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

Abstract

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

Claims

1. A method for implementing an organic synthesis reaction, comprising the following steps: a) preparing a composition containing at least one polymetallic agent, metals of which are selected from metals originating from a plant or a part of a plant, said composition containing less than 10% by weight of organic matter according to the following steps: i) dehydrating a plant or a part of a plant, said plant or said part of said plant belonging to a genus selected from the group consisting of Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Macadamia, Maytenus, Pinus, Phytolacca, Spermacone, Stenocarpus, Virotia and Grevillea, that has accumulated manganese (Mn) and at least a metal selected from the group consisting of magnesium (Mg), iron (Fe), calcium (Ca) and aluminum (Al), and obtaining a dried plant or dried part of said plant; ii) grinding the dried plant or dried part of said plant obtained from step i), and obtaining a grinded mixture; iii) thermally treating the grinded mixture obtained for step ii) and obtaining the composition containing at least one polymetallic agent, said composition comprising Mn and at least a metal selected from the group consisting of Mg, Fe, Ca and Al; b) adding to a reaction mixture the composition obtained from step a); and c) implementing an organic synthesis reaction selected from the group consisting of radical oxidations, epoxidations, oxidations of alcohols located in an alpha position of a heterocyclic or carbocyclic aromatic group or of a double bond, oxidizing cleavage of polyols, oxidation of benzamines, and oxidizing aromatic dehydrogenation of unsaturated and/or conjugated cyclic derivatives optionally comprising a heteroatom, wherein the composition is a catalyst for the organic synthesis reaction.

2. The method according to claim 1, wherein the polymetallic agent is a catalyst comprising manganese (Mn) having a degree of oxidation (II) (Mn (II)), or a degree of oxidation (III) (Mn (III)).

3. The method according to claim 1, wherein the polymetallic agent is a reagent comprising manganese (Mn) having a degree of oxidation (III) (Mn (III)), or a degree of oxidation (IV) (Mn (IV)).

4. The method according to claim 1, wherein the thermally treating of step iii) is followed by an acid treatment step iv) and optionally oxidation and/or electrolysis of a plant or a part of a plant selected from the group consisting of Grevillea exul ssp. Rubiginosa, Grevillea exul ssp. exul and Grevillea gillivrayi that has accumulated manganese (Mn).

5. The method according to claim 4, wherein the acid treatment is carried out with hydrochloric acid, sulphuric acid, acetic acid, trifluoromethanesulphonic acid, nitric acid, perchloric acid, phosphoric acid, trifluoroacetic acid or para-toluenesulphonic acid.

6. The method according to claim 1, wherein the composition is filtered on an inert solid mineral and optionally subsequently purified on an ion-exchange resin.

7. The method according to claim 1, wherein the concentration of Mn is between 15,000 and 280,000 mg/kg of plant dry weight in dried leaves of the plant Grevillea exul ssp. exul.

8. The method according to claim 1, wherein the catalysts comprises Mn (II) obtained from extracts of metallophyte plants that are hyperaccumulators of Mn.

9. The method according to claim 1, wherein the catalysts comprises Mn (III) which can be obtained from a solution comprising extracts of metallophyte plants that are hyperaccumulators of Mn by either: action of dioxygen dissolved in the solution comprising the extracts, in the presence of OH.sup. ions in said solution comprising the extracts and then to a treatment with an anhydride, or action of pyrrole optionally substituted in the presence of an aldehyde in order to obtain the formation of a solution comprising a porphinato-manganese complex with a degree of oxidation (II), wherein the porphinato-manganese complex is subjected to action of dioxygen dissolved in said solution comprising the porphinato-manganese complex, optionally in the presence of one or more co-oxidants for carrying out an organic synthesis reaction.

