BRPI0711835A2 - hybrid polyol (s) based compounds and based on at least one other molecular entity, whether or not polymeric, in particular of the polyorganosiloxane type, their preparation process and their applications - Google Patents

Abstract

POLYOL-BASED HYBRID COMPOUNDS (IS> AND AT LEAST ONE OTHER MOLECULAR ENTITY, POLYMERS OR NOT, NOTES OF POLYORGANOSILOXAN TYPE, PREPARATION PROCESS FOR THE SAME AND ITS APPLICATIONS. at least one polyol (Po) entity - for example, oligomer or polymer - in which at least one of the hydroxyl functions of Po is replaced by at least one entity A that can be of a varied nature, for example polymer (for example, polyorganosiloxane - POS ), hydrocarbon or mineral. The kneecap Ro between that entity Po and that entity A is obtained by "click chemistry" and corresponds to the formula (II.1) or (II.2), Z representing - CH- or -N-. A is an entity chosen from the group comprising polyols other than Po, polyorganosiloxanes (POS), polyalkylene glycols, polyamides, polyesters, polystyrenes, alkyls, alkenyls, alkynyls, aryls and combinations thereof; mineral materials such as silica ica; and their combinations. So-called hybrid compounds can be used as emulsifiers, especially for cosmetics.

Description

POLYOL (IS) HYBRID COMPOUNDS AND AT THE BASIS OF AT LEAST ANOTHER MOLECULAR ENTITY, POLYMERS OR NOT, NOTALLY POLYORGANOSILOXAN TYPE

PREPARATION OF THE SAME AND ITS APPLICATIONS

FIELD OF INVENTION

The present invention relates to novel hybrid structures comprising at least one polyol (Po) entity - for example, oligomer or polymer - and at least one entity A which may be of a varied nature, for example polymer (for example, polyorganosiloxane). POS), hydrocarbon or mineral. The bond or bonds between this Po entity and this A entity are obtained, according to the chemical mechanism designated by the name "click chemistry", in which an azide reagent reacts with an alkynyl or nitrile reagent to form a triazole or tetrazole-type kneecap (Ro).

The invention also relates to the process of obtaining such hybrid structures, as well as their applications as amphiphilic compounds, for example.

Finally, syntones, that is, intermediate products carrying azide and / or alkynyl and / or nitrile functions and involved in the preparation of such hybrid structures are also envisaged by the invention. PREVIOUS TECHNOLOGICAL AND TECHNICAL PLAN

More especially, but not limited to, polyols referred to by the present invention (Po entity) comprise oligosaccharides or polysaccharides (linear or branched or cyclic) at least in part consisting of at least two, preferably at least three monosaccharide units, linked together by each other. These particular polymers, which are polysaccharides, are of some interest, considering their physicochemical properties (hydrophilic, hydrolysable, bioresorbable ...) and their chemical complexity, offering multiple possibilities in terms of structures and of properties, their great availability and their natural origin, among others. This natural origin can make them particularly attractive from an environmental and / or toxicological and / or commercial point of view. Thus, applications of polysaccharides such as starch products and their derivatives or cellulosic products and their derivatives are plethoric.

POS (silicones) is another class of polymers of greater interest in multiple industrial sectors. In addition, the fact that POS is an easily accessible raw material is also characterized by its hydrophobic properties.

Hybrid polysaccharide and POS-based structures have therefore been envisioned to provide, for example, with emulsifying compounds usable notably in cosmetic compositions, such as skin care compositions, protective compositions and sun treatment, shampoo compositions, deodorant and / or antiperspirant compositions, for example in the form of a stick, gel or lotion, among others.

In these particular hybrid structures which are the polysaccharide-POS systems, the polysaccharide entity and the POS entity combine their respective advantages.

The polysaccharide entity, due to the presence of its numerous hydroxyl functions, can develop strong intra or intermolecular interactions in both hydrophobic and hydrophilic environments. This understanding of molecular recognition allows us to obtain gels-like organizations and / or favor interactions with polar surfaces such as textiles (ie cotton), hair.

The POS entity offers two major advantages: the first is flexibility, which gives this POS entity great reactivity and an ability to adapt its molecular conformation to the substrate (s) present; The second advantage, among others, concerns the hydrophobic character of this POS entity that offers low surface energy properties.

By way of example of a commercial product, comprising polysaccharide-POS hybrid structures, one can be cited that distributed under the name "Wacker-Belsil® SPG 128 VP". It is a cyclopentadimethylsiloxane, of which one part of the D-siloxy is replaced by a silicon-linked polyglycoside chain comprising two oxygen bridges and of which another part of the D-siloxy is replaced by an alkyl radical of the type - ( CH2) w-CH3, w being a natural integer.

In all the present. In this document, references will be made to elements of classical nomenclature to designate the M, D, T, Q silos of the POS. By way of reference, one may cite: NOLL "Chemistry and Technology of Silicones", chapter 1.1, page 1-9, Academic Press, 1968 - 2nd edition.

It is known that the preparation of hybrid polysaccharide-POS systems can be made by grafting polysaccharide entities onto a POS entity by two main approaches: hydrosilylation or condensation. By way of illustration of the hydrosilylation pathway, for example, two references may be cited: prior patents, namely EP-B-0612759 and WO-A-2005/087843.

EP-B-0612759 describes organosilicate compounds, comprising a glycosidic residue obtained by reacting an alkenylated monosaccharide or monosaccharide (1 to 10 monosaccharide units) with, for example, a SiH-bearing disiloxane. Alkenyl is introduced directly onto the unprotected oligosaccharide or polysaccharide with the aid of alkyl oxyethanol in the presence of a strong acid at 100 ° C. Hydrosilylation is performed with the aid of Speier's platinum catalyst in isopropanol at 100 ° C. This hybrid compound obtained in the examples corresponds to the following formula: H (C6H10O5) 1,5-O-CH 2 CH 2 O-CH 2 -CH 2 -CH 2 -Si (CH 3) 2-O-Si (CH 3) 3

WO-A-2005/087843 describes a grafted polymer comprising a polyorganosiloxane structure and glycosides (mono and / or polysaccharides). In particular, WO-A-2005/087843 describes the preparation of an allyl-functionalized cellobiose-grafted polydimethylsiloxane. For this, the cellobiose is placed to react with the allylamine. After fixing the allylamine on the cellobiose carbon anomer, the amine function and a part of the primary hydroxyls are protected by acetylation. The remaining hydroxyl functions are protected by replacing their hydrogen with a trimethylsilyl function. The hydrosilylation of

polydimethylsiloxane with dimethylhydrogenosyloxy ends is then performed in the presence of Karstedt platinum at a temperature of 70 ° C. Subprotection of the POS grafted at its ends by the disaccharide cellobiose is performed with the aid of a tetrahydrofuran / methanol mixture in an acid medium. The reaction scheme is as follows:

<formula> formula see original document page 6 </formula>

The difficulties of saccharide protection / deprotection constitute a deficiency for these known polyorganosiloxane / glycoside grafted polymers and the process for obtaining them.

Except for hydrosilylation and condensation grafts, US-B-5 428 142 which describes C1-grafting of an unprotected sugar on the terminal alcohol function of polyoxyethylene grafts attached to a polysiloxane chain can be anecdotally cited. by etherification in strong acid medium at 100 ° C.

On the other hand, the chemical binding mechanism known as "click chemistry" or Huisgen reaction is known. Huisgen and Szeimies [(a) Huisgen, R; Szeimies, G .; Moebius, L. Chem. Ber. 1967, 2494. (b) Huisgen, R .; Knorr, R .; Moebius, L .; Szeimies, G. Chem. Ber. 1965, 98, 4014] which were the first to perform 1,3-dipolar cyclicloading of an azide derivative onto an alkaline derivative at elevated temperature. The scheme of this cycle is as follows:

<formula> formula see original document page 7 </formula>

1,4-disubstituted 1,5-disubstituted

WO-A-03/101972 describes the cycloaddition reaction (so-called "Huisgen"), between azides and alkines, in the presence of a copper I catalyst. This reaction allows to form, in a regiospecific manner, essentially 1 1-4-disubstituted 2,3-triazole. As shown in FIGS. 3A and 3B of WO-A-03/101972, this 1,3-dipolar cycloaddition yields, for example, hybrid systems (cf.

1 to 10), comprising, on the one hand, phenyl nuclei, and, on the other hand, inert or branched, optionally unsaturated and possibly hydroxyl-bearing cyclic molecules, as well as a hybrid system (11) comprising a triazole label, linking, on the one hand a propanediol residue and on the other hand a dihydroxylated polycyclic compound. In addition, it is apparent from Figures 6 to 8 of W0-A-03 / I01972 that it is possible to functionalize aminated biological molecules such as erythromycin (cf. Figure 6) in the same way as molecules comprising polyiazide or polyalkyl (cf) nuclei. 7 and 8).

WO-A-03/101972 does not constitute the state of hybrid compounds, comprising "click chemistry" cyclic linked polyol entities to different polyol entities or to POS, polyalkylene glycol, polyamide, polyester, alkyl, alkenyl, alkynyl, aryl and their entities. combinations, or to mineral materials such as silica.

Application W0-A-2005/118 625 describes other applications of 1,3-dipolar cyclic click-chemistry to produce hybrid systems comprising an entity A corresponding to a carbohydrate linked by a five-chain cyclic label. -2-3 triazole to an entity B consisting of an amino acid or amino acid analogue or an entity C representing one. polypeptide or a polypeptide analog. Such hybrid systems are obtained by reacting the carbohydrate functionalized by an acetylene function or an azide and an amino acid or polypeptide functionalized by a corresponding amide or acetylene function. In the sense of WO-A-2005/118625, the term carbohydrate (cf. p.7, 1.20 to p.8, 1.2) means both mono and polysaccharides, in which hydroxy groups are eventually substituted by hydrogen, by an amino, thiol or heteroatom group.

