Novel compositions for sustainable catalysis of organic synthesis reactions

Abstract

The present invention relates to a composition comprising K2CO3, KCl and optionally K2SO4 and / or KHCO3, the weight content of potassium being between 9.0 and 60.0%, preferably between 10.0 and 50.0%, more preferably between 10.0 and 40.0% and advantageously between 20.0 and 40.0% relative to the total weight of the composition.

Description

[Technical field]

[0001] The present invention relates to compositions containing specific potassium salts and specific amounts of potassium.

[0002] The present invention also relates to methods for preparing these compositions.

[0003] The invention also relates to the use of these compositions as catalysts for chemical synthesis reactions. [Background technology]

[0004] Many basic compounds are known as reactants or catalysts in organic synthesis reactions. However, they are usually obtained by conventional chemical processes that often have a high environmental impact. Also, the conditions under which these organic reactions are carried out require the use of non-biosourced reagents, organic solvents, high temperature conditions that increase the energy budget, purification steps, and generate large amounts of waste.

[0005] Nevertheless, society is increasingly demanding products obtained through processes with a reduced ecological impact: in particular, organic and ethical sourcing of raw materials, ecodesign and eco-friendly processes, waste management, and green chemistry are becoming priorities.

[0006] In this context, basic catalysts derived from natural products rich in calcium (containing more than 50,000 ppm calcium), in particular from plants rich in calcium oxalate and from natural products rich in calcium carbonate, have been developed and are described, for example, in WO 2015 / 036714. To obtain such basic catalysts, these natural products undergo several heat and base / acid treatments. The calcium oxalate contained in the plants is converted to calcium carbonate at about 550° C. and calcium carbonate to calcium oxide at about 800° C. By hydration reactions, calcium oxide is converted to calcium hydroxide. Calcium hydroxide can also be obtained from calcium carbonate by chloroacid treatment to give calcium chloride followed by alkaline hydrolysis. These catalysts have been involved in several organic reactions.

[0007] However, these processes to obtain the final catalysts involve several heat and base / acid treatments that increase their environmental balance. Also, several organic reactions, which are very difficult to carry out according to conventional synthesis techniques, cannot be carried out even with the catalysts described in WO 2015 / 036714. Summary of the Invention

[0008] Objective of the invention One object of the present invention is to solve the technical problem of providing a composition that exhibits good basic catalytic performance.

[0009] Another object of the present invention is to provide a composition obtained by a process having a reduced environmental impact.

[0010] Another object of the present invention is to provide methods for carrying out organic syntheses which are difficult to carry out according to known synthetic techniques and / or in the presence of prior art catalysts.

[0011] Another object of the present invention is to provide a method for carrying out organic synthesis with reduced environmental impact. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention relates to a composition having a potassium content by weight ranging from 9.0 to 60.0%, preferably ranging from 10.0 to 50.0%, more preferably ranging from 10.0 to 40.0%, advantageously ranging from 20.0 to 40.0%, relative to the total weight of the composition. 2 CO 3 , KCl, and optionally K 2 SO 4 and / or KHCO 3 The present invention relates to a composition comprising:

[0013] KHCO 3 and K 2 CO 3 may be in anhydrous or hydrated form. 3 and K 2 CO 3 is a co-crystalline species, e.g., K 2 H(CO 3 ) 1.5 (H 2 O) 0.75 It can also exist as

[0014] The inventors have discovered that starting from plants whose above-ground parts contain a very large amount of potassium, it is possible to obtain compositions according to the invention. Surprisingly, these compositions have been found to be very effective as catalysts in several organic reactions.

[0015] Preferably, the composition according to the invention is a multimetallic composition.

[0016] According to one embodiment, the composition according to the invention comprises sodium, calcium and / or magnesium.

[0017] According to one embodiment, the composition according to the invention comprises calcium and magnesium.

[0018] According to one embodiment, the composition further comprises sodium, calcium and magnesium.

[0019] According to one embodiment, the composition further comprises iron and aluminum.

[0020] Preferably, the composition comprises 0.0001 to 0.30% by weight, preferably 0.0001 to 0.25% by weight, of sodium relative to the total weight of the composition.

[0021] Preferably, the composition comprises 0.1-20.0% by weight, preferably 1.0-20.0% by weight, of calcium relative to the total weight of the composition. According to one embodiment, the composition comprises 0.1-5.0% by weight, preferably 0.5-4.0% by weight, more preferably 1.0-3.0% by weight, of calcium relative to the total weight of the composition. According to another embodiment, the composition comprises 5.0-20.0% by weight, of calcium relative to the total weight of the composition.

[0022] Preferably, the composition comprises 0.0001-10.0% by weight of magnesium relative to the total weight of the composition. According to one embodiment, the composition comprises 2.5-10.0% by weight, preferably 3.0-10.0% by weight of magnesium relative to the total weight of the composition. According to another embodiment, the composition comprises 0.0001-3.0% by weight, preferably 0.1-3.0% by weight of magnesium relative to the total weight of the composition.

[0023] Preferably, the composition comprises 0.0001 to 1.0 wt.-%, preferably 0.001 to 0.8 wt.-%, more preferably 0.01 to 0.6 wt.-%, of iron based on the total weight of the composition.

[0024] Preferably, the composition comprises 0.0001-1.0% by weight of aluminum relative to the total weight of the composition. According to one embodiment, the composition comprises 0.05-0.8% by weight of aluminum relative to the total weight of the composition. According to another embodiment, the composition comprises 0.0001-0.1% by weight of aluminum, preferably 0.01-0.08% by weight, relative to the total weight of the composition.

[0025] According to one embodiment, the composition further comprises manganese.

[0026] Preferably, the composition comprises from 0.0001 to 0.30% by weight, preferably from 0.005 to 0.30% by weight, more preferably from 0.01 to 0.30% by weight and advantageously from 0.01 to 0.20% by weight of manganese relative to the total weight of the composition. According to one embodiment, the composition comprises from 0.0001 to 0.1% by weight, preferably from 0.005 to 0.05% by weight of manganese relative to the total weight of the composition.

[0027] According to one embodiment, the composition further comprises zinc.

[0028] Preferably, the composition comprises 0.0001 to 0.4% by weight, preferably 0.005 to 0.3% by weight, more preferably 0.01 to 0.2% by weight of zinc relative to the total weight of the composition.

[0029] The content of each metal was determined directly on the composition by microwave plasma atomic emission spectroscopy (MP-AES).

[0030] The analysis is carried out using metal analysis of the total dissolved composition in water. For this purpose, the composition is digested in 10 mL of inverse aqua regia (1:2 hydrochloric acid (37%):nitric acid (65%)) under microwave-assisted digestion (Multiwave-Go Anton Paar) with the following program: 20 min at 20-165 °C, then isothermal at 165 °C for 10 min. The sample is filtered and then diluted with 0.4 mg L of nitric acid in 1% aqueous solution. -1The mineral composition is determined by using a microwave plasma atomic emission spectrometer (MP-AES) 4200 (Agilent Technologies) equipped with a concentric nebulizer and a double-pass cyclonic spray chamber. The pump speed during the analysis was kept at 10 rpm and the sample introduction tube diameter was 0.89 mm. The analysis cycle consisted of a 30-s wash with 1% aqueous nitric acid solution, followed by a 25-s sample uptake (pump speed 40 rpm) and then a 20-s equilibration before reading at a preselected integration time (pump speed 10 rpm). The integration time was set at 3 s for all elements. The automatic background correction mode available in the software was used unless otherwise stated. All analytical results are performed in triplicate.

[0031] According to one embodiment, the composition comprises calcium hydroxide Ca(OH) 2 Substantially free of.

[0032] More preferably, the composition comprises calcium hydroxide Ca(OH) 2 does not entirely contain

[0033] According to one embodiment, the composition of the invention is substantially free of calcium oxide, CaO. More preferably, the composition is completely free of calcium oxide, CaO.

