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EP3043906A1 - Verwendung bestimmter organischer materialien mit alkali- oder alkalierdmetallen zur durchführung organochemischer reaktionen - Google Patents

Verwendung bestimmter organischer materialien mit alkali- oder alkalierdmetallen zur durchführung organochemischer reaktionen

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Publication number
EP3043906A1
EP3043906A1 EP14796167.6A EP14796167A EP3043906A1 EP 3043906 A1 EP3043906 A1 EP 3043906A1 EP 14796167 A EP14796167 A EP 14796167A EP 3043906 A1 EP3043906 A1 EP 3043906A1
Authority
EP
European Patent Office
Prior art keywords
calcium
plant
alkaline earth
earth metal
alkali
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14796167.6A
Other languages
English (en)
French (fr)
Inventor
Claude Grison
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite de Montpellier
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Montpellier
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR1358799A external-priority patent/FR3010329A1/fr
Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Montpellier filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3043906A1 publication Critical patent/EP3043906A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/36—Biochemical methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/232—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to the use of materials of organic origin that is to say bio-based materials containing alkaline or alkaline-earthy, preferably calcium for the implementation of chemical reactions.
  • WO 2011/064487 describes in particular the use of Thlaspi c erulescens now called Noccaea c erulescens and Anthyllis vulneraria as well as that of many other metallophyte plants hyperaccumulative heavy metals for the preparation of catalysts used in organic chemistry.
  • the invention described in WO 201 1/064487 relates to the use of a calcined plant or part of a calcined plant having accumulated at least one metal in M (II) form chosen especially from zinc ( Zn), nickel (Ni) or copper (Cu) in which said plant is chosen in particular from the family Brassicaceae, including species of the genus Thlaspi (noccacea) in particular T. goesingense, T. tatrense, T. rotundifolium, T. praecox, species of the genus Arabidopsis, in particular Arabidopsis hallerii, and of the genus Alyssum, in particular A. bertolonii, A.
  • M (II) form chosen especially from zinc ( Zn), nickel (Ni) or copper (Cu) in which said plant is chosen in particular from the family Brassicaceae, including species of the genus Thlaspi (noccacea) in particular T. goesingense, T. tatrense,
  • serpyllifolium Fabaceae, Sapotaceae, in particular the species Sebertia acminata, Planchonella oxyedra, Convolvulaceae, in particular the species Ipomea alpina, Planchonella oxyedra, Rubiaceae, especially the species Psychotriaticianrrei, in particular P. costivenia, P. denmentis, P. vanhermanii, Cunoniaceae, especially the Geissois, Scrophulariaceae, in particular species of the genus Bacopa, in particular Bacopa monnieri, algae, in particular red algae, in particular rhodophytes, more particularly Rhodophyta bostrychia, green algae or brown algae.
  • the plants of the genus Sedum are succulent plants that belong to the crassulaceae family, composed of more than 400 species. They have natural abilities to grow on poor, dry, open soil and difficult conditions. Their foliar system is fleshy and their crops are well-off.
  • Sedum plumbizincicoica and Sedum jinianum have a remarkable ability to extract zinc from polluted soils in southern and eastern China. They have a real potential in phytoextraction and are called "plumbizincicolafor".
  • the alkali or alkaline earth metals according to the invention and in particular calcium, used preferably in the form of salts or hydroxides can be used as reagents or as catalysts.
  • the catalysts or reagents used in the practice of the present invention are basic catalysts.
  • Lemnaceae eg, duckweed
  • Padina eg, Padina
  • Polygonaceae (ex: rhubarb, all the rumex, red algae:
  • knotweed ex: Liagoraceae
  • Plantaginaceae eg large plantain
  • Plantaxaura / Dichotomaria Plantaginaceae (eg large plantain) (Galaxaura / Dichotomaria);
  • Pontederiaceae (ex: Pontederia cor data)
  • Corallinaceae (Amphiroa, Jania) Onagraceae (ex: Jussie creeping); (rhodoliths); Lithothamnium (or Portulacaceae (eg common purslane) lithothamne)
  • Foams such as bryophyte foams:
  • Mushrooms such as polypores
  • Non-calcifying algae but rich in Ca are non-calcifying algae but rich in Ca:
  • Brown algae such as the family Alariaceae: example Undaria pinnatifida (or sea fern), Alaria esculenta, Alaria marginata, Undaria distans, Laminaria digita, Laminaria saccharina
  • Palmariaies family example Palmaria palmata, family of gigartinaceae example: Chondrus crispus, family of Bangiophyceae,
  • the present invention therefore relates to the use as catalyst of materials of organic origin containing alkali or alkaline earth metals, preferably calcium for the implementation of organic synthesis reactions involving said basic catalyst.
  • the present invention therefore also relates to the use as catalyst of materials of organic origin containing alkali or alkaline earth metals, preferably calcium and substantially free of transition metals, metalloids and post-transition metals for the implementation of organic synthesis reactions involving said catalyst.
  • the post-transition metals also called poor metals constitute a metallic element of the block p in the periodic table.
  • This block includes the following metals: Aluminum, Gallium, Indium, Tin, Thallium, Lead, Bismuth, Polonium, Flérovium.
  • catalyst employed can also be used in the reactive sense. Given the nature of the reactions implemented in the present invention, the two words can be used indifferently.
