enzymatic unit, generally defined as the number of μmol of substrate hydrolyzed per minute).

The operation takes place at a temperature close to room temperature (20 to 45 ° C.) and over a period of 1 to 5 hours.

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

Additional dyes

The dye composition may also comprise additional dyes in addition to the compounds of the formula (I) mentioned above.

Among these additional dyes, mention may be made of natural or synthetic direct dyes, optionally oxidizing dyes with bases in combination with couplers, and also combinations thereof.

Said 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 and especially anthraquinone dyes, azine direct Dyes, triarylmethane direct dyes, indoamine direct dyes, and natural direct dyes.

Among the natural direct dyes, lawsonone, juglone, alizarin, alipurin, purpurin, carminic acid, kermesic acid, purpurogallin, Anthrogallol protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, chlorophyll, chlorophyllin, Orcein, hematin, hematoxylin, hematoxylin, brazilin, brazileine, safflower pigments (e.g. carthamine), flavonoids (e.g. Mentions, including morin, apigenidine and sandalwood, anthocyanins (eg, apigeninidin), carotenoids, tannins, sorghum and cochineal carmine or mixtures thereof Can be. Extracts or decoctions containing such natural dyes and in particular henna poultices or extracts may also be used.

Among the above oxidation bases, mention may be made of para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol, bis-para-aminophenol, ortho-aminophenol and heterocyclic bases, and addition salts thereof. .

Among the linking groups, mention may in particular be made of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene linking group and heterocyclic linking group, and addition salts thereof.

The oxidizing base (s) present in the dye composition are each generally present in an amount of 0.001% to 10% by weight, preferably 0.005% to 6% by weight, relative to the total weight of the dye composition.

Each of said linker (s) is generally present in an amount of 0.001% to 10% by weight, preferably 0.005% to 6% by weight, relative to the total weight of the dye composition.

In general, addition salts of oxidizing bases and linking groups which can be used in the context of the present invention are in particular addition salts with acids such as hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, tosylate, Benzenesulfonate, phosphate and acetate.

Aldehyde / Imine Compound

As indicated above, the composition also comprises at least one aldehyde or imine compound selected from the above-mentioned formulas (i) and (ii), and also an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine function.

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

Compounds (i) and (ii) also contain additional primary monoalcohols (R ' ₃ OH), wherein R' ₃ is a symmetric type 1 containing C ₁ -C ₅ alkyl radicals or C ₂ -C ₃ alkyl chains, In the form of 5- or 6-membered cyclic or bicyclic acetals obtained by condensation of 2- or 1,3-diol).

The compounds may also be in the A or A ₁ represents a case of an alkyl radical, n is 0, A or in the form of a hemiacetal obtained by condensation of the hydroxyl groups present on the A _1.

It should be noted that the electrical neutrality of formulas (i) and (ii) is identified by organic or inorganic anions or mixtures of anions, selected from below, which, if desired, can balance the charge (s) of the compound. For example: halides such as chlorides, bromide, fluorides or iodides; hydroxide; sulfate; Hydrogen sulfate; Alkyl sulfates, wherein the linear or branched alkyl moiety is C ₁ -C ₆ , such as methyl sulfate or ethyl sulfate ions; Carbonates and hydrogencarbonates; Salts of carboxylic acids such as formate, acetate, citrate, tartrate and oxalate; Alkylsulfonates, wherein the linear or branched alkyl moiety is C ₁ -C ₆ , such as methylsulfonate ions; Arylsulfonates, wherein the aryl moiety, preferably phenyl, is optionally substituted with one or more C ₁ -C ₄ alkyl radicals, such as 4-tolylsulfonate; And alkylsulfonates such as mesylate.

Nonionic or anionic oxidized polysaccharides comprise one or more aldehyde groups and optionally one or more anionic groups. The anionic group is preferably a carboxyl group or a carboxylate group.

The nonionic or anionic oxidized polysaccharides used can be represented by the following formula (II):

P- (CHO) m (COOX) n (II)

[In the meal,

P represents a polysaccharide chain composed of monosaccharides having at least 5 carbon atoms, preferably at least 6 carbon atoms, more particularly having 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 basic amino acids such as lysine, Is selected from ions derived from arginine, sarcosine, ornithine and citrulline,

m + n is at least 1,

m is the degree of substitution (DS (CHO)) of the polysaccharide having at least one aldehyde group, preferably in the range of 0.001 to 2, preferably 0.005 to 1.5,

n is the degree of substitution (DS (COOX)) of the polysaccharide having at least one carboxyl group, in the range of 0 to 2, preferably 0.001 to 1.5.

The term “degree of substitution of polysaccharides according to the invention DS (CHO) or DS (COOX)” refers to the number of oxidized carbons and basic monosaccharides (even preoxidation) which constitute polysaccharides as aldehyde or carboxyl groups for all repeat units. Open by) means the ratio between the numbers.

CHO and COOX groups can be obtained, for example, during the oxidation of certain carbon atoms in the C2, C3 or C6 position of sugar units of 6 carbon atoms. Preferably, the oxidation can take place in C2 and C3, more particularly by 0.01% to 75%, preferably 0.1% to 50% by the number of rings which can be opened.

The polysaccharide chain represented by P is preferably inulin, cellulose, starch, pectin, guar gum, xanthan gum, pullulan gum, alginate gum, agar-agag gum, carrageenan gum, gellan gum. (gellan gum), gum arabic, xylose and tragaganth gum, and derivatives thereof.

The term "derivative" means a compound obtained by chemical modification of the abovementioned compounds. It may be an ester, amide or ether of the compound.

Oxidation can be carried out according to methods known in the art, for example FR 2 842 200, FR 2 854 161 or in the article "Hydrophobic films from maize bran hemicelluloses" by E. Fredon et al., Carbohydrate Polymers 49, 2002, pages 1 to 12 may occur according to the method described. Another oxidation method is described in the article "Water soluble oxidized starches by peroxide reaction extrusion" Industrial Crops and Products 75 (1997) 45-52-R. E. Wing, J. L. Willet. The oxidation process is simple to carry out, efficient and does not produce any toxic by-products or by-products that are difficult to remove.

The peroxide can 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 from 0.05 to 1 molar equivalent per glucose unit of polysaccharide.

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

The process can also be carried out by contacting the polysaccharide in powder form with a catalyst and a peroxide dissolved in a small amount of water. This method is referred to as the "semi-dry" method.

More preferably, the polysaccharide is inulin, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, starch, starch acetate, hydroxyethyl starch, hydroxypropyl starch, Obtained by oxidation of guar gum, carboxymethyl guar gum, carboxymethylhydroxypropyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, xylose, xanthan gum or carrageenan gum, or mixtures thereof.

Most particularly preferred polysaccharides in the present invention correspond to formula (II), wherein P represents a polymer chain derived from inulin and starch; m is the degree of substitution (DS (CHO)) of the polysaccharide having at least one aldehyde group, in the range from 0.005 to 2.5; n is the degree of substitution (DS (COOX)) of the polysaccharide having one or more carboxyl groups, in the range of 0.001 to 2;

Examples of oxidative oligosaccharides and polysaccharides comprising compounds of formulas (i) and (ii), at least one aldehyde or imine function, which are particularly suitable for the practice of the invention, include the following compounds, salts thereof, isomers thereof and solvates thereof Mention may be made of such compounds, alone or as mixtures:

Preferably, the composition comprises one or more compounds of formula (i).

Advantageously, formula (i) is as follows:

m is 0 or 1;

The radicals R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;

* X represents an oxygen atom;

A represents the following:

* Optionally substituted with one or more hydroxyl groups, linear or branched C ₅ - C ₁₀ Al Kiel radical;

C ₂ -C ₈ alkenyl radicals comprising carbon-carbon double bonds;

Hydroxycarbonyl group (-COOH);

* C ₆ optionally substituted by at least Aryl group :

о hydroxyl group,

о C ₁ -C ₄ alkyl radicals,

o a -CO-OR ' ₄ or -O-COR' ₄ group, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical,

o -OR ' ₅ groups, where R' ₅ represents a C ₁ -C ₆ alkyl radical,

aryl-ethylenyl radicals (the aryl groups are C ₆ and optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals),

o, 1 or 2 selected from O, N and NR _'12 , wherein R' ₁₂ represents a C ₁ -C ₂ alkyl group optionally fused to a saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered ring Unsaturated cationic or non-cationic 5- or 6-membered heterocycles comprising heteroatoms (one of the heteroatoms may be included in two rings; the heterocycle or fused ring is one or more C ₁ -C ₂ May be substituted with an alkoxy radical),

- the aryl group O, N and NR _'13 (wherein, R' ₁₃ is C ₁ -C ₄ represents an alkyl radical), 1 or 2 cyclic 5-or 6-membered heterocycloalkyl containing heteroatoms selected from the groups Optionally fused;

* Preferably from O, N and NR _'14 (wherein, R' ₁₄ represents a hydrogen atom, C ₁ -C ₆ alkyl radical or a C ₆ aryl radical ((R _{'15) 2} NCO- or (R' ₁₅₎ CO- NH- group optionally substituted by (wherein, R _'15 is C ₁ -C ₂ represents an alkyl radical)) represents a) one or two identical, or that contain different heteroatoms cationic or non-cationic is selected from St. , Saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group ;

Said heterocyclic group is optionally fused itself to a 6-membered aryl group optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₄ alkoxy groups;

Said heterocyclic group is optionally substituted with at least:

о hydroxyl group,

o C ₁ -C ₂ alkyl radicals optionally substituted with hydroxyl radicals,

o the amino radical —N (R ′ ₁₆ ) ₂ , wherein R ′ ₁₆ represents a C ₁ -C ₄ alkyl radical which may be the same or different and optionally substituted with a hydroxyl group, said radical R ′ ₁₆ together with the nitrogen atom-containing, and optionally O, N and NR _'17 (wherein, R' ₁₇ is C ₁ -C ₂ alkyl refers to the radical) or other heteroatoms, saturated or unsaturated 5-or 6-containing selected from Can form a heterocycle),

Where appropriate, the compound of formula (i) comprises a cosmetically acceptable anion or mixture of anions An, which ensures the electrical neutrality of the formulation;

The compound (s) of formula (i) may be in acetal or hemiacetal form as described above.

