WO2014016509A1 - Utilisation de certaines plantes accumulatrices de manganese pour la mise en œuvre de reactions de chimie organique - Google Patents
Utilisation de certaines plantes accumulatrices de manganese pour la mise en œuvre de reactions de chimie organique Download PDFInfo
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- WO2014016509A1 WO2014016509A1 PCT/FR2013/051772 FR2013051772W WO2014016509A1 WO 2014016509 A1 WO2014016509 A1 WO 2014016509A1 FR 2013051772 W FR2013051772 W FR 2013051772W WO 2014016509 A1 WO2014016509 A1 WO 2014016509A1
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Definitions
- the invention relates to the use of accumulating plants of metals, more particularly manganese for the implementation of chemical reactions. From a synthetic point of view, it allows for the first time to perform a series of mild oxidation reactions with reactive entities of plant origin and capable of advantageously substituting for conventional oxidants of organic chemistry.
- Soil remediation technologies are difficult to develop because it is a heterogeneous, complex and dynamic environment that plays a key buffer and transformative role for pollutants.
- the Functional and Evolutive Ecology Center is studying the phytostabilisation technique which involves planting soils contaminated by plants capable of to grow in the presence of heavy metals (one speaks of tolerance) (Frérot et al., Specifies interactions between local metallicolous plants improve the phytostabilazation of mines, Plant and Soil, 282, 53-65, 2006). Some of these plant species used have the particularity of accumulating metals in large quantities in their vacuoles (we speak of hyperaccumulating plants). This is phytoextraction.
- Thlaspi caerulescens (synonym Noccacea caerulescens) belonging to the family Brassicaceae
- This plant is able to store zinc at concentrations 100 times higher than that of a conventional plant.
- it is able to extract and concentrate zinc and cadmium in aerial tissues, even on soils with low concentrations of these two metals.
- Zinc chloride is one of the most used and is indispensable in many industrial and laboratory reactions. It is also frequently used in heterocyclic organic chemistry to catalyze many electrophilic aromatic substitutions. It is also a catalyst of choice for carrying out the hydrogenations of primary alcohols with the Lucas reagent, the acetalization or aldolization reactions or the Diels-Aider type cycloaddition reactions.
- the catalysts are also very useful in analytical electrochemistry, electrometallurgy and liquid-solid extraction where the fields of application are numerous and directly involved in the different fields of economic life (batteries, batteries and accumulators, spectroscopic apparatus detectors, metallurgy, welding ...)
- the invention described in WO 2011/064487 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 in particular from zinc (Zn ), nickel (Ni) or copper (Cu) as defined above, in which said plant is chosen in particular from the family Brassicaceae, especially species of the genus Thlaspi in particular T. goesingeme, T. tatrense, T rotundifolhim, T. praecox, species of the genus Arabidopsis, in particular Arabidopsis hallerii, and of the genus Alyssum, in particular A. bertolonii, A.
- serpyllifolium Fabaceae, Sapotaceae, in particular the species Sebertia acuminata, Planchonella oxyedra, Convolvulaceae. , including the species Ipomea alpina, Planchonella oxyedra, Rubiaceae, especially the species Psychotriaticianrrei, in particular P. costivenia, P. denmentis, P. vanhermanii, Cunoniaceae, especially Geissois, Scrophulariaceae, in particular species of the genus Bacopa, in particular Bacopa monnieri, algae, in particular red algae, in particular rhodophytes , especially 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 plumbizincicola 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 inventors of the present application have now discovered that the richness of the soil in mineral species such as manganese, can also be at the origin of the progressive adaptation of plant communities, which become tolerant and hyperaccumulative trace elements metal, in especially Mn (II).
- Examples of plant genera with hyperaccumulator species of manganese are: Alyxia, Azolla, Beanprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea, Macadamia, Maytenas, Pimis, Spermacone, Stenocarpns, Virotia.
- the present application therefore firstly relates to the use after thermal treatment of a plant or part of a plant belonging to one of the genera selected from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea, Helanthius, Macadamia, Maytenus, Binas, Spermacone, Stenocarpus or Virotia having accumulated Manganese (Mn) and optionally a metal or several metals chosen (s) in particular from magnesium (Mg), zinc ( Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al), for the preparation of a composition containing at least one mono or polymetallic agent whose the metal or metals are selected from metals from said plant, said composition being substantially devoid of organic material, for carrying out organic synthesis reactions involving said agent.
- Mn Manganese
- Mg magnesium
- Zn zinc
- the reactive entities of vegetable origin from the manganese storage plants indicated above unlike the plants mentioned in the aforementioned applications, they make it possible to carry out a series of mild oxidation reactions and are capable of advantageously replacing the conventional oxidants of organic chemistry.
- compositions of the invention contain approximately less than 10%, preferably less than 5%, more preferably less than 2% by weight of carbon. In a preferred embodiment of the present invention, the compositions contain less than 0.2% and about 0.1% carbon.
- the present application therefore relates to the use after heat treatment of a plant or part of a plant selected from the genus Grevillea including Grevillea exid ssp. rubiginosa, Grevillea exiû ssp. exul and Grevillea gillivray having accumulated Manganese (Mn) and optionally a metal or several metals chosen (s) in particular from calcium (Ca), magnesium (Mg), iron (Fe) or aluminum (Al) for the preparation of a composition containing at least one active mono or polymetallic agent originating from said plant, said composition having been previously filtered and / or purified on resin and / or oxidized and / or fixed on a support and / or chelated and / or having undergoes electrolysis after acid treatment for the implementation of organic synthesis reactions involving said agent.
- Mn Manganese
- Mg magnesium
- Fe iron
- Al aluminum
- the present application therefore relates to the use of a composition prepared by thermal treatment of a plant or part of a plant belonging to one of the genera selected from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia , Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Helanthhis, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia or Grevillea having accumulated Manganese (Mn) and optionally a metal or several metals chosen, especially from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al) and containing at least one mono or polymetallic agent whose the metal or metals are selected from metals from said plant, said composition being substantially devoid of organic material, for carrying out organic synthesis reactions involving said agent as a catalyst.