  • basic catalysis is preferably meant the use of a catalyst such as the carbonate or oxide of an alkali or alkaline earth metal which is preferably calcium.
  • a catalyst such as the carbonate or oxide of an alkali or alkaline earth metal which is preferably calcium.
  • the plants used in the practice of the invention according to the present application contain calcium in oxalate form.
  • the heat treatment of calcium oxalate leads to calcium carbonate or calcium oxide depending on the temperature of the treatment carried out (see for example the preparation of catalysts A6a and A6b below).
  • calcifying algae and shells contain calcium carbonate.
  • the present invention therefore also relates to the use of extracts of a plant or part of a plant, preferably a plant or part of a plant, an algae or a part of a plant.
  • a high level of alkali or alkaline earth metal preferably calcium (Ca)
  • Ca calcium
  • the present invention therefore also relates to the use indicated above characterized in that the materials of organic origin come from a plant or a part of a plant, preferably a plant or a part of plant, an alga or a portion of alga containing an alkali metal or alkaline earth metal content, preferably calcium (Ca), in an amount preferably greater than 50000 ppm by weight, and substantially free of transitions, metalloids and post-transition metals, preferably containing less than 20000 ppm of metals selected from Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd ), copper (Cu), palladium (Pd) and said optionally heat-treated materials, for the implementation of organic synthesis reactions involving said catalyst.
  • the materials of organic origin come from a plant or a part of a plant, preferably a plant or a part of plant, an alga or a portion of alga containing an alkali metal or alkaline earth metal content,
  • plants are meant plants as well as lower plants such as algae, mushrooms, lichens, mosses and ferns.
  • the alkali metals can be preferably lithium, sodium or potassium, cesium.
  • the alkaline earth metals are preferably selected from magnesium, calcium, or barium, more preferably magnesium or calcium, and more preferably still calcium.
  • the amount of alkali or alkaline earth metal present in the plants which are the subject of the invention is preferably greater than 5000 ppm, more preferably greater than 50000 ppm by weight. In some cases, this amount can reach 400000 ppm.
  • the metal levels expressed in ppm are calculated with respect to the total mass of plants having undergone dehydration and before possible heat treatment.
  • the subject of the present invention is also the use after drying and / or grinding and thermal and / or chemical treatment of an extract of a plant or part of a plant of an alga or part of an algae comprising a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 5000 ppm by weight in the form of a salt such as a carbonate or oxalate for the preparation of a composition containing at least at least one basic metal catalyst, preferably in the form of oxide, salt, preferably carbonates, oxalate, or alkali or alkaline-earth metal hydroxide, preferably calcium (Ca) for carrying out reactions. organic synthesis involving said basic catalyst.
  • a salt such as a carbonate or oxalate
  • a composition containing at least at least one basic metal catalyst preferably in the form of oxide, salt, preferably carbonates, oxalate, or alkali or alkaline-earth metal hydroxide, preferably calcium (
  • the invention is implemented with plants rich in calcium. These plants are particularly rich in calcium oxalate whereas the calcifying algae do not contain calcium oxalate but calcium carbonate.
  • the steps of drying and / or grinding can also be carried out according to the indications of the aforementioned international patent application WO 2011/064487 as well as according to the examples provided below.
  • the grinding can be carried out in demineralized water.
  • the subject of the present invention is also the use after drying and / or grinding and thermal and / or chemical treatment of an extract of a plant or part of a plant comprising a high level of calcium (Ca), in a quantity preferably greater than 5000 ppm by weight, in salt form such as calcium carbonate or oxalate, for the preparation of a composition containing at least one basic metal catalyst in the form of calcium oxide, calcium salt selected from oxalate, carbonate, phosphates such as phytate, simple carboxylates such as citrate or osodic carboxylates such as uronates of alginate or polygalacturonates type, or calcium hydroxide for the implementation of reactions organic synthesis involving said basic catalyst.
  • Ca calcium
  • compositions contain a low percentage of plant material, especially after filtration on sintered glass.
  • the subject of the present invention is also the use of a composition prepared by drying and / or grinding and by thermal and / or chemical treatment of an extract of a plant or part of a plant comprising a high level of calcium (Ca), in an amount preferably greater than 5000 ppm by weight, in salt form such as calcium carbonate or oxalate and containing at least one basic metal catalyst in the form of calcium oxide, salt such as calcium oxalate, or calcium hydroxide, for the implementation of organic synthesis reactions involving said basic catalyst.
  • Ca calcium
  • the subject of the present invention is also the use as defined above, characterized in that the possible chemical treatment or treatments to which the plant or part of a plant extract is subjected is either a hydration reaction by the water of the oxides obtained by heat treatment is a reaction with an inorganic or organic acid, preferably hydrochloric acid followed by a treatment with a base strong, preferably sodium hydroxide at a pH greater than 12 oxides obtained by heat treatment or salts obtained by drying and / or grinding.
  • a hydration reaction by the water of the oxides obtained by heat treatment is a reaction with an inorganic or organic acid, preferably hydrochloric acid followed by a treatment with a base strong, preferably sodium hydroxide at a pH greater than 12 oxides obtained by heat treatment or salts obtained by drying and / or grinding.
