OA17163A - Use of certain manganese accumulating plants for carrying out organic chemistry reactions - Google Patents

Abstract

The invention relates to the use, after heat treatment, of manganese accumulating plants for carrying out chemical reactions.

Description

The invention relates to the use of plants accumulating metals, more particularly manganese, for carrying out chemical reactions. From a synthetic point of view, it makes it possible for the first time to carry out a whole series of gentle oxidation reactions thanks to reactive entities of plant origin and capable of advantageously replacing the conventional oxidants of organic chemistry.

In addition, the biological decontamination of soils polluted by metals, metalloids, industrial and agricultural organic waste and discharges or radioisotopes is a very worrying problem because the soil performs essential functions which largely determine the production of products. food and water quality.

Among the various polluting substances, heavy metals are among the most harmful compounds, because they are not biodegradable and are concentrated in soils. Examples of sites exist in France in Belgium, Luxembourg, in the Jura, the Swiss Prealps or in the Pyrenees, to name only the closest regions as well as in more distant regions such as New Caledonia where the Nickel is more particularly exploited. Different African countries such as Gabon, Mali, South Africa, but also Mexico, China, India or Australia are also demonstrative examples.

Soil remediation technologies are difficult to develop because it is a heterogeneous, complex and dynamic environment, which plays a key role in buffering and transforming pollutants.

Different phytoremediation techniques (phytoextraction, phytodegradation, phytostabilisation, phytostimulation, phytotransformation, phytovolatilization and rhizofiltration) are currently in full development (Terry, N. and Banuelos G., editors, Phytoremédiation of contaminated soil in water, Lewis Publishers, Boca Raton, FI . 2000).

The Functional and Evolutive Ecology Center (CEFE) studies the phytostabilisation technique which consists in revegetating contaminated soils with plants capable of

L ‘* ♦ to grow in the presence of heavy metals (we speak of tolerance) (Frérot et al., Specifies interactions between local metallicolous plants improve the phytostabilazation of mine soils, 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 called phytoextraction.

The team studied in particular two plants, a Thlaspl caerulescens (synonym Noccacea caerulescens) belonging to the Brassicaceae family, has remarkable properties of tolerance and hyperaccumulation of zinc, cadmium, nickel. It concentrates them at the level of the aerial parts (leaves and stems).

This plant is able to store zinc at concentrations 100 times greater than that of a conventional plant. In addition, it is able to extract and concentrate zinc and cadmium in aerial tissues, even on soils with a low concentration of these two metals.

Beyond their unusual tolerance to Zn ²⁺ and Cd ²⁺ and other metals, hyperaccumulative plants are able to extract metals and transfer them to the aerial parts where they concentrate. As a result, the roots contain very few heavy metals unlike non-accumulating plant species. This triple property of tolerance / accumulation / concentration in harvestable parts makes it a relevant tool in phytoremediation.

Furthermore, heavy metals are commonly used in organic chemistry as essential catalysts for carrying out chemical transformations which require significant activation energy. The role of catalysts is then to lower the energy barrier.

Their mode of operation is frequently based on their Lewis acid properties. Zinc chloride is one of the most widely used and is essential in many industrial and laboratory reactions. It is also frequently used in heterocyclic organic chemistry to catalyze many electrophilic aromatic substitutions.

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It is also a catalyst of choice for carrying out hydrogenations of primary alcohols with Lucas's reagent, acetalization reactions, aldolization or Diels-Alder type cycloadditions reactions ...

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, cells and accumulators, detectors of spectroscopic devices, metallurgy, etc. welds ...)

In international application WO 2011/064462 and application WO

2011/064487 published June 3, 2011 is described and claimed to be the Professor's invention

Grison and Doctor Escarré relating to the use of a calcined plant or a calcined part of a plant having accumulated at least one metal in M (II) form chosen in particular from zinc (Zn), nickel (Ni) or copper (Cu), for the preparation of a composition containing at least one metal catalyst, the metal of which is one of the aforesaid metals in M (1I) form originating from said plant, said composition being devoid of chlorophyll, and allowing the implementation of organic synthesis reactions involving said catalyst.

In addition to the species mentioned above (Thlaspi caerulescens now called Noccaea caerulescens and Anthyllis vulnerarid) application WO 2011/064487 describes the use of numerous other metallophyte plants hyperaccumulating heavy metals for the preparation of catalysts which can be used in organic chemistry.

Thus, the invention described in WO 2011/064487 relates to the use of a calcined plant or of a calcined plant part 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 Brassicaceae family, in particular the species of the Thlaspi genus 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. serpyllifolium, Fabaceae, Sapotaceae, in particular the species Sebertia acuminata, Planchonella oxyedra, of Convolvulaceae, in particular the species Ipomea alpina, Planchonella oxyedra, of the Rubiaceae, in particular the species Psychotria douarrei, in particular P. costivenia, P. denial, P. vanhermaniï, of Cunoniaceae, in particular the Geissois, of the Scrophulariaceae, in particular the s 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.

As a result, plant waste is directly recovered and transformed into “green” catalysts or unconventional reagents.

In French patent application No. 12/52045 filed on March 6, 2012 and not yet published, Professor Grison and researchers Escande and Losfeld have unexpectedly shown that certain other plants belonging to the genus Sedum as well as a different plant , Potentilla griflithi, possess different heavy metal hyperaccumulating metallophyte properties which make them particularly interesting for use in catalysis in organic chemistry.

Plants of the genus Sedum are succulents that belong to the Crassulaceae family, which consists of more than 400 species. They have natural aptitudes to develop on poor, dry soils, in open areas and in difficult conditions. Their foliar system is fleshy and their cultures easy.

Among them, three species have developed unusual zinc and cadmium extraction properties. Sedum plumbizindcola and Sedum jinianum in particular have a remarkable ability to extract zinc from polluted soils in southern and eastern China. They have real potential in phytoextraction and are qualified as "plumbizincîcolafor".

The properties of these heavy metal hyperaccumulative metallophytes had already been the subject of several scientific publications, among which we can cite:

1- L.H. Wu, N. Li, Y.M. Luo, Phytoextraction of heavy metal contaminated soil by Sedum plumbizincicola under different agronomie strategies, in: Proc. 5th Int. Phytotech. Conf., Nanjing, China, 2008, pp. 49e50.

2- L.H. Wu, S.B. Zhou, D. Bi, X.H. Guo, W.H. Qin, H. Wang, GJ. Wang, Y.M. Luo, Sedum plumbizincicola, a new species of the Crassulaceae from Zhejiang, China, Soils 38 (2006) 632e633 (în Chînese).

3-Longhua Wu, Changyin Tan, Ling Liu, Ping Zhu, Chang Peng, Yongming Luo, Peter Christie. 2012. Cadmium bioavailability in surface soils receiving long-term applications of inorganic fertilizers and pig manures. Geoderma, 173-174: 224-230

4- Ling Liu, Longhua Wu, Na Li, Yongming Luo, Siliang Li, Zhu Li, Cunliang Han, Yugen Jiang, Peter Christie. 2011. Rhîzosphere concentrations of zinc and cadmium in a meta! contaminated soîl go repeated phytoextraction by Sedum plumbizincicola.

International Journal of Phytoremediation, 13 (8): 750-764

5- Jinping Jiang, Longhua Wu, Na Li, Yongming Luo, Ling Liu, Qiguo Zhao, Lei Zhang, Peter Christie. 2010. Effects of multiple heavy metal contamination and repeated phytoextraction by Sedum plumbizincicola on soîl microbial properties. European

Journal of Soil Biology, 46: 18-26

6- Ling Liu, Longhua Wu, Na Li, Cunliang Han, Zhu Li, JP Jiang, Yugen Jiang, XY Qîu, Yongming Luo, 2009. Effect of planting densities on yields and zinc and cadmium uptake by Sedum plumbizincicola. Huan Jing Ke Xue, 30 (11): 3422-67

7- Longhua Wu, Yongming Luo, Xuerong Xing and Peter Christie. 2004. EDTA- enhanced phytoremediation of heavy metal contaminated soil and associated environmental risk. Agriculture, Ecosystems & Environment, 102 (3): 307-318.

However, the application of extracts of these plants as catalysts had never been described before and is the subject of French patent application No. 12/52045.

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 gradual adaptation of plant communities, which become tolerant and hyperaccumulative of trace metal elements, in particular Μη (II).

Examples of genera of plants with hyperaccumulating manganese species are:

Alyxia, Azolla, Beauprea, Beaupreopsis, Bride! Ia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea, Macadamia, Maytenus, P inus, Spermacone, Stenocarpus, Virotia.

These metallophyte species are thus capable of concentrating in their leaf system up to 110,000 ppm of manganese (in dry matter). Their ability to develop on eroded mining sites, impoverished in organic matter and exposed to drought, gives these plants a great interest in the ecological restoration of sites damaged by intensive mining.

The cultivation of such species, such as for example those of the genus Grevillea, is of complementary interest to ecological restoration. They are the source of new Lewis acid catalysts and high performance oxidizing reagents, the reactivity of which can be adjusted by controlling the degree of oxidation of Mn and the composition of the medium. In a context of environmental crisis and the tightening of European chemicals regulations, the development of new mild, efficient and environmentally friendly oxidizing systems is a real opportunity.

The treatments and preparations of catalysts and oxidizing systems are easy, easy to implement and respect green and ecological constraints.

The first subject of the present application is therefore the use after heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bride lia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea, Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus or Virotia having accumulated Manganese (Mn) and possibly one or more metals chosen (s) in particular among 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 agent or polymetallic, the metal or metals of which are chosen from metals originating from said plant, said composition being practically devoid of organic matter, for the implementation of organic synthesis reactions involving said agent.

As indicated above, from a synthetic point of view, the reactive entities of plant origin derived from the manganese accumulating plants indicated above allow, unlike the plants cited in the applications indicated above, to carry out a whole series of reactions. mild oxidation and are able to replace advantageously the conventional oxidants of organic chemistry.

The expression "substantially free of organic matter" means that the 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.

More particularly, the subject of the present application is therefore the use after heat treatment of a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn) and possibly a metal or more metals chosen 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 undergone electrolysis after acid treatment for the implementation of organic synthesis reactions involving said agent.

More particularly, the present application therefore relates to the use of a composition prepared by heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bride lia, Crolalaria, Dicranopteris, Dîpteris, Eugenia, Gleichenia, Gossia, Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia or Grevillea having accumulated Manganese (Mn) and possibly a metal or several metals chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al) and containing at least one mono or polymetallic agent the metal or metals of which are chosen from metals originating from said plant, said composition being practically devoid of organic matter, for the implementation of organic synthesis reactions involving said agent as catalyst.

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More particularly, the present application therefore relates to the use of a composition prepared by heat treatment of a plant or a part of a plant belonging to one of the genera chosen from Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea melssneri, Maytenus fournieri drakeana, Maytenus fournieri fournieri. Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara, Psorospermum febrifugum Spach, Macadamia neurophylla, Phytolacca Americana, Gossia bidwilla, Phytolacca acinosa Roxb, Macgotiastheria scophyllia inosa Roxb, Macgotadioccadolia scophyllaoccia inosa Roxb, Macgotoccadolia scophyllaoccia, Synamadoccaidae Roxb, Synamadoccadolia inosa Roxb, Acinococciocca, Gossia bidwilla, Gossia bidwilla, Synamadoccadiaoccaocciaociaocciaoccia inoxia, Macaoccaoccaocciaoccia, Macadamiaoccaoccia, Macaoccaoccaoccaoccaoccaoccaoccaoccaocciainosa Roxb, Macgotococcadia inococcadia, Macadamia, Macadamia febrifugia Roxb. sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, Maytenus cunninghamii, Chengiopanax sciadophylloide, Phytolacca americana, Austromyrtus bidwillii, Alyxia rubricaulia, Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, DIPTERIS conjugata, Eleutherococcus sciadophylloides , Ilex crenata, Eugenia clusioides, Pinus sylvestris, Stenocarpus ndnei, Virotia neurophylla, Schima superba, Polygonum hydropiper, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara , Psorospermum febrifugum Spach, having accumulated Manganese (Mn) and optionally one or more metals chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al) and containing at least one mono or polymetallic agent, the metal or metals of which are chosen from metals originating from said plant, said composition being devoid of organic matter, for the implementation of organic synthesis reactions involving said agent as catalyst.

