KR20140072150A - 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 keratin fibers, which comprises in a cosmetically acceptable medium:
* Iridide-based compounds of formula (I), or plant extracts comprising the above:

(Wherein R _{1 is} hydrogen, methyl, hydroxymethyl, aldehyde, -CO ₂ R ₄ , wherein R _{4 is} hydrogen or C ₁ -C ₂ alkyl), R _{2 is a} hydrogen atom, a hydroxyl radical, per radical; R _3: hydrogen, hydroxyl, alkyloxy; R: per radical (aldose or derivatives); an integer ranging from 1 to 5; compound (s) of formula (I) is optionally carried out using an enzyme, a radical Undergoes a preliminary step consisting in replacing R with a hydrogen atom);
** Formula (i) and (ii) at least one aldehyde or imine of the compound, and also at least one aldehyde or imine oxidation of oligosaccharides or polysaccharides containing the functional group:

(Wherein, n is 0 or 1; X: O, NR '1; A: COOH, optionally substituted aryl, with one or two heteroatoms, cationic or non-cationic containing sex, saturated or unsaturated 5-or 6 A ₂ : a divalent alkylene; in the case of an aldehyde, the compound may be in the form of an acetal or hemiacetal).
The present invention also relates to a composition as described above and also to a method of using the multi-compartment device.

Description

DYE COMPOSITION COMPRISING A GLYCOSYL IRIDOID COMPOUND AND A PARTICULAR ALDEHYDE OR IMINE, DYEING PROCESS AND DEVICES THEREFOR BACKGROUND OF THE INVENTION 1. Field of the Invention < RTI ID = 0.0 >

The present invention relates to a dye composition comprising, in a cosmetically acceptable medium, at least one compound of the glycosylidide series extracted from the plant (optionally diglycosylated in advance) and at least one specific aldehyde or imine compound, and And also relates to a dyeing method using such a composition.

Recently, there is an increasing interest in natural compounds that can be used as hair dyes.

For example, the patent application EP 440 494 discloses the use of a compound of the formula (I) in the order Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, One of the (sequo) iridoid-glycosides or non-glycosyl (sequo) iridides (also known as aglycones), extracted from plants such as the genus Ericaceae, Loganiaceae, A hair dyeing method using a composition comprising the above compound is disclosed.

The problem with such staining is that they are not particularly strong or that repeated application of the composition over several days or weeks is required to obtain satisfactory staining.

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

Accordingly, the object of the present invention is to overcome the disadvantages described above.

In particular, surprisingly, it has been found that by combining the compounds with a particular aldehyde or imine compound, using a compound of the type < RTI ID = 0.0 > of niglycosylidide < / RTI > type and derivatives thereof, It can be substantially improved.

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

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

* The following formula (I) of yirido Id series compound, its optical or geometric isomers thereof, inorganic or organic acid salt, solvate thereof, or a plant extract containing the:

[Wherein:

R ₁ is a hydroxymethyl radical, a group -CO ₂ R ₄ , wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; ≪ / RTI >

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

R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl radical, or 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;

The sugar radical is a derivative obtained from aldose or an aldose derivative:

The compound (s) of formula (I) undergoes a preliminary step consisting in replacing the radical R with a hydrogen atom, optionally carried out by an enzyme;

** the following formula (i) and one or more selected from (ii) an aldehyde or imine compound, its optical or geometric isomers thereof, organic or inorganic acid salt, a solvate thereof, and also the oxidation of oligosaccharides comprising at least one aldehyde or imine functional groups Or polysaccharides:

[In the formulas (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:

an additional primary monoalcohol (R ' ₃ OH), wherein R' ₃ is a symmetrical 1,2- or 1,3-diol containing a C ₁ -C ₅ alkyl radical or a C ₂ -C ₃ alkyl chain, Or 5-or 6-membered cyclic or non-cyclic acetals obtained by condensation of the compounds of formula

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;

The monovalent radical A and the bivalent radical A ₁ represent a group selected from the following:

* Hydroxycarbonyl group ( -CO - OH ) :

* At least optionally substituted C ₆ Aryl group :

- a hydroxyl group,

- a C ₁ -C ₄ alkyl radical,

- aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted by one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,

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

-COOH groups in acidic or chlorinated 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 (wherein R" ₆ is the same can be different from each other, it represents a C ₁ -C ₂ alkyl radicals), -SiR _'7 group (wherein, R' is _7, which may be the same or different, represents a C ₁ -C ₂ alkyl radical); Benzyl radicals (-CH ₂ -C ₆ H ₆ ),

According to one particular variation, the two radicals -OR ' ₅ in the ortho position with respect to the C ₆ aryl group may form a 5- or 6-membered heterocycle by two radicals R' ₅ ,

--N (R ' ₈ ) ₂ group wherein R' ₈ may be the same or different and is a hydroxyl group, a carboxyl group (-COOH) in acid or chloride form, or a sulfone group in acid or chloride form (-SO ₃ H) as an optionally substituted C ₁ -C ₆ represents an alkyl radical, the radicals R _'8 together with the nitrogen atom containing them, optionally O, N and NR' ₉ (wherein, R _'9 is C search the heterocycle is optionally substituted with a hydroxyl group),; ₁ -C ₂ alkyl refers to the radical) or a saturated or unsaturated 5-or 6-membered heterocycle comprising another hetero atom can form and is selected from

- -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),

- a halogen atom, preferably selected from chlorine and bromine,

- -O-SO ₂ -C ₆ H ₆ group,

- -SO ₃ H group,

- 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 nonaromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by 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 optionally fused to a C ₆ aryl group,

The 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 (wherein, R _'15 is the same as or may be different, represent a C ₁ -C ₂ alkyl radical) with optionally substituted) represents a) contains one or two identical or different heteroatoms selected from to, cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic 5-or 6-membered heterocyclic group;

Said heterocyclic group is optionally fused to a 6-membered aryl group itself 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 at least one of:

a hydroxyl group,

a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical;

о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this 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 Lt; RTI ID = 0.0 > heterocyclic < / RTI &

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 And where the aryl radical is unsubstituted by the radicals mentioned above, the carbon atom is replaced by 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 A radical (said alkyl or alkenyl radical optionally substituted with one or more hydroxyl groups);

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

If 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.

Another subject of the present invention is a method of staining human keratin fibers, wherein such compositions are used.

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

Another subject also comprises a first compartment comprising at least one compound of formula (I) or a plant extract comprising the same; And a second compartment comprising an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group and an enzyme for replacing the radical R of formula (I) with a hydrogen atom .

Finally, a final subject of the present invention is a pharmaceutical composition comprising a first compartment comprising at least one compound of formula (I) or a plant extract comprising said compound; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or an imine functional group; 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 a variety of shampoo-fast coloring without damaging the hair.

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

It should be noted that, unless stated otherwise, the limits of the range of values set forth in the detailed description are included within that range.

The human keratin fiber treated through the method according to the invention is preferably hair.

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

The inorganic acid salts are more particularly hydrochlorides, hydrobromides, sulfates and phosphates; Organic acid salts are more particularly citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates and acetates.

Solvates are more particularly hydrates.

A compound of formula (I) or a plant extract containing the same

As indicated above, the composition comprises, in a cosmetically acceptable medium, one or more of the compounds 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 C ₆ aldoose, such as allose, altrose, galactose, glucose, gulose, idose, mannose or talose, preferably glucose. With respect to aldoose derivatives, deoxy derivatives such as rhamnose and also dihalides, especially maltose, are preferred.