  • the subject of the present invention is also the use as defined above, characterized in that the materials of organic origin are extracts of a vegetable or part of a vegetable, preferably a plant or a plant. part of a plant, algae or part of algae containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 5000 ppm, more preferably greater than 50000 ppm by weight, having optionally undergone a heat treatment, for the implementation of organic synthesis reactions involving said basic catalyst.
  • the materials of organic origin are extracts of a vegetable or part of a vegetable, preferably a plant or a plant. part of a plant, algae or part of algae containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 5000 ppm, more preferably greater than 50000 ppm by weight, having optionally undergone a heat treatment, for the implementation of organic synthesis reactions involving said basic catalyst.
  • the subject of the present invention is also the use as defined above, characterized in that the materials of organic origin are marine shells or shells of non-marine molluscs, said shells containing a high level of alkali metal or alkaline metal. earth, preferably calcium (Ca), preferably in the form of calcium carbonate, in an amount preferably greater than 80%, more preferably greater than 90% by weight, said shells having optionally undergone grinding and / or heat treatment for the implementation of organic synthesis reactions involving said basic catalyst.
  • earth preferably calcium (Ca)
  • Ca calcium
  • the basic catalyst is an extract of a plant or a plant layer of an alga or part of an alga comprising a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 50000 ppm by weight and containing less than 10000 ppm of metals selected from zinc (Zn), nickel (Ni), Manganese (Mn) Lead (Pb), cadmium (Cd), copper (Cu), palladium (Pd) or marine shells or shells of non-marine molluscs containing a high level of alkali or alkaline earth metal , preferably calcium (Ca), preferably in the form of calcium carbonate, in an amount preferably greater than 80%, more preferably greater than 90% by weight, after drying and / or grinding and / or heat treatment and / or chemical, said catalyst being in oxide form calcium, calcium salt preferably from carbonate, of oxalate, or of al
  • the basic catalyst is an extract of a plant or part of a plant comprising a high level of calcium (Ca), in a quantity of preferably greater than 50000 ppm, and containing less than 10000 ppm of metals selected from Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd), Copper (Cu) , palladium (Pd) or marine shells or shells of non-marine molluscs containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), preferably in the form of calcium carbonate, preferably greater than 80%, more preferably greater than 90% by weight, optionally after drying and / or grinding and heat treatment and / or chemical said catalyst being in the form of calcium oxide, calcium salt selected from oxalate, carbonate, phosphates te as phytate, simple carboxylates such as citrate, or osodic carb
  • the subject of the present invention is also the use as defined above as a catalyst of an extract of a plant or part of a plant of an alga or part of an alga comprising a significant amount of calcium (Ca), in an amount preferably greater than 50000 ppm and containing less than 10000 ppm by weight of metals selected from zinc (Zn), nickel (Ni), manganese (Mn) lead (Pb), cadmium (Cd), copper (Cu), palladium (Pd) prepared by drying and / or grinding and by heat treatment and / or chemical said catalyst being in salt form such as carbonate, or calcium oxalate, under form of calcium oxide or calcium hydroxide, for the implementation of organic synthesis reactions involving said basic catalyst.
  • extract is meant a product derived from or derived from a plant of an algae or shell.
  • the subject of the present invention is also the use as defined above as a catalyst for marine shells or shells of non-marine molluscs containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), preferably in the form of calcium carbonate, in an amount preferably greater than 80%, more preferably greater than 90% by weight, after optional grinding and / or heat treatment and / or chemical said catalyst being in the form of calcium oxide, salt calcium chosen from oxalate, carbonate, simple carboxylates such as citrate, or osodic carboxylates such as uronates of the alginate or polygalacturonate type or of calcium hydroxide for the implementation of organic synthesis reactions involving said basic catalyst.
  • Ca alkali or alkaline earth metal
  • the subject of the present invention is also the use as defined above, characterized in that the possible chemical treatment or treatments to which the plant or part of a plant extract, marine shells or non-marine shellfish shells are subjected to either a hydration reaction with water of the oxides obtained by thermal treatment or a reaction with a mineral or organic acid, preferably hydrochloric acid followed by a treatment with a strong base, preferably sodium hydroxide solution. pH greater than 12 oxides obtained by heat treatment or salts obtained by drying and / or grinding.
  • the optional treatment with water is preferably carried out with stirring.
  • the chemical treatment is preferably carried out with a mineral or organic acid such as hydrochloric acid, sulfuric acid or acetic acid, preferably hydrochloric acid followed by a treatment with a strong base, preferably sodium hydroxide. pH greater than 12,
  • the present invention also relates to the use as described above and characterized in that the plant having a high level of alkali metal or preferably, calcium (Ca), in an amount preferably greater than 50000 ppm by weight, in salt form such that calcium carbonate or oxalate is a common plant naturally rich in carbonate or calcium oxalate, preferably calcium oxalate and containing less than 10000 ppm of metals selected from Zinc (Zn), 3rd Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd), Copper (Cu) ), palladium (Pd) or an alga selected from calcifying algae or non-calcifying algae, preferably calcifying algae.