More specifically, the present application therefore relates to the use after heat treatment of a plant or a part of a plant chosen from Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea meissneri, Maytenus fournieri drakeana, Maytenus fournieri fournieri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camarallara, Psorospermum febrifa, Phytolosa neurophyllosa, Acaccinosa acacia, Macaccolosa acacia, Acaccinosa spachii, Psorospermum febrifa

Roxb, Virotia neurophylla, Macadamia integrifolia, Macadamia tetraphylla, Eleutherococcus sciadophylloides / synonymous Acanlhopanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, Maytenus cunninghamii 5 Chengiopanax sciadophylloides, Phytolacca americana, Austromyrtus bidwillii, Alyxia rubricaulia, Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, Dipteris conjugata, Eleutherococcus sciadophylloides, llex crenata, Eugenia clusioides, Pinus sylvestris, Stenocarpus ndnei, Virotia neurophyllia, synonymia, Spacobaichoptera, Polygonopteris, Dipteris, Schacobaopteria, Virotia neurophyllolia, 10 (10) linearis), Brîdelia ferrugïnea, Lantana camara, Psorospermum febrifugum Spach and preferably the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn) and possibly a metal or more metals chosen 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 electrolysis after acid treatment for the implementation of organic synthesis reactions involving said agent as catalyst.

Plants of the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray are the most abundant plants for the accumulation of Manganese (Mn)

The extracts of the plants which are the subject of the present invention have a different composition from the mixtures of metals compared to the extracts described in application WO 25 2011/064487 and in French application No. 12/52045 in that they contain a large amount of Manganese.

The presence of iron and aluminum is also very beneficial for many syntheses.

It also appears that the different metals present in the unpurified or partially purified mixtures exhibit a polymetallic synergy between them which allows the use of these mixtures in numerous reactions.

The properties of the mixtures derived from the plants which are the subject of the present invention make it possible to use them as very effective catalysts in a very large number of reactions, many not envisaged in the preceding applications.

A subject of the present invention is therefore also the use as described above in which the mono or polymetallic agent is a catalyst comprising manganese (Mn) having the degree of oxidation (II) (Μη (II), or the degree oxidation (III) (Μη (III) and optionally one or more metals chosen from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium ( Ca), Cadmium (Cd), Aluminum (Al).

A subject of the present invention is also the use as described above in which the mono or polymetallic agent is a reagent comprising manganese (Mn) having the degree of oxidation (III) (Μη (III), or the degree of oxidation (IV) (Μη (IV) and optionally one or more metals chosen from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca ), Cadmium (Cd), Aluminum (Al).

More particularly, the present invention relates to the use as described above, after heat treatment followed by an acid treatment and optionally an oxidation and / or an electrolysis of a plant or of a part. of plant chosen 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 metals chosen from among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca) , Cadmium (Cd), aluminum (Al).

It is understood that the plants can only accumulate Manganese at the oxidation degree (II) and that the presence of Mn at the oxidation degree (III) or (IV) results from oxidation reactions subsequent to the heat treatment of the plants or part of plants.

In the various modes of use described above, the present invention relates especially to the use in which the acid treatment is carried out preferably with hydrochloric acid, in particular gaseous HCl, HCl IN to I2N, from

B sulfuric acid, acetic acid, phosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, nitric acid, chloric acid or para-toluenesulfonic acid .

In the various modes of use described above, the present invention has a specific object of the use in which your composition is filtered through an inert mineral solid such as celite and optionally subsequently purified on an ion exchange resin.

In the various modes of use described above, the present invention is particularly concerned with the use in which the concentration of Mn in the dried leaves of the plant Grevillea exul ssp. preferably is between about 15,000 to about 280,000 mg / kg dry weight of plant, the concentration of Fe (111) is between about 2000 to about 35,000 mg / kg of dry weight of plant and the concentration of Al (111 ) ranges from about 1500 to about 80,000 mg / kg dry weight of the plant.

A subject of the present invention is also a process for preparing a composition practically devoid of organic matter and comprising a metallic or polymetallic agent comprising manganese (Mn) having the degree of oxidation (11) (Mn (11), the degree of oxidation (111) (Μη (111) or the degree of oxidation (IV) (Μη (IV) and optionally one or more metals chosen from among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al) characterized in that it comprises the following steps:

a) Dehydration of the biomass of a plant or of a plant extract belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia or Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn), and possibly a metal or metals chosen from among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fc), Calcium (Ca), Cadmium (Cd), aluminum (Al),

b) Grinding of your dry biomass of a plant or a plant extract obtained in stage a)

c) Heat treatment in the oven preferably at a temperature below 500 ° C of the ground mixture and if desired and preferably,

d) Treatment of the ashes obtained in stage c) with an acid preferably chosen from hydrochloric acid, nitric acid, sulfuric acid, acetic acid or trifluoromethanesulfonic acid, nitric acid, acid perchloric or para-toluene sulfonic acid, phosphoric acid, trifluoroacetic acid followed if desired by dehydration of the solution or suspension obtained preferably under reduced pressure so as to obtain a dry residue

And solution or suspension obtained in step d) which, if desired, is submitted

e) when the product obtained in stage d) is a suspension, in a step of removing insoluble matter, for example by filtration through an inert mineral solid such as celite or by centrifugation, a step followed if desired by dehydration of the solution preferably obtained under reduced pressure so as to obtain a dry residue and / or

f) possible total or partial purification on ion exchange resins followed if desired by dehydration of the solution obtained, preferably under reduced pressure so as to obtain a dry residue

g) and dry residue obtained in stage c), d), e) or f) containing Manganese in the degree of oxidation (II) (Mn (II) only if desired to transform the Manganese in the degree of oxidation (II) (Mn (II) in Manganese at the degree of oxidation (III) (Μη (III) one submits either to the action of the dioxygen of the air in the presence of OH “ions then to a treatment with an anhydride such that acetic anhydride is under the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (II) which is subjected to the action of dioxygen air to obtain a complex at oxidation degree (111) and subject the product obtained to dehydration preferably under reduced pressure to obtain a dry residue comprising manganese at oxidation degree (III) (Μη (III) optionally combined with salts such as chlorides, sulphates or acetates or oxides of at least one metal chosen in particular from magnesium (Mg), zinc (Zn), copper e (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al)

h) and product in dry form obtained in stage c), d), e) or f) that if desired is subjected to the action of oxygen in the air in the presence of OH 'ions to convert the manganese to the degree of oxidation (II) (Mn (II) to manganese to degree of oxidation (IV) (Μη (IV) and if desired, the suspension obtained is subjected to an acid treatment and then to dehydration, preferably under reduced pressure so as to obtain a reagent practically devoid of manganese in the form of MnjO4 or Mn2O3 comprising manganese in the degree of oxidation (IV) (Mn 10 (IV) optionally associated with salts such as chlorides or acetates or oxides of less one metal chosen in particular from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al)

i) and product in dry form obtained in stage c), d), e) or f) that if desired is subjected to an electrolysis in an acid medium to obtain manganese in the degree of oxidation (IV) (Μη (IV ) as MnCh virtually free of other metals

j) and product in dry form obtained in stage c), d), e), f), g) or h) which, if desired, is mixed or treated in an acidic medium with a support preferably chosen from silica, montmorillonite, polygalacturonic acid, chitosan or a mixture of these products to obtain a supported catalyst

k) and product 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.

The products obtained in stage h) as well as the products comprising manganese in the degree of oxidation (IV) obtained according to the processes of the present invention are practically devoid of manganese in the MnjCh or ΜήΟϊ form This means that the oxidation products obtained and which are subjected to the disproportionation of MnjO4 and M112O3, into MnCh by return to pH = 3, comprise in total less than 3% by weight of the two oxides MnjCh and M ^ Ch r »

In a preferred mode of carrying out the procedures for preparing the catalysts, the latter comprise steps common to all the preparations:

1. Dehydrat i on of biomass

2. Crushing dry leaves by sorting out stems and impurities

The dried leaves then preferably undergo the following treatment, it being understood that certain steps can be omitted or carried out in a different order:

3. Summarily crush the leaves in a mortar

4. Calcine the leaves in an oven so as to obtain the ashes

5. Grind the ashes in a mortar to obtain a fine powder.

6. Digest with acid

7. Filtration on frit covered with Celite (to avoid clogging it) with suction through a water pump. Wash with acid

8. Evaporate the polymetallic solution with an electric nozzle in a porcelain crucible under a fume hood.

9. Recover the solid phase in the crucible using a spatula and place the catalyst in an oven.

The solid can be used crude or partially purified depending on the desired objectives.

In an alternative ash preparation process, the dewatering and / or grinding step (s) of the leaves can be avoided and the leaves can be directly calcined by the treatment between 300 and 500 ° C.

Optionally, the ash can be used directly if it is desired to catalyze a reaction in basic catalysis using metal oxides.

The preferential conditions for performing these steps are as follows:

Dehydration of the biomass is carried out in an oven at a temperature of approximately 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 ° C., for approximately 5 hours, preferably operating in successive stages.

The acid digestion or treatment of the ashes obtained for example in stage d) of the process indicated above is carried out with acids in solutions such as HCl, IN to I2N, gaseous HCl, sulfuric acid, acetic acid, HNO 3, trifluoromethanesulfonic acid (triflic acid or TfOH), para-toluene su! ionic acid, perchloric acid suitable for the organic syntheses envisaged. About 15 to 20 ml of dilute (1M) or concentrated (up to I2M) acid are introduced per gram of ash 10 into the reaction medium. The reaction mixture is heated to approximately 60 ° C. with stirring for at least 2 h.

The solution obtained for example in stage d) of the process indicated above is optionally filtered through celite or silica. The filtration is carried out on frit, for example of porosity 4, covered with about 3 cm of Celite (to avoid clogging it) with suction 15 by a water pump. The solution is then washed with concentrated hydrochloric acid and optionally concentrated under reduced pressure or lyophilized.

The optional partial purifications are preferably carried out on ion exchange resins (eg Dowex 7) but it is also possible to operate selective precipitation or use liquid-liquid extraction methods. The aim of these purifications is to get rid of cationic elements of physiological origin like Na (I), K (I), Mg (II) and Ca (II), or species hyperaccumulated in plants, like Cd, Pb , Tl, which have no interesting reactivity and which can decrease the reactivity of the catalyst.

However, it appears important to keep the polymetallism of the catalysts, even purified, as confirmed by the results of organic synthesis, where the presence of different metals causes a very interesting synergistic effect. The use of ion exchange resins is the most common method. more suitable for purifications.

After passing through the ion exchange resins, selective precipitation can be considered.

The purification process on ion exchange resins is preferably carried out under the following conditions:

In 12Λ / HCl medium, Μη (II) can be fixed on the anion exchanger. In this way, K (I), Ca (II), Al (III), Mg (II), Νί (II) are separated.

Elution in 8A / then 6Λ / HCl medium releases Mn (II).

Oxidation of Manganese at oxidation degree (II) (Mn (II) to Manganese at oxidation degree (III) (Μη (III).

The originality of the process is the use of a natural oxidant and used under gentle and ecological conditions: dioxygen. The oxidation-reduction reaction becomes possible if it is placed at basic pH. Indeed, the redox potentials of the couples involved decrease with the pH, but in a non-parallel manner. At pH greater than 7, the redox potential of the O2 / H2O pair becomes greater than that of the Μη (III) / Μη (II) pair.