- Mn Manganese
- Mg magnesium
- Zn zinc
- the present application therefore relates to the use of a composition prepared by thermal treatment of a plant or part of a plant belonging to one of the genera selected from Beauprea gracilis, Beauprea montana, Bea preopsis paniculata , Garcinia amplexicaulis, Grevillea ex l, Grevillea exul ssp. rabiginosa, Grevillea exul ssp.
- Grevillea gillivrayi Grevillea meissneri, Maytenus tenteri drakeana, Maytenus tenteri tenteri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara, Psorospermum febrifugum Spac, Macadamia neurophylla, Phytolacca Americana, Gossia bidwillii, Phytolacca acinosa Roxb , Virotia neurophylla, Macadamia integrifolia, Macadamia tetraphylla, Eleutherococcus sciadophylloides (synonym Acanthopanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Go
- the present application therefore relates to the use after heat treatment of a plant or part of a plant selected from Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp.
- Grevillea gillivrayi Grevillea meissneri, Maytenus tenteri drakeana, Maytenus tenteri tenteri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara, Psorospermum febrifugum Spach, Macadamia neurophylla, Phytolacca Americana, Gossia bidwillii, Phytolacca acinosa Roxb, Virotia neurophylla, Macadamia integrifolia, Macadamia tetraphylla, Eleutherococcus sciadophylloides (synonym Acanthopanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gos
- Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn) and optionally a metal or several metals chosen (s) in particular from calcium (Ca), magnesium (Mg), iron (Fe) or aluminum (Al) for the preparation of a composition containing at least one active mono or polymetallic agent originating from said plant, said composition having been previously filtered and / or purified on resin and / or oxidized and / or fixed on a carrier and / or chelated and / or electrolysis after acid treatment for the implementation of organic synthesis reactions involving said agent as a catalyst.
- Mn Manganese
- Mg magnesium
- Fe iron
- Al aluminum
- the extracts of the plants which are the subject of the present invention have a composition different from the mixtures of metals with respect to the extracts described in the application WO 2011/064487 and in the French application N ° 12/52045 in that they contain a large quantity of manganese. .
- the present invention therefore also relates to the use as described above wherein the mono or polymetallic agent is a catalyst comprising manganese (Mn) having the oxidation state (II) (Mn (II), or the degree of oxidation (III) (Mn (III) and optionally one or more metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), Aluminum (Al).
- Mn manganese
- III) Mn (II)
- Mn (III) the degree of oxidation (III)
- metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), Aluminum (Al).
- the mono or polymetallic agent is a reagent comprising manganese (Mn) having the degree of oxidation (III) (Mn (III), or the degree of oxidation (IV) (Mn (IV) and optionally one or more metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), Cadmium (Cd), Aluminum (Al).
- the subject of the present invention is the use as described above, after heat treatment followed by acid treatment and optionally oxidation and / or electrolysis of a plant or a part thereof. of a plant selected from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray, preferably Grevillea exul ssp. exul having accumulated Manganese (Mn) and optionally one or more selected metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca) , Cadmium (Cd), Aluminum (Al).
- Mn Manganese
- Mg manganese
- Zn zinc
- Cu copper
- Fe iron
- Ca Cadmium
- Al Aluminum
- the plants can only accumulate Manganese at the oxidation state (II) and that the presence of Mn at the oxidation (III) or (IV) levels results from oxidation reactions subsequent to the thermal treatment of the oxides. plants or some of the plants.
- the subject of the present invention is especially the use in which the acid treatment is preferably carried out with hydrochloric acid, in particular HC1 gas, HC1 IN at 12N, sulfuric acid, acetic acid, phosphoric acid, acid
- trifluoroacetic acid trifluoromethanesulfonic acid, nitric acid, perchloric acid or para-toluene sulfonic acid,
- the subject of the present invention is especially the use in which the composition is filtered on an inert inorganic solid such as celite and optionally subsequently purified on an ion exchange resin.
- the subject of the present invention is especially the use in which the concentration of Mn in dried leaves of the plant Grevillea exul ssp. preferably between about 15000 to about 280000 mg / kg dry weight of plant, the concentration of Fe (III) is from about 2000 to about 35000 mg / kg dry weight of plant and the concentration of Al (III) ) is from about 1500 to about 80000 mg / kg of plant dry weight.
- the present invention also relates to a process for preparing a composition substantially free of organic material and comprising a metal or polymetallic agent comprising manganese (Mn) having the oxidation state (II) (Mn (II), the degree of oxidation (III) (Mn (III) or the degree of oxidation (IV) (Mn (IV) and optionally one or more metals selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al), characterized in that it comprises the following steps:
- stage c) treatment of the ash obtained in stage c) with an acid chosen preferably from hydrochloric acid, nitric acid, sulfuric acid, acetic acid or trifluoromethanesulphonic acid, nitric acid, acid perchloric or para-toluene sulfonic acid, phosphoric acid, trifluoroacetic acid followed, if desired, by dehydration of the solution or suspension preferably obtained under reduced pressure to obtain a dry residue
- an acid chosen preferably from hydrochloric acid, nitric acid, sulfuric acid, acetic acid or trifluoromethanesulphonic acid, nitric acid, acid perchloric or para-toluene sulfonic acid, phosphoric acid, trifluoroacetic acid followed, if desired, by dehydration of the solution or suspension preferably obtained under reduced pressure to obtain a dry residue
- stage d) which, if desired, is subjected e) when the product obtained in stage d) is a suspension, in a step of removal of insoluble materials for example by filtration on an inert inorganic solid such as the celite or centrifugation step followed if desired dehydration of the solution obtained preferably under reduced pressure to obtain a dry residue
- Mn (III) manganese at oxidation (Mn (III) optionally combined with salts such as chlorides, sulphates or acetates or oxides of at least one selected metal especially among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al)
- step c), d), e) or f) if desired is subjected to the action of air oxygen in the presence of OH "ions to convert the manganese oxidation state (II) (Mn (II) in manganese at the oxidation state (IV) (Mn (IV) and, if desired, the suspension obtained is subjected to acid treatment and then to dehydration, preferably under reduced pressure to obtain a substantially mannanese-free reagent in Mn 3 0 4 or Mn 2 0 3 form comprising manganese with oxidation state (IV) (Mn (IV) optionally combined with salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al)
- stage c) and produced in dry form obtained in stage c), d), e), f), g) or h) that if desired is reacted with ligands preferably organic under the possible action of microwaves to obtain chelated agents, preferably catalysts chelated for example with porphyrins.