[0034] Preferably, the composition of the invention comprises calcium oxide CaO and calcium hydroxide Ca(OH). 2 More preferably, the composition is substantially free of calcium oxide, CaO, and calcium hydroxide, Ca(OH). 2 does not entirely contain

[0035] According to one embodiment, the composition of the invention comprises calcium hydroxide Ca(OH) 2 , potassium hydroxide KOH and magnesium hydroxide Mg(OH) 2 Preferably, the composition is substantially free of calcium hydroxide Ca(OH) 2 , potassium hydroxide KOH and magnesium hydroxide Mg(OH)2 Preferably, the composition of the invention is completely free of calcium oxide CaO, calcium hydroxide Ca(OH) 2 , potassium hydroxide KOH and magnesium hydroxide Mg(OH) 2 More preferably, the composition is substantially free of calcium oxide, CaO, calcium hydroxide, Ca(OH) 2 , potassium hydroxide KOH and magnesium hydroxide Mg(OH) 2 does not entirely contain

[0036] According to one embodiment, the composition of the invention is substantially free of metal hydroxides. Preferably, the composition is completely free of metal hydroxides. Preferably, the composition of the invention is substantially free of metal hydroxides and calcium oxide, CaO. More preferably, the composition is completely free of metal hydroxides and calcium oxide, CaO.

[0037] By "substantially free" of calcium hydroxide, potassium hydroxide, magnesium hydroxide, calcium oxide or metal hydroxides is meant less than 0.1 wt.%, preferably less than 0.01 wt.%, and more preferably less than 0.001 wt.% of calcium hydroxide, potassium hydroxide, magnesium hydroxide, calcium oxide or metal hydroxides, based on the total weight of the composition.

[0038] Metal hydroxides are represented by the formula M, where x is an integer from 1 to 3 and M is a metal selected from Ca, Mg, Zn, Mn, K and Fe. x+ (OH) x It is a compound of the formula:

[0039] Ca(OH) 2 It has been found that these compositions are very effective as catalysts in several organic reactions, despite the absence of calcium hydroxide, a result that was unexpected, since the prior art, and in particular the compositions of WO 2015 / 036714, are mainly composed of calcium hydroxide, which is the active species in the organic synthesis reactions carried out.

[0040] According to one embodiment, the composition is substantially free of metals selected from the group of platinoids, in particular Pt, Pd or Rh, and / or rare earths, in particular Ce, Eu and Yb, and / or metalloids, in particular B, Ge, As, Sb and Te.

[0041] According to one embodiment, the composition is substantially free of transition metals selected from the group consisting of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Cd.

[0042] By "substantially free of metals selected from the group" it is meant that each metal is present in an amount of less than 0.6 wt.%, preferably less than 0.4 wt.%, more preferably less than 0.2 wt.%, based on the total weight of the composition.

[0043] The inventors have observed that in order to obtain a better catalytic performance of the composition according to the invention, it is preferable that the amount of these metals is as low as possible. As a result, the composition according to the invention is completely different from the compositions described in WO 2018 / 178374. In WO 2018 / 178374, the compositions are characterized by a high amount of metals selected from the group of platinoids (Pd, Pt, Rh), rare earths (Ce, Eu, Yb), or from the group comprising Zn, Mn, Ni, Cu, Fe, Al, Ca, Mg, or from the group comprising As, Sb, Cr, Cd, Pb, Ni, Co. This is because these compositions were obtained by contacting raw material from dead plants with a waste liquid containing at least one of these metals. As a result, the obtained composition contains a high amount of said metals, which is not preferred in the case of the compositions according to the invention.

[0044] According to one embodiment, the composition of the present invention comprises K 2 Ca(CO 3 ) 2 Alternatively, or in addition, the compositions of the present invention preferably further comprise Na 2 SO 4 And / or Na 2 CO 3and / or (Ca,Mg)CO 3 Alternatively, or in addition, the composition of the present invention preferably further comprises CaMgSi 2 O 6 and / or SiO 2 and / or CaCO 3 and / or (Mg 6 Al 2 (OH) 16 (CO 3 )(H 2 O) 4.5 ) 0.25 Alternatively, or in addition, the composition of the present invention preferably further comprises K 3 (MnO 4 Alternatively, or in addition, the composition of the present invention preferably further comprises MnS.

[0045] The present invention also relates to a method for preparing a composition according to the invention, comprising the steps of: Selecting a plant, wherein the above-ground part of the plant contains 10.0 to 40.0% by weight of potassium; - heat treating the above-ground part of the plant in air at a temperature between 450 ° C and 650 ° C; Obtaining the composition.

[0046] By above-ground parts of a plant is meant the aerial parts of the plant, i.e. all the visible parts of the plant that grow in the soil. The aerial parts of a plant are all the structures of the plant that are above ground, including stems, leaves, petioles, flowers, fruits and seeds.

[0047] Preferably, the above-ground parts of the plant are the leaves and / or stems and / or branches and / or petioles of the plant.

[0048] According to one embodiment, the above-ground part of the plant is a mixture of two, preferably three parts of the plant from the list consisting of leaves, stems, branches and petioles of the plant. More preferably, the above-ground part of the plant is a mixture of leaves, stems, branches and petioles of the plant.

[0049] To obtain the composition according to the invention, suitable plants are selected by measuring the weight % of K of the above-ground parts of said plants. The weight % of K of the above-ground parts of the plants is determined by MP-AES after heat treatment, preferably under air at 550° C. for 4 hours. A plant is suitable for obtaining a composition according to the invention if its above-ground parts contain 10.0-40.0% by weight of potassium. A plant is suitable for obtaining a composition according to the invention if at least one of its above-ground parts contains 10.0-40.0% by weight of potassium after heat treatment, preferably under air at 550° C. for 4 hours. The process of the invention therefore comprises the steps of selecting a plant by heat treating at least one of the above-ground parts of said plant, preferably under air at 550° C. for 4 hours, followed by analyzing the heat-treated above-ground parts, preferably by MP-AES, and selecting a plant if at least one of the heat-treated above-ground parts contains 10.0-40.0% by weight of potassium.

[0050] Preferably, the heat treatment of the process for preparing the composition according to the invention is carried out under air.

[0051] Preferably, the heat treatment is carried out for a period comprised between 3 hours and 5 hours, advantageously around 4 hours.

[0052] Advantageously, the heat treatment is carried out at a temperature between 400°C and 700°C, preferably between 450°C and 650°C, more preferably between 530°C and 560°C, and even more preferably at about 550°C.

[0053] Surprisingly, the inventors have found that only a single heat treatment of said above-ground parts makes it possible to obtain the composition of the invention, in particular no further heat treatment is required at a temperature higher than that of the heat treatment of the method for preparing the composition according to the invention.

[0054] The present invention therefore also relates to a method for the preparation of a composition according to the invention, which comprises the steps of: - selecting a plant, wherein the heat-treated above-ground part of the plant contains 10.0 to 40.0% by weight of potassium after heat treatment; - heat treating the above-ground part of the plant in air at a temperature between 450 ° C and 650 ° C; Obtaining the composition.

[0055] According to one embodiment, the process for the preparation of the composition according to the invention does not comprise a step of acid treatment and / or does not comprise a base treatment and / or does not comprise a purification step, for example by ion exchange resins, liquid-liquid extraction, selective precipitation or liquid / solid extraction and / or does not comprise an activation step.

[0056] According to one embodiment, in the method for preparing the composition according to the invention, the plant belongs to the genus Fallopia, Salix or Arundo. Preferably, the plant belongs to the genus Fallopia or Salix, more preferably, the plant belongs to the genus Arundo.

[0057] The "binkle" genus is also known as "Reynoutria."

[0058] According to one embodiment, in the method for preparing the composition according to the present invention, the plant is Japanese knotweed (Fallopia japonica), white willow (Salix alba) or Arundo donax.Preferably, the plant is Japanese knotweed or Arundo donax, and more preferably, the plant is Japanese knotweed.

[0059] Preferably, the heat treatment is carried out on the leaves or stems of Japanese knotweed, or the leaves of white willow, or the stems of Chinese lantern plant. Preferably, the heat treatment is carried out on the leaves or stems of Japanese knotweed, or the stems of Chinese lantern plant, and more preferably, the heat treatment is carried out on the leaves or stems of Japanese knotweed.

[0060] The present invention also relates to a composition obtainable from the process described above, said composition preferably having the same characteristics and embodiments as the composition according to the invention.