  • metals selected from Zinc (Zn), 3rd Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd), Copper (Cu)
  • palladium (Pd) or an alga selected from calcifying algae or non-calcifying algae, preferably calcifying
  • the subject of the present invention is also the use as described above and characterized in that the plant comprising a high level of calcium (Ca), in an amount preferably greater than 5000 ppm by weight, in the form of a salt such as calcium oxalate is a plant chosen from:
  • ⁇ green algae such as Halimeda (aragonite); Udotea
  • red algae such as Liagoraceae (Galaxaura / Dichotomaria) Corallinaceae: (Amphiroa, Jania) (rhodoliths); Lithothamnium
  • ⁇ brown algae such as those of the family Alariaceae including Undaria pinnatifida (or sea fern), ⁇ laria Esculenta, Alaria marginata, Undaria distans, Laminaria digita, Laminaria saccharina
  • ⁇ red algae such as those of the family
  • Palmariales including almaria palmata, those of the family Gigartinaceae including Chondrus crispus, those of the family Bangiophyceae,
  • ⁇ green algae such as those of the family Ulvaceae including Ulva lactuca.
  • the subject of the present invention is also the use as described above and characterized in that the plant comprising a high level of calcium (Ca), in an amount preferably greater than 50000 ppm by weight, in the form of a salt such as calcium oxalate or calcium carbonate is a plant selected from:
  • Plantaginaceae preferably large plantain
  • calcifying algae preferably Lithothamnium.
  • the subject of the present invention is also the use as described above and characterized in that the plant comprising a high level of calcium (Ca), in an amount preferably greater than 50000 ppm by weight, in the form of a salt such as Calcium oxalate is a plant chosen from lamb's-quarters, large plantains, common purslanes or the algae called Lithothamnium.
  • a salt such as Calcium oxalate
  • the shells are preferably chosen from molluscs, such as snails such as snails, crepidulae, bivalves such as oysters, scallops, mussels, scaphopods, polyplacophores and monoplacophores, cephalopods, with "Bone” cuttlefish or "feather” squid, egg shells, shells and skeletons such as echinids, cnidarians.
  • the plant which is preferably used may for example be large plantain, rumex, sorrel, lamb's-quarters, corallinades, aragonite halimeda and seaweed, litriothamne.
  • Calcifying algae often have a significant amount of magnesium.
  • Non-calcifying algae may also contain a high level of calcium, for example of the order of 5000 to 100,000 ppm.
  • the shells that are preferably used are oyster shells and mussels that are easily accessible in large quantities.
  • the present invention also relates to the use as described above and characterized in that the materials of organic origin are marine shells such as shells, oysters, mussels, scallops, crepidulae , skeletons, shells and other shells of non-marine molluscs such as snails, containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), preferably in the form of calcium carbonate, preferably in a higher amount at 80%, more preferably greater than 90% by weight for the implementation of organic synthesis reactions involving said basic catalyst.
  • a high level of alkali or alkaline earth metal preferably calcium (Ca), preferably in the form of calcium carbonate, preferably in a higher amount at 80%, more preferably greater than 90% by weight for the implementation of organic synthesis reactions involving said basic catalyst.
  • the present invention also relates to a process for the preparation of a composition as described above and comprising a metallic agent consisting of at least one alkali metal or alkaline earth metal, preferably calcium (Ca), characterized in that it includes the following steps:
  • At. dehydration preferably at room temperature or in an oven at a temperature of the order of 70 ° of the biomass comprising the leaves, stems and / or roots of a plant or a plant extract or a algae or a portion of alga having an alkali or alkaline earth metal content, preferably calcium (Ca), in an amount greater than 50000 ppm by weight in salt form such as carbonate or oxalate and substantially free transition metals, metalloids and posttransition metals, preferably containing less than 20,000 ppm of selected metals among Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd), Copper (Cu), Palladium (Pd) and / or b. Crushing of the dry biomass of a plant or a plant extract, an algae or a portion of algae obtained optionally after dehydration according to stage a)
  • alkali metal or alkaline earth metal salts preferably the calcium (Ca) or the oxides obtained respectively in stages d), and e) are subject to
  • the salts preferably the calcium carbonate obtained in stage d) for treatment with an inorganic or organic acid, preferably hydrochloric acid followed by a treatment with a strong base, preferably sodium hydroxide at a pH greater than 12, and if desired
  • the alkali or alkaline-earth metal salts preferably calcium (Ca), obtained in stage d) and the alkali or alkaline earth metal hydroxides, preferably calcium (Ca), obtained in stages f) or g) are mixed together preferably by co-grinding with a support such as alumina, for example basic alumina, or hydrotalcite to obtain a supported catalyst.
  • alumina for example basic alumina, or hydrotalcite
  • Optional ultrasonic activation is performed by partial immersion of the reactor in an ultrasonic tank containing 0.1% aqueous solution of detergent. The sonication is maintained for about 15 minutes.
  • Sintered glass with a porosity of 0-1 (large pore size 100 to 250 microns) is placed on a vacuum flask using a rubber cone to seal. The filtration is carried out under reduced pressure using a water pump. Only chlorophyll plant residues are retained. However, if operating at temperatures of 1000 to 1100 °, there can no longer be chlorophyll residues and this step does not need to be performed.
  • inorganic supports can be used to support the catalyst and thus perform a supported catalysis.
  • montmorillonite K10, silica, alumina or hydrotalcite have been used as support.