- ligands preferably organic under the possible action of microwaves to obtain chelated agents, preferably catalysts chelated for example with porphyrins.
- the products obtained in stage h) as well as the products comprising manganese at the oxidation state (IV) obtained according to the processes of the present invention are practically free of manganese in the form of Mn 3 0 4 or Mn 2 0 3 .
- This means that the oxidation products obtained and which are subjected to the disproportionation of Mn 3 0 4 and Mn 2 0 3 , in MnO 2 by return to pH 3 comprise in total less than 3% by weight of the two Mn 3 oxides. 0 4 and Mn 0 3 .
- these include steps common to all preparations:
- the solid can be used raw or partially purified according to the desired objectives.
- the dewatering and / or milling step (s) of the sheets can be avoided and the sheets can be directly calcined by the treatment at 300-500 ° C.
- the ashes can optionally be used directly if it is desired to catalyze a reaction in basic catalysis using metal oxides.
- the dehydration of the biomass is carried out in an oven at a temperature of about 60 ° for 72 hours.
- the heat treatment mentioned above consists in calcining the biomass and especially the leaves in an oven at a temperature between 300 and 500 ° C, preferably 400 ° for about 5 hours, preferably operating in successive stages.
- the acid digestion or ash treatment obtained for example in stage d) of the process indicated above is carried out by acids in solutions such as HCl, IN to 12N, gaseous HCl, sulfuric acid, acetic acid, HNO 3 , trifluoromethanesulfonic acid (triflic acid or TfOH), para-toluenesulphonic acid, perchloric acid adapted to organic syntheses envisaged.
- acids in solutions such as HCl, IN to 12N, gaseous HCl, sulfuric acid, acetic acid, HNO 3 , trifluoromethanesulfonic acid (triflic acid or TfOH), para-toluenesulphonic acid, perchloric acid adapted to organic syntheses envisaged.
- About 15 to 20 ml of diluted (1M) or concentrated acid (up to 12M) per gram of ash are introduced into the reaction medium.
- the reaction mixture is heated at about 60 ° C with stirring for at least 2 hours.
- the solution obtained for example in stage d) of the process indicated above is optionally filtered on celite or silica. Filtration is carried out on sintered porosity 4 for example covered with about 3 cm of celite (to avoid clogging) with suction by a water pump. The solution is then washed with concentrated hydrochloric acid and optionally concentrated under reduced pressure or freeze-dried.
- the optional partial purifications are preferably carried out on ion exchange resins (for example Dowex 1), but selective precipitation can also be carried out or liquid-liquid extraction methods may be used.
- the purpose of these purifications is to get rid of cationic elements of physiological origin such as Na (I), K (I), Mg (II) and Ca (II), or hyperaccumulated species in plants, such as Cd, Pb, Tl, which have no interesting reactivity and which can decrease the reactivity of the catalyst.
- the purification process on ion exchange resins is preferably carried out under the following conditions:
- Mn (II) can be attached to the anion exchanger.
- K (I), Ca (II), Al (III), Mg (II), Ni (II) are separated. Elution in HC1 8 then 6M medium releases Mn (II).
- the originality of the process is the use of a natural oxidizer and used under mild and ecological conditions: oxygen.
- the oxidation-reduction reaction becomes possible if it is at basic pH. Indeed, the redox potentials of the couples involved decrease with the pH, but in a nonparallel way. At a pH greater than 7, the redox potential of the pair 0 2 / H 2 0 becomes greater than that of the pair Mn (III) / Mn (II).
- the first step of the process is therefore to be placed in a basic medium by addition of sodium hydroxide to transform M x Cl y M x (OH) Yj and more particularly MnCl 2 Mn (OH) 2 .
- the possible oxidation of the dry residue obtained after acid treatment and possible filtration and / or purification and containing Manganese at the oxidation state (II) (Mn (II) in Manganese at the oxidation state (III) (Mn (III) may therefore be carried out by action of oxygen dioxygen in the presence of OH ⁇ ions preferably provided by sodium hydroxide and then treatment with an excess of anhydride such as acetic anhydride The products are obtained in the form of acetates at the oxidation state (III) after about 30 minutes of refluxing in water.
- Another method that can be used to effect possible oxidation of the dry residue obtained after acid treatment and possible filtration and / or purification and containing Manganese at the oxidation (II) degree (Mn (II) in Manganese at the oxidation degree (III ) (Mn (III) consists in causing the oxygen of the air to act on a porphinato-manganese complex with the oxidation state (II) After action of the dioxygen of the air on this complex, one obtains a porphinato-manganese complex the degree of oxidation (III)
- the porphinato-manganese complex with oxidation state (II) is obtained by reaction of pyirole optionally substituted with a dry residue obtained after acid treatment and optionally filtration and / or purification and containing manganese in the oxidation state (II) (Mn (II) in the presence of an aldehyde is preferably carried out in chloroform at room temperature with 4 equivalent
- Ar represents an aryl radical such as phenyl, p-chlorophenyl, p-toluyl.