The 1,3 dipolar cycloaddition is performed, protecting the saccharide hydroxyl groups by an acetyl group and by the. amino grouping of the amino acid by a Boc group, and using a copper catalyst and diisopropylethylamine in tetrahydrofuran solvent medium. The obtained pseudo-glycoamino acids and glycopeptides may be used for the treatment of bacterial infections. It should be noted that in systems AB or AC according to WO-A-2005/118625, the substitution by B or C of entity A "carbohydrate" is operated exclusively on the anomeric carbon of A. In addition, the cyclic label 5-chain 1,2,3-triazole is directly bound by a covalent bond to that anomeric carbon without spacer. Finally, the protective voltage of the sensitive groups (OH, amine) of A, B and C required in the synthesis of AB or AC systems, according to WO-A-2005/118625, is extremely penalizing, especially in the industrial field.

It is therefore found that the preparation of hybrid systems by click chemistry or 1,3-dipolar cycloaddition of an azide derivative onto an alkaline derivative in the presence of copper is limited to the association of (poly) saccharide polyols with amino acids or ( poly) peptides.

One of the essential purposes of the present invention is to provide other hybrid compounds obtained by click chemistry.

A further essential object of the invention is to provide novel hybrid compounds based on Po polyol entity (s) linked by at least one triazole or pentacyclic tetrazole label to at least one entity A, such hybrid compounds. being able to be exploited in numerous industrial (emulsifying) as well as biological applications.

A further essential object of the invention is to provide hybrid compounds, comprising one or more Po (polymers) -polyols, for example polyaccharide entities, linked by triazole or tetrazole pentacyclic labels obtained by at least one A entity type (polymer) polyol and / or POS and / or polyalkylene glycol, and / or polyamine (peptides), and / or polyester, and / or polystyrene, and / or alkyl, and / or alkenyl, and / or alkynyl, and / or aryl, and / or mineral, such as silica.

Another essential object of the invention is to provide polysaccharide / POS hybrid compounds linked by at least one knob derived from a 1,3-dipolar cycloaddition of an azide or nitrile derivative onto an alkaline derivative with click chemistry copper catalysis. .

Another essential object of the invention is to provide hybrid compounds, comprising one or more Po (polymers) -polysols, for example polysaccharides, such compounds being capable of being prepared without heavy steps of protecting / deprotecting reagents, in particular saccharides .

Another essential object of the invention is to provide cosmetic compositions, shampoo compositions, cleansing compositions comprising hybrid compounds as defined in the above objectives.

These objectives, among others, are achieved by the present invention which initially relates to a Po - Ro - A hybrid compound comprising at least one polyol (Po) entity and in which at least one of the Po atoms is replaced by the one. least one grouping of the following general formula (I):

---- Ro ------- A (I) in which:

- Ro is a bearing of the formula (II.1) or (II.2) below:

<formula> formula see original document page 10 </formula>

with Z representing a carbon atom, for example, substituted by a hydrogen (not represented in formulas (II.1) & (II.2) by convention), is a nitrogen atom; - the polyol entity Po is selected from the polymeric synthetic non saccharide polyols, or from the saccharides (hydrogenated or not), comprising at least two, preferably at least three monosaccharide units;

A is a mineral or organic entity, possibly polymer; and in case of presence of a plurality of entities A per molecule of hybrid compound; these entities A are identical or different from each other, organic entity A being chosen or derived from a compound chosen from the group comprising:

- synthetic polymers, their copolymers or monomer units, enabling them to be obtained;

- alkyls, alkenyls, alkynyls, aryls and combinations thereof;

- and their combinations.

In the sense of the invention, the term "hybrid" means homogeneous (Po is identical to A) or heterogeneous (Po is different from A) Po - Ro - A structures.

Note that if Z represents a carbon atom, it will also be bonded to a hydrogen atom not usually represented in order to satisfy the valence of that carbon.

Preferably, at least one of the hydroxyl functions of the polyol entity (Po) is replaced by at least one group of the following general formula (I): --R A as defined above.

According to an embodiment M1 of the invention, the hybrid compound according to the invention is characterized in that the Ro bearing or at least one of the Ro bearings is attached to the Po entity and / or entity A by a bond. Divalent. In other words, L is a spacer. Advantageously, L may be, for example, a hydrocarbon or an atom, such as O or S. In the sense of the invention, the term "carbonated hydro (geno)" comprises, for example, at least one carbon atom and / or at one less hydrogen. This includes notably the bonds "ester", "amide", "imine" ...

According to an M2 embodiment of the invention, the hybrid compound according to the invention is characterized in that none of the Ro bearings is bound to the Po entity by a divalent -L-bond and that such hybrid compound comprises at least an entity A free of amino acid (s) and / or peptide (s) and / or its analog (s) and / or derivative (s).

These new hybrid compounds are easy to produce at an acceptable cost price. They are therefore perfectly suited for industrial exploitation and open the door to numerous uses, notably in the sector of amphiphil ingredients usable notably in cosmetics or detergent, for example cosmetic care compositions, creams, lotions, gels, deodorant compositions and antiperspirants, soap compositions, shampoo compositions, wash compositions, etc.

The particular hybrid compounds, which are the polysaccharide-Ro-POS and polysaccharide-Ro-alkyl combinations, represent a new group of structures that are particularly interesting in terms of compatibility with industrial requirements, notably cost and environmental impact and in terms of environmental impact. of application.

The present invention also proposes a novel process for obtaining said hybrid compounds. This process is characterized by the fact that:

I. using and / or preparing a Po-X syntonon comprising at least one reagent X having at least one reactive end of formula (VII.1): -C4 E; with E = CH or N;

II. using and / or preparing an A-Y tint comprising at least one Y reagent having at least one dipolar end of formula (VII.2): -N3; the reactive end (VII.2) being able to react with the reactive end (VII.1);

III. reacting the Po-X tuning with the AY tuning, in accordance with a cycloaddition mechanism, to obtain a hybrid compound P0 - R0 - A comprising at least one polyol (Po) entity in which at least one of the hydroxyl functions of Po is replaced by at least one grouping

of the following general formula (I '): ----- Ro --- A; with Ro and A,

as defined above;

IV. eventually separating Po ---- Ro - A from the reaction medium in order to recover it.

This process is particularly advantageous for its simplicity, its economy, its eco-compatibility and the multiplicity (variety) of the products it allows to obtain.

Note, in one embodiment, Po-X and AY syntones, Po-XY mixed syntones, each comprising at least one X reagent and at least one Y reagent and mixed A syntones may be used locally or in addition. -XY, each comprising at least one reactant X and at least reactant Y, such that these Po-XY and A-XY syntones are capable of reacting together or upon themselves.

The invention also relates to:

- Po-X syntones comprising at least one reagent X having at least one reactive end of formula (VII.1.1): <formula> formula see original document page 14 </formula>

with E = CH or Ν, a = 0 or 1, that end being bonded to residue Po by a bond Li which is a divalent hydrocarbon bond;

Po-Y syntones comprising a reagent Y having at least one reactive end of formula (VII.2.1):

<formula> formula see original document page 14 </formula>

with a = 0 or 1; that end being attached to residue Po by an L2 bond which is a divalent hydrocarbon bond;

A-X syntones comprising a reagent X having at least one reagent X having at least one reactive end of formula (VII.1.3):

<formula> formula see original document page 14 </formula>

with E = CH or N, a = 0 or 1 (if a = O, then A is different from a saccharide or peptide and if a = 1, then A will be different from a PDMS), that end being bound to the residue A by an L3 bond which is a divalent hydrocarbon bond;

A-Y syntones comprising a reagent Y having at least one reactive end of formula (VII.2.4):

<formula> formula see original document page 14 </formula>

with a = Ooul (sea = 0, then A will be different from a saccharide or a peptide), that end being attached to residue A by an L4 bond which is a divalent hydrocarbon bond;

- Po-XY mixed syntones in which reagents X and

Y correspond to the same definitions as given above for the Po-X and Po-Y syntones;

- mixed A-XY syntones in which reagents X and

Y correspond to the same definitions as given above for A-X and A-Y.

In the above formulas (VII.1.1), (VII.2.1), (VII.1.3), (VII.2.4) of the Po-X, Po-Y AY, AX syntones, if a = O, then there will be no binding Li, L2, L3, L4 (or spacer), but a direct valential bond (eg, covalent bond).

These syntones are useful and novel intermediate products for the application of said process and for obtaining the hybrid compounds according to the invention.

Finally, the invention is directed to the uses of such hybrid compounds as well as the compositions comprising them.

DETAILED DESCRIPTION OF THE INVENTION The compound Po-Ro-A

The Ro.bond linkage of formula (II.1) or (II.2) is at the center of the hybrid compounds according to the invention.

This kneecap is the result of a click chemistry reaction, ie 1,3-dipolar cyclic charge reaction, on the one hand, of an azide derivative, the reactive end of which carries three nitrogen atoms, and on the other hand , an alkaline derivative (Z = C) or a nitrile derivative (Z = N). Such a Ro-tag is a 5-chain triazole (Z = C) or tetrazol (Ζ = Ν), 1,4-disubstituted (cf formula II.1) or 1,5-disubstituted heterocycle (cf. formula ( II.2) According to the reactive functionalities of azide type, on the one hand, and of acetylenic or nitrile type, on the other hand, are carried by entity Po or entity A, this gives rise to hybrid compounds of different structures.