  • the catalysts on inorganic supports can preferably be prepared by co-grinding.
  • Catalysts on mineral substrates can be prepared as follows:
  • the inorganic support In a balloon provided with a magnetic bar, is introduced the inorganic support and then the catalyst preferably of type CAT Al or CAT A2. Water is then added and the resulting suspension is stirred at room temperature for 5 hours. This is then filtered, the solid is washed with distilled water, and this is collected for drying in an oven (120 ° C) overnight. Once its mass is stabilized, the resulting catalyst is stored in the desiccator.
  • the catalyst may also be supported on mineral solids, in particular of natural or synthetic origin, such as hydrotalcite. This solid is used as a catalyst support prepared according to the following procedure: the hydrotalcite and the CAT Al or CAT A2 type catalyst are placed in a mortar. The mixture is co-worked at room temperature and then placed in an oven until it is used.
  • the basic catalysts according to the present invention are preferably used without support.
  • the present invention also relates to a process as described above for the preparation of a composition
  • a metal agent consisting of at least one alkaline or alkaline earth metal, preferably calcium (Ca), characterized in that includes the following steps:
  • a) dehydration preferably at room temperature or in an oven at a temperature of the order of 70 ° of the biomass comprising the leaves, stems and / or roots of a plant or a plant or plant extract; an alga or part of an alga having an alkali or alkaline earth metal content, preferably calcium (Ca), in an amount greater than 50000 ppm by weight in the form of a salt such as a carbonate or an oxalate and substantially free of transition metals, metalloids and post-transition metals, preferably containing less than 20,000 ppm of metals selected from Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb) , cadmium (Cd), copper (Cu), palladium (Pd) and / or b) grinding of biomass, including leaves, stems and / or roots of a plant or part of a plant , an alga or part of seaweed obtained optionally after dehydration according to stage a), and, if
  • salts such as an alkali metal or alkaline earth carbonate or oxalate, preferably calcium (Ca), obtained in steps a) b) or c) with an inorganic or organic acid, preferably hydrochloric acid followed by treatment with a strong base, preferably sodium hydroxide at a pH greater than 12, followed preferably by centrifugation or by filtration of the precipitated solid and if desired
  • step e) the alkali or alkaline earth metal oxides, preferably calcium (Ca), obtained in step e) are subject to
  • salts such as alkali or alkaline earth carbonate or oxalate, preferably calcium (Ca), obtained in steps a) b) or c) alkali or alkaline earth oxides, preferably calcium (Ca), obtained in stage e) and the alkali or alkaline earth metal hydroxides, preferably calcium (Ca), obtained in stages d), f) or g) are mixed, preferably by co-grinding with a support such as alumina, for example basic alumina, silica, zeolites, for example montmorillonite, or hydrotalcite to obtain a supported catalyst.
  • alumina for example basic alumina, silica, zeolites, for example montmorillonite, or hydrotalcite
  • the present invention also relates to a process for preparing a catalyst comprising a metal agent consisting of at least one alkali metal or alkaline earth metal, preferably calcium (Ca), characterized in that it comprises the following steps:
  • salts such as an oxalate, an alkali metal or alkaline earth metal carbonate, preferably calcium (Ca), obtained in steps a) b) or c) with an inorganic or organic acid, preferably hydrochloric acid followed by a treatment with a strong base, preferably sodium hydroxide at a pH greater than 12, followed preferably by centrifugation or filtration of the precipitated solid and, if desired, the alkali metal oxides or alkaline earth metal oxides preferably calcium (Ca), obtained in stage b) are subject to
  • salts such as an alkali metal or alkaline earth metal carbonate, preferably calcium (Ca), obtained in steps a) b) or c) alkali or alkaline earth metal oxides, preferably calcium (Ca) , obtained in stage b) and the alkali metal or alkaline earth metal hydroxides, preferably calcium (Ca), obtained in stages d), f) or g) are mixed, preferably by co-grinding with a support such as alumina for example, basic alumina, silica, zeolites, for example montmorillonite, or hydrotalcite to obtain a supported catalyst.
  • a support such as alumina for example, basic alumina, silica, zeolites, for example montmorillonite, or hydrotalcite to obtain a supported catalyst.
  • the subject of the present invention is also a process as described above for the preparation of a composition
  • a metal agent consisting of at least one alkaline or alkaline earth metal, preferably calcium (Ca), characterized in that includes the following steps:
  • a) dehydration preferably at room temperature or in an oven at a temperature of the order of 70 ° of the biomass comprising the leaves, stems and / or roots of a plant or a plant or plant extract; an algae or a portion of alga having a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 50000 ppm by weight in the form of a salt such as a carbonate or an oxalate and substantially free of transition metals, metalloids and post-transition metals, preferably containing less than 20,000 ppm of metals selected from Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb), cadmium (Cd) copper (Cu), palladium (Pd)
  • salts such as an alkaline or alkaline earth metal carbonate or oxalate, preferably calcium (Ca), obtained in steps a), b) or c) are subjected to:
  • salts such as an alkali metal or alkaline earth carbonate or oxalate, preferably calcium (Ca), obtained in steps a) b) or c) and alkali or alkaline earth metal hydroxides preferably calcium (Ca), obtained in stage d) are mixed, preferably by co-grinding with a support such as alumina, for example basic alumina, zeolites for example montmorillonite, silica or hydrotalcite to obtain a supported catalyst,
  • a support such as alumina, for example basic alumina, zeolites for example montmorillonite, silica or hydrotalcite to obtain a supported catalyst
  • the present invention also relates to a process as described above for the preparation of a composition
  • a metal agent consisting of at least one alkaline or alkaline earth metal, preferably calcium (Ca) from the leaves, stems and / or roots of a plant or a plant extract or an algae or a portion of alga having a high level of alkali or alkaline earth metal, preferably calcium (Ca), in preferably in excess of 50000 ppm by weight in salt form such as carbonate or oxalate and substantially free of transition metals, metalloids and post-transition metals, preferably containing less than 20000 ppm of metals selected from Zinc (Zn), Nickel (Ni), Manganese (Mn) Lead (Pb), Cadmium (Cd) characterized in that it comprises, before the heat treatment of the mass obtained in stages a) or b ) a step of extracting the chlorophyll with the aid an organic solvent, preferably acetone, ethanol or isopropanol.