- the purification of the manganese salts is not necessary and the presence of the associated metal dichlorides such as FeCl 3 and AlCl 3 active MnO 2 in the oxidation reactions is favorable.
- the solid suspension is treated with concentrated HCl to redissolve the hydroxides.
- MnO 2 is collected in the presence of other metal halides including FeCl 3.
- the oxidation by air is about 15 hours in the case of the controlled oxidation of Mn (II) in Mn (IV) by the dioxygen of air. It is of the order of 30 minutes in the case of the controlled oxidation of Mn (II) to Mn (III).
- Mn (II) The dry residue obtained after acid treatment and possible filtration and / or purification and containing Manganese at oxidation (II) (Mn (II) can be subjected to acid electrolysis to obtain oxidation state manganese (IV). ) (Mn (IV) in the form of MnO 2 substantially free of other metals, a pure MnO 2 type oxidant is obtained.
- the electrolysis is carried out by acid etching of the biomass derived from Grevillea exul exul previously treated at 400 ° C., using sulfuric acid.
- the electrolysis is carried out directly in sulfuric medium using graphite electrodes. Mn0 2 is directly recovered on the electrode by simple scraping.
- the plant mineral extract thus obtained can then be used directly in unsupported catalysis or deposited on a support for use in supported catalysis (all other applications), depending on the needs of organic synthesis.
- the catalysts are either used at the oxidation state existing during phytoextraction, or as cocatalysts or in oxidized form.
- the solution is concentrated under reduced pressure and the residue to dryness is then stored under a protective atmosphere to avoid hydration, see hydrolysis, Lewis acids present.
- the catalyst can be stored for several weeks without degradation before use.
- Supported catalysis The deposition on support can be realized according to different conditions on the same support or on different supports.
- inorganic or organic supports there may be mentioned aluminosilicates such as zeolites, silica Si0 2 , montmorillonite A1 2 0 3 alumina, carbon, metal oxides. It is also possible to use the mixtures of the abovementioned supports as well as the mining wastes such as aluminosilicates loaded with metal oxides.
- organic carriers there may be mentioned or synthetic polymer resins and chiral organic polymers of natural origin such as cellulose, hemicellulose, alginate, tannic acid, polygalacturonic, tartaric, mandelic, quinic or chitosan.
- Lewis acid catalysts Depending on the support employed, Lewis acid catalysts, mixed Lewis acid-Brönsted acid catalysts, and carbon skeleton reduction and elongation catalysts can be prepared.
- the reactions that are preferably carried out by supported catalysis are electrophilic aromatic substitution reactions, functional and functional protections and rearrangements, rearrangements, transpositions, aldol and related reactions, dehydration reactions, transfunctionalizations, heterocycles, multi-component reactions, depolymerizations, oxido-reductions.
- a catalyst supported on a zeolite such as montmorillonite K10 can be prepared from, for example, an unpurified plant extract, preferably Grevillea exu ssp.
- a crude plant extract preferably
- Grevillea exul ssp. exal is introduced into an enamelled crucible previously heated to about 150 ° C and the Montmorillonite is then introduced and crushed until a homogeneous solid. The mixture is then heated for about 10 additional minutes before use in organic synthesis.
- the clay can be replaced by silica, and the same preparation process can be used.
- a Lewis / Bronsted acid catalyst supported on a zeolite such as montmorillonite K10 from, for example, an unpurified plant extract, preferably Grevillea exul ssp. exul
- a crude catalyst mixture, preferably derived from Grevillea exul ssp. exul (Mn content: 58983 ppm) of montmorillonite K10 and 5 M hydrochloric acid is heated to about 70 ° C with stirring.
- the heating is increased to evaporate the medium.
- the solid obtained is stored in an oven (about 80 ° C to 100 ° C for one to two hours) to complete its dehydration and is finely ground with mortar.
- the final Mn content of the catalyst is about 60000 ppm.
- a silica-supported Lewis / Bronsted acid catalyst can also be prepared from, for example, an unpurified plant extract, preferably Grevillea exul ssp. exul
- a catalyst mixture preferably derived from Grevillea exul ssp, exul (Mn content: 58983 ppm) of the silica (35-70 ⁇ ) and 5 M hydrochloric acid is heated to about 70 ° C. ° C, with stirring.
- the operation is carried out as before to evaporate the medium in situ (under a hood, in one to two hours in general or the medium is distilled by means of a conventional distilling assembly with an HC1 trap, which reduces / avoids the discharges of acid in the environment.
- the final Mn content of the catalyst is about 60000 ppm.
- a catalyst supported on a mixed SiO 2 / polygalacturonic acid support from, for example, an unpurified plant extract, preferably Grevillea exul ssp, exul
- the silica and the polygalacturonic acid previously cobroyé are added in solid form; the mixture is stirred for 30 minutes at ambient temperature and then lyophilized; the solid obtained is used directly in organic synthesis.
- polygalacturonic acid can be replaced with chitosan.
- homogeneous catalysis and unsupported catalysis should be considered to have the same meaning. The same is true of heterogeneous catalysis and supported catalysis.
- This product can be obtained under an inert atmosphere (nitrogen or argon) because it is oxidizable in Mn (III) by the dioxygen of the air.
- the subject of the present invention is in particular a process for preparing a composition substantially free of organic matter and comprising a metal agent comprising manganese (Mn), having the oxidation state (II), (III) or (IV), and optionally a metal or several metals selected from calcium (Ca), magnesium (Mg), iron (Fe) or aluminum (Al), characterized in that the process is carried out from a plant or part of a plant selected from the genus Grevil ⁇ ea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exid and Grevillea gillivray, preferably Grevillea exul ssp. Exul.