[0061] The compositions according to the invention can be advantageously used as catalysts for chemical synthesis reactions.

[0062] The present invention also relates to a method for carrying out a chemical synthesis reaction comprising the step of contacting a composition according to the invention with a reactant of the chemical synthesis reaction, said chemical synthesis reaction being selected from the group consisting of 1,4-nucleophilic addition, aldolization / crotonization and similar reactions, functional group exchange reactions and oxidative hydroxylation reactions.

[0063] According to one embodiment, the method of carrying out a chemical synthesis reaction according to the invention is carried out in the absence of any other catalyst, except for the composition according to the invention.

[0064] According to one embodiment, a method for performing a chemical synthesis reaction comprises: - dissolving the crude mixture obtained at the end of the step of contacting the composition with the reactants in an organic solvent, preferably ethyl acetate, to obtain an organic solution having insoluble compounds, followed by - a filtration step to separate the insoluble compounds from the organic solution; and - evaporation of the organic solvent of the organic solution to obtain an organic product; Includes.

[0065] Optionally, when the organic product is a mixture of at least two organic products, the method for carrying out a chemical synthesis reaction further comprises a purification step of the organic products, for example by distillation, preferably under vacuum.

[0066] According to one embodiment, a method for performing a chemical synthesis reaction comprises: - a filtration step to separate insoluble compounds from the crude mixture obtained at the end of the step of contacting the composition with the reactants, followed by - removing excess reactants by distillation, preferably under vacuum, Includes.

[0067] The excess reactants can be recycled and reused.

[0068] According to one embodiment, the method for carrying out a chemical synthesis reaction further comprises a step of heat treating the insoluble compounds separated from the organic product, said heat treatment being carried out at a temperature between 400° C. and 700° C., preferably between 450° C. and 650° C., more preferably between 530° C. and 560° C., to give a reactivated composition. Preferably, said heat treatment is carried out for a period of between 2 hours and 6 hours.

[0069] This step of heat treatment of the insoluble compounds allows for recycling of the composition: the reactivated composition can be reused in another method of carrying out a chemical synthesis reaction.

[0070] According to one embodiment, the method for carrying out a chemical synthesis reaction according to the invention is carried out in the absence of organic solvents, preferably in the absence of any solvent.

[0071] "In the absence of organic solvents" or "in the absence of solvents" means that the chemical transformation of the reactants does not take place in an organic solvent or other solvent, respectively. The solvent is not a reactant in a chemical synthesis reaction. This does not exclude the use of organic solvents or solvents for the treatment of crude materials obtained after chemical transformation of the reactants.

[0072] According to one embodiment, during the method of carrying out a chemical synthesis reaction, the step of contacting the composition according to the invention with the reactants is carried out under activation method.

[0073] Preferably, the step of contacting the composition according to the invention with the reactants is carried out by mechanosynthesis or under microwaves.

[0074] Mechanosynthesis is a chemical synthesis that uses mechanical energy to drive chemical reactions. Mechanosynthesis usually starts from solids without any solvent. The mechanical energy source used to react the molecules is classically obtained by grinding a physical mixture of two (or more) different partners in the jar of a ball mill. Such equipment can be a planetary ball mill apparatus, see TMAX-XQM-12 or RETSCH PM100.

[0075] Preferably, the mechanosynthesis is carried out at a temperature comprised between 25°C and 80°C, preferably between 25°C and 60°C, more preferably between 25°C and 40°C.

[0076] Preferably, the mechanosynthesis is carried out in a ball mill comprising balls with a diameter comprised between 3 mm and 35 mm. The rotation speed is preferably comprised between 250 rpm and 750 rpm, more preferably about 500 rpm. Preferably, the stopping of the rotation of the balls is carried out every hour of reaction. Preferably, the stopping period is comprised between 5 min and 30 min.

[0077] The use of the mechanosynthesis step makes it possible to obtain very high conversions and final yields. The use of the mechanosynthesis step makes it possible to reduce the amount of excess reactants.

[0078] According to one embodiment, the synthesis under microwave conditions is carried out at a pressure comprised between 1 and 55 bar.

[0079] An example of an instrument for carrying out the synthesis under microwaves is a Microwave Accelerated Reaction System for Synthesis, model MARS6, 240V / 50Hz.

[0080] The combination of the composition of the invention with mechanosynthesis or microwave activation makes it possible to carry out reactions under milder conditions than those of conventional processes. The method of carrying out chemical synthesis reactions according to the invention therefore makes it possible to carry out organic syntheses that are difficult to carry out according to known synthesis techniques and / or in the presence of conventional catalysts, in particular syntheses involving reactants that tend to decompose under the conditions of said known synthesis techniques. The method of carrying out chemical synthesis reactions according to the invention therefore gives access to new products that are inaccessible or hardly accessible by conventional processes.

[0081] According to one embodiment, the step of contacting the composition with the reactant of 1,4-nucleophilic addition is carried out in the absence of organic solvents, preferably in the absence of any solvent, more preferably by mechanosynthesis or under microwaves, advantageously by mechanosynthesis.

[0082] "1,4-nucleophilic addition" refers to the addition reaction of a nucleophile to the β-position of an α,β-unsaturated carbonyl compound. Examples of 1,4-nucleophilic addition are: the reaction of a conjugated carbonyl with a secondary amine to form a 3-aminocarbonyl (3-ketoamine), - reaction of conjugated carbonyls with hydrogen cyanide to give 1,4-keto-nitriles, -Michael Addition, -The Stokes enamine reaction, which involves the conjugate addition of an enamine to a conjugate carbonyl. It is.

[0083] The 1,4-nucleophilic addition can be intramolecular or intermolecular.

[0084] Preferably, the 1,4-nucleophilic addition is a Michael-type addition.

[0085] Preferably, the 1,4-nucleophilic addition involves the reaction between a compound having a nucleophilic carbon and a compound having an α,β-unsaturated carbonyl functionality, or the self-reaction of a compound having both a nucleophilic carbon and an α,β-unsaturated carbonyl functionality.

[0086] Preferably, the 1,4-nucleophilic addition is a reaction between a compound having an α,β-unsaturated carbonyl function of formula [1] and a compound having a nucleophilic carbon of formula [2]. [ka] In the formula, R 1 and R 2 are independently selected in the group consisting of H, linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radicals containing 1 to 8 carbon atoms, forming a ring containing 5 to 7 members, or forming an aryl ring; In the formula, R 3 is selected in the group consisting of H and linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radicals containing 1 to 10 carbon atoms, preferably H or a saturated linear hydrocarbon radical containing 1 to 10 carbon atoms, more preferably H or C 5 H 11 and In the formula, R 4 and R 5 are independently selected from the group consisting of H, a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group containing 1 to 8 carbon atoms, and A represents a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group containing 1 to 6 carbon atoms, a group of formula -OA, or form a ring containing 5 to 7 members, preferably independently selected from the group consisting of -OMe and Me, or form a saturated 6-membered ring.

[0087] Advantageously, the compound of formula [1] is 2-cyclopenten-1-one or a derivative of 2-cyclopenten-1-one, where at least one of the ring carbons carries a C1 to C8 saturated alkyl group, advantageously 2-pentyl-2-cyclopenten-1-one.

[0088] Advantageously, the compound of formula [2] is dimethyl malonate.

[0089] According to a particular embodiment, the 1,4-nucleophilic addition is followed by an intramolecular aldol condensation, an intramolecular crotonization, and an intramolecular decarboxylation reaction. 3 =H, R 4 =Me and R 5 More preferably, R 3 =H, R 4 =Me, R 5 = OMe and R 2 ═H. Even more preferably, R 3 =H, R 4 =Me, R 5 =OMe, R 2 =H and R 1 =H or Me.

[0090] According to one embodiment, the 1,4-nucleophilic addition is carried out in the presence of a composition in an amount corresponding to 0.01 to 5 equivalents, preferably 0.05 to 4 equivalents, more preferably 0.1 to 3 equivalents, advantageously 0.1 to 2.5 equivalents of K relative to the limiting reactant.

[0091] Since the weight percent of K is determined by MP-AES according to the method described above, the amount of the composition to use is readily determined by one of ordinary skill in the art.