As examples of preferred compounds (i), mention may be made of the following compounds, isomers thereof, salts thereof or solvates thereof, which compounds may be present alone or as mixtures:

More particularly, the content of the oxidized oligosaccharides or polysaccharides comprising the compound (s) of formula (i) or (ii), or at least one aldehyde or imine function, is from 0.001% to 30% by weight, in proportion to the weight of the composition.

As examples of preferred oxidized oligosaccharides or polysaccharides, the following compounds may be mentioned:

Oxidized starch (Rn 9047-50-1), a 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), known by the following designation: 2,3-Dialdehyde cellulose; 2,3-Dialdehydocellulose; Aldehydocellulose; Cellulose 2,3-dialdehyde; Cellulose dialdehyde; Dialdehyde cellulose;

Inulin oxide (Rn 82446-43-3);

Dextran dialdehyde (Rn 37317-99-0).

Amine

According to one embodiment of the invention, the composition may comprise one or more primary or secondary amines or addition salts thereof, ammonia or hydroxylamine, or mixtures thereof.

In general, addition salts of such amine compounds which can be used in the context of the present invention are, in particular, addition salts with acids such as hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, tosylate, Benzenesulfonate, dodecylbenzenesulfonate, phosphate and acetate, preferably hydrochloride, citrate, succinate, tartrate, phosphate and lactate.

In particular, the primary or secondary amine (s) that can be used in the context of the present invention are selected from amines of the formula (III), amino polymers, purine bases, and also addition salts thereof, and combinations thereof, which are described in detail below.

In particular, formula (III) is as follows:

R ' ₇ R' ₈ NH (III)

In formula (III), R ' ₇ and R' ₈ represent, independently of each other,

Hydrogen atoms;

At least one group containing 1 to 5 carbon-carbon double bonds and / or optionally substituted, optionally comprising a group comprising at least one heteroatom and / or at least one heteroatom or at least one heteroatom, Preferably selected from oxygen, nitrogen, sulfur, C═O, C═S, SO and SO ₂ or a combination thereof), linear, branched and / or cyclic, saturated and / or unsaturated, aromatic Or non-aromatic C ₁ -C ₂₀ hydrocarbon-based radicals; The hydrocarbon radicals R ′ ₇ and R ′ ₈ together with the nitrogen atom attached to each one are a six-membered aromatic, optionally substituted, optionally aromatic, optionally comprising another nitrogen or non-nitrogen heteroatom, or Can form a saturated or unsaturated 5- or 7-membered heterocycle fused to a heteroaromatic nucleus; The hydrocarbon-based radical does not contain any nitro, nitroso, peroxo or diazo functional groups.

The compound of formula (III) is advantageously not an oxidizing base or an oxidative linking group used for dyeing keratin fibers.

Among the groups present as substituents for heterocyclic hydrocarbon-based groups, the following groups may be mentioned:

Carboxylic, sulfone, phosphone, in acidic or chlorided form

Hydroxyl, C ₁ -C ₄ alkoxy, (C ₁ -C ₈ ) alkoxycarbonyl,

(C ₁ -C ₄ ) alkylsulfonate, (C ₁ -C ₈ ) alkylphosphonate,

Tri (C ₁ -C ₄ ) alkylsilyl, tri (C ₁ -C ₄ ) alkoxysilanyl,

Amino, (di) (C ₁ -C ₄₎ alkylamino, tri (C ₁ -C ₄₎ alkyl ammonium,

Thiols, (C ₁ -C ₄ ) alkylthio,

Aminosulfonyl, (di) (C ₁ -C ₄₎ alkyl aminosulfonyl,

Aminocarbonyl, (di) (C ₁ -C ₄₎ alkylamino-carbonyl,

(C ₁ -C ₄ ) alkylcarbonylamino,

Guanidine,

Ureido (N (R) ₂ -CO-NR'-) wherein the radicals R and R 'are independently of each other a hydrogen atom or a C ₁ -C ₄ alkyl or (C ₁ -C ₄ ) alkylsulfonylamino Represent radicals);

Phenyl, indolyl, pyrrolyl, imidazolyl, optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

Preferably, the groups present as substituents are selected from the following groups: carboxylic in acidic or chlorided form; Hydroxyl; C ₁ -C ₄ alkoxy; (C ₁ -C ₈ ) alkoxy carbonyl; Thiols; (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; Phenyl, indolyl, pyrrolinyl, imidazolyl, optionally substituted with one or more C ₁ -C ₂ alkyl or hydroxyl.

In particular, the amine (s) of formula (III) may be the same or different and comprise 1 to 5 primary and / or secondary amine functional groups; The amine (s) do not contain any N-N bonds. In addition, the amine (s) of formula (III) do not comprise more than two heteroatoms bonded together.

Preferably, the amine (s) is a compound of formula (III), more particularly selected from compounds of formulas (IIIa) to (IIIi), (IIIi ′), and also addition salts thereof.

o amino acids and / or derivatives of general formula ( IIIa ):

[Formula (IIIa):

R ₉ is a linear or branched C ₁ -C ₆ substituted with a hydrogen atom, preferably at least one hydroxyl, hydroxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group Alkyl radicals, phenyl radicals optionally substituted with one or more hydroxyls, indolyl radicals optionally substituted with one or more hydroxyls, imidazolyl radicals, pyrrolinyl radicals optionally substituted with C ₁ -C ₂ alkyl groups; Or an unsubstituted phenyl radical;

R ″ ₉ represents hydrogen, a C ₁ -C ₄ alkyl radical or an unsubstituted phenyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

R ″ ₉ and R ₉ together with the nitrogen atom to which they are attached may form a saturated 5- or 6-membered heterocycle.

Examples of compounds of formula (IIIa) that may be most particularly mentioned include asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolysine, serine, threonine, tryptophan and tyrosine, and addition salts thereof. .

According to another variant, the compound of formula (IIIa) is advantageously 2-amino-2-methylpropanoic acid; α-methyl-D, L-phenylalanine; D, L-α- (hydroxymethyl) alanine; D, L-α-methyl-meth-tyrosine; α-methyl-D, L-tryptophan; D, L-α-methylhistidine dihydrochloride; L-2-methylserine; (S) -2-methylcysteine dihydrochloride; (S) -2-methyl-2-pyrrolidinecarboxylic acid.

о from amino acids of general formula ( IIIb ) Derived Esters and / or Derivatives :

[Formula (IIIb):

R ₉ is a hydrogen atom, preferably at least one hydroxyl, hydroxycarbonyl, (C ₁ -C ₄ ) alkoxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group Optionally substituted linear or branched C ₁ -C ₆ alkyl radicals, phenyl radicals optionally substituted with one or more hydroxyls, indolyl radicals optionally substituted with one or more hydroxyls, imidazolyl radicals, C ₁ -C ₂ alkyl groups Substituted pyrrolinyl radicals; Or an unsubstituted phenyl radical;

R ″ ₉ represents hydrogen, a C ₁ -C ₄ alkyl radical or an unsubstituted phenyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

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:

Optionally comprising 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as set forth above, optionally one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, C═O, C═ Linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon-based radicals, wherein one or more groups containing one or more heteroatoms selected from S, SO and SO ₂ or a combination thereof are inserted, wherein the alkyl radical is any nitro, nitro Bovine, peroxo or diazo functional groups are not included);

Unsubstituted benzyl radicals.

According to one particular variant, R ₉ and R ₁₁ may optionally form a saturated five-membered carbon-based ring.

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

As examples of formula (IIIb), methoxytyrosine, 2-ethylpiperidine carboxylate; D, L-phenylalanine methyl ester; L-cystine dimethyl ester dihydrochloride; L-leucine methyl ester; Methyl 2-amino-3-methylbutyrate; L-phenylalanine ethyl ester hydrochloride; L-glutamic acid diethyl ester hydrochloride; Ethyl (S) -2-amino-3-methylbutanoate hydrochloride; D, L-serine methyl ester hydrochloride; Tyrosine methyl ester hydrochloride; L-cysteine ethyl ester hydrochloride; L-histidine methyl ester hydrochloride; Methyl (S) -pyrrolidine-2-carboxylate hydrochloride; Methyl 2-aminoacetate hydrobromide; Ethylglycine; H-D, L-alanine ethyl ester hydrochloride; D, L-tyrosine ethyl ester hydrochloride; Methyl 2- (phenylamino) acetate; Ethyl glutamate; Bis (α, β-tert-butyl) D, L-aspartate hydrochloride; Ethyl L-α-aminoisocaproate hydrochloride; Benzyl glycinate para-toluenesulfonate; D, L-alanine ethyl ester hydrochloride; 5-hydroxy-D, L-tryptophan methyl ester hydrochloride; D, L-threonine methyl ester hydrochloride; D, L-proline tert-butyl ester; D, L-phenylalanine methyl ester hydrochloride may be mentioned.