- the present application also relates to the use of catalysts comprising Mn (II) obtained from Mn hyperaccumulating metallophyte plant extracts belonging to one of the genera selected from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria , Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea Helanthhis, Macadamia, Maytemis, Pinus, Spermacone, Stenocarpus, Virotia for the implementation of organic reactions, including heterocycle construction, the protection of carbonyl derivatives, preferably aldehydes and electrophilic aromatic substitutions, preferably the construction of porphyrins,
- MnCl 2 is a Lewis acid hard, can advantageously replace A1C1 3, FeCl 3 and BF 3 in a number of multicomponent reactions such as the Biginelli reaction.
- the mild Lewis acid properties of Grevillea-derived green catalysts are also illustrated through an acetalization-elimination reaction for example on citronellal catalyzed by the catalytic system object of the present invention.
- reaction is specific for this plant catalytic system.
- entity derived from a Zn (II) hyperaccumulator plant such as those described in French Patent Application No. 12/52045 spontaneously gives an ene-reaction.
- Zn (II) hyperaccumulator plant such as those described in French Patent Application No. 12/52045 spontaneously gives an ene-reaction.
- SEAR Aromatic electrophilic substitutions
- the Lewis acid catalysts object of the present invention are very useful in electrophilic substitution reactions that involve brittle aromatic substrates. Thus, they are capable of catalyzing the reaction of pyrrole with an aromatic aldehyde to form meso-tetraarylporphyrines metallated or not.
- This process is unique and advantageously replaces the Rothemund, Adler and Lindsey processes. It represents an important advance in the synthesis of free and metallized porphyrins, which are of increasing interest in the search for mild anti-cancer therapies. Their natural property of photo-sensitizers currently nourishes many hopes in dynamic phototherapy.
- the subject of the present invention is also the use of one of the compositions containing at least one metallic or preferably polymetallic catalyst as described above in the implementation of the organic synthesis reactions of selected Lewis acid-catalyzed functional transformations.
- electrophilic aromatic substitution reactions the construction of heterocycles, the preparation and protection of carbonyl derivatives, the radical oxidation, the epoxidation, the oxidation of alcohols located in alpha of a heterocyclic aromatic group or carbocyclic or a double bond, the oxidative cleavages of polyols, the oxidation of benzamines, the oxidative aromatic dehydrogenation of unsaturated cyclic derivatives and / or conjugates optionally comprising a heteroatom, the direct halogenation of enolizable compounds, the Hantzsch reaction in Lewis acid catalysis between an aldehyde, a beta-dicarbonyl compound and an ammonium source leading to the formation of dihydropyridines (DHP).
- DHP dihydropyr
- the subject of the present invention is also the use of catalysts comprising Mn (III) obtainable from extracts of Mn hyperaccumulating metallophyte plants.
- co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenyl hypoiodite, for the implementation of organic reactions, in particular oxidation reactions radicals or the oxidation of alkenes, in particular the epoxidation of alkenes.
- the radical oxidants of oxidation degree (III) obtained by the action of oxygen dioxygen in the presence of OFT ions and then treatment with an anhydride such as acetic anhydride are very interesting in organic synthesis because they avoid the preparation halogenated derivatives and the use of toxic derivatives such as trialkyltin hydrides.
- the reagent comprising Mn (III) makes it possible to generate in situ a carbon radical alpha of an attractor group, which is then trapped in an intra- or intermolecular addition reaction.
- This principle is illustrated by the reaction of ethyl acetoacetate on styrene.
- the presence in particular of Cu (II) and Fe (III) accelerates the last step favorably.
- the attraction and originality of the system is to be able to use a catalytic system based on a mixed composition mainly composed of porphyrin-Mn (III) / porphyrin-Fe (III), the most effective oxidizing systems.
- the principle is based on the use of the natural composition of the Mn hyperaccumulating plants described in the process indicated above.
- biomimetic and bio-based catalysts may be associated with many possible oxidising (IOC "PHLO, f-BuOOH, HOOH, ).
- the olefins to be epoxidized are mainly vinyl derivatives conjugated to an aromatic ring where the ring may be mono or disubstituted.
- the subject of the present invention is also the use of catalysts comprising Mn (III) obtainable from extracts of Mn hyperaccumulating metallophyte plants.
- the catalyst is activated by preferably in the form of a porphinato-manganese complex with the degree of oxidation (III) on isoeugenol or ferulic acid, preferably in acetonitrile to obtain vanillin.
- co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenyl hypoiodite
- the catalyst is activated by preferably in the form of a porphinato-manganese complex with the degree of oxidation (III) on isoeugenol or ferulic acid, preferably in acetonitrile to obtain vanillin.
- the subject of the present invention is also the use of catalysts comprising Mn (IV) substantially free of manganese in the form of Mn 3 0 4 or Mn 2 0 3 , preferably containing less than 3% of manganese in Mn 3 0 4 form or mn 2 0 3 and obtainable from extracts of metallophytes hyperaccumulating plants min by the action of oxygen in the air in the presence of OH ions "and if desired by an acid treatment and then to dehydration preferably under reduced pressure so as to obtain a reagent comprising manganese at the oxidation state (IV) (Mn (IV) optionally combined with salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al
- the present invention also relates to the use of a reagent comprising Mn (IV) substantially free of manganese form Mn 3 0 4 or Mn 2 0 3 [% age to be specified] and optionally associated with salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), Cadmium (Cd), aluminum (Al) obtainable from extracts of a plant or part of a plant selected from the genus Grevillea including Grevillea exul ssp. rubiginosa, Grevillea exul ssp.
- salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), Cadmium (Cd), aluminum (Al) obtainable from extracts of a plant or part of a plant selected from the genus Grevillea including Grevillea exul
- the precursor alcohol is a natural substance present and abundant in a number of plant species, such as Cotinus cogyggria,
- the oxidant is of totally natural origin, since it is prepared from plant extract.
- the vanillin thus synthesized can be described as vanillin with natural flavor.
