WO2021009374A1

WO2021009374A1 - Ionic liquid-type compounds and their methods of preparation and uses

Info

Publication number: WO2021009374A1
Application number: PCT/EP2020/070365
Authority: WO
Inventors: Jean-Pierre MBAKIDI; Sandrine Bouquillon
Original assignee: Universite De Reims Champagne Ardenne
Priority date: 2019-07-17
Filing date: 2020-07-17
Publication date: 2021-01-21

Abstract

The present invention relates to ionic liquid-type compounds having formula (I). The invention also relates to the use of such compounds for the dissolution and/or extraction of at least one compound of biological origin, such as a biopolymer or a bioactive molecule.

Description

IONIC LIQUID-TYPE COMPOUNDS, THEIR METHODS OF

PREPARATION AND THEIR USES

OBJECT OF THE INVENTION

The present invention relates to the field of ionic liquids. More particularly, the present invention relates to liquids or ionic compounds derived from choline, their preparation process, and their use for dissolving and / or extracting compounds of biological origin, such as biopolymers or bioactive molecules.

BACKGROUND OF THE INVENTION

An ionic liquid is generally defined as a salt having a melting point of less than 100 ° C. Because of their particular properties, in particular related to their anion / cation structure, and their three-dimensional organization, ionic liquids have become essential solvents in various fields. For example, their high electrochemical stability makes it possible to consider the electrolytic deposition of chemical elements that are inaccessible with conventional solvents or the synthesis of nanostructured materials. Ionic liquids have also demonstrated their interest as a solvent for synthesis or catalysis, because they allow particular interactions between substrates and catalysts.

In addition, the use of ionic liquids for the dissolution and / or the extraction of polymers of biological origin such as cellulose or lignin represents an important stake because these biopolymers allow access to many products with high added value. . For example, cellulose can be made into ether or ester derivatives of cellulose, ethanol, or various monomers or surfactants, while lignin can be chemically modified to produce oxidizing biomaterials, or be depolymerized to produce aromatic molecules, such as than coumaryl alcohol or sinapyl alcohol.

The development of ionic liquids for the extraction of active molecules of biological origin is also an important area of research, because the processes implemented with ionic liquids are more efficient and faster than conventional processes, such as hydrodistillation. , extraction by organic solvent or supercritical fluid, or else Adsorption. In fact, the extraction of curcuminoids with acetone requires at least two successive extractions to obtain better yields (Bajpai et al. Int. J. Biol. Macromol. 2015, 75, 239-247).

Meng et al. (ChemSusChem 2017, 10, 1-13) have described the synthesis of tetralkylammonium carboxylates, and their use for the dissolution of cellulose. However, the dissolution percentages do not exceed 22% by weight cellulose at 90 ° C and 15% by weight cellulose at 80 ° C. The use of a co-solvent resulted in a 20% dissolution rate in the presence of dimethylsulfoxide at 80 ° C.

Due to the environmental constraints generated by excessive use of fossil resources (depletion of natural resources, greenhouse gases), the gradual introduction of materials from biomass into routine chemical processes has become essential in our society. This is why the development of ionic liquids from biobased derivatives, such as choline or betaine, has attracted special attention in recent years. Zhang et al. (Chem. Eur. J. 2012, 18, 1043-1046) have described the use of a "green" ionic liquid, cholinium acetate, for the dissolution of cellulose. It has been shown that cholinium acetate alone does not dissolve cellulose effectively and that the use of tributylmethylammonium chloride as an additive makes it possible to increase the rate of dissolution, which, however, does not exceed 6% by weight of cellulose.

In view of the low rates of dissolution and / or extraction of biopolymers and bioactive molecules obtained, there remains today a real need to develop compounds of the ionic liquid type, in particular from renewable resources, making it possible to dissolve and / or efficiently extract such compounds.

SUMMARY OF THE INVENTION

In this context, the inventors have proposed new compounds of ionic liquid type of formula (I) exhibiting improved rates of dissolution and / or extraction of compounds of biological origin. The present invention therefore relates to a compound of formula (I):

in which :

R is an aliphatic group having 5 to 15 carbon atoms, and

A- is a carboxylate having 3 to 8 carbon atoms.

According to a particular embodiment of the invention, A is chosen from a levulinate, a lactate, a succinate, a malate and a tartrate, preferably from a levulinate and a lactate, and even more preferably A- is a levulinate.

According to another particular embodiment, R is an aliphatic group having 5 to 11 carbon atoms, preferably R is an alkyl group having 5 to 11 carbon atoms, and even more preferably R is a pentyl, a heptyl or a nonyl or an undecyl.

Another subject of the invention relates to a use of a compound of formula (I) according to the invention, for the dissolution and / or the extraction of at least one compound of biological origin, preferably a biopolymer or a bioactive molecule.

The invention also relates to a process for collecting at least one biopolymer of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one biopolymer of biological origin with a compound of formula (I) according to the invention; and

(b) a step of recovering said at least one biopolymer of biological origin with the aid of a hydrophilic solvent, preferably an alcohol.

According to a particular embodiment, said at least one biopolymer of biological origin is chosen from a polysaccharide and a polyphenolic polymer, preferably from cellulose, G hemicellulose, lignin, chitin, and a mixture of these.

According to another particular embodiment, the compound of formula (I) used in the collection process is such that R is an aliphatic group having 5 to 7 carbon atoms.

According to another particular embodiment, the contacting step (a) is carried out at a temperature between 50 ° C and 180 ° C, preferably between 70 ° C and 110 ° C.

According to another particular embodiment, the contacting step (a) is carried out under microwaves, preferably at a power of between 100 W and 350 W. The invention also relates to a process for extracting at least one bioactive molecule of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one bioactive molecule of biological origin with a compound of formula (I) according to the invention; and

(b) a step of recovering said at least one bioactive molecule of biological origin using a hydrophobic solvent, preferably ethyl acetate, 2-methylpropan-1-ol, or 2- methylbutan-2-ol.

According to a particular embodiment, said at least one bioactive molecule of biological origin is chosen from a lipid, a terpene, a terpenoid, a phenol, a polyphenol, an alkaloid, a steroid, a heteroside, an essential oil, a vitamin, and a mixture of these, preferably among a curcuminoid, eugenol and carvacrol.

According to another particular embodiment, the compound of formula (I) used in the extraction process is such that R is an aliphatic group having 9 to 11 carbon atoms.

According to another particular embodiment, the contacting step (a) is carried out at a temperature between 30 ° C and 120 ° C, preferably between 50 ° C and 100 ° C.

According to another particular embodiment, the contacting step (a) is carried out in microwaves, preferably at a power of between 100 W and 350 W.

Another subject of the invention relates to a process for preparing a compound of formula (I), comprising the following successive steps:

(a) a step of reaction of a choline salt of formula (II):

X- 7iU ° ^H

¹ (II).

in which X is a halide, preferably a chloride,

with a compound of the formula R-COOH, wherein R is an aliphatic group having 5 to 15 carbon atoms;

(b) a step of reacting the compound obtained in step (a) with a perchlorate salt, preferably sodium perchlorate; and

(c) a step of reacting the compound obtained in step (b) with a salt containing at least one anion A-, where A- is a carboxylate having 3 to 8 carbon atoms, preferably a levulinate or a lactate. BRIEF DESCRIPTION OF THE FIGURES

Figures IA and IB: Infrared spectrum of native microcrystalline cellulose (IA) and infrared spectrum of cellulose obtained after dissolution with [Chol - Ci2] Lac and precipitation (IB). Figure 2: Thin-layer chromatography profile of a curcuminoid extract obtained by an extraction process of the invention, and a commercial curcuminoid extract.

DETAILED DESCRIPTION

The present invention provides novel compounds of the ionic liquid type of formula (I), which are synthesized from choline, obtained from renewable resources, according to a simple and inexpensive process. The inventors have surprisingly demonstrated that these compounds of formula (I) make it possible to dissolve and / or extract compounds of biological origin:

- in an improved manner compared to commonly used ionic liquids;

- using a fast and efficient process; and

- without using any co-solvent or additive.