Thus, according to a first structure, the free valential bond of nitrogen at position 1 in formulas (II. 1) and (II.2) connects the Ro-Po label and the free valential bond of carbon or atom Z at position 4 or 5 in formulas (II.1) and (II.2) binds the label to Ro to A.

According to a second structure, the free valential bond of nitrogen at position 1 in formulas (II.1) and (II.2) connects the Ro to A label, and the free valential bond of carbon or atom Z at position 4 or 5 in formulas (II.1) and (II.2) binds Ro to Po.

Of course, the hybrid compounds according to the invention are not limited to compounds comprising a single Ro-label, but also encompass hybrid compounds each comprising several identical or different Ro-labels.

These structures with several rod ends, identical or different between them, refer, for example, to multi-point products; branched, e.g. dendrimer-like, star-shaped or other ...

In particular, in the M1 embodiment, wherein the Ro bearing or at least one of the Ro bearings is attached to the Po entity by a divalent -L-link, it may notably comprise at least one of the L1, L2, L3, L4 as defined above in the formulas (VII.1.1), (VII.2.1), (VII.1.3), (VII.2.4) of the Po-X, Po-Y AY, AX syntones. In other words, L is a spacer. The simplified general formulas of the corresponding hybrid compounds may be, among others, those belonging to the group comprising: Po --- Li - Ro - L2 --- Po; Po --- Li-Ro-L4 --- Po; Po --- L2 --- Ro --- L3 --- A; A --- L3 --- Ro --- L4 --- A; Li, L2, L3, L4 are the spacers and are

identical or different from each other, whether considered alone or together.

A is a mineral or organic entity, possibly polymer; and in the case of the presence of a plurality of entities A per molecule of hybrid compound; these entities A are identical or different from each other, organic entity A being chosen or derived from a compound chosen from the group comprising:

- synthetic polymers, their copolymers or monomer units, permitting them to be obtained;

- alkyls, alkenyls, alkynyls, aryls and combinations thereof;

- and their combinations.

The synthetic polymers of entity A may be synthetic polymers of average molar mass greater than 1000 g / mol, preferably greater than 10000 g / mol.

In practice, A is chosen or is derived from a compound chosen from the group comprising:

the synthetic polymeric non-saccharide polyols, their copolymers or the monomer units, allowing them to be obtained (some are further detailed for the Po entity);

- polyorganosiloxanes (POS), their copolymers or monomer units allowing them to be obtained;

- polyalkylene glycols (or further alkylene polyoxides), preferably polyethylene glycols (or further ethylene polyoxides) and / or polypropylene glycols (or further propylene polyoxides) and / or polytetraethylene glycols, and / or their copolymers or co-oligomers, notably statistical or block copolymers or co-oligomers or polypropylene glycols or polypropylene glycols (or statistical or block ethylene and propylene polyoxides), such polyalkylene glycols being optionally functionalized by or over other groups, for example, by or over amino groups (Jeffamines), and / or optionally being terminated at least one end by a hydroxyl group or an alkyl group, for example a C1-C30 alkyl;

- polyamides, their copolymers or the monomer units permitting them to be obtained;

- the polyesters, their copolymers or the monomer units enabling them to be obtained;

the polybutadienes, their copolymers or the monomer units permitting them to be obtained;

the polystyrenes, their copolymers or the monomer units permitting them to be obtained;

- optionally alkyl, alkenyls, alkynyls, aryls and combinations thereof;

- mineral materials such as silica;

- and their combinations.

It may be advantageous for such entity A to comprise polymers or copolymers chosen from the group as mentioned above, or optionally cross-linked straight or branched chains. For example, the molar mass of such entity A is greater than or equal to 100, preferably greater than or equal to 100, and most preferably between 100 and 50000.

According to a preferred embodiment of the invention, entity A comprises at least one M, D, T and / or Q silicon carrier POS, preferably at least one MeD silicon carrier POS, optionally T and / or Q, and most preferably at least one M (D) dM, M (D) d (T) tM, MQ, with d, t rational numbers greater than or equal to 0.

d is, for example, from 1 to 1,000,000, preferably from 1 to 10,000, and t is, for example, from 0 to 50, preferably from 0 to 20.

In practice, these POS are, for example, linear α-ω functional polysiloxanes or well-functionalized in the chain. These POSs can also be more or less branched structures. In practice, these POS are, for example, carriers of glycidyl ether and / or hydrogen function (s).

According to a particular sub-embodiment of the invention, the Po-Ro-POS hybrid compound corresponds to at least one of the following formulas: <formula> formula see original document page 20 </formula>

in which:

R 2, identical or different, is a hydrocarbon group, preferably a methyl group;

R3, identical or different, is a group of formula -Ro - Po in which Ro and Po are as defined above;

R1, identical or different, is an R2 or R3 group;

R is a divalent group comprising an oxygen atom, preferably a -O- group;

- m is an intermediate number other than 0;

n is an intermediate number greater than or equal to 0; - k and 1 are intermediate numbers greater than or equal to 0 and

- o and p identical or different are intermediate numbers greater than or equal to 0.

Preferably,

- m + η is from 0 to 1,000,000, preferably from 0 to 10,000, the ratio of m to η being from 1/1 to 1/100, preferably from 1/20 to 1/50, or

-m + n + o + p is from 0 to 1,000, preferably from 0 to 300, the ratio of η + oem + ρ being from 1/1 to 1/100, preferably from 1/20 to 1 / 50

Entity A may also include polyalkylene glycol type residues, optionally having at least one alkyl ether termination, for example methyl ether.

Examples of polyalkylene glycols include polyoxyethylene glycols, polyoxyethylene glycols monoalkyl (e.g. methyl) ether, polyoxypropylene glycols, polyoxypropylene glycols monoalkyl (e.g. methyl) ether, polyoxytetramethylene glycols.

Polyamides may be constitutive elements of entity A. Examples of polyamides include polyamides 6-6, polyamides 6, polyamides 6 monoamine, polyamines 6-10, polyamides 12-12, and ...

Polyesters may be constituent elements of entity A. Examples of polyesters include poly ε-caprolactone, polylactic acid, poly (ethylene glycol adipate), polyhydroxyalkanoate, and polyester.

Polystyrenes can be constitutive elements of entity A. Examples of polystyrenes include hydroxytelequelic or monofunctional polystyrene ...

Polybutadienes may be constitutive elements of entity A. Examples of polybutadienes include hydroxytelequelic polybutadiene ...

Amino acids and peptides may be constitutive elements of entity A. In the sense of the invention, the term "peptides" means, among others, oligopeptides and polypeptides, even proteins. Amino acid derivatives (or analogs) (natural or synthetic) and peptides are also subject to the invention as an A entity.

All (co) polymers capable of constituting entity A of the Po - Ro-A hybrid compound may be homopolymers, linear or branched or cross-linked, or even cross-linked linear or branched block copolymers, possibly cross-linked.

When A.a (co) polymer, it is considerable that the AX or AY synton used to prepare the hybrid compound comprises a finished (co) polymer or an unfinished monomer, oligomer or polymer unit intended to grow to form a finished polymer after reaction with Po-Y or Po-X.

Alkyl, alkenyl or alkynyl chains capable of being included in entity A comprise, for example, from 2 to 50 carbon atoms, preferably from 4 to 40, and more preferably from 4 to 30 carbon atoms. Examples include butyl, octyl, dodecyl, octadecyl, eicosane ...

Silica is an example of mineral matter capable of forming entity A. For polyol entity Po, it is selected from polymeric synthetic non-saccharide polyols and / or saccharides (hydrogenated or not) comprising at least two, preferably at least three monosaccharide units.

Polymeric synthetic non-saccharide polyols may notably have an average molar mass greater than 1000 g / mol, preferably greater than 10000 g / mol. These are, for example, polyvinyl alcohols (partially hydrolysed or not), polyhydroxyaldehydes H- [CHOH] n-CHO and / or polyhydroxy ketones H- [CHOH] n-CO- [CHOH] M-H

preferably comprising at least 3, more preferably at least 4 carbon atoms. The polymeric synthetic non-saccharide polyols preferably have at least 3 hydroxyls, more preferably at least 4, and most preferably at least 10. They preferably have at least 3 repetitive units, more preferably at least 4, and most preferably at least 10. Note that they may constitute entities A.

With reference to "saccharides" (also called "carbohydrates"), it should be understood that in the context of the invention the generic term "saccharide" includes monosaccharides, disaccharides, oligosaccharides and polysaccharides as well as all saccharide derivatives .

Saccharides, their structures and formulas, are known to the technician. In particular, saccharides are known to have a non-reducing end and a reducing end. The latter implies the presence of an "anomalous hydroxyl" and is located on the right according to the writing convention. It is also known that saccharides have OH groups. According to the invention, when Po comprises a saccharide, the carbon of the saccharide most preferably contained in the bond (s) with the R-ring (s) is the "anomer" carbon. This does not exclude that all or part of the other saccharide carbons may be attached to a Ro bearing. This is possible the more the groups carried by the "non-anomer" carbons do not need protection when synthesizing the hybrid compound.

Monosaccharides are molecules that comprise a single saccharide unit (for example, at C5: pentose or C6: hexose), with no glycosidic connection between several such units. Monosaccharides include, but are not limited to aldoses, dialdoses, aldocetoses, ketoses, dicetoses, as well as deoxysaccharides, aminosaccharides and their derivatives resulting from precursors that at least potentially comprise a carbonyl group.

Examples of monosaccharides include the following saccharides:

D-glucose, fructose, sorbose, mannose, galactose, talose, allose. delicacy, idose, glycosamine, mannosamine, galactosamine, acid, glucuronic acid, rhamnose, arabinose, galacturonic acid, fucose, xylose, lixose, ribose.