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

In formula (IIIc):

R ₉ is a hydrogen atom, preferably at least one hydroxyl, (C ₁ -C ₄ ) alkoxycarbonyl, hydroxycarbonyl, thiol, (C ₁ -C ₄ ) alkylthio, amido, amino or guanidine group Optionally substituted linear or branched C ₁ -C ₆ alkyl radicals, phenyl radicals optionally substituted with one or more hydroxyls, indolyl radicals optionally substituted with one or more hydroxyls, imidazolyl radicals, C ₁ -C ₂ alkyl groups Substituted pyrrolinyl radicals;

R ″ ₉ represents a C ₁ -C ₄ alkyl radical optionally substituted with hydrogen or a hydroxysulfonyl radical;

R ₁₀ represents hydrogen or a C ₁ -C ₄ alkyl radical;

R ″ ₉ and R ₉ together with the nitrogen atom to which they are attached may form a saturated five-membered heterocycle;

R ₁₂ represents:

Hydrogen atom;

* Preferably a C ₁ -C ₆ alkyl radical substituted with one or more hydroxyl, thiols, (C ₁ -C ₄ ) alkylthio, amido or amino, a phenyl radical optionally substituted with one or more hydroxyl, one or more hydroxides Indolyl radicals optionally substituted with oxyl, imidazolyl radicals, pyrrolinyl radicals optionally substituted with C ₁ -C ₂ alkyl groups;

X represents a sulfur or nitrogen atom.

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

X represents a nitrogen atom, R ₁₂ is an alkyl radical as defined above and most particularly alanine, arginine, asparagine, aspartate, cysteine, glutamate, glutamine, glycine, histidine, lysine, methionine, phenylalanine, proline, pi When representing an amino acid residue selected from rolysine, serine, threonine, tryptophan, tyrosine, valine, leucine or isoleucine and / or the corresponding methyl or ethyl ester thereof, the compound of formula (IIIc) represents a dipeptide or oligopeptide.

Examples of the compound of formula (IIIc) include 3-aminodihydrothiophen-2-one hydrochloride; D, L-homocysteine thiolactone; D, L-leucine-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-leucine amide hydrochloride; 2-aminopropanediamide; 2- (2-amino-3-methylbutanamido) propanoic acid; L-tyrosyl-L-alanine; L-valyl-L-phenylalanine; Sarcosyl-L-phenylalanine; L-tyrosyl-β-alanine; Glycyl-L-proline; Glycyl-D, L-valine; 2-aminomalonamide; L-methionamide hydrochloride; 2-amino-3-methylbutanamide; D-alanineamide hydrochloride; L-tyrosineamide hydrobromide; Aspartate acid amide; L-tyrosine amide hydrochloride; L-arginine amide dihydrochloride; Lysine amide dihydrochloride; Threonine amide hydrochloride; Isoleucine amide hydrochloride; Histidine amide dihydrochloride; D, L-alanine amide hydrochloride; 2-amino-3- (4-hydroxyphenyl) propionamide; D, L-tryptophanamide hydrochloride; N-hydroxy-L-arginine acetate (H-ARG-NH 2 2AcOH); Asparagine amide hydrochloride; L-glutamic acid α, γ-diamide hydrochloride; D-phenylalanine amide; D-leucineamide hydrochloride; L-glutamic acid α-amide; L-methionineamide; L-cystine bisamide hydrochloride; Glycinamide acetate; D-lysine amide dihydrochloride; Glycinamide; L-isoglutamine γ-methyl ester hydrochloride; D-arginine amide dihydrochloride; (S) -pyrrolidine-2 carboxamide; Prolyl histamine hydrochloride may be mentioned.

o amino compounds of the general formula ( IIId ):

[Formula (IIId):

R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , independently of one another, represent the following:

Hydrogen atom;

* May contain 1 to 5 optionally aromatic carbon-carbon double bonds, optionally substituted as set forth above, optionally one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO And one or more groups comprising one or more heteroatoms selected from SO ₂ or a combination thereof, optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups, linear, branched and / or cyclic, saturated and And / or unsaturated C ₁ -C ₂₀ hydrocarbon radicals (the radicals 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, are optionally substituted as indicated above, Optionally aromatic, and may form a saturated or unsaturated 5- or 7-membered heterocycle comprising optionally the same nitrogen or non-nitrogen heteroatoms; No tro, nitroso, peroxo or diazo functional groups); More particularly optionally substituted C ₁ -C ₁₀ alkyl radicals; And preferably at least one hydroxyl group, preferably from 1 to 2 hydroxyl groups, optionally a linear or branched C ₁ -C ₈ alkyl radical, a hydroxy carbonyl radical substituted with, ureido radical, a (C ₁ - C ₄ ) alkoxycarbonyl radical; Unsubstituted phenyl radicals;

X represents a nitrogen, oxygen or sulfur atom;

R ₁₇ represents:

Hydrogen atom;

* Optionally comprising 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as set forth above, optionally one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, Linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon-based radicals in which one or more groups comprising one or more heteroatoms selected from SO and SO ₂ or a combination thereof are inserted, wherein the alkyl radical is any nitro, nitroso, No peroxo or diazo functional groups, more particularly R ₁₇ represents hydrogen, an optionally substituted linear or branched C ₁ -C ₁₀ alkyl radical; And preferably a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with hydrogen, one or more hydroxyl groups, preferably 1 to 2 hydroxyl groups;

R ₁₈ represents:

Hydrogen atom;

* Optionally substituted as set forth above and optionally comprising one or more heteroatoms and / or one or more heteroatoms, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof Linear or branched C ₁ -C ₈ alkyl radicals, wherein at least one group is inserted and optionally contains one or more hydroxyl or C ₁ -C ₂ alkoxy groups, the alkyl radicals being any nitro, nitroso, peroxo or diazo functional group Not included);

o is an integer from 0 to 5;

According to another variant of the invention, the radicals R ₁₆ and R ₁₇ are optionally substituted as indicated above, optionally together with the carbon atom attached to R ₁₆ and the X atom attached to the radical R ₁₇ , respectively, and are optionally aromatic , Optionally, a saturated or unsaturated 5- or 6-membered heterocycle comprising another nitrogen or non-nitrogen heteroatom can be formed.

According to another variant of the invention, the radicals R ₁₈ and R ₁₅ are optionally substituted as indicated above, optionally together with the nitrogen atom attached to R ₁₈ and the carbon atom attached to the radical R ₁₅ , respectively, and are optionally aromatic , Optionally, a saturated or unsaturated 5- or 6-membered heterocycle comprising another nitrogen or non-nitrogen heteroatom can be formed.

Examples of the compound of formula (IIId) include L-2-aminohexanoic acid amide hydrochloride; L-phenylalanine amide; (S)-(+)-aminosuccinic acid; (R) -2- (methylamino) succinic acid; Ethyl nifekotate; 3-piperidine carboxylic 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; Dimethyl (S) -aminosuccinate hydrochloride; β-L-alanine methyl ester hydrochloride; 4-carboxyethoxypiperidine; 4-aminobutyric acid; D, L-β-aminoadipic acid; 4- (methylamino) butyric acid hydrochloride; Ethyl γ-aminobutyrate hydrochloride; Hexahydronicotinamide; Piperidine-4-carboxamide; 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine may be mentioned.

o amino compounds of the general formula ( IIIe ):

[Formula (IIIe):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above;

R ₁₉ represents:

Hydrogen atom;

* Optionally substituted as set forth above and optionally comprising one or more heteroatoms and / or one or more heteroatoms, preferably selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof Linear or branched C ₁ -C ₈ alkyl radicals, wherein at least one group is inserted and optionally contains one or more hydroxyl or C ₁ -C ₂ alkoxy groups, the alkyl radicals being any nitro, nitroso, peroxo or diazo functional group Not included);

p is an integer from 0 to 7;

u is an integer of 1 or 2, and when u is 2, the radical R ₁₈ represents hydrogen.

According to another variant of the invention, the radicals R ₁₃ and R ₁₄ may optionally form a saturated 5- or 6-membered heterocycle with the carbon atoms of R ₁₃ and R ₁₄ to which said substituents are attached.

As examples of compound (IIIe), mention may be made of the following acids, enantiomers thereof, and also salts thereof, and hydrates thereof, if present: (1-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-amino Hexylphosphonic acid, diethyl (aminoethyl) phosphonic acid (especially oxalate salt), tetraethyl (aminomethylene) bisphosphonic acid (especially salt thereof), (1-amino-2,2-dimethylpropyl) phosphonic acid , N-methylaminomethylphosphonic acid, (1-aminopentyl) phosphonic acid, (1-amino-2-methylbutyl) phosphonic acid, (1-aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) Phosphon , (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 ethyl esters thereof, (diethyl (3-aminopropyl) phosphonic acid ( Especially oxalate salts), 3- (N-hydroxyamino) propyl phosphonic acid, 2-amino-2-methyl-4-phosphonobutyric acid, diethyl (3-aminopropyl) phosphonate, 2-amino- 4-phosphonobutyric acid, 2-aminoethylphosphonic acid, 2-amino-3-phosphonopropionic acid, diethyl (2-aminoethyl) phosphonate, diethyl (2-aminoethyl) phosphonic acid, (2- ( (2-pyrrolidinylcarbonyl) amino) ethyl) fo Spanic acid, diethyl (2-amino-1-methyl-2-phenyl) ethylphosphonate, diethyl (2-amino-2-phenyl) ethylphosphonate, and / or mixtures thereof.

o amino compounds of the general formula ( IIIf ):

[Formula (IIIf):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above, in addition, the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are, independently of one another, a hydroxyalkyl radical, May also represent (C ₁ -C ₄ ) alkoxycarbonyl radicals, carboxaldehyde radicals, (C ₁ -C ₃ ) alkoxy;

q is an integer from 1 to 18;

X represents an oxygen atom, an SH or OH group, or a methylene group optionally substituted with a hydroxyl radical;

When X represents an oxygen atom, R ₁₈ forms a 5- or 6-membered ring optionally substituted with one or more hydroxy (methyl) groups, preferably 1 to 4 hydroxy (methyl) groups.