The first step of the process is therefore to place itself in a basic medium by adding sodium hydroxide to transform M _x Cl _y into M _x (OH) _y , and more particularly MnCh into Mn (OH) ₂ .

The possible oxidation of the dry residue obtained after acid treatment and possible filtration and / purification and containing Manganese in the degree of oxidation (II) (Mn (II) in Manganese in the degree of oxidation (III) (Μη (III) can therefore be carried out by the action of oxygen from the air in the presence of OH ions preferably supplied by sodium hydroxide and then by treatment with an excess of anhydride such as acetic anhydride The products are obtained in the form of acetates. to the degree of oxidation (III) after about 30 minutes of heating under reflux in water.

Another method which can be used to effect an optional oxidation of the dry residue obtained after acid treatment and optional filtration and / purification and containing Manganese in oxidation degree (II) (Mn (II) to Manganese in oxidation degree ( III) (Μη (III) consists in making the dioxygen of the air act on a porphinato-manganese complex at the degree of oxidation (II). After action of the dioxygen of the air on this complex, a porphinato- complex is obtained. manganese in the degree of oxidation (III). The porphinato-manganese complex in the degree of oxidation (II) is obtained by reaction of the pyrrole optionally substituted with a dry residue obtained after acid treatment and possible filtration and / purification and containing manganese in degree of oxidation (II) (Mn (II) in the presence of an aldehyde The operation is preferably carried out in chloroform at room temperature with 4 equivalents of acetic aldehyde or benzaldehyde and 45 equivalents of pyrrole.

We then obtain for example a product of formula

R

R in which R = H, COOEt, CH ₂ COOEt, CH ₂ CH ₂ COOEt, CHj, CH = CH ₂ , and Ar represents an aryl radical such as phenyl, p-chlorophenyl, p-toluyl.

Preparation of the oxidizing reagent Μη (IV):

The possible oxidation of the dry residue obtained after acid treatment and possible filtration and / purification and containing Manganese in the degree of oxidation (II) (Mn (II) in Manganese in the degree of oxidation (IV) (Μη (IV) can be carried out by deep action IS of the oxygen in the air at basic pH of the order of 8 in the presence of sodium hydroxide in MnO ₂ , MruOi and Mn ₂ Oj, followed by the disproportionation of the last two oxides into MnO ₂ by returning to pH = 3 by addition of hydrochloric acid of the order of 0.9 M.

The purification of the manganese salts is not necessary and the presence of the associated metal dichlorides such as FeCb and AlCb activates MnO ₂ in the oxidation reactions is favorable.

After oxidation, the solid suspension is treated with concentrated HCl to redissolve the hydroxides.

MnOj is collected in the presence of other metal halides including FeCb · "

*

Oxidation by air is of the order of about 15 hours in the case of the controlled oxidation of Μη (II) to Μη (IV) by oxygen in the air. It is of the order of 30 minutes in the case of the controlled oxidation of Μη (II) to Μη (III).

The dry residue obtained after acid treatment and possible filtration and / purification and containing manganese in the degree of oxidation (II) (Mn (II) can be subjected to electrolysis in an acid medium to obtain manganese in the degree of oxidation (IV ) (Mn (IV) in the form of MnCh practically free of other metals. A conventional oxidant of pure MnCh type is obtained.

The electrolysis is carried out by acid attack of the biomass derived from Grevillea exul exul previously treated at 400 ° C, with sulfuric acid. The electrolysis is carried out directly in a sulfuric medium using graphite electrodes. MnOî is directly recovered from 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 for organic synthesis.

Catalysis not supported:

For reactions in the homogeneous phase, the catalysts are either used to the degree of oxidation existing during the phytoextraction, or as co-catalysts or in oxidized form.

As indicated above, the solution is concentrated under reduced pressure and the dry residue is then stored under a protective atmosphere in order to avoid the hydration, see hydrolysis, of the Lewis acids present. The catalyst can be stored for several weeks without degradation before use.

Catalysis supported:

The deposition on a support can be carried out under different conditions on the same support or on different supports.

For the use of the catalysts which are the subject of the present invention in supported catalysis, inorganic or organic supports can be used. Mention may be made, among inorganic supports, of aluminosilicates such as, for example, zeolites, silica

SiO ₂ , montmorillonite alumina AI2O3, carbon, metal oxides. It is also possible to use mixtures of the aforementioned supports as well as mining waste such as aluminosilicates loaded with metal oxides.

Among the organic supports, mention may be made of synthetic polymeric resins and chiral organic polymers of natural origin such as cellulose, hemicellulose, alginate, tannic, polygalacturonic, tartaric, mandelic, quinic or chitosan acids.

Depending on the support employed, Lewis acid catalysts, mixed Lewis acid-Bronsted acid catalysts, carbon skeleton reduction and elongation catalysts can be prepared.

The reactions which are preferably carried out by supported catalysis are electrophilic aromatic substitution reactions, protections and deprotections of functions, rearrangements, transpositions, aldol and related reactions, dehydration reactions, transfunctionalizations, constructs. 'heterocycles, multi-component reactions, depolymerizations, redox.

A catalyst supported on a zeolite such as montmorillonite K10 can be prepared, for example from an unpurified extract of a plant, preferably Grevillea exul ssp. luxury

In a preferred embodiment, a crude plant extract, preferably Grevillea exul ssp. exul is introduced into an enamelled crucible previously heated to about 150 ° C and the Montmorillonite is then introduced and ground until a homogeneous solid is obtained. The mixture is then heated for approximately 10 additional minutes before use in organic synthesis.

You can replace clay with silica, and use the same preparation process.

A Lewis / Bronsted acid catalyst supported on a zeolite such as montmoriBonite K10 can also be prepared, for example from an unpurified plant extract, preferably Grevillea exul ssp. luxury

In a preferred embodiment, a mixture of crude catalyst, 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.

After about 3 hours of stirring at 70 ° C, the heat is increased to evaporate the medium. The solid obtained is stored in an oven (about 80 ° C-100 ° C for one to two hours) to complete its dehydration and it is finely ground in a mortar. The final Mn content of the catalyst is approximately 60,000 ppm.

A Lewis / Bronsted acid catalyst supported on silica can also be prepared, for example from an unpurified plant extract, preferably Grevillea exul 10 ssp. luxury

In a preferred embodiment a mixture of catalyst preferably derived from Grevillea exul ssp. exul (Mn content: 58983 ppm) silica (35-70 µm) and 5 M hydrochloric acid is heated to about 70 ° C, with stirring.

The procedure is 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 distillation assembly with an HCl trap, which reduces / avoids the releases of acid in the environment.

The final Mn content of the catalyst is approximately 60,000 ppm.

A catalyst supported on a mixed SiO 3 / polygalacturonic acid support can also be prepared, for example from an unpurified plant extract, preferably Grevillea exul ssp. luxury

The catalytic solution obtained after acid attack is brought to pH = 2 with 2M sodium hydroxide. The silica and polygalacturonic acid previously co-ground (the mass ratio can vary from 10/1 to 2/1), are added in solid form; the mixture is stirred for 30 minutes at room temperature, then lyophilized; the solid obtained is used directly in organic synthesis.

Using the same process, you can replace polygalacturonic acid with chitosan.

In the present application, the expressions homogeneous catalysis and unsupported catalysis should be considered as having the same meaning. The same is true of the expressions: heterogeneous catalysis and supported catalysis.

An example of preparation for the preparation of chelated agents is given below in the experimental part by the preparation of ligands between manganese (II) and porphyrins. An example given below is the product of formula:

R

R

This product can be obtained under an inert atmosphere (nitrogen or argon) because it is oxidizable to Mn (III) by the oxygen in the air.

A subject of the present invention is in particular a process for preparing a composition practically devoid of organic matter and comprising a metallic agent comprising manganese (Mn), having the degree of oxidation (11), (111) or (IV), and optionally a metal or more metals chosen from calcium (Ca), magnesium (Mg), Iron (Fe) or Aluminum (Al) characterized in that the process is carried out starting from a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray, preferably Grevillea exul ssp. Exul.

A subject of the present application is also the use of catalysts comprising Μη (II) obtained from extracts of metallophyte plants hyperaccumulating Mn belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria , Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia for the implementation of organic reactions, in particular the construction of heterocycles, the protection of carbonyl derivatives, preferably of aldehydes and electrophilic aromatic substitutions, preferably the construction of porphyrins,

- Construction of heterocycles

The reactivity of the polymetallic and concentrated MnCh system can be illustrated by the construction of heterocycles. Without wishing to be limited by any mechanistic explanation, the applicant considers that according to the HSAB theory (Pearson's acid-base concept), MnCb is a hard Lewis acid, capable of advantageously replacing AlCb, FeClj and BF3 in a certain number of multicomponent reactions. such as the Biginelli reaction.

However, its use remains limited by low reactivity. The presence of other di and trivalent cations enhances the classical reactivity of MnCb and gives it an interest in the preparation of heterocyclic structures. An example of the preparation of pyrimidones indicated below in the experimental part illustrates the Lewis acid properties of the polymetallic catalyst derived from Grevillea.

- Protection of carbonyl derivatives

The mild Lewis acid properties of the green catalysts derived from Grevillea are also illustrated through a reaction of the acetalization-elimination type, for example on citronellal, catalyzed by the catalytic system which is the subject of the present invention.

The reaction is specific to this plant catalytic system. The same reaction catalyzed by an entity derived from a plant hyperaccumulating Zn (11) such as those described in French patent application No. 12/52045 spontaneously gives an ene reaction.

- Aromatic electrophilic substitutions (ARES)

The Lewis acid catalysts which are the subject of the present invention in particular when they are supported, for example on montmoriHonite, have a very advantageous activity in the reactions of aromatic electrophilic substitutions of the alkylating and acylating Friedel Craft type.

These results are unexpected, because very few examples of SEAr are known with manganese dichloride: Μη (II).

The Lewis acid catalysts which are the subject of the present invention are very useful in electrophilic substitution reactions which involve fragile aromatic substrates. Thus, they are capable of catalyzing the reaction of pyrrole with an aromatic aldehyde to form meso-tetraarylporphyrins which may or may not be metallated.

This process is unique and advantageously replaces the Rothemund, Adler and Lindsey processes. It constitutes an important advance in the synthesis of free and metallated porphyrins, the interest of which is growing in the search for alternative anti-cancer therapies. Their natural property of photosensitizers currently gives rise to many hopes in dynamic phototherapy.

It is thus possible to prepare meso-tetraphenylporphyrins of formula:

R

R in which R = H, COOEt, CHÆOOEt, CH ₂ CH ₂ COOEt, CHj, CH = CH ₂ , and Ar represents an aryl radical such as phenyl, p-chlorophenyl, p-tolyl.

And represents an ethyl.

A 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 reactions of organic synthesis of functional transformations by Lewis acid catalysis chosen. among the reactions of aromatic electrophilic substitution, the construction of heterocycles, the preparation and the protection of carbonyl derivatives, radical oxidations, epoxidations, oxidations of alcohols located in alpha of a heterocyclic or carbocyclic aromatic group or of a double bond, the oxidative cleavage of polyols, the oxidation of benzamines, the oxidative aromatic dehydrogenation of unsaturated and / or conjugated cyclic derivatives 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 led to nt to the formation of dihydropyridines (DHP).

It should be noted that the reactions of oxidative cleavages of polyols and of oxidative aromatic dehydrogenation of unsaturated cyclic derivatives are particularly important and unexpected.

A subject of the present invention is also the use of catalysts comprising Μη (III) which can be obtained from extracts of metallophyte plants hyperaccumulating Mn either by the action of oxygen in the air in the presence of OH ions and then by a treatment with an anhydride such as acetic anhydride is to the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex in the degree of oxidation (II) which is subjected to the action of dioxygen in the air, optionally in the presence of one or more co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenyl oxygen hypoiodite, for the implementation of organic reactions, in particular radical oxidations or the oxidation of alkenes, in particular the epoxidation of alkenes.