By the way. Examples of di or oligosaccharides include the following saccharides:

- disaccharides: maltose, gentiobiose, lactose, cellobiose, isomaltose, melibiose, laminaribiose, chitobiose, xylobiose, manobiose, soforose, palatinose;

- oligo-saccharides: maltotriose, isomaltotriose, maltotetraose, maltopentaose, xyloglycan, maltoheptaose, manotriose, maninotriose, chitotriose, generally di or oligosaccharides having, for example, β-1-4, α-1-4 or α-1-6. Polysaccharides according to the invention may be linear or branched and may comprise, for example, more than 20 monosaccharide residues or preferably more than 30 monosaccharide residues or more particularly between 25 and 100 monosaccharide residues. These may be identical or different between them.

Polysaccharides according to the invention may contain mono, di, tri, tetra, penta, hexa, hepta, octa, ninth, or decasaccharide linear units, preferably mono, di, tri, or tetrasaccharides. Polysaccharides may comprise at least two, at least three, at least four, at least ten, or noticeably more in the case of polysaccharide polymers of such linear units.

In certain embodiments, polysaccharides according to the invention may comprise recurrent N-acetyl lactosamine-type saccharide units or acetylated saccharide units.

Also cited as examples of polysaccharides:

starch (preferably having at least 5 equivalents of DExtrose DE), and derivatives thereof such as maltodextrins, cyclodextrins and glucose syrups;

- pectin;

- cellulose and its derivatives;

- galactomannans, for example, guar or carob polymers and their derivatives, [The guar or carob macromolecule consists of a straight main chain constructed from sugars, β-D-mannose monomers linked together by bonds (1 -4), and α-D-galactoses side units. linked to β-D-mannoses by bonds (1-6). natural guar is extracted from the albumen of certain plant grains, eg Cyamopsis Tetragonalobus.];

- chitin and chitosan;

- bacterial polysaccharides;

- hyaluronic acid.

According to a particular embodiment, the Po entity is different from a maltodextrin.

According to another particular embodiment of the Po entity is different from a cyclodextrin.

According to another particular embodiment of the Po entity is different from a glucose syrup.

According to yet another particular embodiment of the Po entity is different from a maltodextrin and a cyclodextrin and / or a glucose syrup.

Starchy or cellulosic polysaccharides capable of forming the polyol entity Po are preferably of natural origin but could also be obtained synthetically.

In the case of saccharide derivatives, the following may be mentioned:

- those obtained by reducing the carbonyl group (alditol);

- those obtained by oxidizing one or more terminal groups or not to transform them into, for example, carboxylic acid groups or carboxyalkyl groups (eg carboxymethyl);

those obtained by grafting one or more clusters, for example carboxylic acid clusters, carboxyalkyl clusters (eg carboxymethyl), hydroxyalkyl clusters (eg hydroxyethyl) or alkyl clusters (eg methyl); those obtained by substituting one or more hydroxy groups for a hydrogen atom, an amine group, a thiol group or a similar heteroatomic group;

- those obtained by hydrogenation; glycosides, namely compounds comprising at least one saccharide and at least one aglycone (non-saccharide compound), the saccharide (s), on the one hand, and the non-saccharide component (s) on the other hand, being linked to each other (or each other) by hydrolysable bonds;

- galactomannan derivatives, in particular those derived from guar polymers or carob polymers, obtained by hydrolysis of guar or natural caroba, and possibly by chemical modification (derivatization).

Derivatization may be employed to chemically modify saccharide derivatives other than those mentioned above.

One of the major advantages of the invention is that it proposes hybrid compounds whose synthesis does not require protection from sensitive clusters, in particular those carried by the Po or A saccharides.

Of course, such protection is nevertheless possible, for example, to improve solubility. The process

In another aspect, the invention relates to a process for obtaining hybrid compounds and notably those according to the invention as described above.

This procurement process is the one defined earlier. It comprises four steps (I), (II), (III) and eventually (IV), which are detailed below, by way of non-limiting illustration. Steps (I) and (II): The tunings used

More precisely the Po-X starting tuners:

1. According to a first possibility, Po comprises at least one saccharide with:

Li comprising at least one amino group (e.g. terminal) which has been reacted with the Po anomer carbon;

- and / or Li from a precursor comprising at least one halogen group (e.g. bromine) which has reacted with Po OH (s);

2. according to a second possibility, Po comprises at least one (e.g. saccharide) residue functionalized by at least one functionalization group belonging to the group comprising carboxylic functionalizing groups, carboxylates, anhydrides, thiols, isocyanates and epoxides with :

Li comprising at least one amino group (e.g. terminal) that has reacted with the Po functionalization group (s);

- and / or Li from a precursor comprising at least one halogen group. . (e.g. bromine) which reacted with the Po functionalization group (s);

3. According to a third possibility, the first two possibilities are combined.

Advantageously, such a synton Po-X may be characterized by the fact that Po is a polymer comprising, for example, at least two, preferably at least 3, and most preferably at least monomer units.

The preparation of the Po-X synton may advantageously comprise the following substeps and reaction of the Po-carbon-carried hydroxyl, provided that it is saccharide and / or Po-functionalizing group (s). excess of at least one L1-linker precursor carrying a reactive end (preferably at least one amino function

- possibly terminal)

b- elimination of the precursor.

According to a preferred feature, L1 is -NH- (CH2) q ≥ with a precursor corresponding to:

<formula> formula see original document page 29 </formula>

and most preferably propargylamine:

<formula> formula see original document page 29 </formula>

More precisely the A-X starting tones:

1. According to a first possibility, A comprises at least one saccharide having:

-> L3 comprising at least one amino group (e.g. terminal) which has been reacted with OH carried by the carbon anomer A;

- and / or L3, derived from a precursor, comprising at least one halogen group (e.g. bromine) which has reacted with the OH of Po;

2. According to a second possibility, A comprises at least one (e.g. saccharide) residue functionalized by at least one functionalization group belonging to the group comprising the carboxylic functionalization groups, carboxylates, anhydrides, thiols, isocyanates and epoxides. with: -> L 3 comprising at least one amino group (e.g. terminal) that has reacted with the A functionalizing group (s);

- and / or L3, derived from a precursor comprising at least one halogen group (e.g. bromine) that has reacted with the A functionalizing group (s);

3. according to a third possibility, A comprises at least one residue (e.g., POS) functionalized by at least one functionalization group belonging to the hydrogen group and having at least one ethylenic unsaturation, with L3 comprising at least a group (for example terminal) bearing at least one ethylenic unsaturation that reacted with the A functionalization group (s);

4. According to a fourth possibility, the first three possibilities are combined.

Advantageously, if A comprises a polyol, that A-X tune may be characterized in that such polyol is a polymer, for example comprising at least two, preferably at least three, and most preferably at least 10 monomer units.

The preparation of AX tunon may advantageously comprise the following essential substeps: a-reaction of the carbon-carried hydroxyl anomer and / or A-functionalizing group (s) with an excess of at least one L3-carrier precursor of a reactive end (preferably at least one possibly terminal amino function and / or at least one halogen group) capable of reacting with A; b- elimination of the precursor. According to a preferred feature, L3 is -NH- (CH2) q> 1, with a precursor corresponding to:

<formula> formula see original document page 31 </formula>

and most preferably propargylamine:

<formula> formula see original document page 31 </formula>

In embodiments of this preferred feature, the L3 bond precursor could notably be: acrylonitrile, propargyl alcohol or triethylene glycol monopropargyl.

Where A comprises a POS, the preparation of A-X may be performed as described in Polymer 44 (2003) 6449-6455 Telechelic polydimethilsoloxane with terminal acetylenic groups prepared by phase transfer catalysis.

More precisely the starting syntones Po-Y:

1. According to a first possibility, Po comprises at least one saccharide with:

L 2 comprising at least one amino group (e.g. terminal) having reacted with the carbon anomer of Po;

-> and / or L2. from a precursor, comprising at least one halogen group (e.g. bromine) that reacted with the anomeric OH (s) of Po;

2. according to a second possibility, Po comprises at least one (e.g. saccharide) residue functionalized by at least one functionalization group belonging to the group comprising carboxylic functionalizing groups, carboxylates, anhydrides, thiols, isocyanates and epoxides with :

L 2 comprising at least one arain or hydroxy (e.g. terminal) group that has reacted with the Po functionalizing groups (s);

-> and / or L2 from a precursor which

comprises at least one halogen group (e.g. bromine) which has reacted with the Po functionalization group (s);

3. According to a third possibility, the first two possibilities are combined.

Advantageously, such a Po-Y tune may be characterized in that Po is a polymer comprising, for example, at least two, preferably at least 3, and most preferably at least 10 monomer units.

The preparation of the Po-Y tune may advantageously comprise the following essential substeps:

(a) reaction of the hydroxyl carried by the carbon anomer and / or Po functionalization group (s) with an excess of at least one reactive end L2 link precursor (preferably at least one amino function - optionally terminal - and / or at least one hydroxy function and / or at least one halogen group) capable of reacting with Po;

b) elimination of the precursor.

For example, the precursor of the L2 bond could be notably:

H2N (CH2CH2O) 3 (CH2) N3 'H2NCH (COOH) (CH2) 2N3 or HO (CH2) 6N3. For further details, see JACS 2005, 127, ρ 14942-14949 and JACS 2004, 126, 10958-10602.

