EP-4739664-A1 - PROCESS FOR THE PREPARATION OF ONE OR MORE C-GLYCOSIDE DERIVATIVES COMPRISING A CATALYTIC REDUCTION STAGE

Abstract

The present invention relates to a process for the preparation of one or more C-glycoside derivatives corresponding to the formula (I), preferably corresponding to the formula (I'), and to their optical isomers, geometrical isomers and/or solvates, such as the hydrates, comprising at least one purification stage carried out in an aqueous medium. The invention also relates to a process for the preparation of one or more C-glycoside derivatives corresponding to the formula (I'B), comprising a stage of reduction, carried out in an aqueous medium, of at least one compound of formula (I), preferably of formula (I').

Inventors

• WAFFLART, Florence
• LESEURRE, Lucie
• SCHOONJANS, Jean-Jacques
• GUERREIRO, PATRICIO
• LE GOFF, Guillaume
• TROUILLE, SIMON

Assignees

• L'OREAL

Dates

Publication Date

20260513

Application Date

20240703

Claims (20)

1. 1. Process for the preparation of at least one compound of following formula (I): in which formula (I): - SA' represents a monosaccharide group or a polysaccharide group comprising up to 20 sugar units, in particular up to 6 sugar units, in pyranose and/or furanose form and of the L and/or D series, said monosaccharide group or polysaccharide group having at least one substituted free hydroxyl group, and optionally at least one optionally protected amine group, - the bond between SA' and CH2-X is a bond of C-anomeric nature, - X represents a divalent radical -CH(OR)-, - R represents a hydrogen atom, a C1-C10, preferably C1-C4, alkyl group, such as methyl, or a (Ci-C4)alkylcarbonyl group, such as acetyl, preferably a hydrogen atom, - Ri represents a saturated or unsaturated, linear or branched, cyclic or acyclic, preferably acyclic, C1-C10, preferably C1-C4, more preferentially saturated, hydrocarbon chain, and also one of its optical isomers, geometrical isomers, and/or one of its solvates, such as the hydrates, said process comprising: at least one reaction stage (i) taking place according to the following synthesis scheme (A): in which synthetic pathway (A): ■ Ri and R2 are identical or different, with R2 having the same meaning as Ri in the formula (I), ■ SA' has the same meaning as in the formula (I), ■ D + is an organic or inorganic cation resulting from the alkaline agent; preferably, D + is an inorganic cation; said reaction stage (i) being carried out in an aqueous media in the presence: ■ of at least one compound of formula (II), ■ of at least one compound of formula (III), and ■ of at least one alkaline agent in an equimolar amount or in excess, with respect to the compound of formula (II), preferably in excess, to result in the formation of at least one compound of formula (IA) and of at least one compound of formula (IV), at least one stage of reaction (ii) of at least said compound of formula (IA), in a preferably aqueous medium, to result in the formation of at least one compound corresponding to the following formula (IB): (IB) in which formula (IB) SA', Ri and R have the same meanings as in the formula (I); the reaction stage (ii) is at least one stage of reduction (iil) by catalytic hydrogenation carried out in the presence of at least one metal catalyst, - at least one purification (P) of the reaction medium including at least said compound of formula (IV), carried out in an aqueous medium, comprising: o at least one treatment stage (Pl) carried out with at least one cationic ion-exchange resin in order to convert at least said compound of formula (IV) into a compound of formula (IV) according to the following scheme: said treatment stage (Pl) being carried out at a pH strictly lower than the pKa of the compound of formula (IV) or lower than the lowest pKa of the compounds of formula (IV), if several are present, o at least one stage of separation (P2) of at least said compound of formula (IV) from the reaction medium.