The radical oxidants of oxidation degree (III) obtained by the action of dioxygen in the air in the presence of OH 'ions and then by treatment with an anhydride such as acetic anhydride are very advantageous in organic synthesis because they avoid the preparation of halogenated derivatives and the use of toxic derivatives such as trialkyltin hydrides.

From a mechanistic point of view, the reagent comprising Μη (III) makes it possible to generate in situ an alpha carbon radical of an withdrawing group, which is then trapped in an intra or intermolecular addition reaction. This principle is illustrated by the reaction of ethyl acetoacetate with styrene. The presence in particular of Cu (II) and Fe (III) favorably accelerates the last step.

The principle of the reaction using radical oxidants of oxidation degree (III) obtained by the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (11) that the action of dioxygen in the air is subjected to the action of biomimetic oxidation where the porphyrin reproduces the oxidative activity of cytochromes P-450.

The attraction and the originality of the system is that it can use a catalytic system based on a mixed composition mainly composed of porphyrin-Mn (Hl)! porphyrin-Fe (III), the most efficient oxidizing systems. The principle is based on the use of the natural composition of hyperaccumulating plants in Mn described in the process indicated above.

These biomimetic and biobased catalysts can be associated with many possible oxidants (CIO ′, PhlO, r-BuOOH, HOOH, etc.).

The olefins to be epoxidized are mainly vinyl derivatives conjugated to an aromatic ring where the nucleus can be mono or disubstituted.

A subject of the present invention is also the use of catalysts comprising Μη (ΠΙ) which can be obtained from extracts of metallophyte plants hyperaccumulating Mn either by the action of oxygen in the air in the presence of OH “ions then by a treatment with an anhydride such as acetic anhydride is to the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (II) which is subjected to the action of oxygen in the air, optionally in the presence of one or more co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenylc ioxygen hypoioditc, 25 characterized in that the catalyst is made to act preferably in the form of a porphinato-manganese complex in the degree of oxidation (III) on isoeugenol or ferulic acid, preferably in acetonitrile, to obtain vantllin.

An example of such a preparation using a porphinato-manganese complex in the degree of oxidation (III) is given below in the experimental part.

A subject of the present invention is also the use of catalysts comprising Μη (IV) practically devoid of manganese in the form MfaCh or Mn2Oj, preferably comprising less than 3% of manganese in the form MnsOO or Mn2O3 and which can be obtained from '' extracts of metallophyte plants hyperaccumulating Mn by the action of oxygen from the air in the presence of OH * ions and if desired by an acid treatment followed by dehydration, preferably under reduced pressure, so as to obtain a reagent comprising manganese to the degree of oxidation (IV) (Μη (IV) 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) for the implementation of organic reactions, in particular:

A- oxidation of alcohols located in alpha of a heterocyclic or carbocyclic aromatic group or of a double bond,

B- oxidative cleavages of polyols,

C- oxidation of benzamines,

D- oxidizing aromatic dehydrogenation of unsaturated and / or conjugated cyclic derivatives optionally comprising a heteroatom,

E- direct halogenation of enolizable compounds.

A- oxidations of alcohols located in alpha of a heterocyclic or carbocyclic aromatic group or of a double bond

The oxidation reactions of alcohols located alpha to a heterocyclic or carbocyclic aromatic group or a double bond can be illustrated by the total oxidation of benzyl alcohol to benzaldehyde. An example of such a preparation is given in the experimental part. It should be noted that, under the same conditions, commercial MnCh only leads to traces of aldehyde! A reconstituted mixture of MnCh and Fe (III) results in only 20% oxidation under the same conditions.

This example illustrates the advantage of using hyperaccumulating Mn (II) species to replace commercial MnO ₂ , the reactivity of which is very moderate and ultimately underexploited. In the case of the plant system, the original and polymetallic composition of the medium makes it possible to enhance the oxidizing power of Μη (IV) while controlling the reaction up to the intermediate aldehyde stage.

From this perspective, the present invention also relates to the use of a reagent comprising Μη (IV) practically devoid of manganese in the form ΜηίΟ ₄ or Mn ₂ O ₃ [% age to be specified] and optionally associated with salts such as that 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) being obtainable from extracts of a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray by the action of oxygen in the air in the presence of OH 'ions and if desired by an acid treatment followed by dehydration, preferably under reduced pressure, characterized in that the reagent is made to act on the (3- methoxy 4-hydroxy) benzene methanol preferably in ethyl acetate under reflux to obtain vanillin.

The oxidation of (3-methoxy 4-hydroxy) benzene methanol, or vanillic alcohol is also very effective with the reagent of degree of oxidation (IV): Μη (IV). It leads directly to vanilla in a green process that is remarkable for simplicity and efficiency. This product has the most desirable aroma in the world. The synthesis is totally bio-based:

- the precursor alcohol is a natural substance present and abundant in a number of plant species, such as Cotinus cogyggria,

- the oxidant is of completely natural origin, since it is prepared from plant extract. The vanillin thus synthesized can be described as vanillin with a natural flavor.

An example of such a preparation is given below in the experimental part.

This oxidation reaction is easily transposed to the controlled oxidation of allyl alcohols under similar conditions.

This possibility is illustrated with the example of geraniol which leads to citral A (or geranial) sought after in the food industry for its lemon scent.

From this perspective, the present invention also relates to the use of a reagent comprising Μη (IV) practically devoid of manganese in the form of MnjCh or MmOî [% age to be specified] and 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) obtainable from extracts of a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray by the action of oxygen in the air in the presence of OH ions and if desired by an acid treatment then by dehydration, preferably under reduced pressure, characterized in that the reagent is made to act on the geraniol to obtain the geranial.

An example of such a preparation is given below in the experimental part.

B- Oxidizing clippings of polyots,

The oxidation reaction of great practical importance is also possible on secondary alcohols of the benzyl type; the presence of the potyol system leads to an oxidative cleavage rarely described with conventional manganese dioxide.

This reaction is remarkable and it is very reactive, so it is complete after 5 hours of stirring in dichloromethane at room temperature, without degradation and without competing reaction. It therefore makes it possible to replace very aggressive or highly toxic oxidizing reagents (Ce (NH4) 2 (NO3) 6 or Pb (OAc) 4). This result clearly shows the advantage of using a polymetallic oxidizing system derived from plants which are hyperaccumulating manganese.

An example of such a preparation is given below in the experimental part.

C- Oxidation of benzamines: Oxidation of aniline:

The oxidation of aniline is a reaction of great industrial interest but which is delicate and rarely unequivocal. However, it can lead to azobenzene, a very useful photosensitive compound. This reaction is still being researched to improve its preparedness. The most common ta method is based on the reduction of nitrobenzene in a basic medium and can lead to many side products such as nitrosobenzene, 1,2-diphenylhydrazine 1,2-diphenyl 1-oxide diazene and N-phenyl t, 4-benzene diamine .

An example of such a preparation which is given below in the experimental part shows that the GER-Mn (IV) oxidizing system allows controlled oxidation in a single product, azobenzene (E / Z: 6/1), without formation of secondary products and directly from aniline.

D- oxidative aromatic dehydrogenation of unsaturated and / or conjugated cyclic derivatives optionally comprising a heteroatom,

This interesting and very practical use of the Μη (IV) oxidizing system generated from metallophytes allows the dehydrogenation of heterocycles leading to the synthesis of aromatic structures.

A first example which illustrates this possibility is given below in the experimental part.

Another example is the dehydrogenation of a natural cyclic terpene, Γ aterpînene, to an aromatic derivative, para-methyl cumene, a platform molecule of the chemical industry is also given below in the experimental part.

E- direct halogenation of enolizable compounds.

One of the great advantages of the oxidizing system derived from Grevillea and comprising Μη (IV) is to generate an oxidizing entity in the presence of Lewis acids mixed. This very particular mineral composition makes it possible to carry out successive transformations in situ. An example is the iodization of carbonyl compounds by simply adding alkali iodide to the medium:

The principle of the reaction is based on:

• The oxidation of iodide to iodine by MnÜ2 from GEE-Mn (IV);

• Enolization of the carbonyl compound by the dihalides present;

• Direct iodization of the enol thus formed.

All these steps are carried out successively, in situ, in a single reactor from the naturally available form of iodine, the iodides.

Examples of the iodization of ethyl acetoacetate and cyclohexanone are given below in the experimental part.

The results obtained are remarkable and constitute a new green method allowing easy iodization of carbonyl derivatives which are usually not very reactive. It avoids the use of dangerous and / or toxic reagents (oxone, mercuric chloride) and diodine.

F- Synthesis of pyridines by Hantzsch-oxidation reaction in situ

The Hantzsch reaction involving an aldehyde, a beta-dicarbonyl compound and a source of ammonium results in the formation of dihydropyridines (DHP), under Lewis acid catalysis. According to conventional procedures, the DHP obtained can be oxidized to pyridines, by means of oxidizing agents such as KMnO4, MnOj, HNOj. The manganese-based catalysts have been shown to catalyze both reactions very efficiently, in a single pot, thanks to the presence of traces of Mn ^{, v} (with an oxidizing character) within the catalyst, essentially consisting of Mn ¹¹ , which catalyzes the formation of DHP 20 due to its Lewis acid character. The use of the biobased manganese-based catalyst therefore has certain advantages in terms of catalytic efficiency, handling, reduction in the number of steps and of reagents used. Finally, the use of aggressive oxidizing agents and pollutants is avoided.

The 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:

R ¹

I

NH4OAC

Biosourced Mn catalyst

Examples of Hantzsch reactions are given below in the experimental part.

G- Epoxidation of alkenes

It is possible to selectively obtain the epoxide from the starting alkene. The reaction relies on the formation of peroxymonocarbonate coordinated with the Mn "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 similar catalytic systems, in 4 h at 0 ° C. Both enriched and depleted alkenes are active in this reaction (although yields are lower with depleted alkenes).

R

+ H ⁺

Catalyst Mn ²⁺ + HCO ₄ * -

h ₂ o ₂ H ⁺ Catalyst Mn ^{z +} + HCO ₃ ''

Examples of embodiments of this reaction are given below in the experimental part.

H - Synthesis of vanillin

A new very competitive synthesis of vanillin has been developed, thanks to the presence of several degrees of oxidation of Mn within the catalyst, each of them being involved in a particular step of the transformation. While the classic 5 syntheses of vanillin from isoeugenol require the protection of the phenol, the oxidative cleavage of the alkene and then the deprotection of the phenol, the biobased Mn catalyst allows the direct switch from isoeugenol to vanillin, in a single pot, without protection / deprotection steps. The reaction takes place at room temperature and results in a high yield (81%) of vanillin.

This example is typical of the synthetic possibilities of the method: in an acidic medium, the epoxide is opened into a diol, which in turn is subjected to oxidative cleavage in situ. In a mild basic medium, the epoxy is isolated.

bio-based catalysts H ₂ O / CH ₃ COOH ch ₃ cn O II rdt = 81%

OH

An example of preparation is given below in the experimental part.

I - Ene-reactions

Example:

(R) - (+) - citronellal (R) - (-) - isopulegol

Comments: industrial reaction, not supported, and requiring the delicate preparation of ZnBr ₂ and Znl ₂

GER: Grevillea exul rubiginosa

This possibility is specific to Mn catalysts.

This evolution of isopulegol during its formation is unusual. This result is due to the presence of traces of Mn (IV) in the catalysts derived from Grevillea exul rubiginosa which allows the carbonyl-ene reaction, dehydration and aromatization to be linked. It can be exploited for the direct synthesis of p-cymene which is used in perfumery, cosmetics, pharmacy (expectorant and antitussive agent) and in organometallic catalysis.