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

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

The compounds of formula (I) are generally found in plant extracts of the following plant sources: Abelia grandiflora , Adenorandia kalbreyeri , Adina ( Adina) polycephala ), Aeginetia indica variegacillarisis ( Aeginetia indica there is . gracilis , Asperula sp. sp ), Asystasia bella ), ficus ( Aucuba japonica , Avicennia marina ), Bartsia trick accident ( Bartsia trixago ), Buddleja ( Buddleja Americana , Buddleja crispa , Buddleja japonica ), Canthium schimperianum , Castilleja wightii , Chaenorhinum minus , Clerodendrum serratum , coprosma sp , Cornus officinalis , claviodendron henry, henryi , Cremaspora triflora), Kruger Asia Nella species (Crucianella sp), dapeu you pilrum Cali City num (Daphniphyllum calycinum , Daphniphyllum humile , Daphniphyllum macropodum , Eremostachys glabra , Escallonia sp ), Eucommia ulmoides , Feretia apodanthera , Galium < RTI ID = 0.0 > humifusum , Galium verum , Gardenia jasminoides , Garrya elliptica , Globularia dumulosa , Hedyotis < RTI ID = 0.0 > corymbosa ), Hygrophila difformis , Ixeris chinensis , Lamiaastrum, Lamiastrum galeobdolon ( Lamium galeobdolon ), Lamiophlomis rotata ( Phlomis rotata ), Leotothis nepetaepolia ( Leonotis nepetaefolia ), Linaria sp ), Morinda coreia ), Mussaenda pubescens , Nepeta cilicia ), Nepeta ( Nepeta nuda ssp . Albiflora), Odessa onti Tess Verna (Odeontites verna), all four denran Dia Nose Limbo (Oldenlandia corymbosa , Paederia scandens , Pedicularis ( Pedicularis scandens ), Pedicularis < RTI ID = 0.0 > chinensis , Pedicularis condensate , Pedicularis dolichocymba , Penstemon < RTI ID = 0.0 > confertus , Penstemon deutus , Penstemon, richardsonii , Penstemon serrulatus , Pithecoctenium crucigerum , Plantago alpina ( Plantago alpina , Plantago carinata , Plantago lagopus ), Plantago lanceolata ( Plantago lanceolata , Plantago subulata , Premna barbata , Randia dumetorum , Rhododendron latoucheae , Rothmannia withfieldii , Rubia peregrina , Rubia tinctorum , Saprosma, scortechinii , Scrophularia corainensis , Scrophularia lepidota , Scrophularia ningpoensis , Scyphiphora < RTI ID = 0.0 > hydrophyllacea , Swida controversa , Syringa vulgaris , Tarenna kotoensis ), tecoma heptapila ( Tecoma heptaphylla , < / RTI > Thevetia < RTI ID = gaumeri , Thevetia peruviana , Verbascum laxum , Verbascum nigrum), Berger des Bas Qom flow Rana (Verbascum phlomoides), Bercy Stadium Bath Qom salbiyi poly (Verbascum salviifolium , Verbascum sinuatum , Verbascum, thapsus), Verbier Bath Qom undul ratum (Verbascum undulatum , Veronica derwentiana , Vitex nigrum , Wendlandia formosana ).

Preferably, the plant extract used is gardenia.

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

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

Thus, in the case of an aerial part, it is cleaned and, if desired, after milling is macerated in a suitable solvent, especially ethanol or water, followed by filtration, concentration and optionally drying.

In the case of more specific fruids, it is optionally frozen and rinsed with water to remove any impurities present. It may optionally be sterilized using a solution comprising ethanol and chlorine.

For practical extraction, the fruit is defrosted and, if desired, compressed, for example using a particularly suitable hydraulic press.

Thereafter, if appropriate, the recovered juice may undergo a step of concentration and drying.

In the case of gardenia, there are commercially available extracts with a variable content of compounds of formula (I).

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

The content of the compound of formula (I) in the composition is 0.001 wt% to 10 wt% in proportion to the weight of the composition.

It should be noted that the compound (s) of formula (I) undergo a step consisting in replacing the radical R with a hydrogen atom prior to or simultaneously with the dyeing process.

The reaction can be carried out in any manner known to the person skilled in the art and can be carried out in particular using, for example, enzymes selected from the group consisting of sweet almond and succinic acid (EEC 3.2.1.21) derived from sweet almond.

Thus, if the operation occurs simultaneously with the dyeing process, the enzyme is added to the composition immediately prior to its application to the fiber.

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

The work takes place at a temperature close to room temperature (20-45 [deg.] C) and over a period of time ranging from 1 to 5 hours.

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

Additional dyes

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

Of these additional dyes, mention may be made of natural or synthetic direct dyes, oxidation dyes having bases optionally combined with couplers, and also combinations thereof.

The 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 in particular anthraquinone dyes, Dyes, triarylmethane direct dyes, indoline amine direct dyes and natural direct dyes.

Among the above natural direct dyes, it is possible to use any one of lawsones, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, Anthragallol protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, chlorophyll, chlorophyllin, Orcein, hematin, hematoxylin, brazilin, brazileine, safflower pigments (e.g. carthamine), flavonoids (e. G. (Including, but not limited to, morin, apigenidin and sandalwood), anthocyanins (e.g., apigeninidin), carnenoids, tannins, sorghum and cochineal carmine, . Extracts or decoctions containing such natural dyes and especially henna based 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 these linking groups, mention may be made in particular of meta-phenylenediamine, meta-aminophenol, meta-diphenol, naphthalene linking and heterocyclic linking groups, and addition salts thereof.

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

The coupler (s) are each present in an amount of 0.001 wt.% To 10 wt.%, Preferably 0.005 wt.% To 6 wt.%, Generally proportional to the total weight of the dye composition.

In general, the addition salts of oxidizing bases and linking groups that can be used in the context of the present invention include, in particular, addition salts with acids such as hydrochloride, hydrobromide, sulfate, citrate, succinate, tartrate, lactate, Benzene sulfonates, phosphates and acetates.

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 oxidized oligosaccharides or polysaccharides comprising at least one aldehyde or imine functional group.

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

Compound (i) and (ii) is also an additional primary monoalcohol (R _'3 OH) (wherein, R' ₃ is symmetrical containing ₃ alkyl chain C ₁ -C ₅ alkyl radical or a C ₂ -C 1, 2-or 1,3-diol) of 5-or 6-membered cyclic or bicyclic acetals.

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 the formulas (i) and (ii) is confirmed by a mixture of organic or inorganic anions or anions, which, if desired, can balance the charge (s) For example, halides such as chlorides, bromides, fluorides or iodides; hydroxide; sulfate; Hydrogen peroxide; Alkyl sulfate (wherein the linear or branched alkyl moiety is C ₁ -C ₆ ), such as methyl sulfate or ethyl sulfate ions; Carbonate and bicarbonate; Salts of carboxylic acids such as formate, acetate, citrate, tartrate and oxalate; Alkyl sulfonates wherein the linear or branched alkyl moieties are 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 alkyl sulfonates such as mesylate.

The nonionic or anionic oxidizing polysaccharide comprises at least one aldehyde group and optionally at least one anionic group. The anionic group is preferably a carboxyl group or a carboxylate group.

The nonionic or anionic oxidizing polysaccharide used may be represented by the following formula (II): < RTI ID = 0.0 >

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

[Wherein,

P represents a polysaccharide chain composed of a monosaccharide having 5 or more carbon atoms, preferably 6 or more carbon atoms, more particularly 6 carbon atoms,

X is a hydrogen atom, an alkali metal or alkaline earth metal such as sodium or potassium, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine and 3-amino-1,2-propanediol and basic amino acids such as lysine, Arginine, sarcosine, ornithine, and citrulline.

m + n is 1 or more,

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

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

The term "substitution degree DS (CHO) or DS (COOX) of the polysaccharide according to the present invention" means the number of carbon atoms oxidized as an aldehyde or carboxyl group for all repeating units and the basic monosaccharides constituting the polysaccharide (even preoxidation Quot; open "). ≪ / RTI >

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

The polysaccharide chain represented by P is preferably selected from the group consisting of inulin, cellulose, starch, pectin, guar gum, xanthan gum, pullulan gum, alginate gum, agar-agar gum, carrageenan gum, gellan gum, gum arabic, xylose and tragacanth gum, and derivatives thereof.

The term "derivative" means a compound obtained by chemical modification of the above-mentioned compounds. This may be an ester, an amide or an ether of the compound.

Oxidation can be carried out according to methods known in the art, for example in FR 2 842 200, FR 2 854 161 or in the literature ["Hydrophobic films from maize bran hemicelluloses" by E. Fredon et al., Carbohydrate Polymers 49, 2002, pages 1 to 12]. 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, efficient, and does not produce any toxic by-products or by-products that are difficult to remove.

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

Mixtures of single phthalocyanines or phthalocyanines, for example mixtures of cobalt phthalocyanine and iron phthalocyanine, can be used as catalysts. The amount of catalyst depends on the desired degree of substitution. Generally, small amounts, e. G., Amounts corresponding to 0.003 to 0.016 mole equivalents per 100 glucose units of polysaccharide are suitable for use.

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

More preferably, the polysaccharide is selected from the group consisting of inulin, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, starch, starch acetate, hydroxyethyl starch, hydroxypropyl starch, Is obtained by oxidation of carboxymethyl cellulose, guar gum, carboxymethyl guar gum, carboxymethyl hydroxypropyl 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 within the range of 0.005 to 2.5; and n is the degree of substitution (DS (COOX)) of the polysaccharide having at least one carboxyl group within the range of 0.001 to 2.

Examples of oxidized oligosaccharides and polysaccharides comprising compounds of formulas (i) and (ii), at least one aldehyde or imine functional group, which are particularly suited for the practice of the present invention include the following compounds, their salts, isomers and their solvates , And these compounds exist singly or as a mixture:

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

Advantageously, the 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:

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

A C ₂ -C ₈ alkenyl radical containing a carbon-carbon double bond;

A hydroxycarbonyl group (-COOH);

* At least optionally substituted C ₆ Aryl group :

a hydroxyl group,

a C ₁ -C ₄ alkyl radical,

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

o -OR ' ₅ group (wherein R' ₅ represents a C ₁ -C ₆ alkyl radical),

aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,

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, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by 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. , A saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group ;

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

Said heterocyclic group is optionally substituted at least one of:

a hydroxyl group,

a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical,

о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this 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 Lt; RTI ID = 0.0 > heterocyclic < / RTI &

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

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

As preferred examples of the compound (i), the following compounds, isomers thereof, salts thereof or solvates thereof may be mentioned, and these compounds may be present singly or as a mixture:

More particularly, the content of the oxidized oligosaccharide or polysaccharide comprising compound (s) of formula (i) or (ii), or at least one aldehyde or imine functional group is from 0.001% to 30% by weight, relative 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), starch known under the trade name 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;

Cellulose oxide (Rn 9032-52-4), known under the name: 2,3-Dialdehyde cellulose; 2,3-Dialdehydocellulose; Aldehydocellulose; Cellulose 2,3-dialdehyde; Cellulose dialdehyde; Dialdehyde cellulose;

- oxidized inulin (Rn 82446-43-3);

- dextranaldehyde (Rn 37317-99-0).