[0092] Preferably, the 1,4-nucleophilic addition is carried out in the presence of 1 to 10 equivalents of a compound having a nucleophilic carbon (a compound of formula [2]) relative to the amount of a compound having an α,β-unsaturated carbonyl functional group (a compound of formula [1]).

[0093] According to one embodiment, in the method of carrying out a chemical synthesis reaction according to the invention, the chemical synthesis reaction comprises a 1,4-nucleophilic addition followed by an aldolization / crotonization reaction followed by a decarboxylation reaction.

[0094] By "aldolization / crotonization reactions and similar reactions" is meant all condensation reactions involving the addition of a carbon bearing an activated hydrogen (i.e., an acid hydrogen) on the carbon of a C=O or C=N group. Examples of aldolization / crotonization and similar reactions are the aldol condensation of aldehydes, the cetolic condensation of ketones, the cross condensation between aldehydes, ketones and esters, the Knoevenagel reaction, the Dieckmann reaction.

[0095] Aldolization / crotonization reactions and similar reactions can be intramolecular or intermolecular reactions.

[0096] Preferably, the aldolization / crotonization reaction and similar reactions comprise a condensation reaction between a compound having an enolizable aldehyde or an enolizable ketone or an enolizable ester functional group and a compound having an aldehyde, ketone or ester functional group. Alternatively, the aldolization / crotonization reaction and similar reactions comprise the self-reaction of a compound having both an enolizable aldehyde or an enolizable ketone or an enolizable ester functional group and an aldehyde, ketone or ester functional group.

[0097] Preferably, the aldolization / crotonization and similar reactions are between a compound of formula [9] and a compound of formula

[10] . [ka] In the formula, R 17 and R 18 are independently a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radical containing 1 to 8 carbon atoms or forming a ring containing 5 to 7 members, preferably a saturated 5-membered ring; In the formula, R 19 is a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon group containing 1 to 10 carbon atoms, preferably a saturated linear hydrocarbon group containing 1 to 10 carbon atoms, more preferably C 5 H 11It is.

[0098] Advantageously, the aldolization / crotonization and similar reactions are the aldolization followed by the crotonization of cyclopentanone and pentanal.

[0099] Aldolization / crotonization and similar reactions may also be reactions between compounds of formula

[13] and compounds of formula [5]. [ka] In the formula, R 20 is selected from the group consisting of phenyl radicals and linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radicals containing 1 to 8 carbon atoms, where R 9 and R 10 are independently selected in the group consisting of H, a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radical containing 1 to 8 carbon atoms, and a group of formula -OA, where A represents a linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radical containing 1 to 6 carbon atoms, or forms a ring containing 5 to 7 members.

[0100] According to one embodiment, the reaction between a compound of formula

[13] and a compound of formula [5] is followed by a decarboxylation reaction. 10 More preferably, R 20 =Ph, R 9 =Me and R 10 =OMe.

[0101] Aldolization / crotonization and similar reactions can also be intramolecular reactions of compounds of formula

[32] . [ka] where n is an integer equal to 1, 2 or 3, preferably equal to 1; R 30 is a linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 8 carbon atoms, preferably a saturated linear hydrocarbon group containing 1 to 8 carbon atoms, more preferably CH 3It is.

[0102] Preferably, the aldolization / crotonization reaction and similar reactions are carried out in the presence of a composition in an amount corresponding to 0.01 to 2.0 equivalents, preferably 0.02 to 1.0 equivalents, more preferably 0.05 to 0.5 equivalents of K relative to the limiting reactant.

[0103] A functional group exchange reaction is a reaction in which a substituent of a chemical functional group is replaced with another substituent.

[0104] Preferably, the functional group exchange reaction is a transesterification reaction or a transcarbonation reaction.

[0105] "Transesterification" refers to a reaction in which an organic group R' of an ester functional group -C(O)-OR' of a compound is exchanged with an organic group R" of an alcohol R"OH to give a compound containing another ester functional group -C(O)-OR" and an alcohol R'OH.

[0106] The transesterification reaction is preferably a reaction between a compound containing at least one OH functional group and a compound containing at least an ester functional group. Preferably, the compound containing at least one OH functional group is selected in the group consisting of alcohols of formula R″OH, where R″ is a C1-C10 saturated or C2-C10 unsaturated hydrocarbon group, diols such as ethylene glycol, propane-1,2-diol, butane-1,2-diol, butane-2,3-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, butane-1,3-diol, pentane-1,2-diol, p-menthane-3,8-diol, 2-methylpentane-2,4-diol, and polyols such as glycerol, erythriol, sorbitol, mannitol, or polyglycerol.

[0107] More preferably, the compound containing at least one OH function is methanol or ethanol, advantageously ethanol.

[0108] Preferably, the compounds containing at least an ester function are selected from fatty acid esters, diesters and triglycerides.

[0109] Preferably, the fatty acid ester is a compound of formula

[15] : [ka] In the formula, R 21 is a linear or branched, saturated or at least one unsaturated, optionally substituted, for example by an OH group, hydrocarbon radical containing 1 to 30 carbon atoms, preferably 1 to 25 carbon atoms, R 22 is selected in the group consisting of H, linear or branched, saturated or at least one unsaturated hydrocarbon radicals containing 1 to 30 carbon atoms, preferably 1 to 25 carbon atoms, and linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon radicals containing 1 to 10 carbon atoms. 22 =H. Advantageously, the compound of formula

[15] is geranyl formate.

[0110] Preferably, the triglyceride is a compound of formula

[29] [ka] In the formula, R 24 , R 25 and R 26 are independently linear or branched, saturated or at least singly unsaturated hydrocarbon groups containing 1 to 30 carbon atoms, preferably 1 to 25 carbon atoms.

[0111] Preferably, the compound containing at least ester functional groups is a mixture of at least two triglycerides.More preferably, the compound containing at least ester functional groups is selected from vegetable oils.Even more preferably, the compound containing at least ester functional groups is selected from the group consisting of olive oil, grapeseed oil, rapeseed oil, coconut oil, castor oil and sunflower oil.

[0112] Preferably, the molar ratio between the compound containing at least an ester function and the compound containing at least one OH function is less than or equal to 65, more preferably less than or equal to 40 and advantageously between 4 and 10.

[0113] Preferably, the transesterification is carried out under a pressure comprised between 1 bar and 4 bar, more preferably between 1 bar and 2.5 bar.

[0114] Preferably, the transesterification reaction is carried out at a temperature comprised between 25°C and 150°C, more preferably between 40°C and 120°C and advantageously between 60°C and 110°C.

[0115] Preferably, the transesterification reaction is carried out for a period of from 5 minutes to 2 hours, more preferably from 10 minutes to 1 hour, advantageously from 20 minutes to 40 minutes.

[0116] "Carbonation exchange reaction" means a reaction in which the organic groups R and R' of a carbonate functional group RO-C(O)-OR' of a compound are exchanged with the organic groups R" and R'" of alcohols R"OH and R'"OH to give a compound containing another carbonate functional group R'"OC(O)-OR" and alcohols ROH and R'OH.

[0117] According to one embodiment, the transesterification reaction further comprises a decantation step followed by a filtration step. The insoluble portion corresponds to a composition that can be recycled and reused as described above. After filtration, the resulting solution can be evaporated to remove excess compounds that contain at least one OH functional group. The excess compounds can be recycled and reused in further transesterification reactions.

[0118] Thanks to the use of the composition according to the invention as catalyst, transesterification can be carried out on substrates containing unsaturation, for example polyunsaturated triglycerides or esters of formic acid containing at least one unsaturation, whereas conventional methods of transesterification are not adapted to such substrates. This is due to the fact that the conditions are mild and do not require harsh treatment of the reaction mixture. More generally, the transesterification reaction according to the invention has the following advantages: 1 / heterogeneous catalysis with recyclable catalysts (very rare); 2 / low catalyst loading; 3 / free of hydroxides and therefore no soap formation (common when KOH or NaOH are used); 4 / compatible with mild conditions (temperature and pressure) and fragile substrates; 5 / fast reaction; 6 / quantitative yields are obtained even when the alcohol is EtOH (very rare, the reaction is often limited to the use of methanol with triglycerides), therefore the transesterification according to the invention makes it possible to obtain 100% bio-based fatty acid esters, which is not possible with MeOH, since it is not available in a bio-based form); 7 / 100% bio-based process.