It has also been shown that the compounds of the invention allow cellulose to be dissolved without denaturing it.

The bio-based compounds of the invention also exhibit low ecotoxicity and can be recycled during the implementation of the dissolution and / or extraction processes.

Definitions

By “aliphatic group” is meant a non-aromatic, linear or branched, saturated or unsaturated, cyclic or acyclic hydrocarbon chain.

By “alkyl” is meant an acyclic, linear or branched saturated hydrocarbon group. More particularly, an alkyl having 5 to 11 carbon atoms can in particular denote a pentyl, hexyl, heptyl, octyl, nonyl, decyl, or undecyl.

The term “alkenyl” is understood to mean an acyclic, linear or branched hydrocarbon group having at least one carbon-carbon double bond. More particularly, an alkenyl having 5 to 11 carbon atoms can in particular denote a pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl or undecenyl.

By "alkynyl" is meant an acyclic, linear or branched hydrocarbon group having at least one carbon-carbon triple bond. More particularly, an alkynyl having 5 to 11 carbon atoms can in particular denote a pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl or undecynyl.

By "cycloalkyl" is meant a mono-, bi- or tri-cyclic alkyl group, bridged or not. More particularly, a cycloalkyl having 5 to 11 carbon atoms can in particular denote a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cycloundecyl.

The aliphatic, alkyl, alkenyl, alkynyl, and cycloalkyl groups, as defined above can also be mono or poly substituted by groups including in particular the alkyls, the alkenyls, the alkynyls, the cycloalkyls, the aryls, the perfluoroalkyls, the alkoxy, alkylthio, alkylamino, halogen, cyano, nitro, hydroxy.

By "aryl" is meant a monocyclic or polycyclic hydrocarbon aromatic group. Particularly, an aryl denotes a phenyl, a biphenyl, or a naphthyl, and preferably a phenyl.

By “alkyloxy” or “alkoxy” is meant an —O-alkyl group where the alkyl group is as defined above. Examples of alkoxy are in particular methoxy, ethoxy, propyl, isopropoxy, butoxy, z ^' so-butoxy, ieri-butoxy, pentoxy, or hexyloxy.

By “alkylthio” is meant an -S- (alkyl) group, where the alkyl group is as defined above. An example of an alkylthio is in particular a methylthio.

By “alkylamino” is meant an -NH- (alkyl) or -N (alkyl) 2 group where the alkyl group is as defined above. Examples of alkylamino include methylamino, ethylamino, or dimethylamino.

By "perfluoroalkyl" is meant an alkyl group in which the hydrogens have been replaced by a fluorine. An example of perfluoroalkyl is in particular CF3.

By “halogen” is meant a fluorine, chlorine, bromine or iodine atom.

The term “solvent” is understood to mean both an organic solvent and an inorganic solvent. Examples of non-limiting organic solvents are methanol, ethanol, acetone, cyclohexane, benzene, toluene, acetonitrile, DMF, DMSO, diethyl ether, ethyl acetate, 2 -methylpropan-1-ol, 2-methylbutan-2-ol, tetrahydrofuran, dichl oromethane, and mixtures thereof. An example of an inorganic solvent is in particular water. The term “hydrophilic solvent” is understood to mean an organic solvent which is partially or completely miscible with water, alone or as a mixture with water. Examples of hydrophilic solvent are in particular an alcohol, in particular an alcohol having 1 to 3 carbon atoms, such as methanol, ethanol, or propanol, acetone, dimethylformamide (DMF), dioxane, THF , or a mixture of these. By “hydrophobic solvent” is meant an organic solvent which is substantially immiscible with water. Examples of a hydrophobic solvent are in particular ethyl acetate, an alcohol, in particular an alcohol having at least 4 carbon atoms (for example, an alcohol having 4 to 8 carbon atoms) such as 2-methylpropan-1 -ol, or 2-methylbutan-2-ol, chloroform, dichl oromethane, cyclohexane, cyclopentane, benzene, an ether such as diethyl ether or diisopropyl ether, heptane, hexane , pentane, toluene, xylene, or a mixture thereof.

The solvent, in particular the hydrophilic solvent and the hydrophobic solvent, can be advantageously chosen from solvents limiting the constraints of the ATEX regulations, in particular defined in directives 2014/34 / EU and 1999/92 / EC. Examples of a hydrophobic solvent limiting the constraints of such a regulation are in particular 2-methylpropan-1-ol and 2-methylbutan-2-ol.

By "acid" is meant both a Lewis acid and a Bronsted acid. The acid can be a monoacid or a polyacid. Examples of acids include hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, iodic acid, periodic, tetrafluoroboric acid, hexafluorophosphoric acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, or para-toluenesulfonic acid, and mono- and polycarboxylic acids.

The present invention relates to a compound of formula (I):

in which :

R is an aliphatic group having 5 to 15 carbon atoms, and

A- is a carboxylate having 3 to 8 carbon atoms.

By “carboxylate” is meant an organic anion comprising one or more -CCh- groups. Preferably, the carboxylate is an aliphatic carboxylate.

It is understood that, when said carboxylate A- comprises several -CCh- groups, the number of cations is adapted so that G electroneutrality is respected. For example, when A- comprises two -CCh- groups, the compound of formula (I) then comprises two corresponding cations.

Examples of the carboxylate having 3 to 8 carbon atoms are in particular a propionate, acrylate, lactate, pyruvate, 3-hydroxypriopionate, butyrate, succinate, fumarate, malate, itaconate, sorbate, maleate, mandelate, glycolate, gluconate, glucarate, muconate, levulinate, adipate, citrate, tartrate or 2,5-furandicarboxylate.

According to a particular embodiment, A- is chosen from a levulinate, a lactate, a succinate, a malate and a tartrate. Preferably, A- is selected from a levulinate and a lactate, more preferably, A- is a levulinate.

According to a particular embodiment, R is an aliphatic group having 5 to 11 carbon atoms.

Preferably, said aliphatic group is an alkyl, alkenyl or alkynyl group.

According to a preferred embodiment, R is an alkyl group having 5 to 11 carbon atoms, and better still, R is chosen from a pentyl, a heptyl, a nonyl and an undecyl.

It is understood that, when R in the compound of formula (I) is an aliphatic group having n carbon atoms, the chain - (CO) -R then comprises (n + 1) carbon atoms. For example :

- when R is a pentyl group, the chain - (CO) -R is a hexanoyl chain (CÔ) and the compound of formula (I) is a hexanoylcholinium (denoted [Chol - CÔ]); and

- When R is an undecyl group, the chain - (CO) -R is a dodecanoyl chain (C12) and the compound of formula (I) is a dodecanoylcholinium (denoted [Chol - C12]).

As shown in the present application, a compound of formula (I) denoted [Chol - C (n + i)] (A) comprises an anion A and an aliphatic chain R having n carbon atoms, n being between 5 and 15. For example:

- [Chol - C6] Lev is a compound of formula (I) in which R is an aliphatic chain having 5 carbon atoms and A- is a levulinate; and

- [Chol - Ci2] Lac is a compound of formula (I) in which R is an aliphatic chain having 11 carbon atoms and A- is a lactate.

The term "Lev" refers to a levulinate anion. The term "Lac" denotes a lactate anion.

The compounds of formula (I) advantageously exhibit a melting point suitable for ionic liquids. In particular, the compounds of formula (I) advantageously exhibit a melting point of less than or equal to 120 ° C., preferably less than or equal to at 100 ° C, more preferably less than or equal to 80 ° C, even more preferably less than or equal to 60 ° C.