According to another variant of the invention, the radicals R ₁₆ and R ₁₈ or R ₁₃ and R ₁₈ are optionally together with a carbon atom attached to R ₁₆ (or to R ₁₃ ) and a nitrogen atom attached to the radical R ₁₈ , respectively. , Optionally substituted as set forth above, optionally aromatic, and optionally forming a saturated or unsaturated 5- or 6-membered heterocycle comprising another identical nitrogen or non-nitrogen heteroatom.

According to another variant of the invention, the amine of formula (IIIf) may be a β-amino alcohol derived from the reduction of an acid or ester functional group to an alcohol of one of said 20 esterified or nonesterified amino acids. have.

As examples of compound (IIIf), mention may be made of the following compounds, enantiomers thereof, and also salts and hydrates thereof, if present: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, tro Metamine, 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-aminohexan-1-ol, 1 -Amino-1-cyclopentanmethanol, 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-methylpentan-1-ol, 3-aminopropanethiol, ethyl 2-amino-4-mercaptobutanoate, 6-hydroxyhexylamine, β-D-galactopira Nosylamine, β-D-glucopyranosylamine, 1-amino-2,5-anhydro-D-mannitol, 1-amino-1-deoxy-D-fuructose, D-glucosamine, 2-pyrroli Dinmethanol, 1-amino-2,3-dihydroxypropane, 3-propanolamine, 3-[(2-hydroxyethyl) amino] propan-1-ol, di-β-hydroethylamine, bis (3 -Hydroxypropyl) amine, N-2'-aminoethyl-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, la Urylamine, 1-tetradecylamine, 1-hexadecylamine, 3-amino-2-hydroxypropionic acid, 3-amino-2-hydroxy-4-phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, ethyl 4- Hydroxy-2-pyrrolidinecarboxylate, and mixtures thereof.

o amino compounds of the general formula ( IIIg ):

In formula (IIIg):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above;

R ₂₀ represents:

Linear C ₁ -C ₄ alkyl radicals,

Linear C ₁ -C ₄ alkoxy radicals,

o is an integer from 0 to 5,

v is an integer of 1 or 2, and when v is 2, R ₁₈ represents hydrogen.

As examples of compound (IIIg), aminopropyltriethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan-1-amine, 4- (triethoxysilyl ) Butane-1-amine, N- [3- (trimethoxysilyl) propyl] ethylenediamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine and (3-methyl Aminopropyl) trimethoxysilane, and mixtures thereof, may be mentioned.

o amino compounds of the general formula ( IIIh ):

[Formula (IIIh):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meaning as above, and further, the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are, independently of one another, hydroxyl radicals, ( C ₁ -C ₄ ) alkoxycarbonyl radicals, carboxaldehyde radicals, (C ₁ -C ₃ ) alkoxy may also be represented;

R ₂₁ and R ₂₂ , independently of one another, represent the following:

Hydrogen atom;

* May contain 1 to 5 carbon-carbon double bonds, optionally substituted as set forth above, and optionally one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO and SO One or more groups comprising one or more heteroatoms selected from _two or a combination thereof are inserted, optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups, linear, branched and / or cyclic, saturated and / or Unsaturated C ₁ -C ₂₀ hydrocarbon-based radicals, more particularly optionally substituted C ₁ -C ₁₀ alkyl radicals; And linear or branched C ₁ -C ₄ alkyl radicals optionally substituted with one or more hydroxyl groups, preferably 1 to 2 hydroxyl groups;

R ₂₁ and R ₂₂ together with the nitrogen atom attached thereto are saturated or unsaturated 5- to 7- optionally substituted as indicated above, optionally aromatic and optionally comprising another identical nitrogen or non-nitrogen heteroatom; Can form a heterocycle; The alkyl radical does not contain any nitro, nitroso, peroxo or diazo functional groups,

w is an integer from 1 to 10.

According to another variant of the invention, alkyl radicals R ₁₆ and R ₂₁ are optionally substituted as set forth above, optionally together with a carbon atom attached to R ₁₆ and a nitrogen atom attached to radical R ₂₁ , respectively, and optionally aromatic And optionally form a saturated or unsaturated 5- or 6-membered heterocycle comprising another nitrogen or non-nitrogen heteroatom.

According to another variant of the invention, alkyl radicals R ₁₈ and R ₂₁ are optionally substituted, as indicated above, together with the first nitrogen atom attached to R ₁₈ and the last nitrogen atom attached to radical R ₂₁ , respectively; , Optionally aromatic, and may form a saturated or unsaturated 5- to 14-membered heterocycle comprising another nitrogen or non-nitrogen heteroatom.

Among the compounds of the formula (IIIh), mention may be made in particular of the following amines, enantiomers thereof, if present, and also salts and hydrates thereof: gerontine, N- [3-aminopropyl] -1,4 -Butanediamine, 1,4-butanediamine, 4- (ethylamino) -N-butylamine, 2- [3- (2-hydroxy-1,1-bis-hydroxymethylethylamino) propylamino]- 2-hydroxymethylpropane-1,3-diol, 1,4,8,11-tetraazacyclotedecane, 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-dimethyltri Methylenediamine, 2,2-dimethyl-1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-dia Minopropane, cystamine, 1,5-diaminopentane, 1,6-diaminohexane, lauraminopropylamine, 2-methylheptyl Amine (2- (N-methyl) heptylamine), ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, 3-aminoalanine, piperazine-2-carboxylic acid, β-N-methyl Aminoalanine, methyl piperazine-2-carboxylate, ethyl 3-aminoprolinate, 2,4-diamino-N-butyric acid, N- [3- (trimethoxysilyl) propyl] ethylenediamine, or its mixture.

o amino compounds of the general formulas ( IIIi ) and / or ( IIIi ' ):

[In general formula (IIIi) and / or (IIIi '):

R ₂₃ and R ₂₄ , independently of one another, represent the following:

Optionally substituted C ₁ -C, wherein one or more groups are inserted, optionally including one or more heteroatoms and / or preferably one or more heteroatoms selected from oxygen, nitrogen, sulfur, CO, SO and SO ₂ or a combination thereof ₆ alkyl radicals (the alkyl radicals do not include any nitro, nitroso, peroxo or diazo functional groups);

Alkylcarbonyl radicals (R-CO-), wherein R represents a C ₁ -C ₄ alkyl radical;

Alkylsulfonyl radicals (RSO _2- ), where R represents a C ₁ -C ₄ alkyl radical;

* (Di) (alkyl) aminosulfonyl radicals ((R) ₂ N-SO _2- ), wherein the radicals R independently represent hydrogen or a C ₁ -C ₄ alkyl radical;

* (Di) (alkyl) aminocarbonyl radicals ((R) ₂ N-CO-), wherein the radicals R independently represent hydrogen or a C ₁ -C ₄ alkyl radical;

Halogen atoms, preferably selected from bromine, chlorine and fluorine;

A C ₁ -C ₄ alkoxy group;

A 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 radical;

An alkylcarbonylamino group (RCO-NR′-), wherein the radical R represents a C ₁ -C ₄ alkyl radical and the radical R ′ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical;

An alkylsulfonyl radical (RSO _2- ), wherein the radical R represents a C ₁ -C ₄ alkyl radical;

Y represents a carbon or nitrogen atom;

z, z 'and z ", independently of one another, represent nitrogen atoms substituted with carbon atoms, nitrogen atoms or hydrogen;

x is an integer from 0 to 2; when x is less than 2, the unsubstituted carbon atom (s) contain a hydrogen atom;

x 'is an integer of 0 or 1; when x 'is less than 1, the unsubstituted carbon atom (s) contain a hydrogen atom.

Among the compounds of the formulas (IIIi) and / or (IIIi ′), mention may be made in particular of the compounds listed below, enantiomers thereof, if present, and also salts and hydrates thereof: α-pyridylamine, 2-amino- 3-hydroxypyridine, 2-aminonicotinic acid, 2-amino-3-methylpyridine, 6-methoxy-3-pyridylamine, 3-aminopyridine, 3-amino-4-pyridylamine, 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, ethyl 3-aminobenzoate, 1-amino-3-carboxybenzene, methyl 2-aminobenzoate, ethyl anthranilate, 1H-pyrazol-3-ylamine, 3-amino-4-carb Ethoxy -1H- pyrazole, 5-amino-1-ethyl pyrazole, 1H- benzimidazol-2-amine, 2-imidazole asleep min, 1-methyl-benzimidazol-2-amine, and mixtures thereof.