More precisely, the starting syntones A-Y: 1. according to a first possibility, A comprises at least one saccharide having:

-> L4 comprising at least one amino group (e.g. terminal) having reacted with the OH carried by the carbon A anomer;

- and / or L4 from a precursor, comprising at least one halogen group (e.g. bromine) which has reacted with the OH (s) of A;

2. According to a second possibility, A comprises at least one residue (e.g., POS) functionalized by at least one functionalization group belonging to the group comprising carboxylic functionalizing groups, carboxylates, anhydrides, thiols, isocyanates and epoxides. :

L4 comprising at least one (e.g. terminal) amino group which has reacted with the A functionalizing groups (s);

-> and / or L4 from a NaN3 precursor which reacted with the epoxide A functionalization group (s);

-> and / or L4 comprising at least one halogen group (e.g. bromine) which has reacted with the A functionalizing group (s);

3. according to a third possibility, A comprises at least one residue (e.g. P0S) functionalized by at least one functionalization group belonging to the hydrogen group and having at least one ethylenic unsaturation, with L4 comprising at least one group (e.g. terminal) bearing at least one ethylenic unsaturation that reacted with the A functionalization group (s);

4. According to a fourth possibility, the first three possibilities are combined.

Advantageously, if A comprises a polyol other than Po, that AY synton may be characterized in that A is a polymer comprising, for example, at least two, preferably at least 3 and more preferably at least 10 monomer units. .

The preparation of tune A-Y may advantageously comprise the following substeps:

a) reacting the anomeric hydroxide (s) and / or A functionalizing group (s) with an excess of at least one L4 bond precursor carrying a reactive end or not (preferably at least at least one amine function - possibly terminal - and / or at least one halogen group) and capable of reacting with A;

b) elimination of the precursor.

According to a preferred feature, A-Y is obtained from an entity A carrying epoxide functionalizing groupings reacting with the precursor NaN3.

Within this preferred feature, the precursor of the. L4 bond could, for example, be notably: acrylonitrile, propargyl alcohol or triethylene glycol monopropargyl.

Where A comprises a POS, the preparation of A-X may be made as described in Polymer 44 (2003) 6449-6455 Telechelic polydimethylsiloxane with terminal acetylenic groups prepared by phase transfer catalysis.

More precisely the starting syntones Po-XY and A-XY will refer to the structure and preparation descriptions given above for Po-X, Po-Y, A-X and A-Y.

Step (III): Cycloaddition The cycloaddition mechanism [step (III) in the process core according to the invention is a 1,3-dipolar cycloaddition mechanism of a Po-X or A-Y tint with reagents VII. 2 azide and an A-Y or Po-X tune with acetylenic or nitrile reagents VII.1 under "click chemistry" under copper I catalysis, preferably in aqueous, hydro-organic or organic medium.

This mechanism is particularly attractive because of its simplicity, its non-hazardous character to operators and the environment, its low cost, among others.

It should be noted that, in one embodiment, Po-X and AY syntones may be substituted for or complemented by Po-XY syntones, each comprising at least one X reagent and at least one Y reagent and syntones. A-XY mixtures each comprising at least one reactant X and at least one reactant Y, such that these Po-XY and A-XY syntones are capable of reacting together.

In the sense of the invention, as defined herein, the term "of the order" means that said values are given with an uncertainty, for example about 10%;

More precisely, it is appropriate that the cycloaddition step (III) be carried out in an aqueous, hydroalcoholic or organic medium capable of solubilizing and / or swelling the Po-X and / or AY synton with the aid of at least one catalyst. ionized metallic form, preferably Cu ++, in the presence of at least one Cu ++ reducing agent in Cu +, in situ, such reducing agent being preferably selected from the group comprising: ascorbate, quinone, hydroquinone, vitamin K1, glutathione , cysteine, Fe2 +, Co2 +, applied electric potential, metal of the group comprising Cu, Al, Be, Co, Cr, Fe, Mg, Mn, Ni and Zn, and mixtures thereof.

In practice, the metal catalyst in ionized form, preferably Cu ++, Cu is advantageously presented as salt (ideally sulphate), further preferably comprising at least one activator comprising, for example, at least one salt. organic acid (s) (ideally ascorbic acid) and at least one alkali metal (ideally Na). Thus, the CuSO4 / Sodium Ascorbate system is, for example, entirely adapted.

On the other hand, the cycloaddition step (III) is preferably used in a reaction medium, the temperature of which is between 20 and 100 ° C, preferably between 50 and 80 ° C, for 0.1 to 20 hours, preferably for 30 minutes to 15 hours, and most preferably for 1 to 8 hours.

Heating of the reaction medium is performed by any appropriate medium. Microwave irradiation can be, for example, an interesting heating modality.

Advantageously, the reaction medium of the cycloaddition step (III) is an aqueous, hydro-organic or organic medium, preferably comprising at least one solvent chosen from:

- aprotic polar solvents, preferably dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), acetone, methyl ethyl ketone, butanone;

- protic polar solvents, preferably methanol, isopropyl alcohol (IPA), t-butanol (t-BuOH);

- non-polar solvents, preferably toluene, hexane, xylene,

- the water; - and their mixtures.

Step (IV): Separation

As the separation step (IV) of the Po ---- Ro --- A hybrid compound from the reaction medium, it consists notably of using:

- at least one chromatography, preferably at least one silica gel chromatography, with the aid of an eluent, containing a mixture of a first polar solvent and at least a second less polar solvent; such as the acetonitrile mixture and water;

-> and / or at least one evaporation to dry the product.

According to other such aspects, the present invention relates to the syntones Po-X, Po-Y, AX, AY, Po-XY and A-XY according to the invention, considered as such and defined above within the scope of the disclosure. of the process according to the invention.

The present invention is also directed to the use of a hybrid compound as described above as such or as a product obtained by the process as defined above as an ingredient in compositions selected from the group comprising:

-> detergent / surfactant compositions

-> shampoo compositions

-> soap compositions

-> cleaning compositions / washes

-> cosmetic compositions.

The above compositions also constitute another object of the invention.

In particular, such compositions may be an emulsion of. preferably an oil in water emulsion comprising a hybrid compound according to the invention. Hybrid compounds according to the invention may be notably presented as oils. They may also be presented in dispersed or solubilized form in a vector, for example at a concentration of 10 to 90% by weight. The vector may advantageously be a polymer solvent, for example an optionally volatile silicon compound, for example a linear or cyclic polydimethylorganosiloxane, such as cyclopentasiloxane, disiloxane, linear dimethicones, or a trimethylsiloxyphenyl dimethicone, or a mixture.

Hybrid compounds according to the invention may notably be used as an emulsifying or co-emulsifying agent to prepare or stabilize emulsions. They may, for example, be used in emulsions of which one phase is a silicone oil. Present in the form of solutions in a polyorganosiloxane, for example, cyclopentasiloxane, they may be used as emulsifier for water-in-oil or silicone oil emulsions. They can also be used to make various compounds compatible in the middle of a formulation. They may also be used as an auxiliary agent in the deposit of another compound, or as a precipitant of deposit of another compound. They may also be used as dispersing or co-dispersing agents to prepare or stabilize particle dispersions, for example pigments.

They may in particular be used or comprised in a cosmetic formulation to be rinsed or not for the care of skin and / or hair and / or lips, for example in skin care creams or oils or oils. skin, creams or sunscreen or oils, shampoos, kidney creams, shower gels, makeup compositions, lipsticks, deodorants. In particular, hybrid compounds according to the invention have the advantages in such applications of being low irritating, partially biodegradable and bioresorbable, offering a pleasant touch, and / or providing an interesting dispersion.

Further details of the invention will appear more clearly from the examples given below by way of illustration.

EXAMPLES

The following exemplary hybrid compounds are oligoorganosiloxanes or polyorganosiloxanes, more precisely PolydiMetylSiloxanes (PDMS) with trimethylsilyl end (MDi0M) modified by oligosaccharide groups (cf. structures A, B, C) as well as alkyl chain-modified oligosaccharides (cf. structure). D) according to a v-click chemistry mechanism. "Structure No. A: PDMS Type [MDi0modified CellobioseM] Structure No. 0 B: PDMS Type [MDiomodified ° IoxyoxygenicM] <formula> formula see original document page 40 </formula>

Structure No C: PDMS type [Oligoxyloglycan Modified MDi0 Oligoxyloglycan Modified MDi

<formula> formula see original document page 40 </formula> with Po representing DP7 oligoxyloglycans (m = 0; n = 0), 8 (m, n = 0, 1) or 9 (m = 1; n = 1) and R = CH3.

Structure No. D: Modified oligoxyl glycan alkane (C18H38)

<formula> formula see original document page 41 </formula>

Exact mass: 1760.80 Exact mass: 1598.74 Exact mass: 1436.69

Experimental part

This part describes the experimental steps that allowed to obtain the described structures A, B, C and D. These steps include:

- the synthesis of terminal alkaline derivatives of sugars;

- synthesis of azido derivatives on a polyorganosiloxane or polyalkane base;

- Condensation via the 1,3-dipolar cycloaddition reaction or "click chemistry".

Synton preparation

STEP (I): Synthesis of terminal alkaline sugars (SYNTONS Po-X): STRUCTURE A

N-acetyl-N-propargyl-β-D-glycopyranosyl - (1-4) - β-D-glycopyranosylamine (2).

<formula> formula see original document page 42 </formula>

In a 250 ml flask are placed 15 g cellobiose 1 (43.8 mmol) and 62.3 ml propargylamine (908 mmol, 21 equivalents).

The reaction medium is kept under magnetic stirring for 40 hours at room temperature. In the beginning, the solution is heterogeneous and becomes after 16 hours, homogeneous. The evolution of the reaction is accompanied by thin layer chromatography (CH3CN / H2O - 7: 3 v / v).

The reaction medium is evaporated to dryness and coevaporated with a mixture of MeOH and toluene (1: 1 v / v) to give a yellow solid.