10. The method according to claim 1, wherein the catalysts comprise Mn (IV) and contain less than 3% of manganese in the form Mn.sub.3O.sub.4 or Mn.sub.2O.sub.3 which can be obtained from a solution comprising extracts of metallophyte plants that are hyperaccumulators of Mn by action of dioxygen dissolved in the solution comprising the extracts, in the presence of OH.sup. ions in said solution and, optionally, by an acid treatment and then to dehydration so as to obtain a reagent comprising manganese with a degree of oxidation (IV) (Mn (IV)).

11. The method according to claim 1, wherein a reagent comprising Mn (IV) and containing less than 3% of manganese in the form Mn.sub.3O.sub.4 or Mn.sub.2O.sub.3 which can be obtained from a solution comprising extracts of a plant or a part of a plant selected from the group consisting of Grevillea exul ssp. Rubiginosa, Grevillea exul ssp. exul and Grevillea gillivrayi by action of dioxygen dissolved in the solution comprising the extracts in the presence of OH.sup. ions in said solution and optionally by an acid treatment and then dehydration is reacted with (3-methoxy 4-hydroxy) benzene methanol under reflux in order to obtain vanillin.

12. The method according to claim 1, wherein a reagent comprising Mn (IV) and containing less than 3% of manganese in the form Mn.sub.3O.sub.4 or Mn.sub.2O.sub.3 which can be obtained from a solution comprising extracts of a plant or a part of a plant selected from the group consisting of Grevillea exul ssp. Rubiginosa, Grevillea exul ssp. exul and Grevillea gillivrayi by action of dioxygen dissolved in the solution comprising the extracts in the presence of OH.sup. ions in said solution and, optionally, by an acid treatment and then dehydration is reacted with geraniol in order to obtain geranial.

13. The method according to claim 1, wherein the composition comprises manganese (Mn) in the form Mn (II) in a quantity above 25,000 ppm, calcium (Ca), magnesium (Mg), iron (Fe) or aluminium Al(III).

14. The method according to claim 9, wherein the organic synthesis reaction is a radical oxidation or an oxidation of alkenes.

15. The method according to claim 10, wherein the organic synthesis reaction is selected from the group consisting of oxidations of alcohols located in alpha position of a heterocyclic or carbocyclic aromatic group or of a double bond, oxidizing cleavage of polyols, oxidation of benzamines, and oxidizing aromatic dehydrogenation of unsaturated and/or conjugated cyclic derivatives optionally comprising a heteroatom.

16. The method according to claim 1, wherein the composition contains less than 5% by weight of organic matter.

17. The method according to claim 4, wherein the composition, after acid treatment, has been subjected to at least one treatment selected from the group consisting of filtration, purification resin, oxidation, fixation on a support, chelation, and electrolysis.

18. The method according to claim 1, wherein said plant is selected from the group consisting of Beauprea gracilis, Beauprea montana, Beaupreopsis paniculata, Garcinia amplexicaulis, Grevillea exul, Grevillea exul ssp. rubiginosa, Grevillea exul ssp. exul Grevillea gillivrayi, Grevillea meissnerimeisneri, Maytenus fournieri drakeana, Maytenus fournieri fournieri, Spermacoce latifolia Aubl, Dicranopteris linearis (synonym: Gleichenia linearis), Bridelia ferruginea, Lantana camara, Psorospermun febrifugum Spach, Macadamia neurophylla, Phytolacca americana, Gossia bidwillii, Phytolacca acinosa Roxb, Virotia neurophylla, Macadamia integrifolia, macadamia tetraphylla, Eleutherococcus sciadophylloides (synonym Acanthonanax sciadophylloides), Eleutherococcus sciadophylloides, Ilex crenata, Gossia bamagensis, Gossia fragrantissima, Gossia sankowsiorum, Gossia gonoclada, Maytenus cunninghamii, Chengiopanax sciadophylloides, Phytolacca americana, Austromyrtus bidwillii, Alyxia rubricaulia, Azolla caroliniana, Crotalaria semperflorens, Crotalaria clarkei, Dipteris conjugata, Eugenia Clusioides, Pinus sylvestris, Stenocarpus ndnei, Virotia neurophylla, Schima superba, and Polygonum hydropiper.