- the present invention also relates to the use of a reagent comprising Mn (IV) substantially free of manganese form Mn 3 0 4 or Mn 2 0 3 [% age to be specified] and optionally associated with salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), Cadmium (Cd), aluminum (Al) obtainable from extracts of a plant or part of a plant selected from the genus Grevillea including Grevillea exul ssp.
- Mn (IV) substantially free of manganese form Mn 3 0 4 or Mn 2 0 3 [% age to be specified] and optionally associated with salts such as chlorides or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), Cadmium (Cd), aluminum (Al) obtainable from extracts of a
- aniline The oxidation of aniline is a reaction of great industrial interest but is delicate and rarely unambiguous. Yet, it can lead to azobenzene, a very useful photosensitive compound. This reaction is still being researched to improve its preparation.
- the most common method is based on the reduction of nitrobenzene in a basic medium and can lead to numerous by-products such as nitrosobenzene, 1,2-diphenylhydrazine 1,2-diphenyl-1-oxide diazene and N-phenyl-1,4-benzene diamine .
- Another example is the dehydrogenation of a natural cyclic terpene, ⁇ -terpinene, to an aromatic derivative, ⁇ -methyl-cumene, a platform molecule of the chemical industry is also given below in the experimental part. .
- Grevillea-derived oxidizing system comprising Mn (IV) is to generate an oxidizing entity in the presence of mixed Lewis acids.
- This very particular mineral composition makes it possible to carry out successive transformations in situ.
- An example is the iodination of carbonyl compounds by simple addition of alkaline iodide in the medium:
- the DHH obtained can be oxidized to pyridines by means of oxidizing agents such as KMnO 4 , MnO 2 , HNO 3 .
- Manganese-based catalysts have been shown to catalyze both reactions very efficiently in a single pot, thanks to the presence of traces of Mn IV (oxidizing) in the catalyst, essentially Mn 11 , which catalyzes the formation of of DHP thanks to its acid Lewis character.
- the use of the biosourced manganese-based catalyst thus has certain advantages in terms of catalytic efficiency, handling, reduction of the number of stages and reagents used. Finally, the use of aggressive and polluting oxidizing agents is avoided.
- reaction conditions developed are perfectly compatible with the principles of green chemistry, since the reaction is complete in 5 minutes under microwave irradiation, in solid phase, without the use of organic solvent.
- the reaction scheme is shown below
- the reaction is based on the formation of peroxymonocarbonate coordinated with Mn 11 of the catalyst, the active species being produced from sodium hydrogencarbonate and hydrogen peroxide, reagents chosen for their safety and low environmental impact.
- the reaction leads to excellent epoxidation yields, sometimes higher than those reported in the literature for nearby catalyst systems, in 4 hours at 0 ° C. Both enriched and depleted alkenes are active in this reaction (although yields are lower with depleted alkenes).
- This example is typical of the synthetic possibilities of the method: in an acidic medium, the epoxide is open in diol, which is in turn subjected to an oxidative cleavage in situ. In mild basic medium, the epoxide is isolated.
- composition containing a catalyst or “composition containing at least one catalyst” may be replaced by “catalyst”.
- the subject of the present application is thus the use, after heat treatment, of a plant or part of a plant belonging to one of the genera chosen from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia.
- Mn Manganese
- Mg magnesium
- Zn zinc
- Cu copper
- Fe iron
- Ca calcium
- Cd cadmium
- Al aluminum
- compositions containing at least one metal catalyst for the preparation of a composition containing at least one metal catalyst, the metal of which is one of the aforesaid metals from said plant, said composition being substantially free of chlorophyll or organic material, for the implementation of synthesis reactions organic material involving said catalyst.
- the subject of the present application is thus the use, after heat treatment, of a plant or part of a plant belonging to one of the genera chosen from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia.
- the subject of the present application is thus the use, after heat treatment, of a plant or part of a plant belonging to one of the genera chosen from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia.
- Mn Manganese
- metals selected from magnesium (Mg), zinc (Zn ), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al), for the preparation of a composition containing at least one metal catalyst, the metal of which is one of the aforesaid metals in Mn (II) form from said plant, said composition being devoid of chlorophyll or organic material, for the implementation of organic synthesis reactions involving said catalyst.
- the present application also relates to a composition devoid of organic material and in particular chlorophyll containing at least Mn as a catalyst in the form of chloride or sulfate, and cellulosic fragments of degradation such as cellobiose and / or glucose, and / or glucose degrading products such as 5-hydroxymethylfurfural and formic acid and less than about 2%, especially less than about 0.2% by weight of C, in particular about 0.14%.
- the term devoid of organic matter means that the compositions which are the subject of the invention satisfy the criteria indicated above.
- the present application also relates to compositions as obtained by implementation of the various methods described above.
- the present application also relates to the use after thermal treatment of a plant or part of a plant belonging to one of the genera selected from Alyxia, Azolla, Beaaprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Engenia , Gleichenia, Gossio, Grevillea, Helanthhis, Macadamia, Maytenns, Pinns, Spermacone, Stenocarpus, Virotia having accumulated Manganese (Mn) and optionally a metal or several metals chosen (s) in particular from magnesium (Mg), zinc (Zn ), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminum (Al), for the preparation of a metal catalyst, the metal of which is one of the said metals from said plant, said catalyst being devoid of organic material, for carrying out organic synthesis reactions involving said catalyst.
- Mn Manganese
- Mg magnesium
- Zn zinc
- Cu copper
- Fe iron
- the Manganese content of the compositions of the invention may be between 15,000 and 270,000 ppm.
- the solid can be used raw or partially purified according to the desired objectives.
- Example 1.1 Dehydration of the biomass between 300 and 500 ° C. 1 kg of leaves of GreviJlea exul ssp. exul treated at 400 ° for 5h gives about 150 g of ash. At this stage, the ashes can optionally be used directly if it is desired to catalyze a reaction in basic catalysis using metal oxides.