[0119] According to one embodiment, the transcarbonation is a reaction between a compound containing an alcohol functional group as described above and a compound of formula

[24] , [ka] In the formula, R 27 and R 28 are independently linear, cyclic or branched, saturated or unsaturated, optionally substituted, hydrocarbon groups containing 1 to 8 carbon atoms. 27 and R 28 is a saturated linear hydrocarbon group containing from 1 to 8 carbon atoms, advantageously an ethyl group.

[0120] Preferably, the compound containing an alcohol function is a polyol, advantageously glycerol.

[0121] Preferably, the transcarbonation reaction is carried out at atmospheric pressure and at a temperature comprised between 25°C and 200°C, more preferably between 80°C and 180°C and advantageously between 130°C and 160°C.

[0122] Preferably, the transesterification reaction is carried out for a period of from 10 minutes to 2 hours, more preferably from 30 minutes to 75 minutes, advantageously from 30 minutes to 1 hour.

[0123] Preferably, the functional group exchange reaction is carried out in the presence of a composition in an amount corresponding to 0.01 to 5.0 equivalents, preferably 0.02 to 2.5 equivalents, more preferably 0.05 to 1.5 equivalents of K relative to the limiting reactant.

[0124] According to one embodiment, oxidative hydroxylation is a reaction between a compound containing a phenone or benzaldehyde moiety and an oxidizing agent, preferably hydrogen peroxide.

[0125] Preferably, the phenone or benzaldehyde moiety contains an OH group in the ortho or para position to the ketone or aldehyde group.

[0126] Preferably, the oxidative hydroxylation is carried out in the presence of a composition in an amount corresponding to 0.01 to 0.3 equivalents, preferably 0.05 to 0.1 equivalents of K relative to the compound containing a phenone or benzaldehyde moiety.

[0127] Preferably, the oxidative hydroxylation is carried out for a period of from 1 hour to 5 hours, more preferably from 2.5 hours to 3.5 hours.

[0128] Preferably, the oxidative hydroxylation is carried out at a temperature comprised between 15°C and 30°C.

[0129] According to one embodiment, the aldolization / crotonization and similar reactions and / or functional group exchange reactions and / or oxidative hydroxylation are carried out under microwaves.

[0130] The present invention also relates to a method for preparing methyl dihydrojasmonate, comprising the steps of: a) reacting cyclopentanone with pentanal in the presence of the composition according to the present invention to obtain a compound of formula

[28] ; [ka] b) isomerizing the compound of formula

[28] , preferably in the presence of an acid, to obtain a compound of formula

[29] ; [ka] c) reacting a compound of formula

[29] with dimethyl malonate in the presence of the composition according to the present invention to obtain a compound of formula

[30] ; [ka] d) Decarboxylation of the compound of formula

[30] , preferably under microwave conditions, to obtain methyl dihydrojasmonate.

[0131] Preferably, step a) is an aldolization / crotonization reaction according to the invention. Preferably, step a) is carried out under microwaves. Preferably, step a) is carried out in the absence of any organic solvent.

[0132] Preferably, step b) is carried out at a temperature comprised between 100°C and 200°C, preferably between 120°C and 180°C, more preferably between 130°C and 170°C. Preferably, step b) is carried out for a period comprised between 30 minutes and 3 hours, more preferably between 75 minutes and 2 hours and 30 minutes. Preferably, step b) is carried out in the presence of glycerol. Preferably, the amount of glycerol is comprised between 0.05 and 12 equivalents, more preferably between 0.1 and 8 equivalents, advantageously between 0.2 and 5 equivalents relative to the molar amount of compound

[28] .

[0133] Preferably, step b) is carried out in the presence of an acid. Preferably, the amount of acid is 0.005-0.5 equivalents, more preferably 0.01-0.3 equivalents, advantageously 0.02-0.15 equivalents relative to the molar amount of compound

[28] . Preferably, the acid is selected from the list consisting of oxalic acid, citric acid, tartaric acid, polyphosphoric acid, thiamine hydrochloride and betaine hydrochloride, preferably polyphosphoric acid and betaine hydrochloride.

[0134] Alternatively or in combination, step b) is preferably carried out under microwaves.

[0135] Preferably, step c) is a 1,4-nucleophilic addition reaction according to the invention. Preferably, step c) is carried out in the absence of organic solvents, more preferably by mechanosynthesis.

[0136] Preferably, step d) is carried out at a temperature comprised between 180° C. and 300° C., more preferably between 230° C. and 270° C. Preferably, step d) is carried out for a period comprised between 15 minutes and 2 hours, more preferably between 45 minutes and 75 minutes. Preferably, step d) is carried out in the presence of succinic acid.

[0137] At the end of step d), methyl dihydrojasmonate is obtained as a mixture of cis and trans isomers.

[0138] The two cis isomers of methyl dihydrojasmonate are shown below: [ka]

[0139] The two trans isomers of methyl dihydrojasmonate are shown below: [ka]

[0140] According to the present invention, the amount of cis isomers refers to the amount of the two cis isomers relative to the amount of the two cis isomers and the two trans isomers.

[0141] According to the present invention, the amount of trans isomer refers to the amount of the two trans isomers relative to the amount of the two cis isomers and the two trans isomers.

[0142] Preferably, the methyl dihydrojasmonate obtained at the end of step d) contains at least 10 mol %, preferably at least 15 mol %, more preferably at least 19 mol %, advantageously between 19 mol % and 20 mol % of the cis isomer relative to the total molar amount of cis and trans isomers.

[0143] The preparation method of methyl dihydrojasmonate according to the present invention has the following advantages: - Most of the catalysts, reagents and substrates are biosourced; -Does not contain non-biological solvents; -Limiting reaction processes and therefore reducing waste formation; -Each step involves the latest green chemistry techniques to control the stereoselectivity of the reaction and shorten the reaction time. - reducing the number of steps, the conversion of compound 4 to methyl dihydrojasmonate can be carried out in one step (without toxic solvents such as DMSO) and does not require the usual sequence of saponification / protonation / decarboxylation / esterification; does not involve the use of corrosive and aggressive reagents during step b), since commonly used catalysts based on HCl (used in the patented process by Firmenich) or Pd or Rh are replaced by glycerol, a cheap and biosourced by-product; and - controlling the stereoselectivity during step c) since the conditions developed make it possible to obtain methyl dihydrojasmonate containing at least 10% of the cis isomer.

[0144] The present invention also relates to the use of the composition according to the invention as a catalyst for chemical synthesis reactions.

[0145] Preferably, the chemical synthesis reaction is selected from the group consisting of 1,4-nucleophilic addition, aldolization / crotonization and similar reactions, transesterification reactions and oxidative hydroxylation reactions.

[0146] The invention will be better understood on reading the following non-limiting examples. EXAMPLES

[0147] Example 1: Mineral composition of some plant species

[0148] The mineral composition of some plant parts is determined by MP-AES after heat treatment under air flow at 550 °C for 4 h. MP-AES analysis was performed with metal analysis of total dissolved solutes in water. Samples were digested in 10 mL of inverse aqua regia (1:2 hydrochloric acid (37%):nitric acid (65%)) under microwave-assisted digestion (Multiwave-Go Anton Paar) with the following program: 20–165 °C for 20 min, then isothermal at 165 °C for 10 min. Samples were filtered and then soaked in 1% aqueous nitric acid to obtain 0.4 mg L -1 The mineral composition was determined by using a microwave plasma atomic emission spectrometer (MP-AES) 4200 (Agilent Technologies) equipped with a concentric nebulizer and a double-pass cyclonic spray chamber. The pump speed during the analysis was kept at 10 rpm and the sample introduction tube diameter was 0.89 mm. The analysis cycle consisted of a 30 s wash with 1% aqueous nitric acid solution, followed by a 25 s sample uptake (pump speed 40 rpm) and then a 20 s equilibration before reading at a preselected integration time (pump speed 10 rpm). The integration time was set to 3 s for all elements. The automatic background correction mode available in the software was used unless otherwise stated. All analytical results were performed in triplicate.