Process for preparing a compound of formula (I)

The invention also relates to a process for preparing a compound of formula (I) comprising the following successive steps:

(a) a step of reaction of a choline salt of formula (II):

wherein X is a halide, with a compound of the formula R-COOH, wherein R is an aliphatic group having 5 to 15 carbon atoms;

(b) a step of reacting the compound obtained in step (a) with a perchlorate salt; and

(c) a step of reacting the compound obtained in step (b) with a salt containing at least one anion A-, where A- is a carboxylate having 3 to 8 carbon atoms, preferably a levulinate or a lactate.

Step (a) of the process according to the invention comprises an esterification reaction. More particularly, step (a) comprises the reaction of a choline salt of formula (II):

wherein X is a halide, with a compound of the formula R-COOH, wherein R is an aliphatic group having 5 to 15 carbon atoms. According to a preferred embodiment, X is a chloride.

In a particular embodiment, the compound of formula (II) and the R-COOH compound are brought into contact in the presence of an acid, such as methanesulfonic acid. Said acid can be used pure, in suspension or in solution in a solvent. The amount of acid used in step

(a) is advantageously between 1 and 6 equivalents, preferably between 2 and 4 equivalents, relative to the compound of formula (II).

Preferably, the reaction in step (a) is carried out in the absence of solvent. The reaction in step (a) can be carried out at a temperature between 60 ° C and 170 ° C, preferably between 90 ° C and 130 ° C. The reaction in step (a) can be carried out at a pressure of between 1 mbar and 500 mbar, preferably between 30 mbar and 120 mbar. The amount of compound of formula R-COOH used in step (a) is advantageously between 1 and 6 equivalents, preferably between 2 and 4 equivalents, relative to the compound of formula (II).

Step (a) allows the production of a compound of formula (III):

in which X is a halide, and

R is an aliphatic group having 5 to 15 carbon atoms.

The compound of formula (III) produced in step (a) can in particular be recovered by a process comprising:

- a liquid-liquid aqueous phase / organic phase extraction step, and

- a step of recovering the aqueous phase comprising the compound of formula (III).

The compound of formula (III) can be isolated by removing water from the aqueous phase and then engaged in step (b) of the process of the invention. Preferably, said aqueous phase comprising the compound of formula (III) is used in step (b) of the process of the invention.

Step (b) of the process according to the invention comprises an anion metathesis reaction. More particularly, step (b) comprises reacting the compound obtained in step (a), namely a compound of formula (III) as defined above, with a perchlorate salt.

By “perchlorate salt” is meant a chemical compound which comprises at least one perchlorate anion (CICri-), and at least one cation, such that said chemical compound is electronically neutral.

According to a particular embodiment, said perchlorate salt contains:

- at least one perchlorate anion; and,

- at least one cation chosen from a cation of lithium, sodium, potassium, cesium, magnesium, barium, calcium, copper, manganese, zinc, iron, nickel, cobalt, and silver, preferably.

Examples of perchlorate salt are in particular sodium perchlorate (NaCICri), potassium perchlorate (KCICri), barium perchlorate (Ba (C104) 2), lithium perchlorate (LiCICri), copper perchlorate (Cu (C104) 2), calcium perchlorate (Ca (C104) 2), manganese perchlorate (Mn (C104) 2), and their hydrates. Preferably, the perchlorate salt is sodium perchlorate (NaCICri).

The reaction in step (b) is advantageously carried out in water. The reaction in step (b) can be carried out at a temperature between 5 ° C and 50 ° C, preferably between 15 ° C and 35 ° C. The reaction time in step (b) is advantageously between 30 minutes and 72 hours, preferably between 12 hours and 48 hours, and better still, between 20 hours and 30 hours.

The amount of perchlorate salt used in step (b) is advantageously between 1 and 10 equivalents, preferably between 2 and 5 equivalents, relative to the compound obtained in step (a).

Step (b) allows the production of a compound of formula (IV):

wherein R is an aliphatic group having 5 to 15 carbon atoms.

The compound produced in step (b) is typically obtained in the form of a solid precipitate or an oil.

The compound of formula (IV) produced in step (b) can be recovered directly, in particular by removing the precipitate or the oil. Alternatively, the compound of formula (IV) produced in step (b) can be recovered by a process comprising:

- a liquid-liquid aqueous phase / organic phase extraction step, and

- a step of recovering the organic phase comprising the compound of formula (IV).

Step (c) of the method according to the invention comprises anion metathesis. More particularly, step (c) comprises reacting the compound obtained in step (b) with a salt containing at least one anion A-, where A- is a carboxylate having 3 to 8 carbon atoms.

A salt containing at least one A- anion, where A is as defined above, is a chemical compound containing at least one A- anion, and at least one cation, such that said chemical compound is electronically neutral.

According to a particular embodiment, said salt containing at least one anion A contains:

- at least one anion A chosen from a propionate, acrylate, lactate, pyruvate, 3-hydroxypriopionate, butyrate, succinate, fumarate, malate, itaconate, sorbate, maleate, mandelate, glycolate, gluconate, glucarate, muconate, levulinate, adipate, citrate , tartrate and 2,5-furandicarboxylate, preferably from a levulinate and a lactate, more preferably a levulinate; and

- at least one cation chosen from a lithium, sodium, potassium, cesium, magnesium, barium, calcium, copper, manganese, zinc, iron, nickel, cobalt and silver cation, preferably from a sodium and potassium cation.

Preferably, said salt containing at least one A- anion is potassium lactate or potassium levulinate. The reaction in step (c) is advantageously carried out in an organic solvent, preferably a hydrophilic solvent, such as ethanol. The reaction in step (c) can be carried out at a temperature between 5 ° C and 50 ° C, preferably between 15 ° C and 35 ° C. The reaction time in step (c) is advantageously between 30 minutes and 72 hours, preferably between 12 hours and 48 hours, and better still, between 20 hours and 30 hours.

The amount of said salt containing at least one A- anion used in step (c) is advantageously between 1 and 5 equivalents, preferably between 1 and 2 equivalents, relative to the compound obtained in step (b).

According to a particular embodiment, said salt containing at least one A- anion is used in step (c) in the form of a solution in water.

Step (c) allows the production of a compound of formula (I) as defined in the present application.

The compound of formula (I) produced in step (c) can in particular be recovered by a process comprising:

- a step of removing the insolubles formed in step (c), for example by filtration, and

- a step of removing the solvent, for example by evaporation.

A liquid-liquid aqueous phase / organic phase extraction step, and a step of recovering the aqueous phase comprising the compound of formula (I) can also be carried out to obtain the compound of formula (I).

Applications

In the context of the present invention, the compounds of formula (I) can be used as ionic liquid, and in particular as solvent, to dissolve and / or extract at least one compound of biological origin.

An object of the present invention relates to the use of a compound of formula (I), for the dissolution and / or extraction of at least one compound of biological origin.

By “material of biological origin” is meant any material originating from a unicellular or multicellular living organism. The material of biological origin can in particular comprise one or more tissues of biological origin. According to a particular embodiment of the invention, the material of biological origin is a material of animal or plant origin, preferably a material of plant origin. Examples of biological material of animal origin are in particular a tissue such as a cuticle or an arthropod exoskeleton (in particular, an insect, a spider, or a crustacean), brachiopod, cephalopod (in particular, a squid) or of annelid. Examples of biological material of plant origin are in particular wood, all or part of a plant such as a leaf, a flower, a fruit, a stem, a rhizome, a bulb, a tuber, and / or a root. , a microalga, or all or part of a fungus.

By "compound of biological origin" is meant any mono- or polyatomic, organic or inorganic, ionic or neutral substance, included in or originating from material of biological origin. According to a particular embodiment of the invention, the compound of biological origin is a compound of animal or plant origin, preferably a compound of plant origin.

According to another preferred embodiment of the invention, said at least one compound of biological origin is a biopolymer of biological origin or a bioactive molecule of biological origin.

According to a particular embodiment of the invention, said at least one compound of biological origin is a biopolymer of biological origin. In particular, the biopolymer of biological origin can be chosen from a polypeptide, a protein, a polyterpene, a polynucleotide, a polyhydroxyalkanoate, a polysaccharide and a polyphenolic polymer. Preferably, the biopolymer of biological origin is chosen from a polysaccharide and a polyphenolic polymer.