The solid is N-acetylated selectively by addition of 300 ml of a solution of MeOH and Ac 2 O (5: 1 v / v). The solution is kept under magnetic stirring overnight at room temperature. The solution becomes completely homogeneous. After dry evaporation and co-evaporation with the MeOH / toluene mixture (1: 1 v / v), after lyophilization compound 2 is obtained as a white solid (15.2 g, 36.1 mmol, 83%).

Mass Spectrometry (ESI): m / z = 444.07 [M + Na] 1 H NMR (400 MHz, D 2 O, 298K)

δ (ppm) = 2.28 (s, 0.8H, rotamer, CH3 (Ac.)); 2.22 (s, 2.2H, rotamer, CH3 (Ac.)); 3.14 - 4.18 (m, 14H, H-2,3,4,5,6a, 6bGlcI and GlcI1 and NCH2)); 4.41 (d, 1H, J1 = 7.91 Hz, H-Ig1c11 (β>); 5.04 (d, 1H, rotamer, J1 = 8.68 Hz, H-IgG1 (p>; 5 , 50 (d, 1H, J 12 = 8.86 HZ, H-Ig 1 Cl ((3)) .13 C NMR (100 MHz, D2 O, 298K)

δ (ppm) = 18.8, 19.3 (rotamers, CH3 (Ac.)); 27, 8, 30.5 (rotamers, NHC2); 57.6.58.3 (C-6GlcI and GlcII); 67.2-79.4 (C-2,3,4,5g1cI and GlcII); 84.1 (C-Ig1c1); 100.2 (C 172.3, 17 3.5 (rotamers, C = O (Ac)) IR (KBr): 3391 (OH), 1645 cm -1 (C = O).

STRUCTURE BfC, D

N-acetyl-N-propargyl-β-D-oligoxyglycosylamine (6,7,8) (Po-X syntones)

<formula> formula see original document page 43 </formula>

Exactly. 1396.45 Exact: 1224.40 Exact: 1062.35 7P5®

<formula> formula see original document page 43 </formula>

lubssa lubssa lubssa

Exact: 1465.50 Exact: 1303.44 Exact: 1141.39

In a 25 ml flask, 2 g of the mixture 3, 4 and 5 (.1.58 mmol) (0.15 / 0.35 / 0.5.0 respective ratio), 2 ml of propargylamine (31, 2 mmol, 19.7 equivalents) and 3 mL MeOH.

The reaction medium is kept under magnetic stirring for 3 days at room temperature. The solution is very viscous and orange in color. The evolution of the reaction is followed by thin layer chromatography (CH 3 CN / H 2 O - 7: 3 v / v). The solution is then diluted by 60 mL of a mixture of MeOH and CH 2 Cl 2 in a 1: 2 v / v ratio. A white precipitate appears spontaneously and the solution is stirred for 10 minutes. The solution is filtered and the white solid washed with 60 mL of 1: 2 v / v MeOH / CH 2 Cl 2 mixture. The solid is then subjected to N-acetylation by placing it in 400 mL of a 20: 1 v / v MeOH and Ac20 solution. The reaction medium is kept under magnetic stirring for 1 day at room temperature and the solution is still slightly cloudy. Migration over MCC (CH3CN / H2O - 7: 3 v / v) shows no significant difference compared to non-N-acetylated products.

Compounds 6, 7 and 8 are concentrated and lyophilized and are presented as a white cotton powder (2g, 1.48 mmol, 94%).

Mass Spectrometry (MALDI-T0F):

6 m / z = 1163.87 [MtNa] +

7 m / z = 1325.87 [MtNa] +

8 m / z = 1487.84 [MtNa] +

1 H NMR (400 MHz, D 2 O, 298 K) δ (ppm) = 2.17, 2.23 (s, CH 3 (Ac)); 3.20 - 4.50 (m, H-2,3,4,5,6G1c, Gal and Xyl); 4.60 - 4.90 (d em, H-1glcI and Gal); 5.18, 5.02 (d, H-1xyl); 5.44 (d, J 1-2 = 8.61, H-1 ClCl). IR (KBr): 3402 (O-H), 1645 cm -1 (C = O).

STEP (II): Synthesis of terminal azide derivatives STRUCTURE A, B 1,1,3,5,5,5-Heptamethyl-3- (1'azido-2'-hydroxymethoxypropyl) trisiloxane (10) (SYNTONS AY)

<formula> formula see original document page 44 </formula>

Trisiloxane 9 (12g, 35.7 mmol) is diluted with 60 mL isopropyl alcohol (IPA), then 5 equivalents sodium azide (11.5 g, 178.5 mmol), 40 mL distilled water and 20 mL glacial acetic acid are added. to reach a pH of approximately 6.

The reaction medium is stirred at 50 ° C for 4 hours. The reaction is followed by CCM (9: 1 v / v Toluene / EtOAc).

The reaction medium is diluted with diethyl ether (200 mL) and extracted successively by sat. (2 x 100 mL). The organic phase is recovered, dried over Na 2 SO 4, filtered, then evaporated to dryness to give compound 10 (13.5 g, quantitative yield) as a pale yellow oil and sufficiently pure to be used for the next reaction.

Mass Spectrometry (ESI): m / z = 380 [M + H] + 1 H NMR (300 MHz, CDCl 3, 298K)

δ (ppm) = 0.01 (s, 3H, SiCH 3); 0.06 (m, 18H, 2x Si (CH 3) 3); 0.42 (m, 2H, SiCH 2 (a)); 1.57 (m, 2H, SiCH 2 CH 2 (β)); 2.57 (bs, 1H, OH); 3.40 (m, 6H, CH 2 OCH 2 and CH 2 N 3); 3.90 (m, 1H, CHOH). 13 C-NMR (75 MHz, CDCl 3, 298K)

δ (ppm) = -0.2 (SiCH3); 2.0 (Si (CH3) 3); 13.7 (SiCH2a)); 23.4 (SiCH 2 CH 2 (P)); 53.8 (CH 2 N 3); 69.9 (CHOH); 71.9, 74.4 (CH 2 OCH 2).

IR (KBr): 3432 (O-H), 2957 and 2871 (C-H), 2102 (N3), 1258 (C-O), 1076 and 1053 cm -1 (Si-O).

α, ω-Di- [1-azido-2-propanol; -3- (oxypropyl)] polydimethyl siloxane (12) (A-Y syntones)

<formula> formula see original document page 45 </formula> The average PD polyorganosiloxane equal to 10 11 (2g, ~ 1.81 mmol) is diluted with 13 mL of isopropyl alcohol (IPA), then 5 equivalents of azide are added. sodium chloride (1.93 g, 9.07 mmol), 3.9 mL distilled water and 3.3 mL glacial acetic acid to reach a pH of approximately 6. The reaction medium is stirred at 50 ° C for 7 hours . The reaction is followed by 1 H NMR and stopped when the starting product is almost completely consumed. The reaction medium is diluted with diethyl ether (30 mL) and extracted with water (10 mL). The organic phase is recovered, dried over Na 2 SO 4, filtered, then evaporated to dryness to give compound 12 (1.95 g, 89%) as a colorless oil and sufficiently pure to be used for the next reaction.

1 H NMR (300 MHz, CDCl 3, 298K)

δ (ppm) = 0.05 (m, 72H, 12x Si (CH 3) 2); 0.51 (m, 4H, 2x SiCH 2 (a)); 1.58 (m, 4H, 2x SiCH 2 CH 2 (P)); 3.33-3.43 (m, 12H, 2x CH 2 OCH 2 and CH 2 N 3); 3.91 (m, 2H, 2x CHOH). 13 C-NMR (75 MHz, CDCl 2, 298K) δ (ppm) = - 0.3, 1.2, 1.4 (Si (CH3) 2); 14.3 (SiCH2 (a)); 23.5 (SiCH 2 CH 2 (β)); 53.7 (CH 2 N 3); 69.9 (CHOH); 71.9, 74.5 (CH 2 OCH 2).

IR (KBr): 3415 (O-H), 2962 and 2874 (C-H), 2104 (N3), 1261 (C-O), 1034 and 1070 cm -1 (Si-O).

STRUCTURE D

1-Azido-octadecane (14) (A-Y syntones)

<formula> formula see original document page 46 </formula> 1-Bromo-octadene 13 (1g, 3 mmol) is diluted in 10 mL of DMF, then 2 equivalents of NaN3 (390 mg, 6 mmol) is added. The reaction medium is heated to 50 ° C under magnetic stirring for 2 hours. The reaction is followed by CCM (eluent = petroleum ether).

DMF is suppressed under reduced pressure, then the residue is diluted with 20 mL of CH 2 Cl 2 and extracted with 10 mL of water. The organic phase is recovered, dried over Na2 SO4, filtered, then evaporated to dryness to give compound 14 (885 mg, quantitative yield) as a colorless liquid. This product is pure enough to be directly used for the next reaction. 1 H NMR (300 MHz, CDCl 3, 298K)

δ (ppm) = 0.85 (t, 3H, Jhi8-hi7 = 6Hz, CH3); 1.10 - 1.32 (m, 30H, 15x CH 2); 1.55 (q, 2H, JH18-hi7 = 6Hz, CH3 CH2); 3.22 (t, 2H, Jhi-H 2 = 7.5Hz, CH 2 N 3); 13 C-NMR (75 MHz, CDCl 3, 298K)

δ (ppm) = 14.1 (CH 3); 22, 7, 26, 7, 28, 9, 29, 2, 29, 4, 29, 5, 29, 6, 29, 7, 31, 9 (CH 2); 51.5 (CH 2 N 3). IR (KBr): 2942 and 2855 (CH alkanes), 2096 cm -1 (N3)

STEPS (III) & (IV): Click chemistry condensation compounds

4- [N-acetyl-N- (β-D-glycopyranosyl- (1-> 4) - β-D-glycopyranosyl) -amino methyl] -1- [1'- (1,1,1, 3, 5 , 5,5-heptamethyl-3- (2'-hydroxymethoxypropyl) tri-siloxane)] - 1H- [1,2,3} triazole (15)

<formula> formula see original document page 47 </formula> To a solution of the cellobiose derivative containing terminal alkyne 2 (100 mg, 237 μmol) and azido tri-siloxane derivative 10 (1/1 equiv., 99 mg, 261 μmol) in 0.6 mL of water and 1 mL of iPrOH are added sodium ascorbate (0.1 equiv., 4.7 mg, 24 μmol) and newly dissolved copper sulfate in 0.1 M solution (0.01 equiv., 24 μl, 2.4 μmol).