[0149] The following results were obtained: The content of each metal in each sample is specified as a weight percent relative to the weight of the composition, more or less, and a % standard deviation relative to the value indicated.

[0150] [Table 1]

[0151] [Table 2]

[0152] [Table 3]

[0153] Example 2: Preparation of the catalyst

[0154] The plant seeds are harvested and heat treated at 550°C for 4 hours under air flow. The resulting residue can be used directly as a catalyst. The process is exactly the same as that described in Example 1 above. Therefore, all the compositions described in Example 1 above are compositions according to the present invention and can be used as catalysts.

[0155] EcoKOx-Fj-(1) is further subjected to the following additional treatments: EcoKOx-Fj-(1) is stirred in water at room temperature for 3 hours. The mixture is then filtered on a sintered material with a porosity of 3. The solid residue is washed with 3 x 50 ml of water and dried in an oven at 80 °C. Then, a controlled heat treatment in air (25 °C to 350 °C and 550 °C for 4 hours) is performed to obtain EcoKOx-Fj-(1). * (7.12 g) was obtained. Meanwhile, the filtrate was evaporated in the open air to obtain vegetable KHCO 3 Further heat treatment (25°C to 200°C and 250°C for 2 h) results in Fj-(1) (7.1 g). 2 CO 3 Give Fj-(1).

[0156] The same process was applied to EcoKOx-Fj-(2), and plant-derived KHCO 3 Fj-(2) and plant K 2 CO 3 Fj-(2) was obtained and applied to EcoKOx-Ad-(1), and plant-derived KHCO 3 Ad-(1) and plant K 2 CO 3 Ad-(1) was obtained.

[0157] The metal compositions of some of these materials were analyzed by MP-AES and are shown below.

[0158] [Table 4]

[0159] Example 3: Structural characterization of the composition

[0160] EcoKOx-Fj-(2), vegetable KHCO 3 Fj-(2), vegetable K 2 CO 3 Fj-(2) was analyzed by XRD to detect heterogeneous species contained in these compositions.

[0161] X-ray diffraction (XRD) data measurements were performed using a BRUKER diffractometer (D8 Advance, using CuKα radiation λ=1.54086 Å) equipped with a Lynxeyes detector. Diffraction patterns were analyzed using DIFFRAC-EVA software and several XRD databases (Crystallography Open Data Base 2016, and PDF2011, 2017 or 2018).

[0162] The results are shown in the table below.

[0163] [Table 5]

[0164] The originality of the compositions obtained from Japanese knotweed is particularly evident in Fairchildite: 2 Ca(CO 3 ) 2 , a basic substance that is very difficult to obtain by conventional chemical synthesis.

[0165] Additional crystalline salts of EcoKOx-Fj-(2) were detected by EDS-EBSD, a combination of chemical data from energy dispersive X-ray spectroscopy (EDS) and crystallographic data from electron backscatter diffraction (EBSD).

[0166] [Table 6]

[0167] Each catalyst exhibits a polymetallic structure. Whatever the method of characterization, these compositions represent atypical basic salts, most of which are little known in organic synthesis.

[0168] Example 4: Michael-type nucleophilic addition

[0169] device: For mechanosynthesis: Planetary ball mill equipment reference TMAX-XQM-12 or RETSCH PM100.

[0170] For microwave synthesis: 1) Anton Paar Reactor = Anton Paar Multiwave Go TM is a microwave digestion system. A single magnetron delivers 850 W of microwave power with a magnetron frequency of 2455 W. The maximum temperature is up to 250 °C. The vessel temperature is continuously monitored with an IR temperature sensor. Rotor 12 HVT50 (rotor speed > 5 rpm) is fitted with a PTFE-TFM HVT50 (V min = 3 mL, V max = 25mL, P max The reactor is placed in a 100-milliliter (100-milliliter) casing along with twelve high performance pressure activated vent vessels (50 mL) made to a pressure of 100 psi (20 bar). 2) CEM Discover2.0 Microwave = Microwave Accelerated Reaction System for Synthesis, Single Mode Microwave Cavity, 240V, 50 / 60Hz, 5A-300W- Magnetic Stirring (Variable Speed)- Widest Pressurized Pyrex® Vessel Sizes (10mL, Vmin=0.2mL, Vmax=7mL, Pmax=30bar, Tmax=300°C; 35mL, Vmin=2.0mL, Vmax=25mL, Pmax=20bar, Tmax=300°C; 100mL, Vmin=15mL, Vmax=70mL, Pmax=17bar, Tmax=250°C)- iWave™ Temperature Sensor, Activent™ Technology for releasing unwanted gaseous by-products from the reaction. 3) MARS 6, 240V / 50Hz, characteristics: Mars 6 synthesis, multimode platform 1800W - Magnetic stirring with variable speed at pressures up to 55 bar - Fiber optic temperature control - Passing cavity for cooling fluids on flasks from 250mL to 5L - Possibility of working with a carousel.

[0171] Example 4.1 The loading of various Michael donors onto various Michael acceptors was tested under several conditions and is summarized in the table below. [ka]

[0172] [Table 7]

[0173] Protocol: In a 25 mL vessel filled with 1 / 3 of a 5 mm diameter stainless steel bead, the molecule [2] (R 3 Add the catalyst (1 equivalent to 10 equivalents depending on the amount) and molecule [1] (1 equivalent). The reaction mixture is milled at a rotation speed of 500 rpm (8.33 Hz) for a given time (see Table 7) with a rest interval of 10 minutes every hour. The reaction medium is dissolved in ethyl acetate and filtered through cellulose. After distillation to recover the excess molecule [2], the crude reaction can be used directly in the decarboxylation reaction, if desired.

[0174] Example 4.2: Catalyst Recycling

[0175] The ability to recycle EcoKOx-Fj-(2) was evaluated. Once filtered, the catalyst was heat treated in air (25°C, then 350°C, then 550°C for 4 hours). R 4 =R 5 =OMe molecule [2] (1 equivalent) and R 1 and R 2 to form a cyclopentyl group, and R 3 =H molecule [1] (1 eq.) is added to the recycled EcoKOx-Fj-(2) (0.8 K eq.). The reaction mixture is ground for 2 h at a rotation speed of 500 rpm (8.33 Hz) with a rest interval of 10 min every hour. The reaction medium is dissolved in ethyl acetate and filtered through cellulose. The following results are obtained:

[0176] [Table 8]

[0177] Even after recycling four times, the catalyst performance remains the same.

[0178] Example 4.3: Michael-type tandem nucleophilic addition / aldol condensation / decarboxylation [ka]

[0179] [Table 9]

[0180] Protocol 3: In a 50 mL Teflon reactor, the catalyst (486 mg, 0.14 mmol K, 0.05 equiv K), molecule [5] with R9 = -Me and R10 = -OMe (3.2 mL, 30 mmol, 1 equiv), molecule [4] with R6 = -Me, R7 = R8 = -H (2.5 mL, 30 mmol, 1 equiv) and glycerol (4.5 mL, 60 mmol, 2 equiv) are added. The Teflon reactor is then placed in an Anton Paar microwave reactor and the process starts with a 5 min temperature ramp in single reactor mode, reaching a plateau at 120 °C for 45 min. The organics are extracted with ethyl acetate (3 x 20 mL) and the glycerol is washed with water (20 mL). The final product is distilled under vacuum (Eb=42° C. at P=0.0014 mbar, 3.17 g, 28.8 mmol, Rdt=96%).

[0181] Protocol 4: In a 50 mL Teflon reactor, the catalyst (237 mg, 1.03 mmol Keq, 0.03 Keq), molecule [5] with R9=Me and R10=OMe (3.4 mL, 30 mmol, 1 eq), molecule [4] with R6=R7=R8=H (2 mL, 30 mmol, 1 eq), and glycerol (4.5 mL, 60 mmol, 2 eq) are added. The Teflon reactor is then placed in an Anton Paar microwave reactor and the process starts with a 10 min temperature ramp in single reactor mode, reaching a plateau at 150 °C for 2 h 30 min. The organics are extracted with ethyl acetate (3 × 20 mL) and the glycerol is washed with water (20 mL). The final product is distilled under vacuum (2.36 g, Eb 1.4 mbar=20-22° C., 24.6 mmol, Rdt=82%).