Examples of the polysaccharide include cellulose, G hemicellulose, starch, inulin, chitin, or a mixture thereof. Preferably the polysaccharide is cellulose, G hemicellulose or chitin, and more preferably cellulose.

Examples of polyphenolic polymer are in particular lignin, a tannin or a mixture thereof. Preferably, the polyphenolic polymer is lignin.

According to another particular embodiment of the invention, said at least one compound of biological origin is a bioactive molecule. By “bioactive molecule” is meant any mono- or polyatomic, organic or inorganic, ionic or neutral substance, having a biological activity, such as a therapeutic, prophylactic, antioxidant, anti-inflammatory, anti-cancerous, and / or anti-cancer activity. -microbial or antibacterial. According to a particular embodiment, said bioactive molecule of biological origin is chosen from a lipid, a terpene, a terpenoid, a phenol, a polyphenol, an alkaloid, a steroid, a heteroside, a vitamin, and a mixture of these. this. Examples of lipids are in particular a saturated fatty acid, a monounsaturated fatty acid, a polyunsaturated fatty acid (PUFA) such as docosahexaenoic acid or eicosapentaenoic acid, a sphingolipid, a polyacetylene lipid, and a phospholipid.

Examples of terpenes include Ga-pinene, b-pinene, 3-carene, limonene, carotene, ocimene, menthane, pinane, myrcene, farnesene, and squalene.

Examples of terpenoids include menthol, menthone, terpineol, isoborneol, camphor, nerol, citronellal, citronellol, citral, linalool, geraniol, geranial, myrcenol, farnesol, thymol, eucalyptol, chrysanthemic acid, abietic acid, artemisinin, carvone, pulegone, piperitone, fenchone, a guanacastepene, a carotenoid such as lutein, and a tanshinone such as tanshinone IIA .

Examples of phenols (or phenolic derivatives) are in particular phenol, eugenol, carvacrol, capsaicin, salicylic acid, guaiacol, thymol, vanillin, isoeugenol, chavicol, safrole, l isosafrole, anol, and anethole.

Examples of polyphenols (or polyphenolic derivatives) are in particular a curcuminoid such as curcumin I, curcumin II or curcumin III, Ga-mangostin, a coumaryl alcohol, sinapyl alcohol, a flavonoid such as an (iso) flavone , anthocyanidin, (iso) flavanol, (iso) flavonol or aurone, a coumarin, a tannin, resveratrol, catechol, pyrogallol, and phloroglucinol.

Examples of alkaloids include nicotine, atropine, codeine, lupinine, psilocybin, caffeine, theophylline, theobromine, xanthine, ibogaine, ergine, morphine, thebaine, papaverine, narcotine, noscapine, quinine, colchicine, pilocarpine, vinblastine, vincristine, mescaline, ephedrine, eserine, hygrine, hyoscyamine, sparteine, yohimbine, taxol , herbine, solanidine, funtumine, reserpine, ergotamine, cocaine, and galanthamine.

Examples of steroids include cholesterol, phytosterol, and brassinolide. Examples of heterosides include franguloside, sennoside, aloin, nothofagine, aspalathin, anthracene heteroside, and cascaroside.

Examples of vitamins are in particular thiamine (or aneurin), riboflavin, nicotinamide (or niacin), pantothenic acid, pyridoxine, biotin, folic acid, cobalamin, ascorbic acid, retinol, calciferol, a tocopherol, a tocotrienol, phylloquinone, and menaquinone. According to a preferred embodiment, said bioactive molecule of biological origin is a curcuminoid, tanshinone IIA, Ga-mangostin, eugenol or carvacrol, better still a curcuminoid, eugenol or carvacrol.

According to a particular embodiment, said at least one bioactive molecule is an essential oil. By "essential oil" is meant a mixture of substances typically comprising volatile odoriferous compounds, derived from biological material of plant origin, in particular all or part of a plant. Examples of essential oils include the essential oil of lemon, orange, orange blossom, mint, eucalyptus, clove, verbena, lavender, lavandin, patchouli, sage, geranium, rose, thyme, chamomile, violet, myrtle, vetiver, juniper, rosemary, cypress and jasmine.

By "dissolution of at least one compound of biological origin" is meant the solubilization of at least one compound of biological origin by a compound of formula (I). Dissolution or solubilization can comprise forming a homogeneous mixture, preferably in the form of a solution, in which said at least one compound of biological origin is the solute and said compound of formula (I) is the solvent.

By “extraction of at least one compound of biological origin” is meant the separation of at least one compound of biological origin from the material of biological origin comprising it, and optionally the recovery of said at least one compound of origin. organic. In a particular embodiment of the invention, the extraction of at least one compound of biological origin requires the prior dissolution of said at least one compound of biological origin with a compound of formula (I).

According to a preferred embodiment, a compound of formula (I) is used for the dissolution and / or the extraction of at least one compound of biological origin, in the absence of a co-solvent or additive.

Another object of the invention relates to a process for collecting at least one biopolymer of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one biopolymer of biological origin with a compound of formula (I); and (b) a step of recovering said at least one biopolymer of biological origin using a hydrophilic solvent, preferably an alcohol.

By “collection of at least one biopolymer of biological origin” is meant the separation of at least one biopolymer of biological origin from the material of biological origin comprising it, and optionally the recovery of said at least one biopolymer of origin. organic. By "collection" is also meant the extraction of at least one biopolymer of biological origin.

The rate of dissolution (or percentage of dissolution) of a biopolymer in a compound of formula (I) corresponds to the weight of biopolymer dissolved by the compound of formula (I) relative to the weight of compound of formula (I). The weight of biopolymer dissolved by the compound of formula (I) corresponds to the difference between the initial weight of biopolymer and the weight of biopolymer not dissolved by the compound of formula (I).

The dissolution rate can thus be defined by the following calculation formula (1):

Dissolution rate = (initial weight of biopolymer - weight of biopolymer not dissolved by the compound of formula (I)) / (weight of compound of formula (I)) (1)

The collection rate (or extraction yield) of a biopolymer corresponds to the weight of the biopolymer extracted relative to the total weight of the material of biological origin initially comprising it. It is understood that this collection rate depends on the amount of biopolymer initially included in the material of biological origin.

The collection rate can thus be defined by the following calculation formula (2):

Collection rate = (weight of the extracted biopolymer) / (total weight of the material of biological origin initially comprising it) (2)

In a particular embodiment, the collection method comprises a step (aO) preceding step (a) comprising the preparation of said material of biological origin. In this step, said material of biological origin can in particular be dried, and / or cut into fragments, and / or crushed, for example using a mortar. Said material of biological origin can in particular be prepared in the form of a powder, fibers, a ground material, grains, chips, or else a paste. Step (a) of the collection method comprises bringing a material of biological origin comprising said at least one biopolymer of biological origin into contact with a compound of formula (I).

In a particular embodiment, the contacting step (a) comprises the partial or total dissolution of the material of biological origin comprising said at least one biopolymer of biological origin in a compound of formula (I).

In a particular embodiment, said at least one biopolymer of biological origin is as defined above. Preferably, it is chosen from a polysaccharide and a polyphenolic polymer, more preferably from cellulose, G hemicellulose, lignin, chitin and a mixture thereof, and better still, from cellulose, lignin and a mixture of these.

In a particular embodiment, the contacting step (a) is carried out at a temperature between 50 ° C and 180 ° C, preferably between 70 ° C and 110 ° C. The contacting step (a) can be carried out for 1 minute to 48 hours, preferably for 15 minutes to 2 hours.