Amine

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

In general, such addition salts of amine compounds which can be used in the context of the present invention are those which are obtained by addition of an acid addition salt such as a hydrochloride, hydrobromide, sulphate, citrate, succinate, tartrate, lactate, Benzenesulfonate, dodecylbenzenesulfonate, phosphates and acetates, preferably hydrochloride, citrate, succinate, tartrate, phosphate and lactate.

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

In particular, the formula (III) is as follows:

R ' _7R ' ₈ NH (III)

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

- a hydrogen atom;

- one or more groups which may contain from 1 to 5 carbon-carbon double bonds and / or which may optionally be substituted and which optionally contain one or more heteroatoms and / or one or more heteroatoms or groups comprising one or more heteroatoms Branched and / or cyclic, saturated and / or unsaturated, aromatic (preferably selected from oxygen, nitrogen, sulfur, C = O, C = S, SO and SO ₂ or combinations thereof) Or non-aromatic C ₁ -C ₂₀ hydrocarbon radicals; Wherein said hydrocarbon radicals R ' ₇ and R' ₈ together with the nitrogen atom to which they are attached are optionally substituted and optionally aromatic and optionally substituted by a 6-membered aromatic or heteroaromatic ring containing another nitrogen or non- Form a saturated or unsaturated 5- or 7-membered heterocycle fused to a heteroaromatic nucleus; The hydrocarbon radical does not include any nitro, nitroso, peroxo or diazo functional groups.

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

Among the groups present as substituents of the heterocyclic hydrocarbon group, the following groups may be mentioned:

The carboxyl, sulfone, phosphone,

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

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

Tree (C ₁ -C ₄₎ alkylsilyl, tri (C ₁ -C ₄₎ alkoxy carbonyl silanol,

Amino, (di) (C ₁ -C ₄ ) alkylamino, tri (C ₁ -C ₄ ) alkylammonium,

Thiol, (C ₁ -C ₄₎ alkylthio,

Aminosulfonyl, (di) (C ₁ -C ₄ ) alkylaminosulfonyl,

Aminocarbonyl, (di) (C ₁ -C ₄ ) alkylaminocarbonyl,

(C ₁ -C ₄ ) alkylcarbonylamino,

Guanidine,

Ureido _{(N (R) 2 -CO-} NR'-) ( where the radicals R and R 'are, independently of each other, hydrogen atom or C ₁ -C ₄ alkyl or (C ₁ -C ₄₎ alkylsulfonylamino 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: carboxyl in the acidic or chlorinated form; Hydroxyl; C ₁ -C ₄ alkoxy; (C ₁ -C ₈₎ alkoxycarbonyl; Thiol; (C ₁ -C ₄₎ alkylthio; Amino; Mono- and di (C ₁ -C ₄₎ alkylamino; Aminocarbonyl; Mono- and di (C ₁ -C ₂₎ alkyl-aminocarbonyl; (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 from 1 to 5 primary and / or secondary amine functionalities; The amine (s) do not contain any N-N bonds. In addition, the amine (s) of formula (III) do not contain more than two heteroatoms bonded together.

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

Amino acids and / or derivatives of formula ( IIIa ):

[In formula (IIIa):

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

- R _"9 is hydrogen, C ₁ -C ₄ alkyl radical or unsubstituted represents the 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) which may be mentioned most particularly include asparagine, cysteine, glutamine, histidine, lysine, methionine, phenylalanine, proline, pyrrolizine, serine, threonine, tryptophan and tyrosine, .

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

o from the amino acid of formula ( IIIb ) Derived esters and / or derivatives :

[In formula (IIIb):

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

- R _"9 is hydrogen, C ₁ -C ₄ alkyl radical or unsubstituted represents the 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 containing 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, C = Linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon radical in which one or more groups comprising at least one heteroatom selected from S, SO and SO ₂ or a combination thereof is interrupted, wherein said alkyl radical is any nitro, nitro, Nor contain peroxo or diazo functional groups;

- unsubstituted benzyl radical.

According to one particular variation, R ₉ and R ₁₁ may optionally form a saturated 5-membered carbon-based ring.

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

As examples of the formula (IIIb), methoxytrosine, 2-ethylpiperidine carboxylate; D, L-phenylalanine methyl ester; L-cysteine 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; Ethyl glycine; H-D, L-alanine ethyl ester hydrochloride; D, L-tyrosine ethyl ester hydrochloride; Methyl 2- (phenylamino) acetate; Ethyl glutamate; Bis (?,? - tert-butyl) D, L-aspartate hydrochloride; Ethyl L- alpha -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 can be mentioned.

amides and thioester and / or derivatives derived from amino acids of formula ( IIIc ) :

[In formula (IIIc):

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

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 may, together with the nitrogen atom to which they are attached, may form a saturated 5-membered heterocycle;

- R ₁₂ represents -

A hydrogen atom;

Preferably a C ₁ -C ₆ alkyl radical substituted with one or more hydroxyl, thiol, (C ₁ -C ₄ ) alkylthio, amido or amino, a phenyl radical optionally substituted with one or more hydroxyl, Indolyl radicals optionally substituted with hydroxyl, 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.

Wherein X is a nitrogen atom and R ₁₂ is an alkyl radical as defined above and most particularly an alkyl radical as defined above and most particularly an alkyl radical as defined above wherein R ₁₂ is an alkyl radical as defined above and most especially an alkyl radical as defined above, (IIIc) represents a dipeptide or an oligopeptide when the amino acid residue is an amino acid residue selected from the group consisting of an amino acid residue selected from the group consisting of an amino acid residue selected from the group consisting of:

As examples of the compound of the formula (IIIc), 3-amino dihydrothiophen-2-one hydrochloride; D, L-homocysteine thiolactone; D, L-leucyl-D, L-alanine, aspartame; (S) -pyrrolidine-2-carboxamide; [N - (- acetamido)] - 2-aminoethanesulfonic acid; D, L-alanyl-D, L-phenylalanine; 2- (2-aminoacetamido) -3- (4-hydroxyphenyl) propanoic acid; 2- (2-aminoacetylamino) acetic acid; (R) -3-aminoazepan-2-one; Glycine amide 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- beta -alanine; Glycyl-L-proline; Glycyl-D, L-valine; 2-aminomalonamide; L-methionamide hydrochloride; 2-amino-3-methylbutanamide; D-alaninamide hydrochloride; L-tyrosinamide hydrobromide; Aspartic acid amide; L-tyrosine amide hydrochloride; L-argininamide dihydrochloride; Lysine amide dihydrochloride; Threonamide hydrochloride; Isoleucine amide hydrochloride; Histidine amide dihydrochloride; D, L-alaninamide hydrochloride; 2-Amino-3- (4-hydroxyphenyl) propionamide; D, L-tryptophanamide hydrochloride; N-hydroxy-L-arginine acetate (H-ARG-NH2 2 AcOH); Asparagine amide hydrochloride; L-glutamic acid?,? - diamide hydrochloride; D-phenylalanine amide; D-leucine amide hydrochloride; L-glutamic acid? -Amide; L-methionine amide; L-cysteine bisamide hydrochloride; Glycine amide acetate; D-lysine amide dihydrochloride; Glycine amide; L-isoglutamine gamma-methyl ester hydrochloride; D-argininamide dihydrochloride; (S) -pyrrolidine-2-carboxamide; Porphyryl histamine hydrochloride can be mentioned.