An example of this preparation is given below in the experimental part.

In the description of the application indicated above and in what follows including the claims, the expression "composition containing a catalyst" or "composition containing at least one catalyst" may be replaced by "catalyst".

The present application thus relates to the use after heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia , Gleichenia, Gossia, Grevillea .Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia having accumulated Manganese (Mn) and optionally one or more metals chosen 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 metal catalyst, including the metal is one of the aforementioned metals originating from said plant, said composition being practically devoid of chlorophyll or of organic matter, for carrying out organic synthesis reactions involving said catalyst.

The present application thus relates to the use after heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia , Gleichenia, Gossia, Grevillea .Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia having accumulated Manganese (Mn) and optionally one or more metals chosen) 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 metal catalyst, the metal of which is l one of the aforesaid metals originating from said plant, said composition being practically devoid of chlorophyll, for carrying out organic synthesis reactions involving said catalyst.

The present application thus relates to the use after heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia , Gleichenia, Gossia, Grevillea .Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia having accumulated Manganese (Mn) and possibly a metal or several metals chosen 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 metal catalyst, including the metal is one of the aforementioned metals in Mn (II) form originating from said plant, said composition being devoid of chlorophyll or of organic matter, for the implementation of organic synthesis reactions involving said catalyst.

A subject of the present application is also a composition devoid of organic matter and in particular of chlorophyll containing at least Mn as catalyst in the form of chloride or sulfate, and cellulose degradation fragments such as cellobiose and / or glucose, and / or glucose degradation products such as 5-hydroxymethylfurfural and formic acid and less than about 2%, especially less than about 0.2% by weight of C, especially about 0.14%.

In the present application, the expression devoid of organic matter means that the compositions which are the subject of the invention meet the criteria indicated above.

A subject of the present application is also the compositions as obtained by implementing the various methods described above.

A subject of the present application is also the use after heat treatment of a plant or a part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia , Gleichenia, Gossia, Grevillea, Helanthius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia having accumulated Manganese (Mn) and optionally a metal or several metals chosen 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 originating from said plant, said catalyst being devoid of organic matter, for the implementation of organic synthesis reactions involving said catalyst.

As described below in the experimental part, the manganese content of the compositions of the invention can be between 15,000 and 270,000 ppm.

In the tables appearing in the present application, the values are indicated in ppm unless otherwise indicated.

EXAMPLES

The methods described in international application WO 2011/064462 and application WO 2011/064487 can also, as far as necessary, be used for the preparation and use of the plants and plant extracts described in the present application.

Example 1: Procedures for preparing the catalysts

Steps common to all preparations:

1. Dehydration of the biomass - oven at 60 ° C - 1 to 2 days, up to 72 hours (the progress of the dehydration is monitored by weighing until the mass is stabilized)

2. Grinding the dry leaves preferably by sorting the stems and impurities

The dried leaves then undergo the following treatment:

3. Summarily crush the leaves in a mortar

4. Calcine the leaves in an oven at 400 ° C with a maximum temperature of 500 ° C (program in successive stages) for 5 hours.

5. Grind the ashes in a mortar to obtain a fine powder.

6. Digest with 12M HCl under magnetic stirring for about 12 hours at 60 ° C.

7. Filtration through a porosity 4 frit covered with 3 cm of Celite (to avoid clogging it) with suction through a water pump. Wash with concentrated hydrochloric acid.

8. Evaporate (or distill) the polymetallic solution with an electric nozzle in a porcelain crucible under a fume hood.

9. Recover the solid phase in the crucible using a spatula and place the catalyst in an oven (storage at 90 ° C).

The solid can be used crude or partially purified depending on the desired objectives.

Example 1.1: dehydration of the biomass between 300 and 500 ° C lKg of leaves of Grevillea exul ssp. exul treated at 400 ° for 5 hours gives approximately 150 g of ash.

At this stage, the ash can optionally be used directly if it is desired to catalyze a reaction in basic catalysis using metal oxides.

In all your other cases, the ashes are treated with acids in solutions (for example HCl, HNO3, trifluoromethanesultonic acid) suitable for the organic syntheses envisaged.

1. Is introduced! 5 ml of acid, for example 1-12 M hydrochloric acid per g of ash in the reaction medium.

2. The reaction mixture is heated to 60 ° C. with stirring for at least 2 hours.

3. The solution obtained is filtered through celite or silica.

Example 1.2: purification using a Dowex 1 resin:

This protocol for your purification of manganese catalysts is based on the use of a resin such as Dowex 1. In 12ΛΪ HCl medium, Μη (II) can be fixed on the anion exchanger. K (I), Ca (II), Al (III), Mg (II), Ni (II) are thus separated. Elution in 8Af then 6Λ / HCl medium releases Mn (II).

Protocol:

- Swell 20 g of Dowex-1 polystyrene-di vinylbenzene resin for 24 hours in 12M HCl. In an ion exchange column 20 cm high and 0.03 cm ^2, pour 20 g of resin into the column. Wash this column just before use with concentrated hydrochloric acid (12Λ /).

- Pour a solution in 12Λ / hydrochloric acid medium, containing at most 500 mg of the elements to be separated, on the column. Then elute Μη (II) with 100ml of 8ΛΖ hydrochloric acid then with 100ml of 6M hydrochloric acid (speed: about 0.5 cm / min (i.e. for 40min). Collect the different eluent of interest and evaporate them in order to obtain the solid catalyst Store in a dry place (oven at 90 ° C).

Table 1 below shows the composition of the solid residue before and after purification by ion exchange resin, analyzed by ICP MS (Inductively Coupled

Plasma Mass Spectroscopy). The resin is very selective for manganese. The purified catalyst is less depleted in Fe, Al and Zn than for resins of the IRA 400 type.

The solid residue obtained is stored under nitrogen.

Table 1. Examples of mineral composition established by 1CP MS of three species of the genus Grevillea, Grevillea exul ssp. rubiginosa (GER), Grevillea exul ssp. exul (GEE) and Grevillea gillivray (GG), a species of the genus Dicranopteris, Dicranopteris linearis (DL), Pinus pinea, (P) and Spermacone latifolia (SL) (values expressed in ppm of dry matter treated at 400 ° C for 5h , then treated with 6N HCl at 60 ° C for 12 h).

^M Mg "Al **VS" "Cr "Mn ** Fe "Co "Or “Cu “Zn "AT" ^{, l4} Cd “'Sb ” ⁷ Bn "* Pb GER 52595 2404 104359 311 26694 8961 14 448 159 562 81 6 3 117 75 GEE 46781 3926 109088 590 58983 18075 43 1175 154 666 70 12 4 232 67 GG 36017 5418 139690 245 58297 5419 20 3604 263 1026 10 49 3 120 289 GG Pure. 5306 1535 6203 678 261268 2278 36 867 88 262 14 43 2 35 230 DL 33498 48082 79889 149 33072 9224 66 590 165 3605 35 183 6 2782 174 P 33566 36835 78790 245 77897 30816 131 946 350 747 23 52 5 493 54 SL 32343 70324 67910 257 104860 16833 249 501 228 2153 20 174 0 532 37

A study of the different catalytic solids by X fluorescence confirms these data and allows to affirm that Mn is in Μη (II) form, Fe in Fe (III) form, Ni, Cu, Zn, Co, Cd, Pb, Ba, Mg , Hg and Mg in oxidation state (II).

The counterions are mainly chlorides, accompanied by the corresponding oxides.

The crude sample derived from Grevillea exul, resulting from a heat treatment at 400 ° C of the biomass and having undergone an acid attack with 1-10N HCl for 6-12 h, filtered through Celite and concentrated under vacuum at 100 ° C, is used directly without purification.

Example 2 ΐ Preparation of the oxidizing reagents Μη (III):

Π is possible to generate oxidizing systems of different reactivity and not associated with porphyrin ligands.

l ⁱⁿ method: Mn (lll) is mainly in ΜηΧί form. (X preferably being OAc)

The transformation of Manganese from the degree of oxidation (II) (Mn (II) to Manganese at the degree of oxidation (III) (Μη (III) characterized in that the Manganese of the degree of oxidation (II) is subjected (Mn (II) to the action of oxygen in the air in the presence of OH ions and then to treatment with an anhydride such as acetic anhydride is carried out as follows:

The originality of the process is the use of a natural oxidant and used under gentle and ecological conditions: dioxygen. The oxidation-reduction reaction becomes possible if it is placed at basic pH. Indeed, the redox potentials of the couples involved decrease with the pH, but in a non-parallel manner. At pH greater than 7, the redox potential of the O2 / H2O couple becomes greater than that of the Μη (III) / Μη (II) couple.

The first step of the process is therefore to place itself in a basic medium by adding sodium hydroxide in order to transform M _x Cl _y into M _x (OH) _y , and more particularly MnCl ₂ into Mn (0H) 2.

The presence of the other metal species leads to the consumption of hydroxyl ions, but does not interfere with the redox step, because all of the other transition metals are phytoextracted at their maximum degree of oxidation (Fe ³ *, Cu ²⁺ , Ni ² *, Zn ² * ...).

Process: lg of catalytic solid GG (or GER, or GEE) are placed in a bico balloon! filled with 100 mL of degassed distilled water and placed under an inert atmosphere (nitrogen or argon). 700 mg of soda are then gradually added. A light bubbling of dioxygen is carried out until a quarter of a mole of gas has dissolved (check by weighing). The reaction is stopped after 30 minutes by adding a large excess of acetic anhydride, until an acidic pH (pH = 4) is obtained. The dioxygen can no longer oxidize the Mn cations and the acetates derived from the transition metals are obtained after 30 minutes of heating under reflux. They are filtered, washed with acetic acid and dried under a stream of nitrogen. We then obtain GG-Μη (III) (or GER-Mn (1II), GEE-Mn (111)).

2 ^nd method: liganded G-Mn (IIl): this possibility is exemplified by the preparation of metallated porphyrins:

The transformation of Manganese of the degree of oxidation (II) (Mn (II) into Manganese at the degree of oxidation (III) (Mn (111) characterized in that one subjects the Manganese of the degree of oxidation (II) (Mn (II) to the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (II) which is subjected to the action of oxygen from air and subject the product obtained to dehydration preferably under reduced pressure to obtain a dry residue comprising manganese at the degree of oxidation (111) (Mn (111) optionally associated with sets such as chlorides, sulphates 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) is made as follows:

Example: porphyrins are prepared by condensation of four equivalents of aldehyde and four equivalents of pyrrole. This reaction is carried out in CHCh, with a concentration of 10 ' ² M for the aldehyde substrates and the pyrrole. The GEE or GEE-purified catalysts are used at a concentration of 3.2.1 O * ³ M in Mn (II). The reaction is stirred for 1 hour at room temperature; it darkens regularly The contents of the flask are then poured into 100 mL of an ice-cold aqueous solution (0 ° C) of NaCl (30 g / 100 mL). A green suspension appears. The mixture is filtered through a frying pan, rinsed with copious amounts of water. The aqueous phase is extracted with 2 x 50 mL of ether, dried over NaïSCh, then evaporated. A dark green solid is obtained. It is analyzed by UV-visible spectroscopy by observing the Soret bands and Q bands, and confirmed by 1 H NMR. The product obtained is chloro-m & o-tetraphenylporphinato-manganese 5 (III). It is obtained with a yield of 27% with GEE-purified, which constitutes a marked improvement over conventional methods, which require two steps and the overall yield of which varies between 3 and 18%. The supernatant obtained is purple in color. If it is concentrated, mejo-tetraphenylporphyrin is isolated, purified by chromatography and analyzed by UV-visible. The amount obtained depends on the composition of the catalyst used. This is more important with unpurified GEE, the difference corresponds to the lack of chloro-meso-tetraphenylporphinato-manganese (III). Thus, it is possible to direct the reaction towards the manganic or free porphyrin by adjusting the composition of the catalyst derived from Grevillea.