The following amines, which may or may not be in salt form, may also be used: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, 2-amino-4,5- Dimethylthiazole, hexetidine, mecamylamine, traylcypromine, triamterene, methyl [2- (3-trimethoxysilylpropylamino) ethylamine], bis (Triethoxysilylpropyl) amine, N1- (3- (trimethoxysilyl) 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 amino polymers, and also addition salts thereof. The term "amino polymer" means a rather high molecular weight macromolecule containing one or more primary or secondary amine functional groups. The term "polymer" means a compound comprising at least five repeating units linked in sequence via covalent bonds.

The amino polymer can be synthesized as follows:

Through radical reactions (polyacrylates, polymethacrylates, polyvinyls, etc.),

Through condensation reactions (polyesters, polyethers, polyamides, polyurethanes, polydimethylsiloxanes, polypeptides, etc.),

Via ring-opening reaction (polyester, etc.)

It may optionally be of chemically modified natural origin, for example polysaccharides (cellulose, dextran, chitosan, guar) and amino or thiol derivatives thereof.

The polymer can be any type of topology: linear, branched, star or hyperbranched chains (eg dendrimers), blocks, random or alternating chains.

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

Most particularly preferred are:

1 / polyamino acids containing free OH or NH ₂ or SH or COOH groups, for example polylysine,

2 / natural or modified polysaccharides containing NH ₂ or SH functionality,

3 / amino silicone,

4 / synthetic polymers containing NH ₂ or SH functional groups, in particular polyvinyl vinyls substituted with amine functional groups and polymers prepared from the following commercially available monomers:

,

,

And especially polylysine; Chitosan; Polyethoxylated amines such as carboxyPEG-8 amines, carboxyPEG-12 amines or carboxyPEG-24 amines; Or combinations thereof.

According to another variant of the invention, said amine (s) are purine bases, in particular adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, addition salts thereof , And combinations thereof.

It may not be configured to depart from the context of the present invention to combine some of these variations.

Preferably, when the composition comprises one or more amines, it is preferred that it is formula (IIIa), (IIIb), (IIIc), (IIIe) and ammonia, especially where R ₂₀ represents a linear C ₁ -C ₄ alkoxy group; Compound of (IIIg), and (IIIi ') alone or in a mixture thereof.

If the composition comprises one or more primary or secondary amines, ammonia or hydroxylamine, the content thereof is proportional to the weight of the composition, from 0.001% to 65% by weight, preferably 0.001% to 30% in the composition. Corresponds to the weight percentage.

enzyme

The composition according to the invention optionally comprises, for example, an isolase, for example β-glucosidase (EC 3.2.1.21) derived from sweet almond, alcohol oxidase (EC 1.1.3.13), alcohol dehydro 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, cinnamil 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, long-hydrocarbon-chain alcohol oxidase EC 1.1.3.20, methanol oxidase EC 1.1.3.31, alcohol dehydrogenase EC 1.1.99.20, methylglutamate dehydrogenase EC 1.5.99.5, 2-oxo acid decarboxylase One or more enzymes selected from aze 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.

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

salt

Compositions comprising the compound (s) of formulas (I) and / or (II) may optionally comprise one or more salts.

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

In particular, the anion constituting the salt may be inorganic (chloride, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, silicate, phosphate, hydrogen phosphate, hydroxide, etc.) or organic (aspartate, formate, acetate, lactate, sheet Laterates, gluconates, succinates, maleates, fumarates, orotates, and the like.

Together with the anion, the cation constituting the salt may be an alkali metal (preferably lithium, sodium or potassium), alkaline earth metal (preferably magnesium or calcium) or transition metal (scandium, titanium, vanadium, manganese, Molybdenum, iron, cobalt, nickel, copper, zinc, silver or gold). Other cations such as ammonium may also form salts. Preferably, the cation is selected from alkali metals (lithium, sodium or potassium), alkaline earth metals (magnesium or calcium), ammonium, and also the following transition metals (manganese, molybdenum, iron, copper, zinc, silver and gold). Could be.

If present, the amount corresponds to 0.001% to 40% by weight, and even more preferably 0.001% to 20% by weight, relative to the weight of the composition.

Other ingredients

Cosmetically acceptable media generally comprise at least water or a mixture of water and one or more organic solvents. Examples of organic solvents that may be mentioned include 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-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and Also included are aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

If present, the solvent is preferably present at a ratio of 1% to 99% by weight, more preferably 5% to 95% by weight, relative to the weight of the composition.

The compositions used in the process according to the invention also contain various auxiliaries commonly 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 polymeric mixed thickeners, antioxidants, penetrants, sequestrants, flavoring agents, buffers, dispersants , Modifiers such as volatile or nonvolatile, modified or unmodified silicones such as amino silicones, film formers, ceramides, preservatives, opacifiers and conductive polymers.

The adjuvants are generally present in amounts of from 0.01% to 20% by weight, respectively, in proportion to the weight of the composition.

Needless to say, the person skilled in the art will select the optional additional compound (s) above so that the advantageous properties essentially of the dye composition according to the invention are not negatively affected or substantially affected by the addition (s) in design. Will cover.

The pH of the composition is generally about 3 to 14, preferably about 4 to 11, more preferably 6 to 11. It can be adjusted to the desired value using acidic or basicizing agents conventionally used for dyeing keratinous fibers, or alternatively using standard buffer systems.

Among the acidifying agents that may be mentioned are, for example, 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 acid.

Among the basicizing agents, examples which may be mentioned include aqueous ammonia, alkali metal carbonates and the amines mentioned above.

The composition may be in various forms, such as liquids, creams or gels, powders to be mixed before use to obtain a poultice agent, in the form of sap, or any other form suitable for dyeing keratin fibers, especially hair.

The components of the abovementioned compositions are advantageously stored separately. In particular, the compound of formula (I) or a plant extract comprising the above (compound is dissolved or not dissolved in advance); If appropriate, an enzyme for replacing the radical R with a hydrogen atom if the compound (I) has not been previously dissolved; And oxidized oligosaccharides or polysaccharides containing aldehyde or imine compound (s) or aldehyde or imine functional groups are stored separately.

It should also be noted that when one or more amine compounds are present, these compounds are also stored separately from compound (s) (I) or plant extracts (dissolved or not dissolved) comprising the same.

It may also be advantageous to store the compound (s) of formula (I) or dissolved or insoluble plant extracts comprising the above in at least a closed container.

The composition used in the process according to the invention may also comprise one or more oxidants. In this case, it is referred to as a ready-to-use composition.

Oxidant

In particular, where an oxidant is present, the ready-to-eat composition is advantageously obtained by instant mixing the composition as described above with at least one composition comprising at least one oxidant before application.

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

Oxidants suitable for use also include four-electron redoxases (eg, laccases), two-electron redoxases, in the presence of an enzyme type of oxidizing agent, eg where appropriate, respectively, in the presence of a donor or cofactor thereof. (Eg, uricases), and peroxidases.

Particular preference is given to using hydrogen peroxide.

The oxidant is advantageously formed by hydrogen peroxide in an aqueous solution (aqueous hydrogen peroxide solution), the titer of which may be more particularly in the range from 1 to 40 vol, even more preferably in the range from 5 to 40 vol.

Thus, it should be noted that the compositions used in the present invention can be obtained by instant mixing of several compositions.

Thus, the composition just described is applied to human keratinous fibers, in particular hair.

Dyeing method

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

In this case, the component (compound or extract of formula (I) (dissolved or insoluble); if appropriate comprises an enzyme, aldehyde or imine compound (s), or an aldehyde or imine functional group for replacing the radical R with a hydrogen atom Oxidized oligosaccharides or polysaccharide (s)) are stored separately.

This embodiment is particularly suitable when the composition does not comprise an oxidizing dye (base or linking group).

According to a second embodiment, an instant food composition which has been specified above and which is obtained by instant mixing of the above-described composition free of oxidizing agent with the oxidizing composition is applied to the fibers.

This embodiment is particularly suitable when the composition comprises at least one oxidizing dye (base or linking group) or when it is desired to obtain a lightening effect.

According to a second variant of this embodiment, the oxidant free composition and the oxidizing composition are applied continuously without intermediate rinsing.

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

With regard to organic solvents which may be present in the oxidizing composition, reference may be made to the list given above in the context of the description of the composition according to the invention.

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

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

It may optionally include one or more additives conventionally used in the field of dyeing human keratinous fibers, depending on the function of the desired herbal form. Once again, reference may be made to the list of additives presented above.

Regardless of the selected embodiment (with or without oxidizing agent, instant mixing or continuous application of the composition and oxidizing agent), the mixture applied to the fiber is generally in place for a time of about 1 minute to 5 hours, preferably 10 minutes to 3 hours. To be politicized.

With respect to the temperature at which the composition (s) are applied, it is generally 20 to 200 ° C, advantageously 20 to 55 ° C.

Thus, the operation can be carried out, for example, using a heating hood, an infrared lamp or a straightening iron or curling iron.

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

More particularly, UVA radiation as described above (in particular, irradiance of 0.01 to 0.40 mW / cm ² , preferably 0.1 to 0.2 mW / cm ² , delivered by a continuous-spectrum lamp or a line-spectrum lamp) and / or Application to UVB radiation (especially irradiance of 0.01 to 0.20 mW / cm ² , preferably 0.01 to 0.1 mW / cm ² , delivered by a continuous-spectrum lamp or a line-spectrum lamp). .