[0182] Since acrolein and ethyl acetoacetate are available in natural form, the use of the composition according to the invention as a bio-based catalyst results in 100% bio-based cyclohexenone.

[0183] Example 5: Aldolization / crotonization and similar reactions

[0184] Example 5.1 Crossed aldol / cetol condensations between several reagents were carried out and the results are summarized in the table below. [ka]

[0185] [Table 10]

[0186] Protocol 6: The reaction is divided into twelve 50 mL Teflon reactors. To each reactor, the catalyst, cyclopentanone [9] and valeraldehyde

[10] are added. The Teflon reactors are then placed in an Anton Paar microwave reactor (without stirring) and the process is started in multi-reactor mode with a 5 min temperature ramp and reaches a plateau at 120 °C for 1 h 30 min. The reaction mixture is pooled and filtered on a sinter (pore size 4) with ethyl acetate (100 mL), which is evaporated under a vacuum of 400 mbar at a bath temperature of 25 °C (Buchi B-100, Vacuum Brand Pump). A first distillation is carried out to isolate the excess [9] (cyclopentanone) (61 mL, E b 98 mbar = 58-61 °C, 690 mmol, 76% recovery). A second distillation is carried out to isolate 2-pentylidene-cyclopentanone

[12] (17.8 g, E b 1.3mbar=65℃, 118mmol, Rdt=52%).

[0187] Protocol 7: In a 100 mL microwave reactor, add the catalyst, cyclopentanone [9] (56 mL, 0.633 mmol, 5 eq.) and valeraldehyde

[10] (14 mL, 0.132 mol, 1 eq.). The reaction mixture is subjected to a CEM Discover 2.0 microwave reactor at 120° C. for 5 min, then at 150° C. for 25 min (speed=slow). This operation is repeated 9 times. The reaction mixture is filtered under vacuum and washed with ethyl acetate (250 mL). The solvent is evaporated under vacuum. (2Z)-2-pentylidenecyclopentanone

[12] is obtained after vacuum distillation in 56% yield (101 g, 663 mmol).

[0188] Protocol 8: In a 100 mL microwave reactor, 2 CO 3 (450 mg, 3.26 mmol, 0.2 equiv), cyclopentanone [9] (8.7 mL, 94.12 mmol, 5 equiv) and valeraldehyde

[10] (2 mL, 18.8 mmol, 1 equiv) are added. The reaction mixture is subjected to a CEM Discover 2.0 microwave at 120° C. for 5 min, then at 150° C. for 25 min (speed=fast).

[0189] Example 5.2: Knoevenagel-type reaction [ka]

[0190] [Table 11]

[0191] Protocol: In a 50 mL Teflon reactor, catalyst (237 mg, 2.1 mmol K, 0.07 equiv.), methyl acetoacetate (3.4 mL, 30 mmol, 1 equiv.), benzaldehyde (3 mL, 30 mmol, 1 equiv.), and glycerol (4.5 mL, 60 mmol, 2 equiv.) were added. The Teflon reactor was then placed in an Anto Paar microwave and the process started with a 10 min temperature ramp in single reactor mode, reaching a plateau at 150° C. for 2.5 h. Approximately 28% of the benzaldehyde is converted to 4-phenyl-3-buten-2-one.

[0192] Example 5.3: Dieckmann reaction [ka]

[0193] [Table 12]

[0194] Protocol: In a 10 mL Teflon reactor, catalyst (14 mg, 0.12 mmol, 0.05 equiv.), dimethyl adipate (410 μL, 2.5 mmol, 1 equiv.) and glycerol (205 μL, 2.5 mmol, 1 equiv.) were added. The Teflon reactor was then placed in an Anton Paar microwave at 250° C. for 1 h. The conversion was quantitative. No by-products were detected.

[0195] Example 6: Functional group exchange reaction

[0196] Example 6.1: Transesterification

[0197] Transesterification of fatty acid esters was carried out as shown below. [ka]

[0198] [Table 13]

[0199] Protocol: In a 10 mL flask equipped with a distillation system, under nitrogen, the catalyst (116 mg, 1.05 mmol in K, 0.07 eq in K), geranyl formate (3 mL, 15 mmol, 1 eq) and anhydrous methanol (6 mL, 150 mmol, 10 eq) were introduced. The reaction was heated at 60° C. for 3 h. The methyl formate formed was distilled off as the reaction proceeded (533 mg, 8.9 mmol, 59% recovery). At the end of the reaction, the reaction crude was filtered. Evaporation of the methanol under vacuum gave geraniol (2.28 g, 14.8 mmol, Rdt=98%).

[0200] Transesterification of vegetable oils was also carried out as shown below. [ka]

[0201] [Table 14]

[0202] All yields are based on HPLC-UV data referenced to authentic compounds.

[0203] When ethanol is replaced by methanol, the reaction is completed after 15 minutes instead of 5 hours in a conventional batch mode. With 0.5 equivalents of catalyst, the reaction leads to mono-transesterification after 30 minutes, which allows the preparation of diglycerides.

[0204] Protocol 11: In a 35 mL microwave reactor equipped with a magnetic bar, catalyst (682 mg, 3 mmol K, 1 eq K), oil (3 mmol, 1 eq) and ethanol (2 mL, 34 mmol, 11 eq) are introduced. The reaction mixture is pre-stirred for 2 min and then introduced into a microwave-activated CEM Discover 2.0 reactor with a 2 min temperature ramp up to 100° C. for 30 min (with stirring).

[0205] Protocol 12: In a 35 mL microwave reactor equipped with a magnetic bar, the catalyst (22 mg, 0.15 mmol K, 0.05 eq.), oil (3 mmol, 1 eq.) and ethanol (2 mL, 34 mmol, 11 eq.) are introduced. The reaction mixture is pre-stirred for 2 min and then introduced into a microwave-activated CEM Discover 2.0 reactor with a 2 min temperature ramp up to 100° C. for 30 min (with stirring).

[0206] Example 6.2: Transcarbonation reaction

[0207] The transcarbonation reaction was carried out as shown below. [ka]

[0208] [Table 15]

[0209] Protocol: In a 10 mL microwave reactor equipped with a magnetic bar, the catalyst (70.8 mg, 0.543 mmol K, 0.05 equiv K), glycerol (1 g, 10.86 mmol, 1 equiv), and diethyl carbonate (1.3 mL, 10.86 mmol, 1 equiv) are introduced. The reaction mixture is pre-stirred for 2 min and then introduced into a CEM Discover 2.0 microwave reactor for 45 min with a temperature gradient of 2 min to 150 °C. The conversion of glycerol to 4-hydroxymethyl-1,3-dioxolan-2-one is assessed by HPLC, showing a conversion of 85%. The reaction mixture is diluted in ethyl acetate and washed with water. The organic phase is collected and washed with anhydrous MgSO 4 The solvent is removed on a rotary evaporator and the reaction mixture is dried under vacuum.

[0210] Example 7: Oxidative Hydroxylation Reaction

[0211] Oxidative hydroxylation of para-hydroxybenzaldehyde was carried out as shown below. [ka]

[0212] [Table 16]

[0213] Protocol: In a 10 mL flask, add molecule [7] (1.22 g, 10 mmol, 1 equiv.) with R12 = R13 = R15 = R16 = -H and R14 = -OH, 40% w / v hydrogen peroxide (1.5 mL), catalyst (158 mg, 0.68 mmol K, 0.07 equiv. K). The reaction mixture is stirred at room temperature for 3 h. The organic product is washed with water (3 x 20 mL) and extracted with ethyl acetate (3 x 20 mL). The organic phases are pooled and the ethyl acetate is evaporated under vacuum. Hydroquinone is obtained with 82% conversion.

[0214] Example 8: Synthesis of methyl dihydrojasmonate

[0215] The synthesis of methyl dihydrojasmonate was carried out by the following process: a) reacting cyclopentanone with pentanal according to entries 42-46 of Table 10 to obtain compound

[28] ; b) carrying out isomerization of compound

[28] to obtain compound

[29] ; c) Reacting compound

[29] with dimethyl malonate according to entries 8-12 or 14-15 of Table 7 to give compound

[30] . After decarboxylation,

[29] and

[31] are easily separated by distillation.