19. A method for implementing an organic synthesis reaction, comprising the following steps: a) preparing a composition containing at least one polymetallic agent, metals of which are selected from metals originating from a plant or a part of a plant, said composition containing less than 10% by weight of organic matter according to the following steps: i) dehydrating a plant or a part of a plant, said plant or said part of said plant being selected from the genus consisting of Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Macadamia, Maytenus, Pinus, Phytolacca, Spermacone, Stenocarpus, Virotia or Grevillea, that has accumulated manganese (Mn), and at least a metal selected from the group consisting of magnesium (Mg), iron (Fe), calcium (Ca) and aluminium (Al), and obtaining a dried plant or dried part of said plant; ii) grinding the dried plant or dried part of said plant obtained from step i), and obtaining a grinded mixture; iii) thermally treating the grinded mixture obtained for step ii) and obtaining the composition containing at least one polymetallic agent, said composition comprising manganese (II) and at least a metal selected from the group consisting of magnesium (Mg), iron (Fe), calcium (Ca) and aluminium (Al); b) adding to a reaction mixture the composition obtained from step a); and c) implementing an organic synthesis reaction selected from the group consisting of radical oxidations, epoxidations, oxidations of alcohols located in alpha position of a heterocyclic or carbocyclic aromatic group or of a double bond, oxidizing cleavage of polyols, the oxidation of benzamines, oxidizing aromatic dehydrogenation of unsaturated and/or conjugated cyclic derivatives optionally comprising a heteroatom, wherein the composition is a catalyst for the organic synthesis reaction.

20. A method for implementing an organic synthesis reaction, comprising the following steps: a) preparing a composition containing at least one polymetallic agent, metals of which are selected from metals originating from a plant or a part of a plant, said composition containing less than 10% by weight of organic matter-according to the following steps: i) dehydrating a plant or a part of a plant, said plant or said part of said plant being selected from the genus consisting of Alyxia, Azolla, Beauprea, Beaupreopsis, Bridelia, Crotalaria, Dicranopteris, Dipteris, Eugenia, Gleichenia, Gossia, Macadamia, Maytenus, Pinus, Phytolacca, Spermacone, Stenocarpus, Virotia or Grevillea, that has accumulated manganese (Mn), and at least a metal selected from the group consisting of magnesium (Mg), iron (Fe), calcium (Ca) and aluminium (Al), and obtaining a dried plant or dried part of said plant; ii) grinding the dried plant or dried part of said plant obtained from step i), and obtaining a grinded mixture; iii) thermally treating the grinded mixture obtained for step ii) and obtaining ashes; iv) oxidation of the ashes obtained for step iii) and obtaining the composition containing at least one polymetallic agent, said composition comprising manganese (III) and/or manganese (IV) and at least a metal selected from the group consisting of magnesium (Mg), iron (Fe), calcium (Ca) and aluminium (Al); b) adding to a reaction mixture the composition obtained from step a); and c) implementing an organic synthesis reaction selected from the group consisting of radical oxidations, epoxidations, oxidations of alcohols located in alpha position of a heterocyclic or carbocyclic aromatic group or of a double bond, oxidizing cleavage of polyols, the oxidation of benzamines, oxidizing aromatic dehydrogenation of unsaturated and/or conjugated cyclic derivatives optionally comprising a heteroatom, wherein the composition is a catalyst for the organic synthesis reaction.

21. The method according to claim 20, wherein the oxidation of step iv) is carried out by either: action of dioxygen dissolved in a solution comprising the ashes obtained for step iii) in the presence of OH.sup. ions in said solution, and then to a treatment with an anhydride, or action of pyrrole optionally substituted in the presence of an aldehyde in order to obtain the formation of a solution of a porphinato-manganese complex with a degree of oxidation (II), wherein the porphinato-manganese complex is subjected to action of dioxygen dissolved in said solution comprising the porphinato-manganese complex, or action of dioxygen dissolved in a solution comprising the ashes obtained for step iii) in the presence of OH.sup. ions in said solution and, optionally, by an acid treatment.