2. 2. Process according to Claim 1, characterised in that the reaction stage (i) is carried out in an aqueous medium in the presence: o of at least one compound of formula (II), o of at least one compound of formula (III), ■ preferably, the compound(s) of formula (III)/compound(s) of formula (II) molar ratio is greater than or equal to 1, preferably of between 1 and 5, more preferentially between 1 and 4, more particularly still between 1 and 3, better still between 1 and 2, in particular ranging from 1 to 1.5; in particular, the compound(s) of formula (III)/compound(s) of formula (II) molar ratio is greater than 1; o of at least one mineral alkaline agent, preferentially chosen from the group consisting of alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal (bi)carbonates, and their mixtures; in particular alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, ■ as the alkaline agent is in an equimolar amount or in excess, preferably the alkaline agent(s)/compound(s) of formula (II) molar ratio is greater than or equal to 1, preferably of between 1 and 5, more preferentially between 1 and 4, more particularly still between 1 and 3, better still between 1 and 2, o preferably, the reaction stage (i) takes place: ■ at a temperature ranging from 20°C to 80°C, preferably at a temperature ranging from 20°C to 70°C, more preferentially at a temperature ranging from 30°C to 70°C, better still from 30°C to 60°C, even better still at a temperature ranging from 35°C to 45°C; o preferably, the duration of the reaction varies: ■ from 10 minutes to 10 hours, preferably from 20 minutes to 5 hours, more preferentially from 30 minutes to 4 hours, more preferentially still from 45 minutes to 3 hours.
3. 3. Process according to Claim 1 or 2, characterised in that the purification(s) (P) can be carried out at least once between a reaction stage (i) and at least one reaction stage (ii), and/or at least once after at least one reaction stage (ii); preferably, the purification (P) is carried out at least once on conclusion of the reaction stage(s) (i).
4. 4. Process according to any one of the preceding claims, characterised in that the purification (P) is carried out in an aqueous reaction medium comprising at least said compound of formula (IV) and devoid of any water-miscible organic solvent, preferably devoid of organic solvent chosen from the group consisting of dichloromethane, diethyl ether, ethanol, methanol, isopropanol, butanol, isobutanol, tert-butanol, toluene, isopropanol and their mixtures, more preferentially devoid of any organic solvent.
5. 5. Process according to any one of the preceding claims, characterised in that the treatment stage(s) (Pl) is or are carried out with at least one cationic resin having carboxylic groups and/or at least one sulfonic resin, preferably at least one sulfonic resin.
6. 6. Process according to any one of the preceding claims, characterised in that the treatment stage(s) (Pl) is or are carried out at a pH ranging from 1.5 to 6, preferably ranging from 2 to 4.5, more preferentially ranging from 2 to 3.5, better still in a pH range extending from 2.5 to 3.5.
7. 7. Process according to any one of the preceding claims, characterised in that the separation stage(s) (P2) is or are carried out by distillation or electrodialysis, preferably by vacuum distillation, more preferentially by vacuum distillation at a temperature varying from 30°C to 80°C, preferably from 30°C to 55 °C, preferably from 30°C to 50°C.
8. 8. Process according to any one of the preceding claims, characterised in that, on conclusion of the separation stage (P2), the content of compound(s) of formula (IV) is less than or equal to 10% by weight, preferably is less than or equal to 5% by weight, more preferentially varies from 1% to 5% by weight, better still varies from 1% to 2% by weight, with respect to the total weight of the dry extract containing the compound(s) of formula (I).
9. 9. Process according to any one of the preceding claims, characterised in that the purification (P) comprises, simultaneously or sequentially, preferably sequentially, in particular before or after the treatment stage (Pl), more preferentially before the treatment stage (Pl), at least one stage of neutralisation (P0) of all or part of the excess alkaline agent present in the reaction medium resulting from stage (i).