- the ashes are treated with acids in solutions (for example HCl, HNO 3 , trifluoromethanesulfonic acid) adapted to the envisaged organic syntheses.
- acids for example HCl, HNO 3 , trifluoromethanesulfonic acid
- the reaction mixture is heated to 60 ° C with stirring for at least 2 hours. 3.
- the solution obtained is filtered on celite or silica.
- This protocol for the purification of manganese catalysts is based on the use of a resin such as Dowex 1.
- Mn (II) can be attached to the anion exchanger.
- K (I), Ca (II), Al (III), Mg (II), Ni (II) are separated.
- Elution in HCl 8A then 6M liberates Mn (II).
- Table 1 below shows the composition of the solid residue before and after ion exchange resin purification, analyzed by ICP MS (Inductively Coupled). Plasma Mass Spectroscopy).
- the resin is very selective for manganese.
- the purified catalyst is less depleted of Fe, Al and Zn than for the resins of the IRA 400 type.
- the solid residue obtained is stored under nitrogen.
- Mn is in Mn (II) form, Fe in Fe (III), Ni, Cu, Zn, Co, Cd, Pb, Ba, Mg form. , Hg and Mg at the oxidation state (II).
- the counterions are mainly chlorides, accompanied by the corresponding oxides.
- the crude sample derived from Grevillea exul obtained from a thermal treatment at 400 ° C. of the biomass and having undergone an acid attack with HCl 1-10N for 6-12h, filtered on celite and concentrated under vacuum at 100 ° C. is used directly without purification.
- Mn (III) Oxidizing Reagents It is possible to generate oxidizing systems of different reactivity and not associated with porphyrinic ligands. 1st method:
- the Mn (III) is mainly of the form ⁇ , (X being preferably OAc)
- the originality of the process is the use of a natural oxidizer and used under mild and ecological conditions: oxygen.
- the oxidation-reduction reaction becomes possible if it is at basic pH. Indeed, the redox potentials of the couples involved decrease with the pH, but in a nonparallel way. At a pH greater than 7, the redox potential of the pair 0 2 / 3 ⁇ 40 becomes greater than that of the pair Mn (III) / Mn (II).
- the first step of the process is therefore to be placed in a basic medium by addition of sodium hydroxide to transform M x Cl y M x (OH) yj and more particularly MnCl 2 Mn (OH) 2 . °
- Type 2 G-Mn (III) where Mn (III) is predominantly in MnX 3 form ) (X being preferably OAc)
- the objective here is to precipitate all the metal cations, with an excess of HO- ions for manganese, then to oxidize the mixture obtained to the degree (IV) in air.
- This very advantageous process makes it possible to avoid the use of strong oxidants.
- the purification of the manganese salts is not useful; on the contrary, the presence of the associated metal dichlorides such as active FeCl 3 MnO 2 in the oxidation reactions.
- the solid suspension is treated with concentrated HCl to redissolve the hydroxides. MnO 2 is collected in the presence of other metal halides including FeCl 3 .
- the oxidizing system is denoted G-Mn (IV).
- Example for a sample of calcined Grevillea gillivrayi dissolved in 0.20M hydrochloric acid solution The concentration of NaOH is such that the acid and the other cations except for magnesium are quantitatively hydroxylated.
- the volume of the solution subjected to oxidation is 250 ml.
- the oxidation with air is stopped after about 15 hours (instead of 30 minutes as in the case of the controlled oxidation of Mn (II) in Mn (III)).
- the solid, ocher suspension at first becomes dark brown rather quickly. This coloration does not change substantially after addition of HC1 0.90 M.
- R Me, CH 3 (CH 2 ) 5 -, 3,7-dimethylhept-6-en-H, Me
- radical oxidants are very interesting in organic synthesis because they avoid the preparation of halogenated derivatives and the use of toxic derivatives such as trialkyltin hydrides.
- the green G-Mn (III) reagent makes it possible to generate in situ a carbon radical alpha of an attractor group, which is then trapped in an intra- or intermolecular addition reaction.
- This principle is illustrated by the reaction of ethyl acetoacetate on styrene.
- the presence in particular of Cu (II) and Fe (III) accelerates the last step favorably.
- the olefins to be epoxidized are mainly vinyl derivatives conjugated to an aromatic ring where the ring may be mono or disubstituted.
- the process constitutes a more direct access to vanillin and based on a biomimetic process: the substrate, the isoeugenol, and the oxidizing catalytic species [ G-Mn (III) + Fe (III)] are derived from natural resources and provide access to a "natural" aroma of vanillin.
- This reaction is easily transposable to the controlled oxidation of allyl alcohols under similar conditions.
- the reaction is complete after 5 hours of stirring in dichloromethane at room temperature, without degradation and without concurrent reaction.
- Oxidation of aniline is a transformation of industrial interest Catalyst
- Mn (IV) (15 mmol in Mn (IV)) are added at once. The mixture is refluxed and heated for 8h. The solution gradually becomes orange. This color reflects the formation of the desired azobenzene. After filtration and concentration of the medium, azobenzene is obtained pure.
- Carbohydrate dehydrogenation dehydrogenation Dehydrogenation of a natural cyclic terpene, alpha-terpinene, as an aromatic derivative, para- and yl cumene, which is a platform molecule of the chemical industry.
- the substrate to be iodinated (10 mmol) diluted in 10 ml of dichloromethane and sodium iodide (1 mmol) are placed in a 25 ml monocolumn flask equipped with a refrigerant.
- the GER-Mn (IV) reagent (3 mmol of Mn (IV)) is added all at once and the mixture is stirred for 12 hours at room temperature.
- the solution is filtered on celite and the organic solution washed with sodium thiosulphate solution, dried over sodium sulphate, filtered and concentrated in vacuo.
- the reaction is analyzed by GC-MS and then by RM NMR.