In a particular embodiment, the contacting step (a) is carried out in a microwave, preferably at a power of between 100 W and 350 W, preferably between 150 W and 250 W. In a such embodiment, the contacting step (a) is preferably implemented:

- at a temperature between 50 ° C and 90 ° C, preferably between 60 ° C and 80 ° C, and

- for 1 minute to 20 minutes, better still for 2 minutes to 10 minutes.

In particular, the mixture obtained in step (a) can comprise:

- a first phase comprising a solution of all or part of the biopolymer originating from the material of biological origin in a compound of formula (I); and

- optionally, a second phase, solid or liquid, preferably solid. The second phase typically comprises the part of the material of biological origin which is not solubilized in the compound of formula (I).

Step (b) of the collection process comprises recovering said at least one biopolymer of biological origin using a hydrophilic solvent. In a particular embodiment, the hydrophilic solvent is an alcohol or an alcohol / water mixture. Preferably the alcohol is an alcohol having 1 to 3 carbon atoms, more preferably the alcohol is ethanol. The hydrophilic solvent advantageously allows the precipitation of said at least one biopolymer dissolved in the compound of formula (I). In a particular embodiment, the recovery step (b) comprises the following sub-steps:

(b1) adding water to the mixture obtained in step (a), thus making it possible to obtain an aqueous phase, and optionally a second liquid or solid phase;

(b2) optionally, the separation of the aqueous phase and the second phase obtained in step (b1), for example by filtration or centrifugation;

(b3) the addition of a hydrophilic solvent in the aqueous phase obtained in step (b1) or (b2), preferably an alcohol such as ethanol, thus allowing the precipitation of said at least to the original biopolymer organic ; and

(b4) recovering said at least biopolymer of biological origin, for example by filtration or centrifugation.

At the end of the recovery step (b4), said compound of formula (I) can be recovered in a step (b4 ’) in particular by evaporation and / or lyophilization of the aqueous phase. Said compound of formula (I) recovered can be used again in step (a) of the collection process. This step makes it possible to recycle said compound of formula (I) in the collection process. Preferably, said compound of formula (I) obtained in step (b4 ') is used again one or more times, for example 2, 3, 4, 5, 6, 7, 8, 9, or 10 times, preferably 3, 4, 5, or 6 times, and even more preferably 5 times.

In a particular embodiment, the collection method comprises the following successive steps:

(aO) a step of preparing the material of biological origin;

(a) a step of bringing into contact a material of biological origin comprising said at least one biopolymer of biological origin with a compound of formula (I);

(b3) the addition of a hydrophilic solvent in the aqueous phase obtained in step (b1) or (b2) with a hydrophilic solvent, preferably an alcohol such as ethanol, thus allowing the precipitation of said at least at least one biopolymer of biological origin; and

(b4) recovering said at least biopolymer of biological origin, for example by filtration or centrifugation. According to a preferred embodiment, the compound of formula (I) used in the collection process is such that R is an aliphatic group having 5 to 7 carbon atoms.

In a particular embodiment, a compound of formula (I) is used for the dissolution of at least one biopolymer of biological origin. A process for dissolving at least one biopolymer of biological origin by a compound of formula (I) can comprise a step of bringing at least one biopolymer of biological origin or a material of biological origin comprising said at least one biopolymer of biological origin with a compound of formula (I). The conditions for implementing this contacting step are advantageously similar to the conditions for step (a) of the collection method of the invention. The dissolution process may further comprise a step of transforming said at least one biopolymer of biological origin.

Another object of the invention relates to a process for extracting at least one bioactive molecule of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one bioactive molecule of biological origin with a compound of formula (I); and

The extraction yield of a bioactive molecule corresponds to the weight of the bioactive molecule extracted relative to the total weight of the material of biological origin initially comprising it. It is understood that this extraction yield depends on the amount of the bioactive molecule initially included in the material of biological origin.

The extraction yield of a bioactive molecule can thus be defined by the following calculation formula (3):

Extraction yield = (weight of bioactive molecule extracted) / (total weight of the material of biological origin initially comprising it) (3)

In a particular embodiment, the extraction method comprises a step (aO) preceding step (a) comprising the preparation of said material of biological origin, as defined in the collection method. Thus, in this step, said material of biological origin can in particular be dried, and / or cut into fragments, and / or crushed, for example using a mortar. Said material of biological origin can in particular be prepared in the form of a powder, fibers, a ground material, grains, chips, or else a paste.

Step (a) of the extraction process comprises a step of bringing into contact a material of biological origin comprising said at least one bioactive molecule of biological origin with a compound of formula (I).

In a particular embodiment, the contacting step (a) comprises the partial or total dissolution of the material of biological origin comprising said at least one bioactive molecule of biological origin in a compound of formula (I).

In a particular embodiment, said at least one bioactive molecule is as defined above. Preferably, it is chosen from a lipid, a terpene, a terpenoid, a phenol, a polyphenol, an alkaloid, a steroid, a heteroside, an essential oil, a vitamin, and a mixture thereof, and better still, among a curcuminoid, eugenol and carvacrol.

In a particular embodiment, the contacting step (a) is carried out at a temperature between 30 ° C and 120 ° C, preferably between 50 ° C and 100 ° C. The contacting step (a) can be carried out for 1 minute to 48 hours, preferably for 15 minutes to 1 hour.

- at a temperature between 30 ° C and 90 ° C, preferably between 50 ° C and 80 ° C, and

- for 1 minute to 20 minutes, better still for 2 minutes to 10 minutes.

In particular, the mixture obtained in step (a) can comprise:

- a first phase comprising a solution of all or part of said at least one bioactive molecule originating from material of biological origin in a compound of formula (I); and

In a particular embodiment, the contacting step (a) is carried out in the presence of water. In such an embodiment, the volume ratio of water to the compound of formula (I) is between 5/100 and 50/100, preferably between 15/100 and 35/100. The presence of water can in particular make it possible to reduce the viscosity of the compound of formula (I). Step (b) of the extraction process comprises a step of recovering said at least one bioactive molecule of biological origin using a hydrophobic solvent. According to a particular embodiment, a hydrophobic solvent is chosen from ethyl acetate, 2-methylpropan-1-ol and 2-methylbutan-2-ol. According to a preferred embodiment, the hydrophobic solvent is ethyl acetate. According to another preferred embodiment, the hydrophobic solvent is 2-methylpropan-1-ol or 2-methylbutan-2-ol. Advantageously, the hydrophobic solvent is 2-methylbutan-2-ol.

In a particular embodiment, the recovery step (b) comprises the following sub-steps:

(b1) adding water to the mixture obtained in step (a), thereby obtaining an aqueous phase, and optionally a second liquid or solid phase;

(b3) adding a hydrophobic solvent, such as ethyl acetate, 2-methylpropan-1-ol, or 2-methylbutan-2-ol, to the aqueous phase obtained in step ( bl) or (b2), thus making it possible to obtain an aqueous phase and an organic phase;

(b4) separating the aqueous phase and the organic phase obtained in step (b3); and,

(b5) recovering said at least one bioactive molecule of biological origin included in the organic phase, for example by evaporation of the organic phase.

At the end of the separation step (b5), said compound of formula (I) can be recovered in a step (b5 ’) in particular by evaporation and / or lyophilization of the aqueous phase. Said compound of formula (I) recovered can be used again in step (a) of the extraction process. This step allows said compound of formula (I) to be recycled in the extraction process. Preferably, said compound of formula (I) obtained in step (b5 ’) is used one or more times, for example 2, 3, 4, 5, 6, 7, 8, 9, or 10 times.

In a particular embodiment, the extraction process comprises the following successive steps:

(aO) a step of preparing the material of biological origin;

(a) a step of bringing into contact a material of biological origin comprising said at least one bioactive molecule of biological origin with a compound of formula (I);

(b2) optionally, the separation of the aqueous phase and of the second phase obtained in step (b1), for example by filtration or centrifugation; (b3) adding a hydrophobic solvent, such as ethyl acetate, 2-methylpropan-1-ol, or 2-methylbutan-2-ol, to the aqueous phase obtained in step ( bl) or (b2), thus making it possible to obtain an aqueous phase and an organic phase;

According to a preferred embodiment, the compound of formula (I) used in the extraction process is such that R is an aliphatic group having 9 to 15 carbon atoms, better still R is an aliphatic group having 9 to 11 carbon atoms. carbon.