  • the present invention also relates to a process as described above characterized in that the plant having a high level of calcium (Ca), in an amount preferably greater than 5000 ppm by weight, in the form of a salt such as 1 Oxalate Calcium is a plant chosen from:
  • ⁇ green algae such as Halimeda (aragonite); Udotea ⁇ brown algae such as Padina
  • the dry extracts derived from the above-mentioned plants and algae are readily converted into basic biobased catalysts according to various possible protocols.
  • the process for preparing the basic biobased catalysts is preferably carried out according to the following methods:
  • Metal carbonates can be obtained from ashes derived from the aforementioned species and then used directly supported or not: cat Al;
  • the metal hydroxides can be generated by hydration of the oxides, then used supported or not; (The supports may be basic alumina, silica, zeolites, hydrotalcite): cat A2;
  • the calcifying algae are dried and finely ground. Calcium carbonate is obtained which can be subjected to a heat treatment of the order of 1000 ° to obtain calcium oxide: cat B.
  • CAT Al 420 g of dehydrated samples of plants rich in Ca are burned in a muffle furnace at 50 ° C. for 7 hours. 183 g of a solid rich in metal carbonates are obtained. Supported CAT Al: 1.7 g of a solid rich in metal carbonates are co-milled with 5 g of support (eg basic alumina, montmorillonite), then activated by heating for 15 minutes at 150 ° C.
  • support eg basic alumina, montmorillonite
  • the carbonate-rich solid also includes other anions, especially phosphates.
  • - CAT A2 10 g of metal carbonates from the previous heat treatment are introduced into a beaker and watered with stirring water. 30 ml of water are added. A gray suspension is obtained; agitation is maintained lh.
  • the pH is 10.
  • the medium is concentrated in a rotary evaporator, oven-dried at 80 ° C. 10.1 g of a gray powder are obtained.
  • CAT A2 supported 1.7 g of metal carbonates are co-milled with 5 g of support (eg basic alumina), then activated by heating for 15 minutes at 150 ° C.
  • the plant part is eliminated using a sinter of high porosity (size 1).
  • the residual aqueous phase is centrifuged.
  • the solid residue, rich in calcium oxalate, is treated as in 3 (heat treatment of plantain at 1000 ° C which leads to a composition close to cat A3).
  • compositions are presented below depending on the origin of the natural species. They were analyzed by ICP MS. The results are expressed in mass percentages. In the table below and in the following tables, only the content of metal cations of interest is indicated. The content of anions (in particular oxalates, carbonates or phosphates) does not appear in this table. The sum of the percentages is therefore less than 100%.
  • the 13.9 indication for calcium means that the sample analyzed contains 13.9 g of calcium per 100 g of total mass.
  • the basic entity may be an oxide, a carbonate or preferably a hydroxide of alkaline and especially alkaline earth derivatives. It can be supported or not.
  • CAT A5 The catalyst derived from oyster shells is prepared as follows:
  • the shells are directly placed in a calciner. It is heated to 1000 ° C for about 7 hours.
  • the resulting powder very rich in calcium oxide, is stored under an inert atmosphere, or used directly. In this case, it is rehydrated by progressive additions to the water.
  • the pH is then about 12.
  • the aqueous phase obtained may constitute the reaction medium or undergo the liltration / drying sequence in an oven. In this case, the solid obtained can be used as a catalyst or reagent in another medium, such as an ethanolic medium.
  • CAT A6 95g of fresh plantain, washed and drained are placed in an IL flask containing 500 mL of ethanol. The mixture is refluxed for 1 hour with mechanical stirring. The solution is filtered and the residual solid dried under reduced pressure at 100 ° C.
  • a mineral composition of plantain treated (CAT A6b) or not (CAT A6c) with an organic solvent and then calcined at 1000 ° C. illustrates the modification of the mineral composition expressed in ppm.
  • CAT A6b and CAT A6c have a reactivity similar to CAT A5.
  • the presence of other metal elements allows easy hydration and not exothermic.