- Amino compound of formula ( IIId ):

[In formula (IIId):

- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , independently of one another,

A hydrogen atom;

Optionally containing one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO < RTI ID = 0.0 > And / or cyclic, saturated and / or cyclic, saturated or unsaturated, optionally substituted with one or more groups containing one or more heteroatoms selected from halogen, halogen, and SO ₂ or combinations thereof, optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups. Or an unsaturated C ₁ -C ₂₀ hydrocarbon radical, wherein said 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 form a saturated or unsaturated 5- or 7-membered heterocycle containing the same nitrogen or non-nitrogen heteroatom, said alkyl radical being optionally aromatic, Nor include nitro, nitro, peroxo or diazo functional groups; More particularly an optionally substituted C ₁ -C ₁₀ alkyl radical; And preferably a linear or branched C ₁ -C ₈ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one or two hydroxyl groups, a hydroxycarbonyl radical, a ureido radical, (C ₁ - C ₄ ) alkoxycarbonyl radical; Unsubstituted phenyl radical;

X represents a nitrogen, oxygen or sulfur atom;

- R < ₁₇ > represents -

A hydrogen atom;

Optionally containing 1 to 5 conjugated or non-conjugated carbon-carbon double bonds, optionally substituted as indicated above, optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, A linear or branched, saturated or unsaturated C ₁ -C ₁₈ hydrocarbon radical in which one or more groups comprising at least one heteroatom selected from SO and SO ₂ or a combination thereof is interrupted, wherein said alkyl radical is any nitro, nitroso, More particularly, R ₁₇ represents hydrogen, an optionally substituted linear or branched C ₁ -C ₁₀ alkyl radical; And preferably a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one to two hydroxyl groups;

- R < ₁₈ > represents -

A hydrogen atom;

One optionally substituted as indicated above and optionally containing one or more heteroatoms and / or one or more heteroatoms selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof A linear or branched C ₁ -C ₈ alkyl radical wherein said radical is interrupted and optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups wherein said alkyl radical has any of the nitro, nitroso, peroxo or diazo functional groups Not included);

- o is an integer from 0 to 5;

According to a further 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 , , Optionally form another saturated or unsaturated 5- or 6-membered heterocycle containing another nitrogen or non-nitrogen heteroatom.

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

As examples of the compound of the formula (IIId), L-2-aminohexanoic acid amide hydrochloride; L-phenylalanine amide; (S) - (+) - aminosuccinic acid; (R) -2- (methylamino) succinic acid; Ethylnipecotate; 3-piperidinecarboxylic acid; 3-phenyl-beta-alanine; Ethyl 3-aminobutyrate; 2-carbonylamine; D, L- [beta] -amino adipic 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- [beta] -amino adipic acid; 4- (methylamino) butyric acid hydrochloride; Ethyl? -Aminobutyrate hydrochloride; Hexahydro nicotinamide; Piperidine-4-carboxamide; 3-Carbamoyl-2,2,5,5-tetramethylpyrrolidine can be mentioned.

- Amino compound of formula ( IIIe ):

[In formula (IIIe):

- R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meanings as defined above;

- R < ₁₉ > represents -

A hydrogen atom;

One optionally substituted as indicated above and optionally containing one or more heteroatoms and / or one or more heteroatoms selected from oxygen, nitrogen, sulfur, CO, C = S, SO and SO ₂ or combinations thereof A linear or branched C ₁ -C ₈ alkyl radical wherein said radical is interrupted and optionally containing one or more hydroxyl or C ₁ -C ₂ alkoxy groups wherein said alkyl radical has any of the nitro, nitroso, peroxo or diazo functional groups 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 a further variant of the invention, the radicals R ₁₃ and R ₁₄ , optionally together with the carbon atoms of the substituents R ₁₃ and R ₁₄ , may form a saturated 5- or 6-membered heterocycle.

As examples of the compound (IIIe), the following acids, their enantiomers, if any, and their salts and their hydrates can be mentioned: (1-aminoethyl) phosphonic acid, (aminomethyl) (1-aminopropyl) phosphonic acid, (1-aminobutyl) phosphonic acid, iminovis (methylphosphonic acid), (1-amino- (1-amino-3-methylbutyl) phosphonic acid, 1-aminobenzylphosphonic acid, 1-amino (Aminomethyl) bisphosphonic acid (especially its salt), (1-amino-2,2-dimethylpropyl) phosphonic acid (especially the oxalate salt), hexylphosphonic acid, diethyl (1-amino-2-methylbutyl) phosphonic acid, (1-aminooctyl) phosphonic acid, (1-amino-1-methylpropyl) Force phone , (1-amino-1, 2-dimethylpropyl) phosphonic acid, (1-amino-1,3-dimethylbutyl) phosphonic acid, (Cyclopentyl) phosphonic acid, (1-aminohydroxycarbonyl) propylphosphonic acid, (1-amino-1-methylethyl) phosphonic acid, 1-amino- (2-amino-2-methyl-4-phosphonobutanoic acid and its ethyl ester, (diethyl (3-aminopropyl) phosphonic acid Amino-2-methyl-4-phosphonobutyric acid, diethyl (3-aminopropyl) phosphonate, 2-amino- (2-aminoethyl) phosphonic acid, 2-aminoethylphosphonic acid, 2-aminoethylphosphoric acid, (2-pyrrolidinylcarbonyl) amino) ethyl) morpholine (2-amino-1-methyl-2-phenyl) ethylphosphonate, diethyl (2-amino-2-phenyl) ethylphosphonate, and / or mixtures thereof.

- Amino compound of general formula ( IIIf ):

[In formula (IIIf):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meanings as defined above, and wherein the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are independently of each other a hydroxyalkyl radical, (C ₁ -C ₄ ) alkoxycarbonyl radical, a carboxaldehyde radical, (C ₁ -C ₃ ) alkoxy;

q is an integer from 1 to 18;

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

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

According to a further variant of the invention, the radicals R ₁₆ and R ₁₈ or R ₁₃ and R ₁₈ optionally together with the carbon atom attached to R ₁₆ (or to R ₁₃ ) and the nitrogen atom attached to the radical R ₁₈ , , Optionally substituted as indicated above, optionally aromatic, and optionally a further saturated or unsaturated 5- or 6-membered heterocycle containing the same nitrogen or non-nitrogen heteroatom.

According to a further variant of the invention, the amines of the formula (IIIf) can be? -Aminoalcohols derived from the reduction of one of the abovementioned 20 esterified or non-esterified amino acids of an acid or ester functional group with an alcohol have.

As examples of the compound (IIIf), the following compounds, enantiomers thereof, if any, and salts thereof and hydrates thereof can be mentioned: isopropanolamine, isopropylamine, methylethanolamine, methylglucamine, stearamine, Amino-1-phenylpropane-1, 3-diol, 1,3-dihydroxypropane, 1,3-dimethylpentylamine, octadrine, spermidine, theanine, octamethylamine, 2-methylpropane, 2-amino-2- (hydroxymethyl) propane-1,3-diol tris, 2-amino-1,3-dihydroxy- 2-methylpropan-1-ol, phenylglycinol, 2-aminopropanol, 2-hydroxyethylamine, 2-aminohexan-1-ol, 1 Amino-1-cyclopentanemethanol, histidinol, 2-amino-3- (3-indolyl) propanol, 3- (4-hydroxyphenyl) , 2-amino-1-propanol, 2-amino-1 Amino-3-methyl-1-butanol,? -Aminobenzenepropanol, 2-aminopropane-1-ol, 2-amino- Amino-4-methylpentan-1-ol, 3-aminopropane thiol, ethyl 2-amino-4-mercaptobutanoate, 6-hydroxyhexylamine, Amino-1-deoxy-D-fructose, D-glucosamine, 2-pyrrolidine Propanol amine, 3 - [(2-hydroxyethyl) amino] propan-1-ol, di- beta -hydroethylamine, bis N-propanolamine, 4-amino-N-butanol, methyl 3-amino-3-deoxy- alpha -D-mannopyranoside, N-butyl Heptanediol, 1-hexylamine, 1-octylamine, 1-nonylamine, 1-decylamine, 1-ethylhexylamine, For example, Amino-2-hydroxy-4-phenylbutanoic acid, 4-amino-3-hydroxybutyric acid, ethyl 4- Hydroxy-2-pyrrolidinecarboxylate, and mixtures thereof.

- Amino compound of formula ( IIIg ):

[In formula (IIIg):

- R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meanings as defined above;

- R < ₂₀ > represents -

Linear C ₁ -C ₄ alkyl radicals,

A linear C ₁ -C ₄ alkoxy radical,

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.