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Priority Applications (7)
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EP13756583.4A EP2874742A1 (fr) | 2012-07-23 | 2013-07-23 | Utilisation de certaines plantes accumulatrices de manganese pour la mise en uvre de reactions de chimie organique |
CN201380048941.6A CN104703692B (zh) | 2012-07-23 | 2013-07-23 | 某些锰累积性植物用于实施有机化学反应的用途 |
AU2013294842A AU2013294842A1 (en) | 2012-07-23 | 2013-07-23 | Use of certain manganese-accumulating plants for carrying out organic chemistry reactions |
US14/416,404 US10702860B2 (en) | 2012-07-23 | 2013-07-23 | Use of certain manganese-accumulating plants for carrying out organic chemistry reactions |
CA2879059A CA2879059A1 (fr) | 2012-07-23 | 2013-07-23 | Utilisation de certaines plantes accumulatrices de manganese pour la mise en oeuvre de reactions de chimie organique |
JP2015523594A JP6496923B2 (ja) | 2012-07-23 | 2013-07-23 | 有機化学反応を行うためのマンガン蓄積植物の使用 |
US16/886,418 US11731117B2 (en) | 2012-07-23 | 2020-05-28 | Compositions of certain manganese accumulating plants |
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FR1257135A FR2993480B1 (fr) | 2012-07-23 | 2012-07-23 | Utilisation de certaines plantes accumulatrices de manganese pour la mise en oeuvre de reactions de chimie organique |
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US16/886,418 Division US11731117B2 (en) | 2012-07-23 | 2020-05-28 | Compositions of certain manganese accumulating plants |
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CN (1) | CN104703692B (fr) |
AU (1) | AU2013294842A1 (fr) |
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WO2014128283A1 (fr) * | 2013-02-22 | 2014-08-28 | Centre National De La Recherche Scientifique | Utilisation de compositions obtenues par calcination de plantes particulières accumulant des métaux pour la mise en œuvre de réactions catalytiques |
FR3008323A1 (fr) * | 2013-07-15 | 2015-01-16 | Centre Nat Rech Scient | Utilisation de certaines plantes accumulatrices de platinoides pour la mise en œuvre de reactions de chimie organique |
FR3010329A1 (fr) * | 2013-09-12 | 2015-03-13 | Centre Nat Rech Scient | Utilisation de certaines plantes contenant des metaux alcalins ou alcalino-terreux pour la mise en oeuvre de reaction de chimie organique |
WO2015036714A1 (fr) * | 2013-09-12 | 2015-03-19 | Centre National De La Recherche Scientifique | Utilisation de certains materiaux d'origine organique contenant des metaux alcalins ou alcalino-terreux pour la mise en oeuvre de reactions de chimie organique |
US9149796B2 (en) | 2009-11-26 | 2015-10-06 | Centre National De La Recherche Scientifique | Use of metal-accumulating plants for implementing chemical reactions |
WO2016009116A1 (fr) | 2014-07-15 | 2016-01-21 | Centre National De La Recherche Scientifique (C.N.R.S.) | Utilisation de certaines plantes hyperaccumulatrices de métaux de transition pour des réductions de composés organiques par voies vertes |
CN112209907A (zh) * | 2020-10-21 | 2021-01-12 | 南京先进生物材料与过程装备研究院有限公司 | 一种利用微通道反应装置合成含1,3-茚二酮螺环骨架的二氢呋喃的方法 |
US11254597B2 (en) | 2017-03-31 | 2022-02-22 | Centre National De La Recherche Scientifique | Method for the production of a material of plant origin that is rich in phenolic acids, comprising at least one metal, for carrying out organic synthesis reactions |
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EP4215267A1 (fr) * | 2022-01-25 | 2023-07-26 | Centre national de la recherche scientifique | Nouvelles compositions de catalyse durable de réactions de synthèse organiques |
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- 2013-07-23 CA CA2879059A patent/CA2879059A1/fr not_active Abandoned
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US9149796B2 (en) | 2009-11-26 | 2015-10-06 | Centre National De La Recherche Scientifique | Use of metal-accumulating plants for implementing chemical reactions |
WO2014128283A1 (fr) * | 2013-02-22 | 2014-08-28 | Centre National De La Recherche Scientifique | Utilisation de compositions obtenues par calcination de plantes particulières accumulant des métaux pour la mise en œuvre de réactions catalytiques |
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US10066029B2 (en) | 2013-07-15 | 2018-09-04 | Centre National De La Recherche Scientifique (C.N.R.S) | Uses of certain platinoid accumulating plants for use in organic chemical reactions |
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WO2015036714A1 (fr) * | 2013-09-12 | 2015-03-19 | Centre National De La Recherche Scientifique | Utilisation de certains materiaux d'origine organique contenant des metaux alcalins ou alcalino-terreux pour la mise en oeuvre de reactions de chimie organique |
WO2016009116A1 (fr) | 2014-07-15 | 2016-01-21 | Centre National De La Recherche Scientifique (C.N.R.S.) | Utilisation de certaines plantes hyperaccumulatrices de métaux de transition pour des réductions de composés organiques par voies vertes |
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Also Published As
Publication number | Publication date |
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FR2993480B1 (fr) | 2024-03-22 |
US20150174566A1 (en) | 2015-06-25 |
US11731117B2 (en) | 2023-08-22 |
JP6496923B2 (ja) | 2019-04-10 |
FR2993480A1 (fr) | 2014-01-24 |
US20200290032A1 (en) | 2020-09-17 |
EP2874742A1 (fr) | 2015-05-27 |
CN104703692B (zh) | 2017-08-22 |
CA2879059A1 (fr) | 2014-01-30 |
AU2013294842A1 (en) | 2015-02-05 |
US10702860B2 (en) | 2020-07-07 |
CN104703692A (zh) | 2015-06-10 |
JP2015527932A (ja) | 2015-09-24 |
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