Description

EXAMPLES

(1) The methods described in international application WO 2011/064462 and application WO 2011/064487 may also, in so far as required, be used for the preparation and the use of the plants and extracts of plants described in the present application.

Example 1: Procedures for the Preparation of the Catalysts

(2) Steps that are common to all the preparations: 1. Dehydration of the biomassoven at 60 C.1 to 2 days, up to 72 hours (the progress of dehydration is monitored by weighing until the weight has stabilized) 2. Grinding of the dry leaves, preferably separating the stems and impurities The dried leaves then undergo the following treatment: 3. Briefly grind the leaves in a mortar 4. Calcine the leaves in an oven at 400 C. with a maximum temperature of 500 C. (programme with successive stages) for 5 h. 5. Grind the ash in a mortar in order to obtain a fine powder. 6. Digest with 12M HCl with magnetic stirring for about 12 h at 60 C. 7. Filtration on a frit of porosity 4 covered with 3 cm of Celite (to prevent clogging) with aspiration by a water jet pump. Wash with concentrated hydrochloric acid. 8. Evaporate (or distil) the polymetallic solution on an electric heater in a porcelain crucible under a hood. 9. Recover the solid phase from the crucible using a spatula and placed the catalyst in the oven (storage at 90 C.).

(3) The solid may be used crude or partially purified, depending on the sought objectives.

Example 1.1: Dehydration of the Biomass Between 300 and 500 C.

(4) 1 kg of leaves of Grevillea exul ssp. exul treated at 400 for 5 h gives about 150 g of ash.

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

(6) In all other cases, the ash is treated with acids in solution (for example HCl, HNO.sub.3, trifluoromethanesulphonic acid) suitable for the organic syntheses envisaged.

(7) 1. 15 mL of acid, for example 1-12 M hydrochloric acid per g of ash, are introduced into the reaction mixture.

(8) 2. The reaction mixture is heated to 60 C. under stirring for at least 2 h.

(9) 3. The solution obtained is filtered on Celite or silica.

Example 1.2: Purification Using Dowex 1 Resin

(10) This protocol for purification of the manganese catalysts is based on the use of a resin such as Dowex 1. In a 12M HCl medium, Mn (II) can be fixed on the anion exchanger. K(I), Ca(II), ARM), Mg(II), Ni(II) are thus separated. Elution in HCl medium, 8M and then 6M, releases Mn (II).

(11) Protocol: Allow 20 g of polystyrene-divinylbenzene resin Dowex-1 to swell in 12M HCl for 24 h. Pour 20 g of resin into a 0.03 cm.sup.2 ion exchange column with a height of 20 cm. Wash this column with concentrated hydrochloric acid (12M) just before use. Pour a solution in 12M hydrochloric acid medium, containing at most 500 mg of the elements to be separated, onto the column. Then elute Mn (II) with 100 ml of 8M hydrochloric acid and then with 100 ml of 6M hydrochloric acid (rate: about 0.5 cm/min (i.e. for 40 min). Collect the various eluents of interest and evaporate them in order to obtain the solid catalyst. To be stored in a dry place (oven at 90 C.).

(12) Table 1 below shows the composition of the solid residue before and after purification with 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 of Fe, Al and Zn than for the resins of type IRA 400.

(13) The solid residue obtained is stored under nitrogen.