  • the present invention also relates to the use of a composition as described above containing at least one basic metal catalyst comprising a extract having optionally undergone heat treatment of a plant or part of a plant, of an alga or part of an alga having a high level of alkali or alkaline earth metal, preferably calcium (Ca) in an amount preferably greater than 50000 ppm by weight and substantially free of transition metals, metalloids and post-transition metals, preferably containing less than 20000 ppm of metals selected from Zinc (Zn), Ni (Ni ), Manganese (Mn) Lead (Pb), Cadmium (Cd) or marine shells or shells of non-marine molluscs containing a significant level of alkali or alkaline earth metal, preferably calcium (Ca), preferably in the form of calcium carbonate, in an amount preferably greater than 80%, more preferably greater than 90% by weight for the implementation of organic synthesis reactions of functional transformations by catalysis involving the a basic catalyst
  • the present invention also more specifically relates to the use of a composition as described above containing at least one basic metal catalyst comprising an extract having optionally undergone heat treatment of a plant or part of a plant, of an alga or part of an alga having a high level of alkali or alkaline earth metal, preferably calcium (Ca), in an amount preferably greater than 5000 ppm by weight or sea shells or shells of non-marine molluscs containing a high level of alkali or alkaline earth metal, preferably calcium (Ca), preferably in the form of calcium carbonate, in amount preferably greater than 80%, more preferably greater than 90% by weight for the implementation of organic synthesis reactions functional transformations by catalysis involving said basic catalyst characterized in that said organic synthesis reactions are selected from the reactions of preparation of ⁇ , ⁇ -ethylenic carbonyl derivatives by isomerization, the cross-linked aldolization reactions using variously functionalized aldehydes such as vanillin or masked in
  • the present invention also more specifically relates to the use of a composition as described above containing at least one basic metal catalyst for the implementation of organic synthesis reactions involving said basic catalyst, the alkali metal concentration. or alkaline earth, preferably calcium (Ca) is between 5,000 and 400,000 mg.kg- 1 for calcium and between 3,000 and 300,000 mg.kg- 1 for magnesium contained in the catalysts from the leaves , stems and / or roots of a plant or part of a plant or of an algae or a portion of alga having a high level of alkali or alkaline earth metal.
  • Ca calcium
  • the present invention also relates to one of the compositions as obtained by implementing the method described above.
  • the present invention also more specifically relates to one of the compositions as obtained by carrying out the method described above and containing at least one basic metal catalyst selected from an alkali metal or alkaline earth metal, preferably calcium (Ca), in an amount greater than 5,000 ppm, preferably in an amount greater than 50,000 ppm, and in particular greater than 100,000 ppm for calcium (Ca) and in an amount greater than 3,000 ppm, preferably greater than 40 000 ppm, and in particular greater than 80 000 ppm magnesium (Mg), comprising at least one of said metals in oxide form, salt such as carbonate or calcium oxalate or hydroxide.
  • the invention is preferably implemented with a high level of calcium to generate a catalyst as basic as possible. The other cations are not generally necessary and the invention can be implemented with a low transition metal content.
  • Magnesium generally gives lower experimental results than calcium. It is therefore preferable to lower the level present in the catalysts.
  • This disposal can be carried out under the following conditions:
  • the biomass constituted by the extracts of a plant or a part of a plant, preferably a plant or part of a plant, an algae or a portion of a seaweed can be treated by the ethanol or acetone so as to pass chlorophyll in solution.
  • the filtrate thus obtained is substantially free of chlorophyll and can be used for subsequent reactions. It is thus possible to obtain a reduction of about 5 to 10% of the solid mass of catalyst.
  • catalysts or reagents of the invention which consist of alkali or alkaline earth metals, preferably salts such as carbonates or calcium hydroxides is the possibility, at the end of reaction of remove them from the aqueous reaction phase by passage with calcium oxalate (by addition of oxalic acid) which is a salt insoluble in water and precipitates.
  • isomerization is the migration of a double bond under thermodynamic control. It can be catalyzed quantitatively by a biosourced CATA1 type catalyst preferably supported on basic alumina, montmorillonite or hydrotalcite.
  • Gf functional group, R 1, R 2 , R 3 , R 4 - alkyl group, aryl, heteroatom
  • the advantage of the catalysts is to allow gentle hydrolysis on fragile or multifunctional substrates and then to facilitate the reaction treatments. This is for example the hydrolysis of an ethyl ester carried by a quaternary carbon: unlike the alkali hydroxides, it is possible to avoid the secondary reactions of decarboxylation and isomerization.
  • This reaction is preferably carried out with a catalyst derived from oyster shells or a mixture of oyster shells and mussels or crepidulae.
  • R H, Me, OH;
  • R ' linear or branched alkyl, cycloalkyl, aryl 10 mmol of methyl benzoate are added to 100mg of biosourced catalyst preferably CATA3 type.
  • a minimum of the H 2 O / MeOH mixture is added to ensure good agitation.
  • oxalic acid is added.
  • the medium is concentrated. Sublimation of the medium makes it possible to obtain very pure benzoic acid.
  • CAT A5 catalyst derived from a mixture of oyster shells and mussels (90% CaO of the total mass of the cat, 1 eq in Ca) is introduced in small portions into a 250 mL three-necked flask with stirring magnetic.
  • the reaction medium is refluxed for 90 minutes (the coloring of the milky medium can change from a very slightly green tint to yellow or orange depending on the catalyst batch).
  • the pH, initially at 12, reaches the value of 9.