EXAMPLES

The invention will be better understood in the light of the following examples, which are given purely by way of illustration and not by way of limitation.

Example 1: Synthesis of a compound of formula (I)

1.1. Method

Step (a): In a 500 mL two-necked flask, Choline chloride (40 g; 0.286 mol; 1 eq.) And methane sulfonic acid (55.73 mL; 0.8589 mol; 3 eq.) Were added with the various carboxylic acids (2 eq., either hexanoic acid (72.22 mL; 0.572 mol), octanoic (90.65 mL; 0.572 mol), decanoic (98.53 g; 0.572 mol), dodecanoic ( 114.59g; 0.572 mol), or hexadecanoic (146.68 g; 0.572 mol)). The reaction medium was heated to a temperature of 110 ° C. under reduced pressure (50-100 mbar) for a period of 1 hour 30 minutes. After 1 hour 30 minutes, the reaction mixture became homogeneous and brown in color. A brown solution was thus obtained and was cooled to room temperature and under atmospheric pressure. Water was added (10 mL) to the reaction crude which was washed first with diethyl ether (6 x 200 mL) and then with ethyl acetate (2 x 50 mL) to remove excess carboxylic acid.

Step (b): In a second step, the aqueous phase recovered was introduced into a 1 L Erlenmeyer flask. The excess sodium perchlorate (3 eq.) Previously dissolved in a minimum of water (20 mL) was then added. Depending on the carboxylic acid, either two phases (with the C6 acid) and either a precipitate (C8, CIO, C 12 and Cl 6 acids) were obtained instantly and the reaction medium was left under stirring for 24 h in order to optimize the anionic metathesis between the chloride and perchlorate ions. Ethyl acetate was then added to the reaction medium to either dissolve the precipitate (case of C8, CIO, C12 and C16 acids) or to recover the oil formed (case of C6 acid). After several washes with water (5 x 50 mL) to remove unreacted choline chloride and excess methane sulfonic acid and sodium perchlorate; the organic phase was evaporated under reduced pressure. Finally, the addition of diethyl ether made it possible to precipitate the compound which was filtered off and dried under vacuum. The products were recovered as a white powder.

Step (c): In an Erlenmeyer flask, the product recovered as a white powder in step (b) (1 eq.) Was dissolved in ethanol (100 mL). A solution of potassium levulinate or lactate (1 eq.) In water (10 mL) was added and the mixture was allowed to stir at room temperature for 24 h. Potassium perchlorate precipitated. After filtration of the potassium perchlorate, the ethanol was evaporated. A water / ethyl acetate wash was performed to remove the remainder of the product obtained in step (b) which would not have reacted. After evaporation and drying under vacuum of the aqueous phase, the product was obtained in quantitative yield and in the form of more or less viscous liquids or waxes of yellow-brown color.

1.2. Compounds of formula (I) synthesized

Hexanoylcholinium lactate [Chol - CeJLac

Mass obtained (m = 64 g, yield over the 3 stages: 62%). Liquid at room temperature. ATG! T decomposition ⁼ 198 ° C.

¾ NMR: ÔH (250 MHz; DMSO - de): 0.86 (3H, t, J = 7.5Hz); 1.03 (3H, d, J = 7.5Hz); 1.21 (4H, m); 1.52 (2H, t, J = 7.5Hz); 2.31 (2H, t, J = 7.5Hz); 3.06 (9H, s); 3.27 (1H, q, J = 7.5Hz); 3.78 (2H, t, J = 7.5Hz); 4.56 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 14.35; 18, 87; 22.54; 24.64; 29, 13; 40, 16; 53.41; 53.61; 53.67; 67.56; 172.87; 177.99.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C14H29NO5: C 57.71; H 10.03, N 4.81%. Result obtained: C 57.54; H 9.98; N 4.32%.

Octanoylcholinium lactate [Chol - C _H ] Lac

Mass obtained (m = 83 g, yield over the 3 stages: 79%). Liquid at room temperature. ATG: T decomposition ⁼ 218 ° C. ¾ NMR: ÔH (250 MHz; DMSO - de): 0.86 (3H, t, J = 7.5Hz); 1.07 (3H, d, J = 7.5Hz); 1.25 (8H, m); 1.54 (2H, t, J = 7.5Hz); 2.34 (2H, t, J = 7.5Hz); 3.16 (9H, s); 3.47 (1H, q, J = 7.5Hz); 3.71 (2H, t, J = 7.5Hz); 4.45 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 14.05; 18, 25; 21.88; 22.54; 24.53; 29.15; 29.27; 41.16; 53.21; 53.41; 53.67; 66.96; 172.47; 177.79.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C16H33NO5: C 60.16; H 10.41; N 4.38%. Result obtained: C 59.64; H 9.98; N 4.32%.

Lactate decanoylcholittium [Chol Cio] Lac

Mass obtained (m = 80 g, yield over the 3 stages: 70%). Melting point 56 ° C. ATG: Tdecomposition ⁼ 226 ° C.

¾ NMR: ÔH (250 MHz; DMSO - de): 0.82 (3H, t, J = 7.5Hz); 1.03 (3H, d, J = 7.5Hz);

1.27 (8H, m); 1.48 (2H, t, J = 7.5Hz); 2.53 (2H, t, J = 7.5Hz); 3.08 (9H, s); 3.49 (1H, q, J = 7.5Hz); 3.75 (2H, t, J = 7.5Hz); 4.51 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 14.65; 19, 22; 21.38; 22.54; 24.43; 28.86; 29, 15;

29.27; 31.71; 42.06; 52.51; 53.01; 53.77; 68.96; 171.97; 178.09.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C18H37NO5: C 62.22; H 10.73; N 4.03%. Result obtained: C 62.64; H 10, 98; N 4.41%.

Dodecanoylcholinium lactate [Chol - Cn] Lac

Mass obtained (m = 78 g, yield over the 3 stages: 57%). Melting point 76 ° C.

ATG! Tdecomposition ^- 248 ° C.

¾ NMR: ÔH (250 MHz; DMSO - de): 0.86 (3H, t, J = 7.5Hz); 1.06 (3H, d, J = 7.5Hz); 1.25 (16H, m); 1.51 (2H, t, J = 7.5Hz); 2.35 (2H, t, J = 7.5Hz); 3.15 (9H, s); 3.47 (1H, q, J = 7.5Hz); 3.69 (2H, t, J = 7.5Hz); 4.51 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dô): 15, 18; 17.97; 19, 32; 21.22; 22.34; 22.33; 24, 13; 27.66; 29.02, 32.04; 33.55; 41.96; 52.07; 53.64; 54.28; 69.26; 172.76; 177.86.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C20H41NO5: C 63.96; H 11.00; N 3.73%. Result obtained: C 63, 58; H 10, 89; N 3, 41%.

Hexadecanoylcholinium lactate [Chol Cn] Lac

Mass obtained (m = 80 g, yield over the 3 stages: 47%). Melting point 95 ° C. ATG: Tdecomposition = 264 ° C. ¾ NMR: ÔH (250 MHz; DMSO - de): 0.85 (3H, t, J = 7.5Hz); 1.11 (3H, d, J = 7.5Hz); 1.28 (24H, m); 1.43 (2H, t, J = 7.5Hz); 2.45 (2H, t, J = 7.5Hz); 3.09 (9H, s); 3.48 (1H, q, J = 7.5Hz); 3.70 (2H, t, J = 7.5Hz); 4.55 (2H, t, J = 7.5Hz). ¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 13.98; 15.04; 17.52; 18.87; 19, 52; 21.32; 22, 14; 22.53; 24.33; 25.32; 27.86; 29.22, 31.74; 32, 15; 33.75; 42.26; 52.61; 53.61; 53.78; 68.76; 172.96; 178.36.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C24H49NO5: C 66.78; H 11.44; N 3.24%. Result obtained: C 66.58; H 10, 98; N 3, 31%.