(14) TABLE-US-00001 TABLE 1 Examples of mineral composition established by ICP MS from three species of the genus Grevillea, Grevillea exul ssp. rubiginosa (GER), Grevillea exul ssp. exul (GEE) and Grevillea gillivrayi (GG), one 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 5 h, and then treated with 6N HCl at 60 C. for 12 h). .sup.24Mg .sup.27Al .sup.44Ca .sup.52Cr .sup.55Mn .sup.56Fe .sup.59Co .sup.60Ni .sup.63Cu .sup.66Zn .sup.75As .sup.114Cd .sup.121Sb .sup.137Ba .sup.208Pb 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 Pur. 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

(15) Examination of the various catalytic solids by X-ray fluorescence confirms these data and makes it possible to state that Mn is in the form Mn (II), Fe in the form Fe(III), Ni, Cu, Zn, Co, Cd, Pb, Ba, Mg, Hg and Mg with a degree of oxidation (II).

(16) The counter-ions are predominantly chlorides, accompanied by the corresponding oxides.

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

Example 2: Preparation of the Mn (III) Oxidizing Reagents

(18) It is possible to generate oxidizing systems of different reactivity, not combined with the porphyrin ligands.

(19) 1st Method: The Mn (III) is Mainly in the Form MnX.sub.3 (X Preferably Being OAc)

(20) The conversion of manganese with a degree of oxidation (II) (Mn (II)) to manganese with a degree of oxidation (III) (Mn (III)), characterized in that manganese with a degree of oxidation (II) (Mn (II)) is subjected to the action of dioxygen of the air in the presence of OH.sup. ions and then to treatment with an anhydride such as acetic anhydride, is carried out as follows:

(21) The originality of the method lies in the use of a natural oxidant, which is used under mild and environmentally friendly conditions: dioxygen. The redox reaction becomes possible at basic pH. In fact, the redox potentials of the couples used decrease with the pH, but not in parallel. At pH above 7, the redox potential of the O.sub.2/H.sub.2O couple becomes greater than that of the Mn (III)/Mn (II) couple.

(22) The first step of the method is therefore to make the medium basic by adding soda to convert M.sub.xCl.sub.y to M.sub.x(OH).sub.y, and more particularly MnCl.sub.2 to Mn(OH).sub.2.

(23) ##STR00008##

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

(25) Method:

(26) 1 g of GG (or GER, or GEE) catalytic solid is placed in a two-necked flask filled with 100 mL of degassed distilled water and placed under an inert atmosphere (nitrogen or argon). 700 mg of soda is then added gradually. Gentle bubbling with dioxygen is carried out until a quarter mole of gas has dissolved (monitored by weighing). The reaction is stopped after 30 minutes by adding a large excess of acetic anhydride, until an acid pH is obtained (pH=4). 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 nitrogen stream. GG-Mn (III) (or GER-Mn (III), GEE-Mn (III)) is then obtained.

(27) 2nd Method: G-Mn (III) with Ligand: this Possibility is Illustrated by the Example of the Preparation of the Metallated Porphyrins:

(28) The conversion of manganese with a degree of oxidation (II) (Mn (II)) to manganese with a degree of oxidation (III) (Mn (III)), characterized in that manganese with a degree of oxidation (II) (Mn (II)) is subjected to the action of pyrrole optionally substituted in the presence of an aldehyde in order to obtain formation of a porphinato-manganese complex with a degree of oxidation (II), which is subjected to the action of dioxygen of the air and the product obtained is subjected to dehydration preferably under reduced pressure in order to obtain a dry residue comprising manganese with a degree of oxidation (III) (Mn (III)) optionally associated with salts such as the chlorides, sulphates or acetates or oxides of at least one metal in particular selected from magnesium (Mg), zinc (Zn), copper (Cu), iron (Fe), calcium (Ca), cadmium (Cd), aluminium (Al), is carried out as follows:

Example

(29) the porphyrins are prepared by the condensation of four equivalents of aldehyde and four equivalents of pyrrole. This reaction is carried out in CHCl.sub.3, with a concentration of 10.sup.2 M for the aldehyde substrates and the pyrrole. The GEE or purified-GEE catalysts are used at a concentration of 3.210.sup.3 M of Mn (II). The reaction mixture is stirred for 1 h at ambient temperature; it gets progressively darker. The flask contents are then poured into 100 mL of an iced aqueous solution (0 C.) of NaCl (30 g/100 mL). A green suspension appears. The mixture is filtered on a frit, and rinsed abundantly with water. The aqueous phase is extracted with 250 mL of ether, dried over Na.sub.2SO.sub.4, and 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 .sup.1H NMR. The product obtained is chloro-meso-tetraphenylporphinato-manganese (III). It is obtained with a yield of 27% with purified GEE, which constitutes a clear improvement relative to the conventional methods, which require two steps and the overall yield of which varies between 3 and 18%. The supernatant obtained is of purple colour. If it is concentrated, meso-tetraphenylporphyrin is isolated, purified by chromatography and subjected to UV-visible analysis. The quantity obtained depends on the composition of the catalyst used. It is greater with unpurified GEE, the difference corresponds to the deficit of chloro-meso-tetraphenylporphinato-manganese (III). Thus, it is possible to orient the reaction towards manganic or free porphyrin by adjusting the composition of the catalyst derived from Grevillea.

(30) ##STR00009##

(31) TABLE-US-00002 chloro-meso- meso- tetraphenylporphinato- tetraphenylporphyrin % manganese(III) % Crude GEE 42 21 GEE purified on 6 27 resin

Example 3

Example 3.1: Preparation of the G-Mn (III) Oxidizing Reagents

(32) Type 1: G-Mn (III) with ligand: this possibility is illustrated by the example of the preparation of the metallated porphyrins in the preceding paragraph

(33) Type 2: G-Mn (III) where Mn (III) is mainly in the form MnX.sub.3 (X preferably being OAc)

Example 3.2: The Controlled Oxidation of Phytoextracted Mn (II) to Mn (IV)

(34) Preparation of the Mn (IV) Oxidizing Reagent

(35) The objective here is to precipitate all of the metal cations, with an excess of HO-ions for manganese, and then to oxidize the obtained mixture in the air to degree (IV). This very advantageous method makes it possible to avoid the use of strong oxidants. Thus, the preferred method is the simplest possible, of low cost and without environmental impact. This is thorough the oxidation of phyto-extracted, isolated Mn (II) by the dioxygen of the air at pH=8 to MnO.sub.2, Mn.sub.3O.sub.4 and Mn.sub.2O.sub.3, followed by the dismutation of the two last-mentioned oxides to MnO.sub.2 by return to pH=3. Once again, the purification of the manganese salts is not required; on the contrary, the presence of the associated metal dichlorides such as FeCl.sub.3 activates MnO.sub.2 in the oxidation reactions.

(36) After oxidation, the solid suspension is treated with concentrated HCl in order to redissolve the hydroxides. MnO.sub.2 is collected in the presence of other metal halides, including FeCl.sub.3. The oxidizing system is denoted G-Mn (IV).

(37) Another alternative is the preparation of Mn (IV) by electrolysis, but the polymetallic composition is lost and a conventional oxidant of the pure MnO.sub.2 type is obtained.

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

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

(40) The solid suspension, ochre initially, becomes dark brown quite quickly. This coloration shows practically no change after the addition of 0.90 M HCl.

(41) The appearance of blue coloration in a test in an ammoniacal medium shows that the copper hydroxide is redissolved. A previous test at pH 7 shows that all the manganese(II) has been converted; the oxidation is complete. The oxidizing system derived from Grevillea gillivrayi obtained is denoted GG-Mn (IV).