Examples of the compound (IIIg) include aminopropyltriethoxysilane, (aminomethyl) trimethylsilane, 2- (trimethylsilyl) ethanamine, 3- (trimethylsilyl) propan- (Trimethylsilyl) propylamine, 3- (trimethoxysilyl) propylamine, 3-triethoxysilyl-1-propanamine and (3- Aminopropyl) trimethoxysilane, and mixtures thereof.

o Amino compounds of formula ( IIIh ):

[In formula (IIIh):

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₈ have the same meanings as defined above and, furthermore, the radicals R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ independently of one another are a hydroxyl radical, C ₁ -C ₄ ) alkoxycarbonyl radical, a carboxaldehyde radical, (C ₁ -C ₃ ) alkoxy;

- R < ₂₁ & R < ₂₂ > independently of one another represent:

A hydrogen atom;

Optionally substituted with one or more heteroatoms and / or preferably oxygen, nitrogen, sulfur, CO, C = S, SO and SO, optionally substituted as indicated above, _2, or it is inserted into at least one group containing one or more heteroatoms selected from combinations thereof, optionally containing a one or more hydroxyl or C ₁ -C ₂ alkoxy, linear, branched and / or cyclic, saturated and / or Unsaturated C ₁ -C ₂₀ hydrocarbon radicals, more particularly optionally substituted C ₁ -C ₁₀ alkyl radicals; And preferably a linear or branched C ₁ -C ₄ alkyl radical optionally substituted with one or more hydroxyl groups, preferably one to two hydroxyl groups;

- R ₂₁ and R ₂₂ , together with the nitrogen atom to which they are attached, are optionally substituted as indicated above and optionally saturated or unsaturated 5- to 7-membered heterocyclic ring optionally containing another same nitrogen or non-nitrogen heteroatom, Lt; / RTI > may form a one-membered heterocycle; The alkyl radical does not include any nitro, nitroso, peroxo or diazo functional groups,

w is an integer from 1 to 10;

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

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

Of the compounds of the formula (IIIh), mention may in particular be made of the following amines, if present, their enantiomers, and also their salts and their hydrates: gerontine, N- [3-aminopropyl] Butanediamine, 4- (ethylamino) -N-butylamine, 2- [3- (2-hydroxy- 1,3-diol, 1,4,8,11-tetraazacyclotetradecane, 1,4-diazacycloheptane, 1,3-diamino-2-hydroxypropane, N , N'-bis (2-aminoethyl) propane-1,3-diamine, 3-methylaminopropylamine, 1,3-diaminopropane, N, N'-dimethyltrimethylenediamine, 2,2- Methylene diamine, 2,2-dimethyl-1,3-diaminopropane, N- (2-hydroxyethyl) -1,3-diaminopropane, N- (2-hydroxyethyl) Aminopropane, cystamine, 1,5-diaminopentane, 1,6-diaminohexane, lauraminopropylamine, 2-methylheptyl Amines such as amine (2- (N-methyl) heptylamine), ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, 3-aminoalanine, piperazine- Aminolane, methylpiperazine-2-carboxylate, ethyl 3-aminoprolinate, 2,4-diamino-N-butyric acid, N- [3- (trimethoxysilyl) propyl] ethylenediamine, mixture.

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

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

- R < ₂₃ & R < ₂₄ > independently of one another represent:

Optionally substituted C ₁ -C 8 alkyl, optionally interrupted by one or more heteroatoms and / or one or more groups comprising at least one heteroatom, preferably selected from oxygen, nitrogen, sulfur, CO, SO and SO ₂ or combinations thereof ₆ alkyl radical wherein said alkyl radical does not contain any nitro, nitroso, peroxo or diazo functional groups;

* Alkylcarbonyl radical (R-CO-) (wherein, R represents a -C ₄ alkyl radical, C _1);

* An alkylsulfonyl radical (RSO ₂ -), wherein 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;

A halogen atom, preferably selected from bromine, chlorine and fluorine;

A C ₁ -C ₄ alkoxy group;

A C ₂ -C ₄ (poly) hydroxyalkoxy group;

A 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 each other represent a carbon atom, a nitrogen atom or a nitrogen atom substituted by 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) contains a hydrogen atom.

Of the compounds of formula (IIIi) and / or (IIIi '), in particular the compounds listed below, if any, the enantiomers thereof, and also their salts and their hydrates, can be mentioned: [alpha] -pyridylamine, Amino-3-methylpyridine, 3-amino-4-pyridylamine, 2,5-dihydroxypyridine, 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- Hydroxybenzoic acid, ethyl 3-aminobenzoate, 1-amino-3-carboxybenzene, methyl 2-aminobenzoate, ethyl anthranilate, 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 the form of a salt, can also be used: lauroylethylenediamine, octopamine, oleamine, palmitamine, 2- (2-aminoethoxy) ethanol, Methyl [2- (3-trimethoxysilylpropylamino) ethylamine], bis (trimethylsilyl) aminomethylamine, (Triethoxysilylpropyl) amine, N1- (3- (trimethoxysilyl) propyl) hexane-1,6-diamine, diethylenetriaminopropyltrimethoxysilane, N- ) Ethylenediamine, N- (3-trimethoxysilylethyl) ethylenediamine.

According to another variant of the invention, the amines are selected from amino polymers, and also addition salts thereof. The term "amino polymer" means a macromolecule of higher molecular weight that contains one or more primary or secondary amine functionalities. The term "polymer" refers to a compound comprising five or more repeating units in turn linked through a covalent bond.

The amino polymer may be synthesized as follows:

- through a radical reaction (polyacrylate, polymethacrylate, polyvinyl, etc.),

- through condensation (polyester, polyether, polyamide, polyurethane, polydimethylsiloxane, polypeptide, etc.)

- through a ring opening reaction (such as a polyester).

Which may be optionally chemically modified natural sources such as polysaccharides (cellulose, dextran, chitosan, guar) and amino or thiol derivatives thereof.

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

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

The following are most particularly preferred:

1 / polyamino acids containing free OH or NH ₂ or SH or COOH groups, such as polylysine,

2 / NH ₂ or SH functional groups, natural or modified polysaccharides,

3 / aminosilicone,

4 / NH ₂ or SH functional groups, especially polyvinylvinyl substituted with amine functional groups, and polymers made from the following commercial monomers:

,

,

And in particular polylysine; Chitosan; Polyethoxylated amines such as carboxy PEG-8 amine, carboxy PEG-12 amine or carboxy PEG-24 amine; Or a combination thereof.

According to a further variant of the invention, the amine (s) are selected from the group consisting of purine bases, especially adenine, adenosine, guanine, guanosine G, thymine, thymidine T, uracil, uridine U, cytosine, cytidine C, , And combinations thereof.

It is not possible to configure it to depart from the context of the present invention in order to combine some of these variations.

(IIIa), (IIIb), (IIIc), (IIIe), and (IIIb) when R ₂₀ represents a linear C ₁ -C ₄ alkoxy group, (IIIg), and (IIIi ') alone or a mixture thereof.

When the composition comprises one or more primary or secondary amines, ammonia or hydroxylamine, its content is in the range of 0.001% to 65% by weight, preferably 0.001% to 30% by weight, Weight%.

enzyme

The composition according to the invention may optionally be formulated with, for example, β-glucosidase (EC 3.2.1.21), alcohol oxidase (EC 1.1.3.13), alcohol dehydrogenase Dehydrogenase EC 1.1.1.1, alcohol dehydrogenase EC 1.1.1.2, alcohol dehydrogenase EC 1.1.1.71, aromatic alcohol dehydrogenase EC 1.1.1.90 (also known as aryl alcohol dehydrogenase , Aromatic alcohol dehydrogenase EC 1.1.1.97, 3-hydroxybenzyl alcohol dehydrogenase EC 1.1.1.97, coniferyl alcohol dehydrogenase EC 1.1.1.194, cinnamyl alcohol dehydrogenase EC 1.1 .1.195, methanol dehydrogenase EC 1.1.1.244, aromatic alcohol oxidase EC 1.1.3.7 (also known as aryl alcohol oxidase), alcohol oxidase EC 1.1.3.13, 4-hydroxymandelerate oxidase EC 1.1 , The long-hydrocarbon-chain alcohol oxidase EC 1.1.3.20, the methanol oxidase EC 1.1.3.31, the alcohol dehydrogenase EC 1.1.99.20, the methyl glutamate dehydrogenase EC 1.5.99.5, the 2-oxo acid decarboxylase At least one enzyme selected from azeotriazole 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, and preferably from 0.05% to 10% by weight, relative to the weight of the composition, in proportion to the total weight of the composition.

salt

Compositions comprising compound (s) of formula (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 combinations thereof.

In particular, the anion constituting the salt may be an inorganic salt such as an inorganic salt (such as a chloride, a carbonate, a bicarbonate, a sulfate, a hydrogen sulfate, a silicate, a phosphate, a hydrogen phosphate or a hydroxide) or an organic (aspartate, formate, acetate, lactate, Gluconate, succinate, malate, fumarate, orotite, and the like).

The cation constituting the salt together with the anion may be an alkali metal (preferably lithium, sodium or potassium), an alkaline earth metal (preferably magnesium or calcium) or a transition metal (scandium, titanium, vanadium, manganese, Molybdenum, iron, cobalt, nickel, copper, zinc, silver or gold). Other cations, such as ammonium, can 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) It will be possible.

If present, the content is from 0.001% to 40% by weight, more preferably from 0.001% to 20% by weight, relative to the weight of the composition, in proportion to the weight of the composition.

Other ingredients

Cosmetically acceptable vehicles 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 in a proportion of from 1% to 99% by weight, more preferably in a proportion of from 5% to 95% by weight, relative to the weight of the composition, proportionally to the weight of the composition.

The composition used in the process according to the invention may also contain various auxiliaries conventionally used in hair dye compositions such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic , Nonionic, amphoteric or biphilic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric mixed thickeners, antioxidants, penetrants, sequestrants, flavoring agents, , Modifying agents such as volatile or nonvolatile, modified or unmodified silicon such as amino silicone, 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, those skilled in the art will appreciate that the optional addition of the above-mentioned optional addition compound (s), so that the advantageous properties inherent in the dye compositions according to the present invention are not negatively affected or substantially unaffected by the addition (s) .