Hexanoylcholinium levulinate [Chol CeJLev

Mass obtained (m = 70 g, yield over the 3 stages: 62%). Liquid at room temperature. ATG! T decomposition ⁼ 206 ° C.

¾ NMR: ÔH (250 MHz; DMSO - de): 0.82 (3H, t, J = 7.5Hz); 1.21 (4H, m); 1.53 (2H, t, J = 7.5Hz); 2.16 (3H, s); 2.24 (2H, t, J = 7.5Hz); 2.36 (2H, t, J = 7.5Hz); 2.55 (2H, t, J = 7.5Hz); 3.21 (9H, s); 3.77 (2H, t, J = 7.5Hz); 4.51 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - de): 14, 18; 22.57; 24.57; 28.92; 29.13; 32.61; 40.45; 53.60; 58.24; 64.15; 172.83; 176.59; 209.96.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C16H31NO5: C 60.54; H 9.84; N 4.41%. Result obtained: C 60, 19; H 9.56; N 4.22%.

Octanoylcholinium levulinate [Chol Cs] Lev

Mass obtained (m = 85 g, yield over the 3 stages: 76%). Melting temperature 50 ° C. ATG! Tdecomposition ⁼ 229 ° C.

¾ NMR: ÔH (250 MHz; DMSO - de): 0.85 (3H, t, J = 7.5Hz); 1.24 (8H, m); 1.53 (2H, t, J = 7.5Hz); 2.06 (3H, s); 2.21 (2H, t, J = 7.5Hz); 2.33 (2H, t, J = 7.5Hz); 2.51 (2H, t, J = 7.5Hz); 3.16 (9H, s); 3.72 (2H, t, J = 7.5Hz); 4.45 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - de): 14.15; 22.37; 24.17; 28.71; 29.21; 29.31; 29.32; 32.43; 40.15; 53.06; 58.44; 63, 12; 172.71; 176.61; 208.87.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C18H35NO5: C 62.58; H 10.21; N 4.05%. Result obtained: C 62, 19; H 9.98; N 4.32%.

Decanoylcholinium levulinate [Chol CioJLev

Mass obtained (m = 88 g, yield over the 3 stages: 71%). Melting point 58 ° C. ATG! Tdecomposition ⁼ 232 ° C. ¾ NMR: ÔH (250 MHz; DMSO - de): 0.87 (3H, t, J = 7.5Hz); 1.22 (12H, m); 1.57 (2H, t, J = 7.5Hz); 2.05 (3H, s); 2.24 (2H, t, J = 7.5Hz); 2.37 (2H, t, J = 7.5Hz); 2.56 (2H, t, J = 7.5Hz); 3.27 (9H, s); 3.74 (2H, t, J = 7.5Hz); 4.53 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 14.25; 22.51; 24.32; 28.51; 29, 15; 29.25; 29.30; 29.99; 31.73; 32.74; 40.27; 53, 16; 58.41; 63.25; 172.78; 176.31; 208, 14.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C20H39NO5: C 64.31; H 10.52; N 3.75%. Result obtained: C 64, 19; H 10.08; N 3.32%.

Dodecanoylcholinium levulinate [Chol - CnJLev

Mass obtained (m = 86 g, yield over the 3 stages: 59%). Melting point 77 ° C. ATG: Tdecomposition = 247 ° C. Ή NMR: ÔH (250 MHz; DMSO - de): 0.84 (3H, t, J = 7.5Hz); 1.23 (16H, m); 1.52 (2H, t, J = 7.5Hz); 2.06 (3H, s); 2.20 (2H, t, J = 7.5Hz); 2.32 (2H, t, J = 7.5Hz); 2.50 (2H, t, J = 7.5Hz); 3.15 (9H, s); 3.71 (2H, t, J = 7.5Hz); 4.44 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - de): 16.25; 21.54; 18.26; 20.36; 24, 12; 28.56; 29.25; 29.41; 29.53; 30.09; 31.75; 32.64; 40.57; 52.26; 55.46; 63.65; 171.75; 176.51; 209.07. IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C22H43NO5: C 65.80; H 10.79; N 3.49%. Result obtained: C 65.59; H 10, 38; N 3, 22%.

Hexadecanoylcholinium levulinate [Chol Cu] Lev

Mass obtained (m = 89g, yield over the 3 stages: 49%). Melting point 98 ° C. ATG: Tdecomposition = 265 ° C. Ή NMR: ÔH (250 MHz; DMSO - de): 0.82 (3H, t, J = 7.5Hz); 1.20 (24H, m); 1.51 (2H, t, J = 7.5Hz); 2.03 (3H, s); 2.22 (2H, t, J = 7.5Hz); 2.30 (2H, t, J = 7.5Hz); 2.48 (2H, t, J = 7.5Hz); 3.18 (9H, s); 3.74 (2H, t, J = 7.5Hz); 4.48 (2H, t, J = 7.5Hz).

¹³ C NMR: ôc (62.5 MHz; DMSO - dd): 15.20; 21.04; 16.96; 18.03; 18.43; 20, 16; 23.43; 24.02; 25.76; 28.36; 29.12; 29.38; 29.50; 30, 19; 31.45; 32.84; 41.25; 52.41; 54.48; 62.97; 172.87; 176.72; 209.18.

IR: u (cm ¹ ) 1746.

Elemental Analysis: Wedge for C26H51NO5: C 68.23; H 11.23; N 3.06%. Result obtained: C 68.59; H 11:38; N 3, 25%. Example 2: Dissolution of cellulose

2.1. Method Cellulose of the AVICEL PH 101 type (m = 400 mg), with a degree of polymerization of 101 and an average diameter of 50 μm, was added to a compound of formula (I) in different percentages by weight. The mixture was heated at 100 ° C for 1 hour. Good dissolution of the cellulose was observed at different mass percentages varying depending on the compound of formula (I) tested.

The cellulose was regenerated by adding an EtOHÆLO (80/20) solution in which it precipitates. After filtration, the cellulose was collected and then dried under vacuum for analysis by IR, ATG and XRD.

2.2. Results

Dissolution

Table 1 below groups together the results of dissolution of microcrystalline cellulose (in% by mass) obtained with various compounds of formula (I), compared with the results obtained with various non-biobased ionic liquids commonly used as solvent.

Table 1

The results of Table 1 show that the cellulose dissolution percentages obtained with the compounds of the invention (17.5% to 32.5%) are predominantly greater than the percentages obtained with ionic liquids [EMIMJAc, [DiC4] Ac , and [DiC4] (8% to 20%). Regeneration of cellulose

IR analyzes (Figures IA and IB) showed no derivatization of cellulose with the compounds of formula (I) tested, [Chol-Ci2] Lac.

Example 3: Dissolution of kraft lignin

3.1. Method

Kraft lignin (m = 800 mg) was added to a compound of formula (I) in different percentages by mass. The mixture was heated at 100 ° C for 1 hour. Good dissolution of the lignin was observed at different mass percentages varying depending on the compound of formula (I) tested.

3.2. Results Table 2 below groups together the results of dissolution of kraft lignin (in% by mass) obtained with various compounds of formula (I), compared with the results obtained with various ionic liquids commonly used as solvent.

Table 2

The results of Table 2 show that the most effective compounds for dissolving lignin are the compounds of the invention. In fact, dissolution percentages between 25% and 65.4% by weight of lignin were obtained with the compounds of the invention, while percentages ranging from 2% to 20% were obtained with the comparative compounds.

In addition, Table 2 indicates that ionic liquids derived from unesterified choline ([CholJLev) or having an R chain of less than 5 carbon atoms ([Chol - C2] Lev) do not allow efficient dissolution of lignin.