Example 4: Applications of the Agents in Organic Synthesis

(42) Application, in organic synthesis, of the Mn (II) phytoextracted as MnCl.sub.2 associated with the metal chlorides obtained according to Table 1:

Example 4.1: Construction of Heterocycles

(43) The reactions are carried out according to the following diagram:

(44) ##STR00010##

(45) TABLE-US-00003 Species Catalyst beta- Grevillea dicarbonylated Urea/ exul rubiginosa aldehyde compound thiourea Number of 0.20 2.0 2.0 1.0 equivalents

Example

(46) A, The catalyst derived from Grevillea exul rubiginosa GER (0.25 mmol of Mn) dispersed on 425 mg of montmorillonite K10, and then 2.5 mmol of benzaldehyde, 2.5 mmol of ethyl acetoacetate and 1.25 mmol of urea in 15 mL of ethanol are introduced into a flask equipped with a magnetic stirring bar, a condenser, a dropping funnel and a thermometer. The mixture is refluxed for 12 h. The reaction is monitored by TLC (development UV-eluent: dichloromethane/EtOAc), then the mixture is filtered and the filtrate is concentrated. The crude product is purified by crystallization from the EtOH/H.sub.2O mixture, and then analyzed by .sup.1H NMR, .sup.13C NMR, COSY, HSQC and IR. The yield reaches 88%.

Example 4.2: Protection of Carbonylated Derivatives

(47) The reactions are carried out according to the following diagram:

(48) ##STR00011##

(49) TABLE-US-00004 Species Catalyst Grevillea exul rubiginosa aldehyde ethanol Number of 0.10 1.0 85.7 equivalents

Example

(50) 5 mL of absolute ethanol and the GER catalyst (0.30 mmol of Mn (II)) are introduced into a 25-mL flask equipped with a magnetic stirring bar, a condenser, a dropping funnel and a thermometer. Heat under reflux and stir, and then introduce 540 L (462 mg, 3.0 mmol) of citronellal dropwise. Continue stirring and heating for 6 h, the reaction is complete. The reaction products may easily be analyzed by GC-MS and IR.

Example 4.3: Aromatic Electrophilic Substitutions

(51) The reactions are carried out according to the following diagram:

(52) ##STR00012##

Examples

(53) TABLE-US-00005 R = Cl GER supported 1g/ 0.32 eq. Mn/ 2 h, 40 C., E = Bn on montmorillonite K10 1.5 g BnCl 100% R = OMe GER supported 1 g/ 4 eq. Mn/ 6 h, 70 C., Er = Ac on montmorillonite K10 1.5 g Ac.sub.2O 80%

(54) ##STR00013##

(55) TABLE-US-00006 Catalyst Grevillea Species exul exul aldehyde Pyrrole Number of 0.32 4.0 4.0 equivalents

Example

(56) As indicated above, in the section describing the preparation of the Mn (III) reagents with ligands, the meso-tetraphenylporphyrin is isolated, purified by chromatography and subjected to UV-visible analysis. The quantity obtained depends on the composition of the catalyst used. It is greater with unpurified GEE, the difference corresponds to the deficit of chloro-meso-tetraphenylporphinato-manganese(III). Thus, it is possible to direct the reaction towards manganic or free porphyrin by adjusting the composition of the catalyst derived from Grevillea.

Example 4.4: Radical Oxidations Using the Mn (III) System of Vegetable Origin: Mn (III) Obtained by the 1st Method Given Above in Example 2

(57) Radical oxidants of this kind are very useful in organic synthesis as they avoid the preparation of halogenated derivatives and the use of toxic derivatives such as the trialkyl tin hydrides.

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

(59) ##STR00014##

(60) TABLE-US-00007 Catalyst Grevillea beta- exul dicarbonylated Species rubiginosa styrene compound Number of 0.20 1.0 1.0 equivalents

Example

(61) An equimolar mixture (15 mmol) of ethyl acetoacetate and styrene is placed in 20 mL of acetic acid under a nitrogen atmosphere. GER-Mn (III) (3 equivalents of Mn) is added in one go. The mixture is heated to 45 C. and then stirred for one hour. It is diluted with water, and then extracted with ether, dried and concentrated. The product is purified by silica chromatography (hexane/Et.sub.2O: 4/1) and analyzed by .sup.1H NMR.