[29] can be used in another Michael addition. d) Decarboxylation of compound

[30] , preferably under microwave conditions, to obtain methyl dihydrojasmonate. [ka]

[0216] Isomerization protocol (step b): Protocol 1: 2-Pentylidenecyclopentanone

[28] , glycerol and acid (polyphosphoric acid or betaine hydrochloride, 1 equivalent) are added in a batch reactor. The reaction mixture is stirred at 180 °C for 2 h. The organic phase is then extracted with ethyl acetate and washed with water. The organic phase is washed with anhydrous MgSO 4 The mixture is dried at rt and then evaporated in vacuum. The amounts of reagents and associated isolated yields are given in the table below.

[0217] [Table 17]

[0218] Protocol 2: The reaction is divided into 12 x 50 mL Teflon reactors. To each of the reactors, 2-pentylidenecyclopentanone

[29] (1 mL, 6.57 mmol, 1 eq.) and glycerol (5 mL, 67.9 mmol, 10 eq.) are added. The Teflon reactors are then placed in an Anton Paar microwave and the process starts with a 5 min temperature ramp in multi-reactor mode, reaching a plateau at 150 °C for 2 h. The reaction mixtures are combined, extracted with ethyl acetate (200 mL) and washed with water (200 mL). The organic phase is diluted with anhydrous MgSO 4 The mixture is dried at 40° C. and then evaporated under vacuum (Buchi B-100, vacuum brand pump). 2-Pentylcyclopent-2-en-1-one is obtained as a brown oil (11.4 g, yield=95%). The crude product

[30] is used directly in the next step.

[0219] Decarboxylation protocol (step d): In a 100 mL CEM Discover 2.0 microwave reactor equipped with a magnetic bar, product

[30] (10 g, 35.2 mmol, 1 equiv.) and succinic acid (8.30 g, 70.3 mmol, 2 equiv.) are added. The reaction mixture is microwaved for 1 h with a 2 min gradient to 250 °C. The product

[31] is obtained after distillation (E b 7.10-2mbr =95-96℃).

[0220] Both the aldolization / crotonization step and the Michael addition step were carried out using all compositions according to the invention, i.e. the catalysts EcoKOx-Fj-(X), EcoKOx-Sa-(X), EcoKOx-Ad-(X), plant-derived KHCO 3 and plant-based K 2 CO 3 This can be implemented using:

[0221] Example 9: Comparison of EcoKOx-Fj composition with a commercial mixture of potassium salts

[0222] The aldolization / crotonization of Example 8 was carried out using EcoKOx-Fj-(2) or K 2 CO 3The experiment was carried out in the presence of a 1:1 mixture of HCl / KCl under the following conditions: a) Catalyst (EcoKOx-Fj-(2), 0.2 K equiv.), cyclopentanone (56 mL, 0.68 mol, 5 equiv.), valeraldehyde (14 mL, 0.13 mol, 1 equiv.) at 160 °C for 15 min under microwave. b) K 2 CO 3 (260 mg, 1.88 mmol, 0.2 equiv), KCl (140 mg, 1.88 mmol, 0.2 equiv), cyclopentanone (4.2 mL, 3.92 mmol, 5 equiv), valeraldehyde (1 mL, 9.4 mmol, 1 equiv), 160 °C for 15 min in microwave.

[0223] The results are summarized in the table below.

[0224] [Table 18]

[0225] The composition EcoKOx-Fj-(2) obtained from the above-ground parts of the plant is more interesting from a catalytic point of view than the mixture of commercial salts, in particular thanks to its polymetallic nature: this composition makes it possible to obtain a total conversion of valeraldehyde and a much higher selectivity.

Claims

1. K ２ CO ３ , KCl, and optionally K ２ SO ４ and / or KHCO ３ wherein the weight content of potassium is between 9.0 and 60.0% by weight, preferably between 10.0 and 50.0%, more preferably between 10.0 and 40.0%, advantageously between 20.0 and 40.0%, relative to the total weight of the composition.

2. 10. The composition of claim 1 further comprising sodium, calcium and magnesium.

3. 3. The composition of claim 1 or 2, further comprising iron and aluminum.

4. Calcium hydroxide Ca(OH) ２ 3. The formulation of claim 1 or 2, which is substantially free of:

5. 3. The composition according to claim 1, characterized in that it is substantially free of platinoids, in particular Pt, Pd or Rh, and / or rare earths, in particular Ce, Eu and Yb; and / or metals selected from the group consisting of metals, in particular B, Ge, As, Sb and Te.

6. 3. The composition of claim 1, wherein the composition is substantially free of a transition metal selected from the group consisting of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and Cd.

7. 3. A method for preparing a composition according to claim 1 or 2, said method comprising: - selecting a plant, wherein the heat-treated above-ground part of said plant contains 10.0 to 40.0% by weight of potassium; - heat treating the above-ground parts of the plant in air at a temperature between 450°C and 650°C; - obtaining said composition, A method comprising:

8. 8. The method according to claim 7, characterized in that it does not comprise a step of acid treatment, and / or does not comprise a base treatment, and / or does not comprise a purification step, such as ion exchange resins, liquid-liquid extraction, selective precipitation or liquid / solid extraction, and / or does not comprise an activation step.

9. 8. The method according to claim 7, wherein the plant belongs to the genus Bindweed, Salix or Salix.

10. 10. A method for carrying out a chemical synthesis reaction comprising contacting the composition of claim 1 or 2 with a reactant of the chemical synthesis reaction, wherein the chemical synthesis reaction is selected from the group consisting of 1,4-nucleophilic addition, aldolization / crotonization and similar reactions, functional group exchange reactions, and oxidative hydroxylation reactions.

11. 11. The method according to claim 10, characterized in that the step of contacting said composition with the reactants of the 1,4-nucleophilic addition is carried out in the absence of organic solvents, preferably in the absence of any solvent, more preferably by mechanosynthesis or under microwaves, advantageously by mechanosynthesis.

12. 11. The method according to claim 10, characterized in that the 1,4-nucleophilic addition is carried out in the presence of a composition in an amount corresponding to 0.01 to 5 equivalents, preferably 0.05 to 4 equivalents, more preferably 0.1 to 3 equivalents, advantageously 0.1 to 2.5 equivalents of K relative to the limiting reactant.

13. 11. The method of claim 10, wherein the chemical synthesis reaction comprises a 1,4-nucleophilic addition followed by an aldolization / crotonization reaction followed by a decarboxylation reaction.

14. The method according to claim 10, characterized in that the aldolization / crotonization reaction and similar reactions are carried out in the presence of a composition in an amount corresponding to 0.01 to 2.0 equivalents, preferably 0.02 to 1.0 equivalents, more preferably 0.05 to 0.5 equivalents of K relative to the limiting reactant.

15. The method according to claim 10, characterized in that the functional group exchange reaction is carried out in the presence of a composition in an amount corresponding to 0.01 to 5.0 equivalents, preferably 0.02 to 2.5 equivalents, more preferably 0.05 to 1.5 equivalents of K relative to the limiting reactant.

16. 11. The method according to claim 10, characterized in that the aldolization / crotonization and similar reactions, and / or the functional group exchange reaction, and / or the oxidative hydroxylation reaction are carried out under microwave conditions.

17. 1. A method for preparing methyl dihydrojasmonate, said method comprising: a) reacting cyclopentanone with pentanal in the presence of the composition of claim 1 or 2 to obtain a compound of formula [28]; 【Chemistry 1】 b) isomerizing the compound of formula [28], preferably in the presence of an acid, to obtain a compound of formula [29]; 【Chemistry 2】 c) reacting the compound of formula [29] with dimethyl malonate in the presence of the composition according to claim 1 or 2 to obtain a compound of formula [30]; 【Transformation 3】 d) decarboxylation of the compound of formula [30], preferably under microwave conditions, to obtain methyl dihydrojasmonate; A method comprising:

18. 3. Use of the composition according to claim 1 or 2 as a catalyst for chemical synthesis reactions.

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