Example 4: Method for collecting lignin from Douglas wood

A sample of Douglas-fir sapwood (m = 1 g) containing 27.7% by weight of lignin relative to the total weight of biopolymer present in this wood was added to the compound [Chol-C8] Lac (V = 4 mL). The mixture was heated either:

by conventional heating at 100 ° C for 24 h.

by microwave heating (P = 190 watts at 70 ° C) for 5 min.

Then, water was added to decrease the viscosity of the ionic liquids and to extract the lignin by simple filtration. The wood residue was dried and the filtrate evaporated to remove water.

The mass of lignin obtained after extraction under conventional heating conditions is 60.5 mg, or 6% by mass relative to the mass of Douglas wood. The mass of lignin obtained after extraction under microwave heating conditions is 181.1 mg, ie 18% by mass relative to the mass of Douglas wood.

The compounds of the invention therefore make it possible to efficiently extract lignin. In addition, microwave heating allows extraction three times more efficient than conventional heating, and in a much shorter time (5 min). Example 5 Process for extracting curcuminoids from Curcuma longa

5.1. Method of extraction with the compounds of the invention

Powdered turmeric longa (m = 2 g) was mixed into a compound of formula (I) (V = 3 mL). The mixture was heated to 70 ° C with magnetic stirring for 30 min. Water (50 mL) was then added to decrease the viscosity of the ionic liquids and aid filtration. The resulting solution was filtered to remove insoluble residue. Ethyl acetate (AcOEt, 2 x 100 mL), 2-methylpropan-1-ol (2M1P, 100 mL) or 2-methylbutan-2-ol (2M2B, 70 mL), was then added to the filtrate obtained. Curcumins I, II and III were recovered in the organic phase (AcOEt, 2M1P, or 2M2B) and the compound of formula (I) in the aqueous phase. The compound of formula (I), after evaporation of the water, could thus be regenerated.

5.2. Method of extraction with acetone, ethyl acetate, 2-methylpropan-1-ol or 2-methylbutan-2-ol

Powdered turmeric longa (m = 2 g) was mixed in a solvent (acetone, ethyl acetate, 2-methylpropan-1-ol or 2-methylbutan-2-ol) (V = 30 mL). The mixture was heated to 70 ° C with magnetic stirring for 30 min. The resulting solution was filtered to remove insoluble residue. The procedure was repeated a second time: the insoluble residues were mixed with the solvent (V = 30 mL), the mixture was heated at 70 ° C with magnetic stirring for 30 min, then the resulting solution was filtered.

The filtrates were combined, and curcumin I, II and III were recovered after evaporation of the solvent.

5.3. Results

The curcuminoid extracts recovered by the method described above (5.1.) Were compared with a commercial extract. The profile obtained by Thin Layer Chromatography (TLC) is shown in Figure 2 and shows that the extract obtained with the compounds of formula (I) has the same composition as the commercial reference. Table 3 below shows the extraction yields of curcumin I, II, and III determined by UV spectroscopy (420 nm) with the compounds of the invention, as well as with acetone, ethyl acetate , 2M1P, 2M2B, and 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM-BF4], a commercial ionic liquid.

Table 3

The results of Table 3 show that good curcumin extraction yields are obtained with the compounds of the invention, using different regeneration solvents, such as ethyl acetate, 2-methylpropan-1-ol or 2-methylbutan-2-ol. The best results are obtained with 2-methylbutano-2-ol as regeneration solvent, used in small quantities (70 mL, against 200 mL with ethyl acetate).

The results of Table 3 show moreover that the curcumin extraction yields obtained with the compounds of the invention are mainly higher than those obtained with acetone, ethyl acetate, 2M1P, or 2M2B, which furthermore require several extractions.

The yields obtained with the compounds of the invention are also mainly higher than that obtained with the ionic liquid [EMIM-BF4]. Example 6: Process for extracting carvacrol from oregano

6.1. Method

The method used for extracting carvacrol from oregano from oregano powder is identical to that described for extracting curcuminoids (5.1.). Additional acid-base purification was also performed at the end of the method.

The extraction yields were determined by gas chromatography with a TR -1 column. The conditions used are specified below. The retention time of carvacrol is approximately 14.34 min in diethyl ether.

Conditions with the TR-1 column: Initial temperature: 60 ° C; Initial time: 5 min; Gradient: 10 ° C / min; Final temperature: 220 ° C; Final time: 20 min

6.2. Results

Table 4 below groups together the carvacrol extraction yields obtained with different compounds of formula (I) and determined by gas chromatography.

Table 4

Excellent extraction yields have been obtained with the compounds [Chol - Ci2] Lac and [Chol - Cio] Lac Up to ten times higher than the yields obtained by the most widely used carvacrol extraction method, namely hydrodistillation (yield ~ 5%, Galehassadi et al., Stand. Sci. Res. Essays, 2014, 438-450).

The yields obtained with [Chol - C6] Lac and [Chol - Cs] Lac are lower, but remain competitive with respect to hydrodistillation, which requires several hours, unlike the extraction process of the invention which can be completed in just about 30 minutes.

Claims

1. Compound of formula (I):

in which :

R is an aliphatic group having 5 to 15 carbon atoms, and

A- is a carboxylate having 3 to 8 carbon atoms.

2. Compound according to claim 1, wherein A- is selected from a levulinate, a lactate, a succinate, a malate and a tartrate, preferably from a levulinate and a lactate, and even more preferably A- is a levulinate. .

3. A compound according to claim 1 or 2, wherein R is an aliphatic group having 5 to 11 carbon atoms, preferably R is an alkyl group having 5 to 11 carbon atoms, and even more preferably R is pentyl. , a heptyl, a nonyl or an undecyl.

4. Use of a compound as defined according to any one of claims 1 to 3, for the dissolution and / or extraction of at least one compound of biological origin, preferably a biopolymer or a bioactive molecule.

5. Method for collecting at least one biopolymer of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one biopolymer of biological origin with a compound of formula (I) as defined according to any one of claims 1 to 3; and

6. The collection method according to claim 5, wherein said at least one biopolymer of biological origin is chosen from a polysaccharide and a polyphenolic polymer, preferably from cellulose, T hemicellulose, lignin, chitin, and a mixture of these.

7. The collection method according to claim 5 or 6, wherein the compound of formula (I) is such that R is an aliphatic group having 5 to 7 carbon atoms.

8. Collection method according to any one of claims 5 to 7, wherein the contacting step (a) is carried out at a temperature between 50 ° C and 180 ° C, preferably between 70 ° C and 110 ° C.

9. A collection method according to any one of claims 5 to 8, wherein the contacting step (a) is carried out in a microwave, preferably at a power of between 100 W and 350 W.

10. Process for extracting at least one bioactive molecule of biological origin, comprising the following successive steps:

(a) a step of bringing into contact a material of biological origin comprising said at least one bioactive molecule of biological origin with a compound of formula (I) as defined according to any one of claims 1 to 3; and

11. The extraction process according to claim 10, wherein said at least one bioactive molecule of biological origin is chosen from a lipid, a terpene, a terpenoid, a phenol, a polyphenol, an alkaloid, a steroid, a heteroside, an essential oil, a vitamin, and a mixture of these, preferably among a curcuminoid, eugenol and carvacrol.

12. The extraction process according to claim 10 or 11, wherein the compound of formula (I) is such that R is an aliphatic group having 9 to 11 carbon atoms.

13. The extraction process according to any one of claims 10 to 12, wherein the contacting step (a) is carried out at a temperature between 30 ° C and 120 ° C, preferably between 50 ° C and 100 ° C.

14. The extraction method according to any one of claims 10 to 13, wherein the contacting step (a) is carried out in a microwave, preferably at a power between 100 W and 350 W. .

15. A process for preparing a compound as defined in any one of claims 1 to 3, comprising the following successive steps:

(a) a step of reaction of a choline salt of formula (II):

in which X is a halide, preferably a chloride,