10. 10. Process according to any one of the preceding claims, characterised in that the at least one purification stage (P), carried out in an aqueous reaction medium, comprises: o at least one treatment stage (P0) to neutralise all or part of the excess alkaline agent present in the reaction medium resulting from the at least one stage (i), o at least one stage of treatment (Pl) of the reaction medium resulting from stage (i) with at least one cationic ion-exchange resin carried out at a pH value strictly lower than the pKa of the compound of formula (IV) or lower than the lowest pKa of the compounds of formula (IV), o at least one stage of separation (P2) of at least said compound(s) of formula (IV) from the reaction medium, o at least one stage of separation (P'O) of the compound(s) of formula (III) present in the reaction medium on conclusion of the reaction(s) (i).
11. 11. Process according to Claim 9 or 10, characterised in that the neutralisation stage (P0) can be carried out with at least one cationic ion-exchange resin at a pH value strictly lower than the pKa of the compound of formula (IV) or by adding at least one organic or mineral, preferably mineral, acidifying agent to the reaction medium resulting from stage (i).
12. 12. Process according to any one of the preceding claims, characterised in that the reaction stage (ii) is a reduction stage (iil) taking place in an aqueous medium according to the following synthetic pathway (B): Reduction in which synthetic pathway (B): ■ SA' and Ri have the same meanings as in the formula (I).
13. 13. Process according to Claim 12, characterised in that the reaction stage (ii) is at least one stage of reduction (iil) by catalytic hydrogenation, carried out in the presence of at least one metal catalyst chosen from ruthenium (Ru), nickel (Ni) or palladium (Pd).
14. 14. Process according to any one of the preceding claims, characterised in that the compound of formula (I), in which X corresponds to a divalent radical - CH(OR)-, is in solution in a liquid which comprises a content of at least 25% by weight of active material (I), preferably in a content ranging from 25% to 80% by weight, more preferentially ranging from 25% to 75% by weight, more preferentially ranging from 30% to 75% by weight, with respect to the total weight of the solution.
15. 15. Process according to any one of the preceding claims, characterised in that it comprises at least one stage (iv) of addition of at least one bactericidal or bacteriostatic, preferably bacteriostatic, agent, preferably derived from glycol, such as propylene glycol, pentylene glycol or caprylyl glycol.
16. 16. Process according to any one of the preceding claims, characterised in that SA' represents a monosaccharide group chosen from the group constituted of glucose, in particular D-glucose, xylose, in particular D-xylose, fucose, in particular L-fucose, arabinose, in particular L-arabinose, rhamnose, in particular L-rhamnose, glucuronic acid, in particular D-glucuronic acid, galacturonic acid, in particular D- galacturonic acid, iduronic acid, in particular D-iduronic acid, N-acetylglucosamine, in particular N-acetyl-D-glucosamine, and N-acetylgalactosamine, in particular N- acetyl-D-galactosamine, and preferably SA' is chosen from D-glucose, D-xylose, L- fucose, L-arabinose, L-rhamnose, D-glucuronic acid, D-galacturonic acid or D- iduronic acid.
17. 17. Process according to any one of the preceding claims, characterised in that Ri represents a saturated or unsaturated, linear or branched, cyclic or acyclic, Ci- Cio, preferably Ci-Ce, more preferentially C1-C4, in particular Ci, hydrocarbon chain.
18. 18. Process according to any one of the preceding claims, characterised in thatRi and R2 are identical and represent a saturated or unsaturated, linear, acyclic, Ci- Ce, more preferentially C1-C4, in particular Ci, hydrocarbon chain.
19. 19. Process according to any one of the preceding claims, characterised in that X represents a divalent radical -CH(OH)-.
20. 20. Process according to any one of the preceding claims, characterised in that D + is a cation chosen from the group consisting of alkali metal cations, alkaline earth metal cations and the ammonium ion (NH4 + ), preferably alkali metal cations and alkaline earth metal cations, in particular from the group consisting of the calcium ion (Ca 2+ ), the magnesium ion (Mg 2+ ), the sodium ion (Na + ) and the potassium ion (K + ).