The solution is brought to 50 ° C in an airtight tube and stirred for 1 hour. The reaction is followed by CCM (CH3CN / H2O - 7: 3 v / v).

The medium is then diluted in MeOH (5 mL), then evaporated to dryness in the presence of silica.

The residue is deposited on a silica gel column. After purification by flash chromatography on silica gel (acetonitrile / water: 9-1 v / v), compound 15 is obtained in 89% yield (168 mg, 210 μmol) and as a white powder after freeze drying. .

Mass Spectrometry (ESI): m / z = 823.46 [M + Na] + 1 H NMR (400 MHz, CD 3 OD, 298 K)

δ (ppm) = 0.04 (s, 3H, SiCH 3); 0.10 (m, 18H, 6xSi (CH 3) 3; 0.49 (m, 2H, SiCH 2 Ma)); 1.61 (m, 2H, SiCH 2 CH 2 (β)); 2.08, 2.22 (2xs, 3H, rotamers, CH 3 (Ac)); 3.25-3.89 (m, 15H, H-2,3,4,5,6a, 6bGlcl and Glc11 and CH 2 OCH 2); 4.09 (m, 1H, CHOH); 4.40 (m, 1H, CH (OH) CH 2 N); 4.44 (d, 1H, J1-2 = 7.88 Hz, H-Ig1 Cl (I); 4.56 (m, 1H, CH (OH) CH2 N); 4.62 (m, 2Η, rotamers CH 2 N (Ac)) 5.00 (d, 0.18H, rotamer, J 1-2 = 8.21 Hz, H-GlCl ((5)); 5.66 (d, 0.82H, rotamer, J1 -2 = 9.20 Hz, H-Ig1cm (β)); 7.86, 8.02 (s, 1H, H-5 triazo1) .13 C NMR (100 MHz CD3OD, 298K)

δ (ppm) = 0.0 (SiCH3); 2.1 (Si (CH 3) 3); 14.7 (SiCH2 (α)); 22.1 (CH3 (Ac.)); 24.6 (SiCH 2 CH 2; (β)); 37.5 (CH 2 N (Ac)); 54.7 (CH (OH) CH 2 siN); 61.9, 62.6 (C-6GlcI and GlcII); 70, 5.71, 5, 72, 1, 73.3, 73.4, 75.0, 75.4, 76.6, 78.0, 78.3, 78.9, 80.0 (c- 2,3,4,5 GlcI and G1CII, CH 2 OCH 2, CHOH); 88.9 (C-IGlcI); 104.7 (C-1G1CII); 126.1 (C-5triazo1), 146.4 (C-1triazo1), 174.5 (C = O (NAc)). 4- [N-acetyl-N- (β-D-oligoxylglycosyl) amino methyl] -1- [1'- (1,1,1,3,5,5,5-heptamethyl-3- (2'- hydroxyl methoxypropyl) triloxane)] -1H- [1,2,3] triazole (16,17,18)

<formula> formula see original document page 49 </formula>

To a solution of the oligoxyl glycan derivatives containing terminal alkyne 6 (DP7), 7 (DP8), 8 (DP9) (10.9 g, 8.1 mmol) and the azido tri-siloxane derivative 10 (1.5 equiv., 8, 4 g, 12.1 mmol) in 120 mL of water and 180 mL of iPrOH are added sodium ascorbate (1 equiv., 1.6 g, 8.1 mmol) and freshly dissolved copper sulfate in IM solution ( 0.5 equiv., 4.04 mL, 4.04 mmol).

The solution is brought to 50 ° C in an IL flask and stirred for 1 hour. The reaction is followed by CCM (CH3CN / H2O - 7: 3 v / v).

The medium is then diluted in MeOH (25 mL), then evaporated to dryness in the presence of silica. The residue is deposited on a silica gel column. After purification by flash chromatography on silica gel (acetonitrile / water: 8-2 v / v), we found a copper (II) contamination of fractions with compounds 16, 17 and 18, visualized by a bluish color. These fractions are pooled, then concentrated and subjected to a column filled with a Dowex M4195 chelating resin, previously treated with a 2M NH4OH solution, then washed with distilled water to a pH of 7. Compounds 16, 17 and 18 are recovered by pouring water over the column and are perfectly decontaminated as shown by the colorless appearance of the solution and the conductivity measurement.

Compounds 16, 17 and 18 are obtained in 87% yield (12 g, 7 mmol) and as a white powder after lyophilization.

Mass Spectrometry (MALDI-TOF):

6 m / z = 1561.51 [M + Na, H 2 O +

7 m / z = 1705.60 [M + Na] +

m / z = 1723.57 [M + Na, H 2 O +

8 m / z = 1867.67 [M + Na] +

1 H NMR (400 MHz, D 2 O, 298K)

δ (ppm) = -0.01 (m, 21H, SiCH 3 and 6x Si (CH 3) 3); 0.35 (m, 2H, SiCH 2 (a)); 1.63 (m, 2H, SiCH 2 CH 2 (β)); 2.12, 2.28 (2xs, 3H, rotamers, CH3 (Ac.)); 3.29-3.89 (m, H-2,3,4,5,6a, 6b H-2,3,4,5,6Glc 'Gal and Xyl and CH 2 OCH 2); 4.09 (m, 1H, CHOH); 4.40 - 4.88 (m, CH (OH) CH 2 N, CH (OH) CH 2 N, CH 2 N (Ac), H-Ig 1c and Gal); 5.09, 4.97 (d, H-Ixyl); 5.45 (m, H-Clcip); 7.86, 7.94 (s, 1H, H-triazole;

4- [N-acetyl-N- (β-D-oligoxyglycosyl) -aminomethyl] -1- [α, ω-di-1- (propanol-3- (oxypropyl) polydimethylsiloxane) J-1H- [1,2,3 ] - triazole (19).

<formula> formula see original document page 50 </formula>

^ 0

R = DP7 otigoxoglycans. 8 or 9

N .. ΙΤΙΤΟΟΟ ^ ^ΓΓΓΓ ^ ^ ^ ^ A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A solution of terminal 6 (DP7), 7 (DP8), 8 (DP9) terminal alkynyl glucans derivatives (2 equiv., 500 mg, 370 µmol ) and the medium DP 10 polyiorosiloxane derivative 12 (220 mg, 185 μmol) in 3 mL of water and 5 mL of iPrOH are added sodium ascorbate (2 equiv, 73.4 mg, 370 μmol) and copper sulfate. freshly dissolved in 1M solution (1 equiv., 185 μL, 185 μmol).

The solution is brought to 50 ° C in an airtight tube and stirred for 1 hour. The reaction is followed by CCM (CH3CN / H2O -7: 3 v / v).

The medium is then diluted in MeOH (25 mL), then evaporated to dryness in the presence of silica. The residue is deposited on a silica gel column. After purification by flash chromatography on silica gel (acetonitrile / water: 8-2 v / v), compounds 19, consisting of a multitude of condensable product combinations and impossible to determine, are obtained in 81% mass yield ( 583 mg) and as a white powder after lyophilization.

1H NMR (300 MHz, D2 O, 298K)

δ (ppm) = -0.07 (m, 57H, ~ 9.5xSi (CH3) 2); 0.35 (m, 4H, 2xSi CH 2 (a); 1.49 (m, 4H, 2xSi CH 2 CH 2 (β)); 2.03, 2.18 (2xs, rotamers, CH 3 (Ac)); -4.88 (m, H-2, 3, 4, 5, 6Glc 'Gal and Xyl and CH 2 OCH 2 Si CHOHSi, CH (OH) CH 2 N, CH (OH) CH 2 N, CH 2 N (Ac), H-IG 1c and Gal); 4.97-5.09 (m, H-1Xyl); 5.32 (m, H-1Glc Iβ); 7.82, 7.93 (s, 1H, H-5 triazo1).

IR (KBr): 3383 (OH), 2961 (C-H), 1644 (C = O), 1261 (C-O), 1044 and 1090 cm -1 (Si-O).

4- [N-Acetyl-N- (β-D-oligoxylglycosyl) -aminomethyl] -1- (1-octadecane) -1H- [1,2,3] -triazole (20, 21 and 22) <formula> see original document page 52 </formula>

To a solution of the terminal 6 alkine containing oligoxyloglycan derivatives (DP7). 7 (DP8), 8 (DP9) (200 mg, 150 μmol) and 1-azidooctadecane 14 (1.1 equiv., 48 mg, 160 μmol) in 1.5 mL water and 3 mL iPrOH is Sodium ascorbate (1 equiv., 29 mg, 150 μmol) and recently dissolved copper sulfate in 1 M solution (0.5 equiv., 75 μL, 75 μmol) were added.

The solution is brought to 50 ° C in an airtight tube and stirred for 1 hour. The reaction is followed by CCM (CH3CN / H2O -7: 3 v / v).

The medium is then diluted with MeOH (10 mL), then evaporated to dryness in the presence of silica. The residue is deposited on a silica gel column. After purification by flash chromatography on silica gel (acetonitrile / water: 8/2 v / v), compounds 20, 21 and 22 are obtained in 81% yield (180 mg, 121 μπιοί) and as a powder. white after freeze drying.