The pH of the composition is generally about 3 to 14, preferably about 4 to 11, more preferably 6 to 11. Can be adjusted to the desired value using acidic or basic agents commonly used in dyeing keratin fibers, or alternatively using standard buffer systems.

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

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

The components of the above-mentioned compositions are advantageously stored separately. In particular, compounds of formula (I) or plant extracts comprising them (compounds are not previously dissolved or dissolved); An enzyme for replacing the radical R with a hydrogen atom, if the compound (I) is not previously dissolved; And oxidized oligosaccharides or polysaccharides containing aldehyde or imine compound (s) or aldehyde or imine functional groups are individually stored.

It should also be noted that, in the presence of more than one amine compound, such compounds are also separately stored with the compound (s) (I) or plant extracts containing them (dissolved or not dissolved).

In addition, it may be advantageous to store the compound (s) of the formula (I) or the dissolved or unsweetened plant extract containing the above at least in an airtight container.

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

Oxidant

In particular, when an oxidizing agent is present, the instantaneous composition is advantageously obtained by instantly mixing the composition as described above with one or more compositions comprising one or more oxidizing agents, prior to application.

The oxidizing agent is preferably selected from the group consisting of hydrogen peroxide, urea peroxide, alkali metal bromate or ferricyanide, peroxides, such as persulfates, perborates and percarbonates of alkali metals or alkaline earth metals such as sodium, potassium and magnesium .

Suitable oxidizing agents for use also include, in the presence of an oxidizing agent of the enzyme type, e. G., Where appropriate, each of the donors or cofactors, a 4-electron oxidoreductase (such as laccase) (E. G., Uricase), and peroxidases.

It is particularly preferred to use hydrogen peroxide.

The oxidizing agent is advantageously formed by hydrogen peroxide in an aqueous solution (aqueous hydrogen peroxide solution), and its inverse more particularly may be in the range of from 1 to 40 volumes, more preferably from 5 to 40 volumes.

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

Thus, the composition just described above is applied to human keratinous fibers, especially hair.

Dyeing method

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

In this case, the components (including compounds or extracts of formula (I) (dissolved or not dissolved), if appropriate, enzymes, aldehydes or imine compound (s) for replacing radicals R with hydrogen atoms, or aldehydes or imine functionalities Oxidized oligosaccharide or polysaccharide (s)) are separately stored.

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

According to a second embodiment, the instantaneous composition obtained by the above-described detailed, pre-application, oxidizing agent-free composition of the instant invention is immediately applied to the fibers.

This embodiment is particularly suitable when the composition comprises one or more oxidation dyes (bases or linking groups) or when it is desired to obtain a lightening effect.

According to a second variant of this embodiment, the oxidizer-free and oxidizer compositions are applied continuously without intermediate rinsing.

The oxidizing composition used comprises at least one oxidizing agent as defined above.

With regard to the organic solvent which may be present in the oxidizing composition, reference can 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.

Which may optionally comprise one or more additives commonly used in the art of dyeing human keratinous fibers, depending on the function of the desired herbal form. Once again, a list of the above-mentioned additives can be referred to.

Regardless of the embodiment selected (with or without oxidizing agent, instantaneous mixing or continuous application of the composition and the oxidizing agent), the mixture applied to the fibers will generally be in the range of about 1 minute to 5 hours, preferably 10 minutes to 3 hours .

With respect to the temperature to which the composition (s) is applied, is generally from 20 to 200 캜, advantageously from 20 캜 to 55 캜.

Thus, the work can be performed using, for example, a heating hood, an infrared lamp, or 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 (in particular a radiation intensity 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 pre-spectral lamp) and / or Is applied to the treated keratin fibers with UVB radiation (in particular, a radiation intensity 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 pre-spectral lamp) .

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

According to a preferred variant of the invention, the stimulating agent is selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate or ammonium carbonate in a cosmetically acceptable medium; Sodium hydrogencarbonate or potassium hydrogencarbonate; Calcium chloride, lithium chloride or sodium chloride; Ammonium sulphate, magnesium sulphate or magnesium sulphate; Sodium silicate; Monobasic sodium phosphate or potassium phosphate; Lt; / RTI > and sodium acetate.

The composition advantageously has a salt content ranging from 0.001% to 40% by weight, more preferably from 0.001% to 20% by weight, relative to the weight of the composition, in proportion to the weight of the composition.

But can not be configured to deviate from the context of the present invention in order to perform several successive steps that combine different stimuli.

After a leave-on time, the keratin fibers can be rinsed with water, optionally shampooed, rinsed with water, dried or allowed to dry.

A further subject of the present invention is a pharmaceutical composition comprising a first compartment comprising at least one compound of formula (I) or a plant extract comprising said compound undergoing a preliminary step consisting of replacing the radical R with a hydrogen atom; And a second compartment comprising at least one compound of formula (i) or (ii), an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or an imine functional group.

Yet another subject is a first compartment comprising at least one compound of formula (I) or a plant extract comprising the same; And a second compartment comprising an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii), at least one aldehyde or imine functional group and an enzyme for replacing the radical R of formula (I) with a hydrogen atom .

Finally, a final subject of the present invention is a pharmaceutical composition comprising a first compartment containing at least one compound of formula (I) or a plant extract comprising the same; And at least one compound of formula (i) or (ii), a second compartment containing oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or imine functional group; And a third compartment comprising an enzyme for replacing the radical R of formula (I) with a hydrogen atom.

Preferably, the compound (s) of the dissolving or not dissolving formula (I) is protected from air and is advantageously stored under an inert atmosphere.

The apparatus may optionally comprise one or more amines, or an additional compartment comprising one or more salts.

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

Example  One

The gardenia extract, which is more or less concentrated, is first dissolved in the presence of β-glucosidase. Then, the extract-derived genipin is isolated by crystallization after 100 kD ultrafiltration. The extract thus obtained is enriched in 99% of genipin.

5 × 10 ^-3 mol% of gardenia extract with enenegrine concentration of 99% and vanadium 5 × 10 ^-3 or 25 × 10 ^-3 mol% were dissolved in an aqueous buffer solution to pH 9 with an ultrasonic generator for 30 minutes, A composition is obtained.

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

Thereafter, the head is rinsed, rinsed with shampoo, and dried with a hair dryer.

Example  2

A dye composition was obtained by dissolving 5 × 10 ^-3 mol% of dissolved ginger extract having a genipin concentration of 93% and 2.5 × 10 ^-2 mol% of oxidized starch in a buffer solution to pH 9 for 30 minutes with an ultrasonic generator do.

The composition is applied to natural gray hair containing 90% white hair (1 g of the head per 2 g of solution) and allowed to stand at 100 캜 (hot plate) for 5 minutes.

After the residence time, the head is rinsed, rinsed with shampoo, and dried with a hair dryer.

Rust-black coloration is obtained.

Example  3

In the presence of a salt or an amine, to the nipin 99% is solubilized gardenia extract 5 × 10 ^-3 mol%, and vanillin to 10 × 10 ^-3 pH for 30 minutes with an ultrasonic generator 9 mol% in concentration buffer solution To obtain a dye composition.

Each composition is applied to a natural gray hair tress containing 90% white hair (bath ratio; BR: 1 g of a head per 10 g solution) and the head is placed under cellophane at 40 占 폚 for 2 hours.

Thereafter, each head is rinsed, rinsed with shampoo, and dried with a hair dryer.

Example  4

(1 wt.%), Benzyl alcohol (5 wt.%), And benzyl alcohol (5 wt.%) Were dissolved in an amount of 5 x ^10-3 mol% and 10 x ^10-3 mol% ), Ethanol (15% by weight), buffered aqueous solution (79%) to pH 9, to obtain a dye composition.

Each composition is applied to a natural gray hair tress containing 90% white hair (bath ratio (BR): 1 g of a head per 10 g of solution) and the head is placed under cellophane at 50 캜 for 30 minutes.

Thereafter, the head is rinsed, washed with a shampoo, and dried with a hair dryer.

Example  5

In the presence of salt (saturated solution), 5 × 10 ^-3 mol% of dissolved gum arabic extract and 10 × 10 ^-3 mol% vanillin, in which the genipin is concentrated to 99%, are dissolved in an aqueous solution for 30 minutes by means of an ultrasonic generator, A composition is obtained.

Each composition is applied to natural and / or permial gray hair tresses containing 90% white hair (BR): 1 g of the head per 5 g of solution) and the head is placed under cellophane at 40 占 폚 for 2 hours.

Thereafter, the head is rinsed, washed with a 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 containing 15% by weight of ethanol, a buffer aqueous solution (79%) at pH 9.

Each composition is applied to a natural gray hair tress containing 90% white hair (bath ratio (BR): 1 g of a head per 10 g of solution) and the head is placed under cellophane at 50 캜 for 30 minutes.