R

R meso-tetraphenylporphyrin +

R

R chloro-meso-tetraphenyl porphlnatomanganese (lil)

mesotetraphenylporphyrin % chloro-mesotetraphenyl porphinatomanganese (III) % Gross GEE 42 21 EGE purified on resin 6 27

Example 3;

Example 3.1: Preparation of the oxidizing reagents G-Μη (III)

Type 1: G-Mn (III) ligandé: this possibility is exemplified by the preparation of the metallated porphyrins of the previous paragraph

- Type 2: G-Mn (III) where Mn (III) is mainly in the MnXî form, (X preferably being OAc)

Example 3J: Controlled oxidation of Μη (II) phytoextract in Μη (IV):

Preparation of the oxidizing reagent in Μη (IV)

The objective here is to precipitate all of the metal cations, with an excess of HO- ions for manganese, then to oxidize the mixture obtained in air to degree (IV). This very advantageous process makes it possible to avoid the use of strong oxidants. Thus, the preferred method is as simple as possible, inexpensive and without environmental impact. This is the advanced oxidation of Μη (II) phyto-extracted and isolated by oxygen from the air at pH = 8 in MnO ₂ , MmOj and Mn ₂ Oj, followed by the disproportionation of the last two oxides in MnO ₂ by returning to pH = 3. Again, purification of manganese salts is not helpful; on the contrary, the presence of associated metal dichlorides such as FeClj activates MnO ₂ in the oxidation reactions.

After oxidation, the solid suspension is treated with concentrated HCl to redissolve the hydroxides. MnO ₂ is collected in the presence of other metal halides including FeClj. The oxidizing system is denoted G-Μη (IV).

An alternative is also the preparation of Μη (IV) by electrolysis, but the polymetallic composition is lost and a conventional oxidant of pure MnO ₂ type is obtained.

Example for a sample of calcined Grevillea gillivrayi placed in 0.20 M hydrochloric acid solution. The NaOH concentration is such that the acid and the other cations except magnesium are quantitatively hydroxylated.

The volume of the solution subjected to the oxidation is 250 mL. Oxidation by air is stopped after about 15 hours (instead of 30 minutes as in the case of the controlled oxidation of Μη (II) to Μη (III)).

The solid suspension, ocher at first, turns dark brown quite quickly. This coloration hardly changes after adding 0.90 M HCl.

The redissolution of copper hydroxide is demonstrated by the appearance of the blue coloration by a test in an ammoniacal medium. A preliminary test at pH 7 shows that all the manganese (II) has been transformed, the oxidation is complete. The oxidizing system derived from Grevillea gillivray obtained is denoted GG-Mn (IV).

Example 4; Applications of agents to organic synthesis;

Application in organic synthesis of Μη (II) phytoextract in MnCl ₂ associated with the metal chlorides obtained according to Table I:

Example 4.1: Construction of heterocycles:

The reactions are carried out according to the following scheme:

R I

CHO

X = OS R = Ph, o-MeOPh, m-OHPh, p-OEtPh, m-OMe, p-OHPh / -Bu R '= OEt, Me, R = Me. R' = R = -CH ₂ -CH ₂ -

Species Catalyst Grevillea exul rubiginosa aldehyde Betadicarbonyl compound Urea / thiourea Number of equivalents 0.20 2.0 2.0 1.0

Example: The catalyst derived from Grevillea exul rubiginosa GER (0.25 mmol in Mn) dispersed over 425 is introduced into a flask fitted with a magnetic bar, a condenser, an introduction funnel and a thermometer. mg of montmorillonite KiO, then 2.5 mmol of benzaldehyde, and 2.5 mmol of ethyl acetoacetate and 1.25 mmol of urea in 15 mL of ethanol. The mixture is brought to reflux for 12 h. The reaction is followed by tcm (UV-eluent visualization: dichloromethane / AcOEt), then the filtered medium and the concentrated filtrate. The crude product is purified by crystallization from EtOH! H ₂ O, then analyzed by 1 H NMR, ¹³ C, COZY, HSQC and IR. The yield reaches 88%.

Example 4.2: Protection of carbonyl derivatives:

The reactions are carried out according to the following scheme:

R = Me. CH ₃ (CH ₂ ) 5-, 3,7-dimethythept-6-en R '= H, Me

Species Catalyst Grevillea exul rubiginosa aldehyde ethanol Number of equivalents 0.10 1.0 85.7

Example: In a 25 mL flask, fitted with a magnetic bar, a condenser, an introductory funnel and a thermometer, introduce 5 mL of absolute ethanol and the GER catalyst (0.30 mmol in Mn (II)). Heat to reflux and stir, then add 540 µL (462 mg, 3.0 mmol) of citronellal dropwise. Continue stirring and heating for 6 hours, the reaction is complete. The analysis of the reaction products can be done easily in GC-MS and IR

Example 43: Electrophilic aromatic substitutions

The reactions are carried out according to the following scheme:

E-X / montmorillonite K10

GER

R = MeO, Me, H, Cl

E = Ac, Ph X = Cl, OAc

Examples:

R = CI GER supported 19 ^

E = Bn on montmorillonite K10 1> 5g

0.32 eq. Mn / BnCI 2h, 40'C, 100%

R = OMe GER supported 1g /

E = Ac on montmorillonite K10 1.5g

4eq Mn / Ac ₂ 0

6h, 70 “C, 80%

R

♦ ArCHO

meso-tetraphenylporphynne

chloro-mesotetraphenyt porphinatomanganese (III)

Species Catalyst Grevillea exulexul aldehyde Pyrrole Number of equivalents 0.32 4.0 4.0

Example: As indicated above, in the chapter describing the preparation of the liganded Mn (111) reagents, the m & o-tetraphenylporphyrin is isolated, purified by chromatography and analyzed by UV-visible. The amount obtained depends on the composition of the catalyst used. This is more important with unpurified GEE, the difference corresponds to the defect of chloro-meso-tetraphenylporphinato-manganese (111). Thus, it is possible to orient the reaction towards manganic or free porphyrin by adjusting the composition of the catalyst derived from Grevillea.

Example 4.4: Radical oxidation using the Μη (III) system of plant origin: Mn (IIl) obtained by the l ^ert method indicated above in Example 2:

Such radical oxidants are of great interest in organic synthesis because they avoid the preparation of halogenated derivatives and the use of toxic derivatives such as trialkyltin hydrides.

From a mechanistic point of view, the green reagent G-Μη (III) makes it possible to generate in situ an alpha carbon radical of an withdrawing group, which is then trapped in an intra or intermolecular addition reaction. This principle is illustrated by the reaction of ethyl acetoacetate with styrene. The presence in particular of Cu (II) and Fe (111) favorably accelerates the last step.

O 0 ^R AA _a 1 ° ΛΑβ GER-Mn (lll) \ Γ ^OEt type 2 R /

R = H, heptenyl R ‘= Ph if R = H

Species Catalyst Grevillea exul rubiginosa styrene Betadicarbonyl compound Number of equivalents 0.20 1.0 1.0

Example: An equimolar mixture (15 mmoles) of ethyl acetoacetate and of styrene is placed in 20 ml of acetic acid under a nitrogen atmosphere. GER-Mn (III) (35 equivalents in Mn) is added all at once. The mixture is brought to 45 ° C. and then stirred for one hour. It is diluted with water, then extracted with ether, dried and concentrated. The product is purified by chromatography on silica (hexane / Et ₂ 0: 4/1) and analyzed by 1 H NMR.

Example 4.5: Oxidations catalyzed by the tetraphenylporphînato-metallated system (Mn (III) obtained by the 2 ^tMC method Indicated above:

The principle of the reaction is that of biomimetic oxidation where porphyrin reproduces the oxidative activity of cytochromes P-450. The attraction and originality of the system is that it can 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 hyperaccumulating plants in Mn described in the type 1-B process. These biomimetic and biobased catalysts can be associated with many possible oxidants (CIO, PhIO, / -BuOOH, HOOH, ...). The olefins to be epoxidized are mainly vinyl derivatives conjugated to an aromatic ring where the nucleus can be mono or disubstituted.

R porphyrin-metal type 1-B cooxidant

R-H, 3-O-alkyl R '= H, 4-O-alkyl, OH R = H. alkyl. COOH

Species Catalyst porphyrlneGrevillea exul rubiglnosa alkene co-oxidant Number of equivalents 0.10 1.0 1.0

Example: 30 mmoles of / raru-methyl isoeugenol are diluted in 5 mL of acetonitrile. 10% of metallated porphyrins (type 2) are added, ie 3 mmol of 5 active species (Mn (IH) + Fe (III)), then 30 mmol of 30% hydrogen peroxide. 3 drops of acetic acid are added, then the mixture is stirred at 35 ° C. The progress of the reaction is monitored by GC MS. The reaction results in 55% dimethoxybenzaldehyde and 21% epoxide, which can then be converted to dimethoxybenzaldehyde in a following sequence (hydrolysis / treatment with G-Mn (IV)).

In the case where R = OMe, R ’= OH and R” = Me, the process constitutes the most direct access to vanillin and is based on a biomimetic process. The substrate, isoeugenol, and the oxidizing catalytic species [G-Μη (III) + Fe (III)] are obtained from natural resources and provide access to a "natural" aroma of vanillin.

Example 5: Uses of the Μη (IV) system of plant origin, in organic synthesis

G-Mn (IV) allows the controlled oxidation of various organic functions:

- A. Alcohols in alpha of an aromatic group (heterocycle or carbocycle), of a double bond,

- B. Oxidizing cleavages of polyols,

- C. Oxidation of Benzamines,

- D. Oxidizing aromatic dehydrogenation of unsaturated and / or conjugated cyclic derivatives, whether or not carrying a heteroatom,

- E. Direct halogenation of enolizable compounds

Example 5.1: Total oxidation of benzyl alcohol to benzaldehyde

In a single neck flask placed under an inert atmosphere, 1.15 mmol of alcohol, 1 g of catalyst and 25 mL of hexane are added. The reaction is followed in IR. The controlled oxidation of alcohol to aldehyde is complete after 6 hours of reaction. After filtration and washing of the solid with hexane, then evaporation, the aldehyde is characterized by IR and 1 H NMR.

Under the same conditions, commercial MnCh only leads to traces of aldehyde! A reconstituted mixture of MnCh and Fe (III) results in only 20% oxidation under the same conditions. This example illustrates the advantage of using hyperaccumulating species of Mn (11) to replace commercial MnCh, whose reactivity is very moderate and ultimately underexploited. In the case of the plant system, the original and polymetaltic composition of the medium makes it possible to enhance the oxidizing power of Μη (IV) while controlling the reaction up to the intermediate aldehyde stage.

The oxidation of (3-methoxy 4-hydroxy) benzene methanol, or vanil alcohol is also very effective with GEE-Mn (IV). Under-exploited

Species Catalyst Grevillea gillivray Mn (IV) alcohol Number of equivalents 0.54 1.0

Standard protocol: the alcohol (10 mmol) is placed in 20 ml of AcOEt under a nitrogen atmosphere. 500 mg of GEE-Mn (IV) catalytic solid are added all at once, and the mixture is stirred at reflux for 3 h. After filtration and concentration of the reaction medium, the medium is analyzed by IR and 1 H NMR. The C = O vibration band of the ester function is identified at 1713 cm ¹ and the aldehyde formed is identified at 1673 cm ¹ . A white product crystallizes quickly.

This reaction is easily transposed to the controlled oxidation of allyl alcohols under similar conditions.

H

This possibility is illustrated with the example of geraniol which leads to citra! A (or geranial) sought after in the food industry for its lemon scent.

100%

Example 5.2: Controlled oxidative cleavage of polyols:

The reaction is complete after 5 hours of stirring in dichloromethane at room temperature, without degradation and without competing reaction.