Preferably, such compounds are alkali metal, alkaline earth metal or ammonium, carbonate, hydrogen carbonate, chloride, sulfate, silicate, monobasic phosphate or acetate salts.

According to one preferred variant of the invention, the stimulus is selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate or ammonium carbonate in a cosmetically acceptable medium; Sodium bicarbonate or potassium bicarbonate; Calcium chloride, lithium chloride or sodium chloride; Ammonium sulfate, sodium sulfate or magnesium sulfate; Sodium silicate; Monobasic sodium or potassium phosphate; By using a composition comprising 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, more preferably in proportion to the weight of the composition, in the range of 0.001% to 20% by weight.

It may not be configured to depart from the context of the present invention in order to perform several successive steps of combining different stimuli.

After the leave-on time, the keratinous fibers can be rinsed with water, optionally washed with shampoo, rinsed with water, dried or left to dry.

Another subject of the invention is a first compartment comprising at least one compound of formula (I) or a plant extract comprising said compound, wherein said compound undergoes a preliminary step consisting of replacing a radical R with a hydrogen atom; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidative oligosaccharide or a polysaccharide comprising at least one aldehyde or imine function.

In addition, another subject matter includes a first compartment comprising at least one compound of formula (I) or a plant extract comprising the above; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidative oligosaccharide or polysaccharide comprising at least one aldehyde or imine function and an enzyme for replacing the radical R of formula (I) with a hydrogen atom It consists of a multi-compartment device.

Finally, a final subject matter of the present invention comprises a first compartment containing at least one compound of formula (I) or a plant extract comprising the above; 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 function; And a third compartment comprising an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

Preferably, the dissolved or undissolved compound (s) of formula (I) are protected from air and are advantageously stored under inert atmosphere.

The device may optionally comprise additional compartments comprising one or more amines, or one or more salts.

The following examples illustrate the invention and are not intended to limit the scope of the invention.

Example  One

Gardenia extract with more or less concentrated geniposide is first dissolved in the presence of β-glucosidase. The extract-derived genipine is then isolated by crystallization after 100 kD ultrafiltration. The extract thus obtained was 99% concentrated in the genipine.

5 × 10 ⁻³ mol% and 5 × 10 ⁻³ or 25 × 10 ⁻³ mol% of Gardenia jasminoides extract with 99% concentration of genipine was dissolved by sonication in a buffered aqueous solution at pH 9 for 30 minutes. Obtain the composition.

Each composition is applied to natural gray hair comprising 90% white hair (1 g of tress per 2 g of solution) and the tress is placed under different application conditions (hotplate, see table below).

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

Example  2

A dye composition was obtained by dissolving 5 × 10 ⁻³ mol% of dissolved gardenia extract and 2.5 × 10 ⁻² mol% of oxidized starch, which had 93% concentration of genipine, in a buffer solution at pH 9 for 30 minutes with an ultrasonic generator. do.

The composition is applied to natural gray hair comprising 90% white hair (1 g of tress per 2 g of solution) and left at 100 ° C. (hotplate) for 5 minutes.

After the remaining time, the tress is rinsed, washed with shampoo and dried with a hair dryer.

Greenish-black coloration is obtained.

Example  3

In the presence of salts or amines, 5 × 10 ⁻³ mol% of dissolved Gardenia extract and 10 × 10 ⁻³ mol% of vanillin with 99% concentration of genipine in sonicator in a buffer solution at pH 9 for 30 minutes. By dissolving, a dye composition is obtained.

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

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

Example  4

Nipin to 93% is a gardenia extract 5 × 10 was dissolved in concentrated ^-3 mol%, component × 10 ^-3 mol% benzoic acid 10 (1% by weight) for 30 minutes with an ultrasonic generating device, benzyl alcohol (5% by weight ), A dye composition is obtained by dissolving in a medium comprising ethanol (15% by weight), aqueous buffer solution (79%) to pH 9.

Each composition is applied to a natural gray hair tress comprising 90% white hair (bath ratio (BR): tress 1 gram per 10 grams of solution) and the tress is placed under cellophane for 30 minutes at 50 ° C.

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

Example  5

In the presence of salt (saturated solution), 5 × 10 ⁻³ mol% of dissolved gardenia extract and 10 × 10 ⁻³ mol% of vanillin with 99% concentration of genipine were dissolved in an aqueous solution for 30 minutes with an ultrasonic generator. Obtain the composition.

Each composition is applied to natural and / or perm gray hair tress comprising 90% white hair (BR): 1 g of tress per 5 g of solution) and the tress is placed under cellophane for 2 hours at 40 ° C.

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

Example  6

Nipin to 93% is solubilized gardenia extract 5 × 10 ^-3 mol%, component × 10 ^-3 mol% ultrasonic waves 10 generated by the device 1/30% by weight of benzoic acid, benzyl alcohol 5% by weight while the concentration, The dye composition is obtained by dissolving in a medium comprising 15% by weight of ethanol, aqueous buffer solution (79%) to pH 9.

Each composition is applied to a natural gray hair tress comprising 90% white hair (bath ratio (BR): tress 1 gram per 10 grams of solution) and the tress is placed under cellophane for 30 minutes at 50 ° C.

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

Example  7

Each dye composition was obtained by dissolving 1.13 g% of dissolved Gardenia extract and vanillin (1.56 g%, if present) in an aqueous solution of pH 8 (KHCO ₃ ) for 20 minutes with a sonicator condensed with 93% concentration of genipine. do.

Each composition is applied to a natural gray hair tress containing 90% white hair (1 g of tress per 5 g of solution) and the tress is left at 30 ° C. for 60 minutes (hotplate).

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

The result is:

It is evident from the results that the color becomes more intense with vanillin.

Example  8

Preparation of Imine Type Compounds

In the presence of acetic acid, imine is prepared by reacting vanillin (0.4 g%) with 3-aminopropanol (0.2 g%) in a mixture of water (5 ml) / ethanol (1 ml) at ambient temperature for 30 minutes.

The imine obtained is then added to 1.13 g% of dissolved Gardenia extract and vanillin (1.56 g%, if present), with 93% concentration of genipine.

Thereafter, the pH of the composition is adjusted to 8 by adding KHCO ₃ and then placed in an ultrasonic generator for 20 minutes.

The composition is applied to natural gray hair comprising 90% white hair (1 g of tress per 6 g of solution) and the tress is left at 40 ° C. for 60 minutes (hotplate).

The color of hair is dark green-blue.

Example  9

A dye composition is obtained by dissolving 1.13 g% of dissolved gardenia extract and inulin oxide (1.13 g%) in which genipine is 93% concentrated in an aqueous solution of pH 8 (addition of KHCO ₃ ) for 20 minutes by sonicator.

Each composition is applied to natural gray hair comprising 90% white hair (1 g of tress per 5 g of solution) and the tress is left at 40 ° C. for 60 minutes (hotplate).

The hair is colored golden yellow.

Claims (15)

A method of dyeing human keratin fibres, to which a composition comprising the following is applied in a cosmetically acceptable medium:
Iridoid family compounds of formula (I) , optical or geometrical isomers thereof, inorganic or organic acid salts thereof, solvates thereof, or plant extracts comprising the above:

[In meals:
R ₁ represents a hydroxymethyl radical, a —CO ₂ R ₄ group wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; Represents sugar radicals;
R ₂ represents a hydrogen atom, a hydroxyl radical or a sugar radical;
R ₃ , which may be the same or different, represents a hydrogen atom, a hydroxyl radical, a (C ₁ -C ₄ ) alkyloxy radical; The number of hydroxyl groups does not exceed 2;
R represents a sugar radical;
N is an integer from 1 to 5;
Sugar radicals are obtained from aldose or aldose derivatives;
The plant extracts are being origin to the plant: flowers Abelia Mosanensis (Abelia grandiflora), adenovirus is Dia Carl Bray young (Adenorandia kalbreyeri), Adina poly Seppala (Adina polycephala), ah Guinea Tia Indica variants that raksil lease (Aeginetia indica var gracilis ), Asperula sp , Asystasia bella , Aucuba japonica , Avicennia marina , Bartsia trixago , Budreza Americana ( Buddleja Americana , Buddleja crispa , Buddleja japonica , Canthium schimperianum , Castilleja wightii , Caenorhinum minus ), Clerodendrum serratum , Coprosma sp , Cornus officinalis , Craibiodendron henr yi ), Cremaspora triflora , Crucianella sp , Daphniphyllum calycinum , Daphniphyllum humile , Daphniphyllum macropodum , Yerevan Mostar Keith Glidden Bra (Eremostachys glabra), S. Carlo Catania species (Escallonia sp), Eucommia (Eucommia ulmoides), Tampere Tia Apo-stage TB (Feretia apodanthera), go Solarium aft pusum (Galium humifusum), go Solarium Bærum (Galium verum ), Gardenia jasminoides , Garrya elliptica , Globularia dumulosa , Hedyotis corymbosa , Hygrophila difformis , Ixeris chinensis , Lamiastrum galeobdolon ( Lamium galeobdolon ), Lamiophlomis rotata ( Plomis rotata ), Leonotis nepetaefolia , Linaria sp , Morinda coreia , Mussaenda pubescens , Nepeta cilicia , Nepeta nuda subspecies Albiflora ( Nepeta nuda ssp. Albiflora), Odessa onti Tess Verna (Odeontites verna), come denran Dia Nose Limbo Inc. (Oldenlandia corymbosa), paella de Patria Skan dense (Paederia scandens), Peddie Kula lease Chinen system (Pedicularis chinensis), Peddie Kula lease condenser Sata (Pedicularis condensata , Pedicularis dolichocymba , Penstemon confertus , Penstemon deutus , Penstemon richardsonii , Penstemon richardsonii Lulatus ( Penstemon serrulatus ), Pithecoctenium crucigerum , Plantago alpina , Plantago carinata , Plantago lagopus , Plantago lagopus (Plantago lanceolata), other ing flange can ride (Plantago subulata), Prem and other Barbarez (Premna barbata), Grandi Oh dume torum (Randia dumetorum), Rhododendron Lato Kea in (Rhododendron latoucheae), Lot Only California wit Piel diimide (Rothmannia withfieldii), rubiah Tampere But, install isolated (Rubia peregrina), Western madder (Rubia tinctorum), four Pro Smart's Corte kiniyi (Saprosma scortechinii), Pula Ria korayi to Norilsk Scrophularia korainensis , Scrophularia lepidota , Ginseng ( Scrophularia ningpoensis ), Scyphiphora hydrophyllacea , Swida controversa , Syringa vulgaris ( Syringa vulgaris) vulgaris , Tarenna kotoensis , Tecoma heptaphylla , Thevetia gaumeri , Thevetia peruviana , Verbascum laxum , Verbascum laxum Verbascum nigrum , Verbascum phlomoides , Verbascum salviif olium , Verbascum sinuatum , Verbascum thapsus , Verbascum undulatum , Veronica derwentiana , Vitex nigrum , Wendlandia formosana ; And
** at least one aldehyde or imine compound selected from formulas (i) and (ii), an optical or geometric isomer thereof, an organic or inorganic acid salt thereof, a solvate thereof, or an oxidized oligosaccharide comprising at least one aldehyde or imine functional group or Polysaccharides:

[Formula (i) and (ii),
M is an integer of 0 or 1,
X represents an oxygen atom, NR ″ ₁ , wherein R ″ ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl radical;
The radicals R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;
Monovalent radical A and divalent radical A ₁ represent a group selected from:
* Hydroxycarbonyl group (-CO-OH) :
* A C ₆ aryl group optionally substituted by at least:
-Hydroxyl group,
C ₁ -C ₄ alkyl radicals,
Aryl-ethylenyl radicals (where said aryl groups are C ₆ and optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals),
-CO-OR ' ₄ or -O-COR' ₄ groups, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group;
-COOH groups in acidic or chlorided form,
-OR ' ₅ group, wherein R' ₅ represents a C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups, benzyl radical (-CH ₂ -C ₆ H ₅ ),
-According to one particular variant, two radicals -OR ' ₅ in the ortho position relative to the C ₆ aryl group can form a 5- or 6-membered heterocycle by two radicals R' ₅ ,
—N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and may be a hydroxyl group, an acidic or chlorinated carboxyl group (—COOH), or an acidic or chlorinated sulfone group A C ₁ -C ₆ alkyl radical optionally substituted with (-SO ₃ H), said radical R ' ₈ together with the nitrogen atom containing it contains a saturation comprising another heteroatom optionally selected from O and N or May form an unsaturated 5- or 6-membered heterocycle, which heterocycle is optionally substituted with a hydroxyl group),
- -COR _'10 group (where, R' ₁₀ represents an optionally substituted 6-membered hydrocarbon ring fused to a C ₆ aryl substituted with one or more C ₁ -C ₂ alkyl radical),
- -SR _'11 group (where, R' ₁₁ represents a C ₁ -C ₂ alkyl radical),
Halogen atoms selected from chlorine and bromine,
-O-SO ₂ -C ₆ H ₅ group,
-SO ₃ H group,
Unsaturated cationic or noncationic 5- or 6-membered heterocycles comprising one or two heteroatoms selected from O and N (one of said heteroatoms may be included in two rings; said heterocycle or Fused ring may be substituted with one or more C ₁ -C ₂ alkoxy radicals),
Said aryl group is optionally fused to a 5- or 6-membered heterocyclic group comprising one or two heteroatoms selected from O and N, said heterocycle optionally fused to a C ₆ aryl group,
Said aryl group is optionally fused to a C ₆ aryl group optionally substituted with one or more C ₁ -C ₂ alkoxy groups;
Cationic or noncationic, saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic groups comprising one or two identical or different heteroatoms selected from O and N;
Said heterocyclic group is optionally fused itself to a 6-membered aryl group optionally substituted with one or more C ₁ -C ₂ alkyl, C ₁ -C ₄ alkoxy or phenoxy groups;
Said heterocyclic group is optionally substituted with at least:
о hydroxyl group,
o C ₁ -C ₂ alkyl radicals optionally substituted with hydroxyl radicals;
o the amino radical —N (R ′ ₁₆ ) ₂ , wherein R ′ ₁₆ represents a C ₁ -C ₄ alkyl radical which may be the same or different and optionally substituted with a hydroxyl group, said radical R ′ ₁₆ Together with the containing nitrogen atom, it may form a saturated or unsaturated 5- or 6-membered heterocycle optionally comprising another heteroatom selected from O and N),
о one or more -COOH, R _'18 CONH- group (wherein, R' ₁₈ is C ₁ -C ₂ alkyl radical represents a) an optionally substituted C ₆ aryl radicals (wherein the C ₆ aryl radical to the nitrogen of the heterocyclic group Optionally linked to an atom, when the aryl radical is not substituted with the abovementioned radicals, the carbon atom is substituted with a hydrogen atom);
Divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ via a carbon, oxygen or nitrogen atom;
Where appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion or mixture of anions An, which ensures the electrical neutrality of the formulation;
Said dyeing method comprising the step consisting of replacing a radical R of the compound (s) of formula (I) with a hydrogen atom before or simultaneously with the dyeing method. delete The process of claim 1 wherein the content of compound (s) of formula (I) in the composition is from 0.001% to 10% by weight, proportional to the weight of the composition. The method of claim 1 wherein the compound of formula (i) or (ii) is X represents an oxygen atom. The method of claim 1 wherein the compound (s) is of formula (i) and is
m is 0 or 1;
The radicals R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;
* X represents an oxygen atom;
A represents the following:
Hydroxycarbonyl group (-COOH);
* A C ₆ aryl group optionally substituted by at least:
о hydroxyl group,
о C ₁ -C ₄ alkyl radicals,
o a -CO-OR ' ₄ or -O-COR' ₄ group, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical,
o -OR ' ₅ groups, where R' ₅ represents a C ₁ -C ₆ alkyl radical,
aryl-ethylenyl radicals (the aryl groups are C ₆ and optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals),
o an unsaturated cationic or noncationic 5- or 6-membered heterocycle comprising one or two heteroatoms selected from O and N (one of said heteroatoms may be included in two rings; said heterocycle or Fused ring may be substituted with one or more C ₁ -C ₂ alkoxy radicals),
Said aryl group is optionally fused to a 5- or 6-membered heterocyclic group comprising 1 or 2 heteroatoms selected from O and N;
Cationic or noncationic, saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic groups comprising one or two identical or different heteroatoms selected from O and N ;
Said heterocyclic group is optionally fused itself to a 6-membered aryl group optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₄ alkoxy groups;
Said heterocyclic group is optionally substituted with at least:
о hydroxyl group,
o C ₁ -C ₂ alkyl radicals optionally substituted with hydroxyl radicals,
o the amino radical —N (R ′ ₁₆ ) ₂ , wherein R ′ ₁₆ represents a C ₁ -C ₄ alkyl radical which may be the same or different and optionally substituted with a hydroxyl group, said radical R ′ ₁₆ Together with the containing nitrogen atom, it may form a saturated or unsaturated 5- or 6-membered heterocycle optionally comprising another heteroatom selected from O and N),
Where appropriate, the compound of formula (i) comprises a cosmetically acceptable anion or mixture of anions An, which ensures the electrical neutrality of the formulation;
The compound (s) of formula (i) may be in acetal or hemiacetal form. The method according to claim 1, wherein the content of the compound (s) of formula (i) or (ii), or the content of oxidized oligosaccharides or polysaccharides comprising at least one aldehyde or imine function, is from 0.001% by weight to proportion of the weight of the composition 30% by weight. The method of claim 1 further comprising one or more organic or inorganic salts selected from:
Chloride, carbonate, hydrogen carbonate, sulfate, hydrogen sulphate, silicate, phosphate, hydrogen phosphate, hydroxide, or aspartate, formate, acetate, lactate, citrate, gluconate, succinate, Organic anions selected from maleates, fumarates, orotates,
Alkali metal, alkaline earth metal, transition metal, or ammonium. 8. The method of claim 7, wherein the content of said at least one organic or inorganic salt (s) is in a range from 0.001% to 40% by weight, proportional to the weight of the composition. 9. The process according to claim 8, wherein the step consisting of replacing the radical R with a hydrogen atom is carried out using an enzyme selected from isolase and β-glucosidase (EC 3.2.1.21). The method of claim 1 wherein a temperature of 30 to 200 ° C. is applied. The method of claim 1, wherein the UVA radiation is applied at an irradiance of 0.01 to 0.40 mW / cm ² and / or the UVB radiation is applied at an irradiance of 0.01 to 0.20 mW / cm ² . A first compartment comprising at least one compound of formula (I) or a plant extract comprising the same according to claim 1 which undergoes a preliminary step consisting of replacing a radical R with a hydrogen atom, and claims 1, 4 and A multicompartment device comprising a second compartment comprising at least one compound of formula (i) or (ii) according to any one of claims 5, an oxidative oligosaccharide or polysaccharide comprising at least one aldehyde or imine function. A first compartment comprising at least one compound of formula (I) or a plant extract comprising same according to claim 1 and at least one formula according to any one of claims 1, 4 and 5) i) or a second partition comprising a compound of (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine function and an enzyme for replacing the radical R of formula (I) according to claim 9 with a hydrogen atom Multi-compartment device made. A first compartment comprising at least one compound of formula (I) or a plant extract comprising same according to claim 1 and at least one formula according to any one of claims 1, 4 and 5) i) or a second compartment comprising an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine functionality, and an enzyme for replacing the radical R of formula (I) according to claim 9 with a hydrogen atom A multi-compartment device comprising a third compartment comprising. A composition for dyeing human keratinous fibers, comprising in a cosmetically acceptable medium:
Iridoid family compounds of formula (I) , optical or geometrical isomers thereof, inorganic or organic acid salts thereof, solvates thereof, or plant extracts comprising the above:

[In meals:
R ₁ represents a hydroxymethyl radical, a —CO ₂ R ₄ group wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; Represents sugar radicals;
R ₂ represents a hydrogen atom, a hydroxyl radical or a sugar radical;
R ₃ , which may be the same or different, represents a hydrogen atom, a hydroxyl radical, a (C ₁ -C ₄ ) alkyloxy radical; The number of hydroxyl groups does not exceed 2;
R represents a sugar radical;
N is an integer from 1 to 5;
Sugar radicals are obtained from aldose or aldose derivatives:
When treating the composition, the compound (s) of formula (I) undergo a preliminary step consisting in replacing the radicals R with hydrogen atoms, optionally carried out by enzymes.
The plant extracts are being origin to the plant: flowers Abelia Mosanensis (Abelia grandiflora), adenovirus is Dia Carl Bray young (Adenorandia kalbreyeri), Adina poly Seppala (Adina polycephala), ah Guinea Tia Indica variants that raksil lease (Aeginetia indica var gracilis ), Asperula sp , Asystasia bella , Aucuba japonica , Avicennia marina , Bartsia trixago , Budreza Americana ( Buddleja Americana , Buddleja crispa , Buddleja japonica , Canthium schimperianum , Castilleja wightii , Caenorhinum minus ), Clerodendrum serratum , Coprosma sp , Cornus officinalis , Craibiodendron henr yi ), Cremaspora triflora , Crucianella sp , Daphniphyllum calycinum , Daphniphyllum humile , Daphniphyllum macropodum , Yerevan Mostar Keith Glidden Bra (Eremostachys glabra), S. Carlo Catania species (Escallonia sp), Eucommia (Eucommia ulmoides), Tampere Tia Apo-stage TB (Feretia apodanthera), go Solarium aft pusum (Galium humifusum), go Solarium Bærum (Galium verum ), Gardenia jasminoides , Garrya elliptica , Globularia dumulosa , Hedyotis corymbosa , Hygrophila difformis , Ixeris chinensis , Lamiastrum galeobdolon ( Lamium galeobdolon ), Lamiophlomis rotata ( Plomis rotata ), Leonotis nepetaefolia , Linaria sp , Morinda coreia , Mussaenda pubescens , Nepeta cilicia , Nepeta nuda subspecies Albiflora ( Nepeta nuda ssp. Albiflora), Odessa onti Tess Verna (Odeontites verna), come denran Dia Nose Limbo Inc. (Oldenlandia corymbosa), paella de Patria Skan dense (Paederia scandens), Peddie Kula lease Chinen system (Pedicularis chinensis), Peddie Kula lease condenser Sata (Pedicularis condensata , Pedicularis dolichocymba , Penstemon confertus , Penstemon deutus , Penstemon richardsonii , Penstemon richardsonii Lulatus ( Penstemon serrulatus ), Pithecoctenium crucigerum , Plantago alpina , Plantago carinata , Plantago lagopus , Plantago lagopus (Plantago lanceolata), other ing flange can ride (Plantago subulata), Prem and other Barbarez (Premna barbata), Grandi Oh dume torum (Randia dumetorum), Rhododendron Lato Kea in (Rhododendron latoucheae), Lot Only California wit Piel diimide (Rothmannia withfieldii), rubiah Tampere But, install isolated (Rubia peregrina), Western madder (Rubia tinctorum), four Pro Smart's Corte kiniyi (Saprosma scortechinii), Pula Ria korayi to Norilsk Scrophularia korainensis , Scrophularia lepidota , Ginseng ( Scrophularia ningpoensis ), Scyphiphora hydrophyllacea , Swida controversa , Syringa vulgaris ( Syringa vulgaris) vulgaris , Tarenna kotoensis , Tecoma heptaphylla , Thevetia gaumeri , Thevetia peruviana , Verbascum laxum , Verbascum laxum Verbascum nigrum , Verbascum phlomoides , Verbascum salviif olium , Verbascum sinuatum , Verbascum thapsus , Verbascum undulatum , Veronica derwentiana , Vitex nigrum , Wendlandia formosana ; And
** at least one aldehyde or imine compound selected from formulas (i) and (ii), an optical or geometric isomer thereof, an organic or inorganic acid salt thereof, a solvate thereof, or an oxidized oligosaccharide comprising at least one aldehyde or imine functional group or Polysaccharides:

[Formula (i) and (ii),
M is an integer of 0 or 1,
X represents an oxygen atom, NR ″ ₁ , wherein R ″ ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl radical;
The radicals R ′ ₁ and R ′ ₂ independently of one another represent a hydrogen atom or an unsubstituted linear C ₁ -C ₆ alkyl radical;
Monovalent radical A and divalent radical A ₁ represent a group selected from:
* Hydroxycarbonyl group (-CO-OH) :
* A C ₆ aryl group optionally substituted by at least:
-Hydroxyl group,
C ₁ -C ₄ alkyl radicals,
Aryl-ethylenyl radicals (where said aryl groups are C ₆ and optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals),
-CO-OR ' ₄ or -O-COR' ₄ groups, wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group;
-COOH groups in acidic or chlorided form,
-OR ' ₅ group, wherein R' ₅ represents a C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups, benzyl radical (-CH ₂ -C ₆ H ₅ ),
-According to one particular variant, two radicals -OR ' ₅ in the ortho position relative to the C ₆ aryl group can form a 5- or 6-membered heterocycle by two radicals R' ₅ ,
—N (R ′ ₈ ) ₂ groups, wherein R ′ ₈ may be the same or different and may be a hydroxyl group, an acidic or chlorinated carboxyl group (—COOH), or an acidic or chlorinated sulfone group A C ₁ -C ₆ alkyl radical optionally substituted with (-SO ₃ H), said radical R ' ₈ together with the nitrogen atom containing it contains a saturation comprising another heteroatom optionally selected from O and N or May form an unsaturated 5- or 6-membered heterocycle, which heterocycle is optionally substituted with a hydroxyl group),
- -COR _'10 group (where, R' ₁₀ represents an optionally substituted 6-membered hydrocarbon ring fused to a C ₆ aryl substituted with one or more C ₁ -C ₂ alkyl radical),
- -SR _'11 group (where, R' ₁₁ represents a C ₁ -C ₂ alkyl radical),
Halogen atoms selected from chlorine and bromine,
-O-SO ₂ -C ₆ H ₅ group,
-SO ₃ H group,
Unsaturated cationic or noncationic 5- or 6-membered heterocycles comprising one or two heteroatoms selected from O and N (one of said heteroatoms may be included in two rings; said heterocycle or Fused ring may be substituted with one or more C ₁ -C ₂ alkoxy radicals),
Said aryl group is optionally fused to a 5- or 6-membered heterocyclic group comprising 1 or 2 heteroatoms selected from O and N, said heterocycle optionally fused to a C ₆ aryl group,
Said aryl group is optionally fused to a C ₆ aryl group optionally substituted with one or more C ₁ -C ₂ alkoxy groups;
Cationic or noncationic, saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic groups comprising one or two identical or different heteroatoms selected from O and N;
Said heterocyclic group is optionally fused itself to a 6-membered aryl group optionally substituted with one or more C ₁ -C ₂ alkyl, C ₁ -C ₄ alkoxy or phenoxy groups;
The heterocyclic group is optionally substituted with at least:
о hydroxyl group,
o C ₁ -C ₂ alkyl radicals optionally substituted with hydroxyl radicals;
o the amino radical —N (R ′ ₁₆ ) ₂ , wherein R ′ ₁₆ represents a C ₁ -C ₄ alkyl radical which may be the same or different and optionally substituted with a hydroxyl group, said radical R ′ ₁₆ Together with the containing nitrogen atom, it may form a saturated or unsaturated 5- or 6-membered heterocycle optionally comprising another heteroatom selected from O and N),
о one or more -COOH, R _'18 CONH- group (wherein, R' ₁₈ is C ₁ -C ₂ alkyl radical represents a) an optionally substituted C ₆ aryl radicals (wherein the C ₆ aryl radical to the nitrogen of the heterocyclic group Optionally linked to an atom, when the aryl radical is not substituted with the abovementioned radicals, the carbon atom is substituted with a hydrogen atom);
Divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ via a carbon, oxygen or nitrogen atom;
Where appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion or mixture of anions An, which ensures the electrical neutrality of the formulation.