Thereafter, the head is rinsed, washed with a shampoo, and dried with a hair dryer.

Example  7

Each dye composition was obtained by dissolving 1.13 g% of dissolved ganoderma lucidum enriched in genipin 93% and vanillin (1.56 g%, if present) in an aqueous solution of pH 8 (KHCO ₃ ) for 20 minutes with an ultrasonic generator do.

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

Thereafter, the head is rinsed, washed with a shampoo, and dried with a hair dryer.

The results are as follows:

It is clear from the above result that the color becomes stronger with vanillin.

Example  8

Preparation of imine type compounds

Amine was 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 in the presence of acetic acid.

The resulting imine is then added to 1.13 g% dissolved ganoderma extract and to vanillin (1.56 g% if present) in which 93% of the enipnin is concentrated.

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 containing 90% white hair (1 g of the head per 6 g of solution) and the head is left at 40 캜 for 60 minutes (hot plate).

The color of the hair is dense rust-blue.

Example  9

A dye composition is obtained by dissolving 1.13 g% of dissolved gum arabic extract and 1.13 g% of oxidized inulin (93% enriched in nepheline) in an aqueous solution of pH 8 (KHCO ₃ added) for 20 minutes with an ultrasonic generator.

Each composition is applied to natural gray hair containing 90% white hair (1 g of the head per 5 g of solution) and the head is left at 40 캜 for 60 minutes (hot plate).

The hair is colored with golden yellow.

Claims (15)

A method for staining a human keratin fiber to which a composition comprising, in a cosmetically acceptable medium, is applied:
* The following formula (I) of yirido Id series compound, its optical or geometric isomers thereof, inorganic or organic acid salt, solvate thereof, or a plant extract containing the:

[Wherein:
R ₁ is a hydroxymethyl radical, a -CO ₂ R ₄ group, wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; ≪ / RTI >
R ₂ represents a hydrogen atom, a hydroxyl radical or a sugar radical;
R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl radical, or 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;
The sugar radical is obtained from aldose or aldose derivatives:
The compound (s) of formula (I) undergo a step consisting in replacing the radical R with a hydrogen atom before or simultaneously with the dyeing process;
** the following formula (i) and one or more selected from (ii) an aldehyde or imine compound, its optical or geometric isomers thereof, organic or inorganic acid salt, a solvate thereof, and also the oxidation of oligosaccharides comprising at least one aldehyde or imine functional groups Or polysaccharides:

[In the formulas (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:
an additional primary monoalcohol (R ' ₃ OH), wherein R' ₃ is a symmetrical 1,2- or 1,3-diol containing a C ₁ -C ₅ alkyl radical or a C ₂ -C ₃ alkyl chain, Or 5-or 6-membered cyclic or non-cyclic acetals obtained by condensation of the compounds of formula
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;
The monovalent radical A and the bivalent radical A ₁ represent a group selected from the following:
* Hydroxycarbonyl group ( -CO - OH ) :
* At least optionally substituted C ₆ Aryl group :
- a hydroxyl group,
- a C ₁ -C ₄ alkyl radical,
- aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted by one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,
-CO-OR ' ₄ or -O-COR' ₄ group (wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group);
-COOH groups in acidic or chlorinated 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 (wherein R" ₆ is the same can be different from each other, it represents a C ₁ -C ₂ alkyl radicals), -SiR _'7 group (wherein, R' is _7, which may be the same or different, represents a C ₁ -C ₂ alkyl radical); Benzyl radicals (-CH ₂ -C ₆ H ₆ ),
According to one particular variation, the two radicals -OR ' ₅ in the ortho position with respect to the C ₆ aryl group may form a 5- or 6-membered heterocycle by two radicals R' ₅ ,
--N (R ' ₈ ) ₂ group wherein R' ₈ may be the same or different and is a hydroxyl group, a carboxyl group (-COOH) in acid or chloride form, or a sulfone group in acid or chloride form (-SO ₃ H) as an optionally substituted C ₁ -C ₆ represents an alkyl radical, the radicals R _'8 together with the nitrogen atom containing them, optionally O, N and NR' ₉ (wherein, R _'9 is C search the heterocycle is optionally substituted with a hydroxyl group),; ₁ -C ₂ alkyl refers to the radical) or a saturated or unsaturated 5-or 6-membered heterocycle comprising another hetero atom can form and is selected from
- -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),
- a halogen atom, preferably selected from chlorine and bromine,
- -O-SO ₂ -C ₆ H ₆ group,
- -SO ₃ H group,
- 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 nonaromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by 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 optionally fused to a C ₆ aryl group,
The 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 (wherein, R _'15 is the same as or may be different, represent a C ₁ -C ₂ alkyl radical) with optionally substituted) represents a) contains one or two identical or different heteroatoms selected from to, cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic 5-or 6-membered heterocyclic group;
Said heterocyclic group is optionally fused to a 6-membered aryl group itself 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 at least one of:
a hydroxyl group,
a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical;
о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this 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 Lt; RTI ID = 0.0 > heterocyclic < / RTI &
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 And where the aryl radical is unsubstituted by the radicals mentioned above, the carbon atom is replaced by 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 A radical (said alkyl or alkenyl radical optionally substituted with one or more hydroxyl groups);
A _divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ through 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. The method according to claim 1, wherein the plant extract is of the following plant origins: Abelia grandiflora , Adenorandia kalbreyeri), Adina poly Seppala (Adina polycephala), ah Guinea Tia Indica variants that raksil lease (Aeginetia indica var. gracilis), Ah Spain Lula species (Asperula sp), Assisi star Shia Bella (Asystasia bella), Aucuba japonica (Aucuba such as Buddhist japonica , Avicennia marina , Bartsia trixago , Buddleja Americana , Buddleja crispa , Buddleja japonica , Canthium schimperianum , Castilleja wightii , Chaenorhinum minus , Clerodendrum serratum , coprosma sp , Cornus officinalis , claviodendron henry, henryi , Cremaspora triflora), Kruger Asia Nella species (Crucianella sp), dapeu you pilrum Cali City num (Daphniphyllum calycinum , Daphniphyllum humile , Daphniphyllum macropodum , Eremostachys glabra , Escallonia sp ), Eucommia ulmoides , Feretia apodanthera , Galium < RTI ID = 0.0 > humifusum , Galium verum , Gardenia jasminoides , Garrya elliptica , Globularia dumulosa , Hedyotis < RTI ID = 0.0 > corymbosa ), Hygrophila difformis , Ixeris chinensis , Lamiaastrum, Lamiastrum galeobdolon ( Lamium galeobdolon ), Lamiophlomis rotata ( Phlomis rotata ), Leotothis nepetaepolia ( Leonotis nepetaefolia ), Linaria sp ), Morinda coreia ), Mussaenda pubescens , Nepeta cilicia ), Nepeta ( Nepeta nuda ssp . Albiflora), Odessa onti Tess Verna (Odeontites verna), all four denran Dia Nose Limbo (Oldenlandia corymbosa , Paederia scandens , Pedicularis ( Pedicularis scandens ), Pedicularis < RTI ID = 0.0 > chinensis , Pedicularis condensate , Pedicularis dolichocymba , Penstemon < RTI ID = 0.0 > confertus , Penstemon deutus , Penstemon, richardsonii , Penstemon serrulatus , Pithecoctenium crucigerum , Plantago alpina ( Plantago alpina , Plantago carinata , Plantago lagopus ), Plantago lanceolata ( Plantago lanceolata , Plantago subulata , Premna barbata , Randia dumetorum , Rhododendron latoucheae , Rothmannia withfieldii , Rubia peregrina , Rubia tinctorum , Saprosma, scortechinii , Scrophularia corainensis , Scrophularia lepidota , Scrophularia ningpoensis , Scyphiphora < RTI ID = 0.0 > hydrophyllacea , Swida controversa , Syringa vulgaris , Tarenna kotoensis ), tecoma heptapila ( Tecoma heptaphylla , < / RTI > Thevetia < RTI ID = gaumeri , Thevetia peruviana , Verbascum laxum , Verbascum nigrum), Berger des Bas Qom flow Rana (Verbascum phlomoides), Bercy Stadium Bath Qom salbiyi poly (Verbascum salviifolium , Verbascum sinuatum , Verbascum, thapsus), Verbier Bath Qom undul ratum (Verbascum undulatum , Veronica derwentiana , Vitex nigrum , Wendlandia formosana , preferably gardenia. 3. The method according to claim 1 or 2, wherein the content of compound (s) of formula (I) in the composition is from 0.001% to 10% by weight, in proportion to the weight of the composition. 4. The method according to any one of claims 1 to 3, wherein the compound of formula (i) or (ii), wherein X represents an oxygen atom. 5. The method of any one of claims 1 to 4, wherein the compound (s) is of formula (i)
* 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:
* Optionally substituted with one or more hydroxyl groups, linear or branched C ₅ - C ₁₀ An alkyl radical ;
* Carbon - C ₈ - C ₂ containing a carbon-carbon double bond Alkenyl Radical ;
A hydroxycarbonyl group (-COOH);
* At least optionally substituted C ₆ Aryl group :
a hydroxyl group,
a C ₁ -C ₄ alkyl radical,
-CO-OR ' ₄ or -O-COR' ₄ group (wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical),
o -OR ' ₅ group (wherein R' ₅ represents a C ₁ -C ₆ alkyl radical),
aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,
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, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by 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. , A saturated or unsaturated, aromatic or non-aromatic 5- or 6-membered heterocyclic group ;
Said heterocyclic group is optionally fused to a 6-membered aryl group itself optionally substituted with one or more C ₁ -C ₂ alkyl or C ₁ -C ₄ alkoxy groups;
Said heterocyclic group is optionally substituted at least one of:
a hydroxyl group,
a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical,
о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this 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 Lt; RTI ID = 0.0 > heterocyclic < / RTI &
If appropriate, the compound of formula (i) comprises a cosmetically acceptable mixture of anions or anions An, which ensures the electrical neutrality of the formulation;
The compound (s) of formula (i) may be in the form of acetal or hemiacetal. 6. The composition of any one of claims 1 to 5 wherein the content of the oxidized oligosaccharide or polysaccharide comprising compound (s) of formula (i) or (ii) or one or more aldehyde or imine functional groups is proportional to the weight of the composition By weight, and 0.001% to 30% by weight. 7. The method according to any one of claims 1 to 6, comprising at least one organic or inorganic salt selected from:
Salts of inorganic acids such as hydrochloride, carbonate, bicarbonate, sulfate, hydrogen sulfate, silicate, phosphate, hydrogen phosphate, hydroxide or aspartate, formate, acetate, lactate, citrate, gluconate, succinate, Organic anions selected from maleate, fumarate, oroate,
* Transition metals such as alkali metals, alkaline earth metals, scandium, titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold, or ammonium. 8. The composition according to any one of claims 1 to 7, wherein the content of salt (s) is in the range of 0.001% to 40% by weight, more preferably in proportion to the weight of the composition, % ≪ / RTI > to 20% by weight. 9. The method according to any one of claims 1 to 8, wherein the step of replacing the radical R with a hydrogen atom is carried out using an enzyme selected from isolaazine and? -Glucosidase (EC 3.2.1.21). 10. A process according to any one of claims 1 to 9, wherein a temperature of from 30 to 200 占 폚 is applied. The method according to any one of claims 1 to 10, UVA radiation, especially from 0.01 to 0.40 mW / are applied to the irradiance of cm ² and / or UVB radiation, in particular irradiance of 0.01 to 0.20 mW / cm ² Applied method. A first compartment comprising at least one compound of formula (I) or a plant extract comprising said compound according to claims 1 or 2 undergoing a preliminary step consisting in replacing the radical R with a hydrogen atom, A multi-compartment device comprising a second compartment comprising an oxidized oligosaccharide or polysaccharide comprising at least one compound of formula (i) or (ii) according to any one of claims 4 and 5, at least one aldehyde or an imine functional group . A pharmaceutical composition comprising a first compartment comprising at least one compound of formula (I) according to claims 1 or 2 or a plant extract comprising said compound, and one according to any one of claims 1, 4 and 5 A composition comprising a compound of formula (i) or (ii) above, an oxidized oligosaccharide or polysaccharide comprising at least one aldehyde or an imine functional group, and an enzyme for replacing the radical R of formula (I) Multi-block devices that contain blocks. A pharmaceutical composition comprising a first compartment comprising one or more compounds of formula (I) according to claims 1 or 2 or a plant extract comprising the same, and a first compartment comprising a plant according to any one of claims 1, 4 and 5 A second compartment comprising a compound of formula (i) or (ii) above, an oligosaccharide or polysaccharide comprising at least one aldehyde or an imine functional group, and a radical R of formula (I) according to claim 9 with a hydrogen atom And a third compartment containing the enzyme for the first compartment. Composition for dyeing human keratin fibers, which comprises in cosmetically acceptable medium:
* The following formula (I) of yirido Id series compound, its optical or geometric isomers thereof, inorganic or organic acid salt, solvate thereof, or a plant extract containing the:

[Wherein:
R ₁ is a hydroxymethyl radical, a -CO ₂ R ₄ group, wherein R ₄ represents a hydrogen atom or a C ₁ -C ₂ alkyl radical; ≪ / RTI >
R ₂ represents a hydrogen atom, a hydroxyl radical or a sugar radical;
R ₃ may be the same or different and represents a hydrogen atom, a hydroxyl radical, or 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;
The sugar radical is obtained from aldose or aldose derivatives:
The compound (s) of formula (I) undergoes a preliminary step consisting in replacing the radical R with a hydrogen atom, optionally carried out by an enzyme;
** the following formula (i) and one or more selected from (ii) an aldehyde or imine compound, its optical or geometric isomers thereof, organic or inorganic acid salt, a solvate thereof, and also the oxidation of oligosaccharides comprising at least one aldehyde or imine functional groups Or polysaccharides:

[In the formulas (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:
an additional primary monoalcohol (R ' ₃ OH), wherein R' ₃ is a symmetrical 1,2- or 1,3-diol containing a C ₁ -C ₅ alkyl radical or a C ₂ -C ₃ alkyl chain, Or in the form of a 5-or 6-membered cyclic or bicyclic acetal,
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;
The monovalent radical A and the bivalent radical A ₁ represent a group selected from the following:
* Hydroxycarbonyl group ( -CO - OH ) :
* At least optionally substituted C ₆ Aryl group :
- a hydroxyl group,
- a C ₁ -C ₄ alkyl radical,
- aryl-ethylenyl radical, wherein the aryl group is C ₆ , optionally substituted by one or more C ₁ -C ₂ alkyl or C ₁ -C ₂ alkoxy radicals,
-CO-OR ' ₄ or -O-COR' ₄ group (wherein R ' ₄ represents a C ₁ -C ₂ alkyl radical or a phenyl group);
-COOH groups in acidic or chlorinated 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 (wherein R" ₆ is the same can be different from each other, it represents a C ₁ -C ₂ alkyl radicals), -SiR _'7 group (wherein, R' is _7, which may be the same or different, represents a C ₁ -C ₂ alkyl radical); Benzyl radicals (-CH ₂ -C ₆ H ₆ ),
According to one particular variation, the two radicals -OR ' ₅ in the ortho position with respect to the C ₆ aryl group may form a 5- or 6-membered heterocycle by two radicals R' ₅ ,
--N (R ' ₈ ) ₂ group wherein R' ₈ may be the same or different and is a hydroxyl group, a carboxyl group (-COOH) in acid or chloride form, or a sulfone group in acid or chloride form (-SO ₃ H) as an optionally substituted C ₁ -C ₆ represents an alkyl radical, the radicals R _'8 together with the nitrogen atom containing them, optionally O, N and NR' ₉ (wherein, R _'9 is C search the heterocycle is optionally substituted with a hydroxyl group),; ₁ -C ₂ alkyl refers to the radical) or a saturated or unsaturated 5-or 6-membered heterocycle comprising another hetero atom can form and is selected from
- -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),
- a halogen atom, preferably selected from chlorine and bromine,
- -O-SO ₂ -C ₆ H ₆ group,
- -SO ₃ H group,
- 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 nonaromatic 5- or 6-membered ring, An unsaturated cationic or non-cationic 5- or 6-membered heterocycle comprising a heteroatom, wherein one of said heteroatoms may be contained within two rings, said heterocycle or fused ring containing one or more C ₁ -C ₂ Which may be substituted by 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 optionally fused to a C ₆ aryl group,
The 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 (wherein, R _'15 is the same as or may be different, represent a C ₁ -C ₂ alkyl radical) with optionally substituted) represents a) contains one or two identical or different heteroatoms selected from to, cationic or non-cationic, saturated or unsaturated, aromatic or non-aromatic 5-or 6-membered heterocyclic group;
Said heterocyclic group is optionally fused to a 6-membered aryl group itself 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 at least one of:
a hydroxyl group,
a C ₁ -C ₂ alkyl radical optionally substituted with a hydroxyl radical;
о amino radical -N (R _{'16) 2} (wherein, R' ₁₆ is the same as or may be different and represents a C ₁ -C ₄ alkyl radical optionally substituted by a hydroxyl group, the radicals R _'16 is this 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 Lt; RTI ID = 0.0 > heterocyclic < / RTI &
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 And where the aryl radical is unsubstituted by the radicals mentioned above, the carbon atom is replaced by 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 A radical (said alkyl or alkenyl radical optionally substituted with one or more hydroxyl groups);
A _divalent radical A ₂ represents a linear C ₁ -C ₁₀ alkylene chain connecting two radicals A ₁ through a carbon, oxygen or nitrogen atom;
Where appropriate, the compounds of formulas (i) and (ii) comprise a cosmetically acceptable anion or a mixture of anions An, which ensures the electrical neutrality of the formulation.