Species Catalyst Grevillea gillivray Mn (IV) diol Number of equivalents 0.81 1.0

Protocol: 183 mg of furan derivative (R = OEt, R '= Me) are placed in 20 ml of CH2Cl2. 500 mg of GEE-Mn (IV) catalytic solid are added all at once, and the mixture is stirred. The reaction is followed by IR. The C = O vibration band of the ester function is identified at 1713 cm ' ¹ and the aldehyde formed is identified at 2732 and 1687 cm' *. The product crystallizes after filtration through Celite and evaporation. The 1 H NMR analysis confirms the obtaining of the aldehyde formed by the presence of a singlet at 9.7 ppm, the screening of the aromatic proton at 7.5 ppm and the disappearance of the polyol system.

Example 53: Oxidation of benzamine: example of aniline.

The oxidation of aniline is a transformation of industrial interest

Species Catalyst Grevillea gillivray Mn (IV) aniline Number of equivalents 1.5 1.0

/ 1

Protocol: 10 mmoles of aniline are placed in 15 ml of ethyl acetate. GERMn (IV) (15 mmoles in Mn (IV)) are added all at once. The mixture is brought to reflux and heated for 8 h. The solution gradually turns orange. This color reflects the formation of the desired azobenzene. After filtration and concentration of the medium, the azobenzene is obtained pure.

Example 5.4: Aromatizing dehydrogenation of heterocycles and carbocyls:

Species Catalyst Grevillea gillivray Mn (IV) Derivative to flavor Number of equivalents 1.0 1.0

Process :

To a stirred solution of 420 mg (1.0 mmol) of benzoylated furan derivative in 25 mL of toluene is added GEE-Mn (IV) (1.0 mmol of Mn (IV). The medium is stirred and heated to reflux for 12 h, then filtered. The residual solid is washed with dichloromethane then the filtrate is evaporated off under reduced pressure. The crude obtained is purified on a silica column, elution of hexane / ethyl acetate, resulting in a yield of 80% of compound difuranic.

Another example: Aromatizing dehydrogenation of carbocyls

Dehydrogenation of a naturally occurring cyclic terpene, alpha-terpinene, to the aromatic derivative, pnra-methyl cumene, which is a platform molecule for the chemical industry.

p-methyl cumene a-terpinene

Species Catalyst Grevillea gillivray Mn (lV) Derivative to flavor Number of equivalents 2.0 1.0

Process: 10 mmoles of terpinene are placed in 15 ml of dichloromethane. GEE-Mn (IV) is added all at once at a rate of 2 molar equivalents of Μη (IV). The medium is stirred for 12 h at 45 ° C., then filtered through Celite and concentrated under vacuum. The aromatic structure is easily confirmed by GC MS, IR and H NMR.

Example 5.5: Direct halogenation of enolizable compounds

Example of the iodization of ethyl acetoacetate:

OO GER-Mn (IV) * ^zZ ^ ^z ^ ^x OEt Nal / CHjCIj

The conversion of ethyl acetoacetate is complete. Very fine GC MS analysis shows traces of ethyl iodoacetate, suggesting possible iodination of ethyl acetate. This result is surprising because generally such a reaction is described only on easily enolizable compounds (alpha-ketoesters, diones, malonates, ...: Organic Syntheses, Coll. Vol. 9, 310-314 (1998), LF Tietze and U. Beifuss). To verify this unexpected result, direct iodination by the one-pot iodide oxidation to diode enolization-enol iodination sequence was investigated with GER-Mn (IV) and cyclohexanone:

naked n

The direct iodination reaction of cyclohexanone was carried out in a yield of 64%. This result is remarkable and constitutes a new green method allowing easy iodization of carbonyl derivatives which are usually not very reactive. It avoids the use of dangerous and / or toxic reagents (oxone, mercuric chloride) and diode.

Species Catalyst Grevillea gillivray Mn (IV) Substrate to iodine sodium lodide Number of equivalents 0.3 1.0 1.0

General protocol for iodizing carbonyl derivatives and carboxylic esters: ie substrate to be iodized (10 mmol) diluted in 10 mL of dichloromethane and sodium iodide (1 mmol) are placed in a 25 mL single neck flask equipped with a refrigerant. The GER-Mn (IV) reagent (3 mmol of Μη (IV)) is added all at once and the mixture is stirred for 12 h at room temperature. The solution is filtered through Celite and the organic solution washed with sodium thiosulfate solution, dried over sodium sulfate, filtered and concentrated in vacuo. The reaction is analyzed by GC-MS and then by ’H NMR.

Example 6; Synthesis of pyridines by Hantzsch-oxidation reaction in situ

By applying the following reaction scheme:

R ¹

I

NH _x OAc

Bio-based Mn catalyst

% on average

Species Catalyst Grevillea exul rublglnasa aldehyde Betadicarbonyl compound Ammonium acetate Number of equivalents 0.10 1.0 2.0 1.5

and the following operating mode:

Into a scintillation tube, 1 mmol of aldehyde, 2 mmoles of ethyl acetoacetate, 1.5 moles of ammonium acetate and 0.1 mmoles (manganese equivalent) of catalyst supported on SiCh (1 : 1 equivalent by mass). The mixture is placed in a microwave oven for 5 min (stirring after 1 min) at 600W.

The following structures were obtained:

Pyridine / yield (%)

Yield (%)

O

Example 7; Epoxidation of acenes:

Using the following Standard Conditions:

Species Catalyst Grevillea exulexul alkene NaHCOj Hydrogen peroxide 30% Number of equivalents 0.05 1.0 0.2 3.2

In a hemolysis tube, 1 mL of DMF is introduced, as well as the volume of water indicated for each alkene. The alkene (0.25 mmol) is added and the mixture is cooled to 0 ° C with stirring in an ice bath. The K \ 0 / Grevillea exul exul catalyst is then added all at once (mfcataiyscur. In mg / rVaicènc, in mmol) = 144). Stirring is continued for 5 minutes, then a 30% H2O2 mixture (85 pL; 0.8 mmol) and 0.2 M NaHCO 3 (250 pL; 0.05 mmol), previously stirred for 5 minutes, is added in 3 times out of 30 minutes. Stirring is continued at 0 ° C for 4 h, then a sample is taken for extraction with ether and GC-MS analysis, the following alkenes have thus been epoxidized, with yields often higher than those described:

Alkene ¹ Water volume (PL) ¹ t (h) T (-c) Epoxy yield (%) zb 0 4 0 99 100 4 0 43 4 0 4 0 75

0 4 0 63 AT 600 4 0 72 600 4 0 27 Y 100 4 0 74 ch ₃ 2 300 4 0 78 y. 600 4 0 74 -. 0 4 0 42

. H h / 0 4 0 23 CO 600 4 0 98 O 0 4 0 55 O 0 4 0 89

Adding a small amount of water has been found to be beneficial, leading to a large increase in yield in most cases.

Example 8: Synthesis of vanillin:

Procedure:

Species Catalyst Grevillea exul rublginosa isoeugenol Hydrogen peroxide 30% Acetic acid Number of equivalents 0.10 5.0 1.0 9.5

In a 25 mL flask, are introduced: 5 mL of acetonitrile, 30.5 pL (0.2 mmol) of isoeugenol, the mass of suitable bio-based Mn catalyst, calculated so as to initiate 10% reaction (in mol of limiting reagent) of the specific metal species of the selected catalyst, 4.1 pL (0.04 mmol) of 30% hydrogen peroxide, 22 pL (0.38 mmol) of acetic acid and 4.66 pL (0.04 mmol) acetophenone which serves as an internal standard.

The mixture is stirred at AT for 48 h, then analyzed in GC-MS. The vanillin yield is 81%, based on the internal standard introduced.

Example 9: Ene-reactions:

Summary of operating conditions:

catalyst / citronellal / solvent solvent duration % isopulegol % p-cymene lOOmgGER / 154mg (l mmol, 1 equiv) / 10mL CHîCh 1 hour 95 0 100 mg GER + SiO ₂ 1 g / 154 mg (1 mmol, 1 equiv) 1 hour 5 80

Species Catalyst Grevillea exul rublginoso aldehyde Number of equivalents 0.05 1.0

- Description of the preparation of isopulego! :

In a 25mL tetracol flask fitted with a CaCi ₂ guard, a thermometer, a magnetic bar, a condenser and a bromine funnel, 1 mmol of citronellal diluted in 10 mL of dichloromethane is added. . The GER catalyst (100 mg of catalyst, activated by heating at 150 ° C for 15 min) is suspended in the solvent. The whole is stirred for 60 minutes at 40 ° C. (the reaction is followed by tcm (eluent: hexane / ether 4/1, revelation I ₂ )). The reaction mixture is filtered, the organic phase washed with a hydrogencarbonate solution, dried and concentrated. The yield and the stereoselectivity are estimated by NMR and GC MS.

- Description of the preparation dup-cymene:

The process is similar to the previous one with 100 mg of catalyst supported on I g silica, but the reaction is carried out without solvent at 90 ° C. for 1 hour. The evolution of isopulegol enp-cymene is easily followed by GC MS.

Claims (22)