  • the acidification of the reaction medium is carried out with a natural organic acid, oxalic acid.
  • Catalyst CAT A5 is also a transesterification catalyst. Thus, it is capable of facilitating the transesterification of ethyl butyrate by methanol. Supported on a porous silica, the leaching phenomena are limited.
  • n 0.1
  • Basic biobased catalysts are able to promote alkylation reactions.
  • R alkyl, cycloalkyl, aryl
  • R z alkyl, akenyl
  • the protocol is exemplified with an alkylating agent such as propyl bromide and acetic acid.
  • the second-order beta-elimination can be catalyzed by biobased catalysts.
  • R alkyl, aryl, functional group éEectroattractor
  • X Cl, Br, 1, OSO 2 alkyl or aryl
  • alkyl represents a linear or branched 1 to 6 carbon atom unit, preferably methyl and aryl is preferably a phenyl radical.
  • aryl is preferably a phenyl radical. This is, for example, the conversion of 2-bromoethylbenzene to styrene which is easily carried out with all CATA 1-5 and CATB catalysts by microwave activation (2 minutes, 400 ° C., 600W).
  • Reactions involving an acidic hydrogen alpha to one or two electron-withdrawing functional groups and an electrophilic partner such as a carbonyl derivative (aldehyde or ketone) or an acid derivative (nitrile, ester or carboxylic anhydride) are promoted by basic biosourced catalysts.
  • Z, Z 1 H, alkyl, aryl, nitro, aldehyde, ketone, nitrile, carboyl ester
  • Gf functional group aldehyde, ketone, nitrile, carboyl ester, acid anhydride
  • Ketonic or aldehyde groups illustrate these possibilities by intra- and intermolecular routes.
  • Intramolecular aldolization reactions are feasible whatever the catalyst used and the natural species from which it originates. They allow access to key molecules in the cosmetics industry, such as dihydrojasmone.
  • 2,5-undecadione (0.5 mol) is diluted in a mixture of water and ethanol (80/20 mL).
  • the solution is refluxed 16h, then extracted with ether.
  • a follow-up of the reaction by GC MS shows the complete formation of the dihydrojasmone.
  • the catalyst is recycled by filtration, washing with water, with ethanol and acetone and drying for 4 hours at 120 ° C. * intermolecular: intermolecular aldolization reactions are also possible.
  • 0.1 mole of benzaldehyde and 0.1 mole of acetophenone are diluted in 20 ml of absolute ethanol.
  • 500 mg of catalyst consisting of a co-milled mixture of 200 mg of rumex hydroxide (CATA3) and of basic alumina are added to the reaction medium. After stirring for 2 h at reflux, the reaction medium is cooled with an ice-water bath. The precipitated solid is filtered and recrystallized from ethanol. Extraction of the aqueous phase with hexane makes it possible to obtain a quantitative yield.
  • the cross-aldol condensation reaction can be extended to multifunctional aromatic aldehydes and ketones. Examples of industrial interest leading to synthetic flavors, compounds used in certain cosmetic creams or analgesics. Their synthesis is carried out from vanillin, corresponding ketones and basic catalysts developed. This is for example the green synthesis
  • Knoevenagel reactions are also very effective thanks to this new type of biosourced catalysis. This possibility is proved by the reaction between a ⁇ -ketoester and the masked aldehyde function of an aldose. The hemiacetal balance is easily shifted to the aldehyde form; the adduct undergoes in situ a dehydration reaction. The removal product is then subjected to an intramolecular Michael reaction.
  • the ⁇ -ketoester can be replaced by a ⁇ -dione;
  • the aldose may be a hexose, a pentose, or a deoxyaidosis.
  • the carbonylolefination reaction can also be performed on the hemiacetal function of an aldose.
  • the carbonylolefination-Michael dehydration sequence leads to a C-glycoside of interest.
  • the catalyst is an unsupported hydroxide derived from a species rich in calcium oxalate such as rumex, prolonged agitation allows the hydrolysis of ethyl cinnamate formed in situ cinnamic salt.

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EP14796167.6A 2013-09-12 2014-09-12 Verwendung bestimmter organischer materialien mit alkali- oder alkalierdmetallen zur durchführung organochemischer reaktionen Withdrawn EP3043906A1 (de)

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FR1457550 2014-08-01
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FR3023732A1 (fr) * 2014-07-15 2016-01-22 Centre Nat Rech Scient Utilisation de certaines plantes hyperaccumulatrices de metaux de transition pour des reductions de composes organiques par voies vertes
FR3029914B1 (fr) 2014-12-16 2018-06-15 Centre National De La Recherche Scientifique Nouveau procede de preparation d'intermediaires de synthese utilisant des produits d'origine naturelle et application des intermediaires obtenus
FR3034767A1 (fr) 2015-04-07 2016-10-14 Centre Nat Rech Scient Reduction des fonctions carbonyles de glucides et derives de glucides en milieu aqueux par le dithionite de sodium
WO2017125495A1 (en) * 2016-01-19 2017-07-27 Stratoz Process for preparing a catalyst composition from microalgae
CN106179172B (zh) * 2016-07-20 2018-12-04 灵武市海德鸿工业产品设计有限公司 一种改性氧化钙基高温二氧化碳吸附剂的制备方法
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