Description

DESCRIPTION TITLE: Process for the preparation of one or more C-glycoside derivatives comprising a catalytic reduction stage The present invention relates to a process for the preparation of one or more C-glycoside derivatives corresponding to the formula (I), as described below, preferably corresponding to the formula (f) or (I"), and to their optical isomers, geometrical isomers and/or solvates, such as the hydrates, comprising at least one purification stage carried out in an aqueous reaction medium. The invention also relates to a process for the purification of at least one aqueous reaction medium including at least one C-glycoside derivative corresponding to the formula (I) and at least one impurity of formula (IV), as described below. Processes for the synthesis of water-soluble organic active agents having advantageous cosmetic properties can result in the formation of impurities, which are in an ionic form, which generally prove to be tedious to minimise, indeed even to remove, without impacting to a greater or lesser extent the yield of the final cosmetic active compound. Moreover, such impurities, when they are present with the final cosmetic active compound, can generate a colour, a modification in texture or an odour which is not desired in the cosmetic compositions employing said active agent. Thus, such impurities can be the source of an unpleasant and marked odour, for example a pungent and strongly vinegary odour, liable to manifest itself, even after several purification operations have been carried out, and to prove to be inconvenient and persistent even after formulation for consumers, all the more so since the current trend is to use fewer and fewer fragrances in cosmetic products to mask or neutralise odours of this type. Such impurities can also give rise to problems of compatibility with other additives optionally present in the final cosmetic formulations. Such impurities can also be salts of acids or of bases which will have an effect on the pH in an aqueous medium. This effect is all the more of a nuisance as the cosmetic active agent is isolated in the form of a concentrated aqueous solution. In addition, the presence of such impurities, in particular of inorganic and/or organic salts, can induce a considerable increase in the viscosity of the aqueous reaction medium comprising the cosmetic active agent(s), thus making it difficult, in certain cases, to obtain concentrated solutions of cosmetic active agents intended for the formulation. By way of example, C-glycoside derivatives are water-soluble organic compounds, the properties of which are generally advantageous in the field of cosmetics, in particular in care compositions, in order to be used to stimulate the synthesis of glycosaminoglycans present in the dermis and in particular to provide density and firmness to the skin (see, for example, the scientific paper entitled: Synthesis of Pro-Xylane™: A New Biologically Active C-glycoside in Aqueous Media, M. Dalko-Csiba el al., Bioorganic & Medicinal Chemistry Letters, 19 (2009), 845-849). C-glycoside derivatives, such as xylose C-glycoside derivatives, are generally synthesised by means of a reaction, known as the Lubineau reaction (Rodrigues, F., Canac, Y. and Lubineau, A., A Convenient, One-Step, Synthesis of P-Glycosidic Ketones in Aqueous Media, Chemical Communications, 2000 (20), 2049-2050), from a monosaccharide or a polysaccharide which is unprotected, for example D-xylose, and a P-dicarbonyl compound, for example acetyl acetone, in an aqueous medium in the presence of alkaline agent(s). The Lubineau reaction is carried out with at least one alkaline agent, such as sodium bicarbonate or sodium hydroxide, present in an equimolar amount or in excess with respect to the monosaccharide or polysaccharide, preferably in excess, for a reaction time capable of varying from 5 minutes to 20 hours depending on the nature of the alkaline agent and/or on the reaction parameters, such as the concentration and/or the temperature. However, such a synthesis reaction exhibits in particular the major pitfail of resulting in the formation of impurities, being in particular in the form of salts, for example in the form of an organic salt, such as sodium acetate, the residual amounts of which can prove to be significant and difficult to reduce, even by carrying out several conventional purification and/or washing operations. On conclusion of this reaction, the aqueous reaction medium can be neutralised with at least one, in particular mineral, acidifying agent, for example hydrochloric acid, in order to convert the organic acid salt into an organic acid, in particular by converting sodium acetate into acetic acid, in order to subsequently reduce the amounts of organic acid to commercially acceptable contents. However, the neutralisation of the reaction medium with at least one mineral acidifying agent, such as hydrochloric acid, also results in the formation of salts, in particular of so