1. Use after heat treatment of a plant or part of a plant belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Macadamia, Maytenus, Pinus, Phytolacca, Spermacone, Stenocarpus, Virotia or Grevillea having accumulated Manganese (Mn) and optionally one or more metals chosen 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, the metal or metals of which are chosen from among the metals originating from said plant, said composition being practically devoid of organic matter, for carrying out organic synthesis reactions involving said agent as catalyst. 2. Use of a composition prepared by heat 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, Hélant hius, Macadamia, Maytenus, Pinus, Spermacone, Stenocarpus, Virotia or Grevillea having accumulated Manganese (Mn) and optionally a metal or several metals chosen in particular 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 metal or metals are chosen from among metals originating from said plant, said composition being practically free of organic matter, for carrying out organic synthesis reactions involving said agent as catalyst. 3. Use according to claim 2 of a composition prepared by heat treatment of a plant or part of a plant belonging to one of the genera chosen from Beauprea gracilis, Beauprea montana, Beaupreopsispaniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea luxury ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea meissneri, Maytenus fournieri drakeana, Maytenus fournierifournierî, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bride! ta ferruginea, Lantana camara, Psorospermum, Phaccolophya neurophylla neurophya, Gleichenia linearis, Macaccolophya, Phaccolophya neurophylla, Gleichenia linearis) Roxb, Pirofia neurophylla Macadamia integrifolia, Macadamia tetraphylla, Eleutherococcus sciadophylloides / synonymous Acanthopanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, Maytenus cunninghamii Chengiopanax sciadophylloide, Phytolacca americana, Austromyrtus bidwillii, Alyxia rubricaulia , Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, Dipteris conjugata, Eleutherococcus sciadophylloides, Ilex crenata, Eugenia clusioides, Pinus syivestris, Stenocarpus ndnei, Virotia neurophylla, Schima superba latiiper, Spermaco hydropiper folia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bride lia ferruginea, Lantana camara, Psorospermum febrifugum Spach, having accumulated Manganese (Mn) and possibly a metal or several metals chosen (s) in particular among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al) and containing at least one mono or polymetallic agent including metal or metals are chosen from the metals obtained from said plant, said composition being devoid of organic matter, for carrying out organic synthesis reactions involving said agent as catalyst. 4. Use according to claim 1 after heat treatment of a plant or a part of a plant chosen from Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea meissneri, Maytenus fournieri drakeana, Maytenus fournieri fournieri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea.Lantana camara, Psorospermum febaccola, Phaccolosa neurophylla neurophylla, Gleichenia linearis, Psorospermum febaccola, Phaccolia neurophylla, Phaccolophya, Phaccolophya neurophylla , Virotia neurophylla, Macadamia integrifolia, Macadamia tetraphylla, Eleutherococcus sciadophylloides (synonym Acanthopanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, May bare you cunninghamii Chengiopanax sciadophylloides, Phytolacca americana, Austromyrtus bidwillii, Alyxia rubricaulia, Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, Dipteris conjugata, Eleutherococcus sciadophylloides, Hex crenata, Eugenia clusioides, Pinus syivestris, Stenocarpus ndnei, Virotia hydropiperiumceba, Schaco superbaiperba, Schaco superbaceba, Schaco superba latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara, Psorospermum febrifitgum Spach and preferably the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn) and possibly a metal or more metals chosen 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 a electrolysis after acid treatment for the implementation of organic synthesis reactions involving said agent as catalyst. 5. Use according to one of claims 1 to 4 wherein the mono or polymetallic agent is a catalyst comprising manganese (Mn) having the degree of oxidation (II) (Mn (II), or the degree of oxidation (111) (Μη (III) and optionally a metal or more metals chosen from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al). 6. Use according to one of claims 1 to 5 wherein the mono or polymetallic agent is a reagent comprising manganese (Mn) having the degree of oxidation (III) (Μη (III), or the degree of oxidation (IV) (Μη (IV) and optionally one or more metals chosen from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al). 7. Use according to one of claims 1 to 6 after heat treatment followed by an acid treatment and optionally an oxidation and / or an electrolysis of a plant or a part of a plant chosen 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 metals chosen from among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca ), Cadmium (Cd), Aluminum (Al). 8. Use according to one of claims 1 to 7, wherein the acid treatment is preferably carried out with hydrochloric acid, in particular gaseous HCl, HCl IN Δ 12N, sulfuric acid, acetic acid. , trifluoromethanesulfonic acid, nitric acid, perchloric acid, phosphoric acid, trifluoroacetic acid or para-toluenesulfonic acid. 9. Use according to one of claims 1 to 4, wherein the composition is filtered through an inert mineral solid such as celite and optionally subsequently purified on ion exchange resin. 10. Use according to claims 1 to 9, wherein the Mn concentration is between about 15,000 to about 280,000 mg / kg dry weight of plant in the dried leaves of the plant Grevillea exul ssp. exul. 11. Use according to one of claims 1 to 10 of catalysts comprising Mn (II) obtained from extracts of metallophyte plants hyperaccumulating Mn belonging to one of the genera chosen from Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia , Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Grevillea, Helanthius, Macadamia, Maytenus, P inus, Spermacone, Stenocarpus, or Virotia for the implementation of organic reactions, in particular the construction of heterocycles, the protection of carbonyl derivatives, preferably aldehydes and electrophilic aromatic substitutions, preferably constructing porphyrins. ι * 12. Use according to one of claims 1 to 11 wherein the composition containing at least one metal catalyst or preferably polymetallic as described in one of these claims is used in the implementation of organic synthesis reactions of transformations. functional by Lewis acid catalysis chosen from aromatic electrophilic substitution reactions, construction of heterocycles, preparation and protection of carbonyl derivatives, radical oxidations, epoxidations, oxidation of alcohols located in alpha of an aromatic group heterocyclic or carbocyclic or of a double bond, the oxidative cleavage of polyols, the oxidation of benzamines, the oxidative aromatic dehydrogenation of unsaturated and / or conjugated cyclic derivatives optionally comprising a heteroatom, the direct halogenation of enolizable compounds, the reaction of Hantzsch in Lewis acid catalysis between an aldehyde, a beta-dicarbonyl compound and a source of ammonium leading to the formation of dihydropyridines (DHP). 13. Process for preparing a composition substantially free of organic matter and comprising a metallic or polymetallic agent comprising manganese (Mn) having the degree of oxidation (II) (Μη (II), the degree of oxidation (111) (Mn (111) or the degree of oxidation (IV) (Μη (IV) and possibly a metal or more metals chosen from among magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (AI) characterized in that it comprises the following steps: a) Dehydration of the biomass of a plant or of a plant extract belonging to one of the genera chosen from among Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Hélanthiiis, Macadamia, Maytenus, Pinus, Phytolacca Spermacone, Stenocarpus, or Virotia or Grevillea and in particular Grevillea exul ssp, rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray having accumulated Manganese (Mn), and optionally one or more metals chosen from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), Calcium (Ca), Cadmium (Cd), aluminum (Al), b) Grinding of the dry biomass of a plant or of a plant extract obtained in stage a) " c) Heat treatment in the oven preferably at a temperature below 500 ° C of the ground mixture And if desired, and preferably d) Treatment of the ashes obtained in stage c) with an acid preferably chosen from hydrochloric acid, nitric acid, sulfuric acid, acetic acid or trifluoromethanesulfonic acid, nitric acid, acid perchloric, phosphoric acid, trifluoroacetic acid or para-toluene sulfonic acid followed if desired by dehydration of the solution or suspension obtained preferably under reduced pressure so as to obtain a dry residue and solution or suspension obtained in stage d) which , if desired, is submitted e) when the product obtained in stage d) is a suspension, in a step of removing insoluble matter, for example by filtration through an inert mineral solid such as celite or by centrifugation, a step followed if desired by dehydration of the solution preferably obtained under reduced pressure so as to obtain a dry residue when and / or f) a possible total or partial purification on ion exchange resins followed if desired by dehydration of the solution obtained, preferably under reduced pressure so as to obtain a dry residue g) and dry residue obtained in stage c), d), e) or f) containing Manganese in the degree of oxidation (II) (Mn (II) only if desired to transform the Manganese in the degree of oxidation (II) (Mn (II) in Manganese at the degree of oxidation (III) (Μη (III) is subjected either to the action of oxygen in the air in the presence of OH ~ ions then to treatment with an anhydride such as that acetic anhydride is under the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (II) which is subjected to the action of dioxygen air and subjects the product obtained to dehydration, preferably under reduced pressure to obtain a dry residue comprising manganese in the degree of oxidation (III) (Μη (III) optionally associated with salts such as chlorides, sulphates 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). h) and product in dry form obtained in stage c), d), e) or f) only if desired is subjected to the action of oxygen in the air in the presence of OH 'ions to transform the manganese to the degree of oxidation (11) (Mn (ll) to manganese to the degree of oxidation (IV) (Μη (IV) and if desired, the suspension obtained is subjected to an acid treatment and then to dehydration, preferably under reduced pressure so to obtain a reagent practically devoid of manganese in the form MnjO4 or M112O3 [<3%] comprising manganese in the degree of oxidation (IV) (Μη (IV) 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) . i) and product in dry form obtained in stage c), d), e) or f) that if desired is subjected to an electrolysis in an acid medium to obtain manganese in the degree of oxidation (IV) (Μη (IV ) as MnCh practically free from other metals. j) and product in dry form obtained in stage c), d), e), f) g) or h) that if desired is mixed or treated in an acidic medium with a support preferably chosen from silica, montmorillonite , polygalacturonic acid, chitosan or a mixture of these products to obtain a supported catalyst k) and product in dry form obtained in stage c), d), e), f) g) or h) that if desired is reacted with preferably organic ligands under the optional action of microwaves to obtaining chelated agents, preferably catalysts chelated for example with porphyrins. 14. The method of claim 13 for preparing a composition substantially free of organic material and comprising a metallic agent comprising manganese (Mn), having the degree of oxidation (II), (111) or (IV), and optionally a metal or more metals chosen from among calcium (Ca), magnesium (Mg), Iron (Fe) or Aluminum (Al) characterized in that the process is carried out from a plant or a part of a plant chosen from the genus Grevillea and in particular "·" Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray, preferably Grevillea exul ssp. Exul. 15. Use according to one of claims 1 to 12 of catalysts comprising Mn (111) obtainable from extracts of metallophyte plants hyperaccumulating Mn either by the action of oxygen in the air in the presence of OH ions then to a treatment with an anhydride such as acetic anhydride or to the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex in the degree of oxidation (II) which is subjects to the action of dioxygen in the air, optionally in the presence of one or more co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenyl ioxygen hypoiodite, for carrying out organic reactions, in particular radical oxidations or the oxidation of alkenes, in particular the epoxidation of alkenes. 16. Use according to one of claims I to 12 of catalysts comprising Mn (III) obtainable from extracts of metallophyte plants hyperaccumulating Mn either by the action of oxygen in the air in the presence of OH ions ~ then to a treatment with an anhydride such as acetic anhydride or the action of pyrrole optionally substituted in the presence of an aldehyde to obtain the formation of a porphinato-manganese complex at the degree of oxidation (II) that the is subjected to the action of dioxygen in the air, optionally in the presence of one or more co-oxidants such as hydrogen peroxide, sodium hypochlorite, ter-butyl peroxide or phenyl hypoiodite ioxygen , characterized in that the catalyst is made to act preferably in the form of a porphinato-manganese complex in the degree of oxidation (III) on isoeugenol, preferably in acetonitrile, to obtain vanillin. 17. Use according to one of claims 1 to 12 of reagents comprising Mn (IV) practically devoid of manganese in the form of MnjOj or MniOj which can be "·" obtained from extracts of metallophyte plants hyperaccumulating Mn by the action oxygen from the air in the presence of OH 'ions and if desired by an acid treatment followed by dehydration, preferably under reduced pressure, so as to obtain a reagent comprising manganese at the degree of oxidation (IV) (Μη (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) for the implementation of organic reactions, in particular the oxidation of alcohols located in alpha of a heterocyclic or carbocyclic aromatic group or of a double bond, oxidative cleavage of polyols, oxidation of benzamines, dehydrogenation has oxidizing romatic of unsaturated and / or conjugated cyclic derivatives optionally comprising a heteroatom, the direct halogenation of enolizable compounds. 18. Use according to one of claims 1 to 12 of a reagent comprising Mn (IV) practically devoid of manganese in the form of MmCh or Mn ^ Ch and 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) obtainable from extracts of a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray by the action of oxygen in the air in the presence of OH * ions and if desired by an acid treatment followed by dehydration, preferably under reduced pressure, characterized in that the reagent is made to act on the (3- methoxy 4-hydroxy) benzene methanol preferably in ethyl acetate under reflux to obtain vanillin. 19. Use according to one of claims 1 to 12 and 15 of a reagent comprising Μη (IV) practically devoid of manganese in the form of MnjCh or Mn ^ Oj and 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 ( A1) obtainable from extracts of a plant or a part of a plant chosen from the genus Grevillea and in particular Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul and Grevillea gillivray by the action of oxygen from the air in the presence of OH 'ions and if desired by an acid treatment then by dehydration, preferably under reduced pressure, characterized in that the reactant is made to act on the geraniol to obtain the geranial. 20. A composition as obtained by carrying out the method according to claim 13. 21. Composition according to claim 20 practically devoid of organic material and in particular of chlorophyll containing at least one metal catalyst, the metal of which is chosen in particular from manganese (Mn) in Μη (II) form in an amount greater than 25,000 ppm, preferably in quantity greater than 50,000 ppm, and in particular greater than 200,000 ppm, calcium (Ca), magnesium (Mg), iron (Fe) or aluminum Al (111) comprising at least one of said metals in the form of chloride or of sulfate or in the form of a complex with a chloride of another metal, for example ferric chloride FeCh, and cellulose degradation fragments such as cellobiose and / or glucose, and / or glucose degradation products such as 5 -hydroxymethylfurfural and optionally formic acid and less than about 2%, in particular less than about 0.2% by weight of carbon, in particular about 0.10% of carbon. 22. Composition according to one of claims 20 or 21 practically devoid of organic material and in particular of chlorophyll containing at least one metallic or polymetallic reagent comprising manganese (Mn) in Μη (III) or Μη (IV) form as well as a or more metals preferably chosen from calcium (Ca), magnesium (Mg), iron (Fe) or aluminum Al (III) said reagent comprising at least one of said metals in the form of salts such as chlorides, sulphates or acetates in the form of an oxide, a chelate or in the form of a complex with a chloride of another metal, for example ferric chloride FeCb