1 H NMR (400 MHz, D 2 O, 298 K) δ (ppm) = 0.76 (m, 3H, CH 3); 1.10-1.32 (m, 30H, 15xCH 2); 1.63 (m, 2H, CH 3 CH 2); 1.90, 2.08 (2xs, 3H, rotamers, CH 2 (Ac)); 3.12 - 4.86 (m, δ -2, 3, 4, 5, 6Glc, Gal and Xyl); 4.75 (m, H-IGlc and Gal); 5.08 (d, H-IXyl; 7.77, 7.90 (s, 1H, H-5 triazo1) IR (KBr): 3402 (OH), 2921, 2851 (C-H).

Claims (21)

1. Po - Ro - A hybrid compound comprising at least one polyol entity (Po) and in which at least one of the Po atoms is replaced by at least one group of formula (I) below: --- -Ro -------- A where: - Ro is a following formula (II.1) or (II.2) label: <formula> formula see original document page 54 </formula>) with Z represents a carbon or nitrogen atom; - the polyol entity Po is selected from polymeric synthetic non-saccharide polyols, or from saccharides (hydrogenated or not), comprising at least two, preferably at least three monosaccharide units; - A is a mineral or organic entity, possibly polymer; and in case of presence of a plurality of entities A per molecule of hybrid compound; these A entities are identical or different from each other, the organic A entity being chosen from or coming from a compound selected from the group comprising: - synthetic polymers, their copolymers or monomer units, allowing them to be obtained; - alkyls, alkenyls, alkynyls, aryls and combinations thereof; - and their combinations. Hybrid compound according to claim 1, characterized in that at least one of the hydroxyl functions of the polyol entity (Po) is replaced by at least one group of the following general formula (I): ----- A as defined in claim 1. Hybrid compound according to claim 1, characterized in that Ro or at least one of the Ro bearings is bound to entity Po and / or entity A by a -L-divalent bond, L preferably being a hydrocarbon or an atom such as O or S. Hybrid compound according to claim 1, characterized in that none of the Ro labels is bound to the Po entity by a divalent -L-bond and that said hybrid compound comprises at least one acid-free entity A ( amino acid (s) and / or peptide (s) and / or its analog (s) and / or derivative (s). Hybrid compound according to any one of the preceding claims, characterized in that entity A is selected from or derived from a compound selected from the group comprising: synthetic polymeric non-saccharide polyols, their copolymers or the units thereof. monomers, allowing them to be obtained; - polyorganosiloxanes (POS), their copolymers or monomer units allowing them to be obtained; - polyalkylene glycols (or further alkylene polyoxides), preferably polyethylene glycols (or further ethylene polyoxides) and / or polypropylene glycols (or further propylene polyoxides) and / or polytetraethylene glycols and / or their copolymers. or co-oligomers, notably statistical or block copolymers or co-oligomers or polypropylene glycols (or statistical or block ethylene and propylene polyoxides), such polyalkylene glycols being optionally functionalized by or on other groups, for example, by or over amino groups (Jeffamines), and / or optionally being terminated at least one end by a hydroxyl group or an alkyl group, for example a C1-C30 alkyl; polyamides, their copolymers or the monomer units permitting them to be obtained; - the polyesters, their copolymers or monomer units permitting them to be obtained; - polybutadienes, their copolymers or monomer units allowing them to be obtained; - polystyrenes, their copolymers or monomer units to be obtained; - optionally alkyl, alkenyls, alkynyls, aryls and combinations thereof; - mineral materials such as silica; - and their combinations. Hybrid compound according to any one of the preceding claims, characterized in that the nitrogen-free valential bond at position 1 in formulas (II. 1) and (II. 2) binds the Ro-Po label and the bond. free carbon or Z-atom at 4 or 5 in formulas (II.1) and (II.2) connects Hybrid compound according to any one of the preceding claims, characterized in that the nitrogen-free valential bond at position 1 in the formulas (II. 1) and (II. 2) binds the Ro-A label and the bond. The free carbon or Z-atom at 4 or 5 in formulas (II.1) and (II.2) binds Ro to Po. Hybrid compound according to any one of the preceding claims, characterized in that the polyol entity Po or the polyols capable of being included in entity A are selected from: the synthetic polymeric non-saccharide polyols; and / or saccharides (hydrogenated or not) comprising at least two, preferably at least three monosaccharide units. The preceding claim is characterized in that A comprises at least one M and D silicon-carrying POS, T and / or Q, and preferably at least one MeD silicon-carrying POS, optionally T and / or Q, and more preferably at least one M (D) dM, M (D) d (T) tM, MQ POS with d, t being rational numbers greater than or equal to 0. of the preceding claims, characterized in that match at least one of the following formulas: 9. Hybrid compound according to any of 10. Hybrid compound according to any <formula> formula see original document page 57 </formula> <formula> formula see original document page 58 </formula> where: R2, identical or different, is a hydrocarbon of preferably a methyl group; R 3, identical or different, and a group of the formula -Ro-Po wherein Ro and Po are as defined in at least one of claims 1 to 7; - R1 identical or different, is a group R2 or R3; R is a divalent group comprising an oxygen atom, preferably a -O- group; - m is an intermediate number other than 0; - η is an intermediate number greater than or equal to 0; k and 1 are intermediate numbers greater than or equal to 0; and - o and p, identical or different, are intermediate numbers greater than or equal to 0. Process for obtaining, notably the hybrid compound according to any one of the preceding claims, characterized in that: I. utilizes and / or prepares a Po-X synton, comprising at least one reagent X, having at least one reactive end of formula (VII.1): -C = E; with E = CH or N; II. using and / or preparing an A-Y syntonon comprising at least one Y reagent having at least one reactive end of formula (VII.2): -N3; the reactive end (VII.2) being able to react with the reactive end (VII.1); III. reacting the Po-X synton with the AY synton according to a cycloaddition mechanism to obtain a Po - Ro - A hybrid compound comprising at least one polyol (Po) entity in which at least one of the hydroxyl functions of Po is replaced by at least one group of the following formula (I '): ----- Ro --- A; with Ro and A as defined in at least one of claims 1 to 10; IV. eventually separate Po ---- Ro - A from the reaction medium in order to recover it. Process according to Claim 11, characterized in that the step (III) of cycloaddition is carried out in an aqueous, hydroalcoholic or organic medium capable of solubilizing and / or swelling the Po-X synton and / or the AY synton. with the aid of at least one metal catalyst in ionized form, preferably Cu ++, in the presence of at least one Cu ++ reducing agent in Cu +, in situ, such reducing agent preferably being selected from the group comprising: ascorbate , quinone, hydroquinone, vitamin K1, glutathione, cysteine, Fe2 +, Co2 +, applied electrical potential, metal of the group comprising Cu, Al, Be, Co, Cr, Fe, Mg, Mn, Ni and Zn, and mixtures thereof. Process according to either of Claims 11 and 12, characterized in that the reaction medium comprises at least one solvent chosen from: - the aprotic polar solvents, preferably dimethylformamide (DMF), dimethylacetamide (DMAc), acetone, methyl ethyl ketone, butanone; protic polar solvents, preferably methanol, isopropyl alcohol (IPA), t-butanol (t-BuOH); - nonpolar solvents, preferably toluene, hexane, xylene, - water; - and their mixtures. Process according to any one of claims 11 to 13, characterized in that the possible separation (IV) of Po ---- Ro --- A from the reaction medium, is notably to use: -> at least chromatography, preferably at least one silica gel chromatography, with the aid of an eluent, containing a mixture of a first polar solvent and at least one second less polar solvent, such as the mixture acetonitrile and water ; -> and / or at least one evaporation to dry the product. 15. Sinton Po-X comprising at least one reagent X having at least one reactive end of formula (VII.1.1): <formula> formula see original document page 60 </formula> with E = CH or Ν a = 1, said end being attached to the Po residue by an L1 bond which is a divalent hydrocarbon bond. Sinton Po-X according to claim -15, characterized in that: -1. according to a first possibility, Po comprises at least one saccharide having: -> L1 comprising at least one amino group (e.g. terminal) that has reacted with the Po anomer carbon; - and / or L1 from a precursor comprising at least one halogen group (e.g. bromine) which has reacted with the OH of Po; -2. according to a second possibility, Po comprises at least one (e.g. saccharide) residue functionalized by at least one functionalization group belonging to the group comprising carboxylic functionalizing groups, carboxylates, anhydrides, thiols, isocyanates and epoxides having: > L1 comprising at least one amino group (e.g. terminal) that has reacted with the Po functionalization group (s); -> and / or L1 from a precursor comprising at least one halogen group (e.g. bromine) which has reacted with the Po functionalization group (s); -3. According to a third possibility, the first two possibilities are combined. Synton Po-X according to claim 15 or 16, characterized in that Po is a polymer. A Po-Xy Po-synton as claimed in claim 1, 4 or 8, comprising at least one reagent X as defined in claim 15 and at least one reagent Y having at least one reactive end of formula (VII.2.1): with a = 1; that end being attached to the Po residue by an L2 bond which is a divalent hydrocarbon bond. Use of a hybrid compound according to any one of claims 1 to 10, or obtained by the process according to any one of claims 11 to 14, as an ingredient in compositions selected from the group comprising: detergent / surfactant compositions; -> shampoo compositions; -> soap compositions; -> cleaning / washing compositions; -> cosmetic compositions. Composition according to the use of claim 19. Emulsion, preferably oil in water emulsion, comprising a hybrid compound according to any one of claims 1 to 10, or obtained by the process according to any one of claims 11 to 14.