Example 4.5: Oxidations Catalyzed by the Tetraphenylporphinato-Metallated System, Mn (III) Obtained by the 2nd Method Indicated Above

(62) The principle of the reaction is that of biomimetic oxidation, where porphyrin reproduces the oxidizing activity of the P-450 cytochromes. The attraction and originality of the system is that it is possible to use a catalytic system based on a mixed composition predominantly composed of porphyrin-Mn (III)/porphyrin-Fe(III), the most efficient oxidizing systems. The principle is based on the use of the natural composition of the Mn hyperaccumulating plants described in the method of type 1-B. These biomimetic and biosourced catalysts may be combined with many possible oxidants (ClO.sup., PhIO), t-BuOOH, HOOH, etc.). The olefins to be epoxidized are mainly vinyl derivatives conjugated to an aromatic ring, where the ring may be mono- or disubstituted.

(63) ##STR00015##

(64) TABLE-US-00008 Catalyst porphyrin- Grevillea exul Species rubiginosa alkene co-oxidant Number of 0.10 1.0 1.0 equivalents

Example

(65) 30 mmol of trans-methyl isoeugenol is diluted in 5 mL of acetonitrile. 10% of metallated porphyrins (type 2) are added, i.e. 3 mmol of active species (Mn (III)+Fe(III)), and then 30 mmol of 30% hydrogen peroxide. 3 drops of acetic acid are added, and then the mixture is stirred at 35 C. The progress of the reaction is monitored by GC MS. The reaction leads to 55% of dimethoxybenzaldehyde and 21% of epoxide, which can then be converted to dimethoxybenzaldehyde in a subsequent sequence (hydrolysis/treatment with G-Mn (IV)).

(66) In the case where ROMe, ROH and R=Me, the method provides the most direct access to vanillin, based on a biomimetic process. The substrate, isoeugenol, and the oxidizing catalytic species [G-Mn (III)+Fe(III)] originate from natural resources and give access to a natural vanillin aroma.

Example 5: Uses of the Mn (IV) System of Vegetable Origin, in Organic Synthesis

(67) G-Mn (IV) allows the controlled oxidation of various organic functions: A. Alcohols in the alpha position of an aromatic group (heterocycle or carbocycle), of a double bond, B. Oxidizing cleavage of polyols, C. Oxidation of benzamines, D. Oxidizing aromatic dehydrogenation of unsaturated and/or conjugated cyclic derivatives bearing or not bearing a heteroatom, E. Direct halogenation of enolizable compounds.

Example 5.1: Total Oxidation of Benzyl Alcohol to Benzaldehyde

(68) 1.15 mmol of alcohol, 1 g of catalyst and 25 mL of hexane are introduced into a single-necked flask under an inert atmosphere. The reaction is monitored by IR. The controlled oxidation of the alcohol to aldehyde is complete after reaction for 6 h. After filtration and washing of the solid with hexane, and then evaporation, the aldehyde is characterized by IR and .sup.1H NMR.

(69) ##STR00016##

(70) Under the same conditions, commercial MnO.sub.2 only leads to traces of aldehyde! A reconstituted mixture of MnO.sub.2 and Fe(III) only leads to 20% oxidation under the same conditions. This example illustrates the advantage of using species that are hyperaccumulators of Mn (II) instead of commercial MnO.sub.2, the reactivity of which is very modest and finally under-utilized. In the case of the vegetable system, the original polymetallic composition of the medium makes it possible to intensify the oxidizing power of Mn (IV) while controlling the reaction up to the intermediate aldehyde stage.

(71) The oxidation of (3-methoxy 4-hydroxy) benzene methanol, or vanillic alcohol, is also very efficient with GEE-Mn (IV). Under-utilized

(72) ##STR00017##

(73) TABLE-US-00009 Catalyst Grevillea gillivrayi Species Mn (IV) alcohol Number of 0.54 1.0 equivalents

(74) Standard Protocol:

(75) the alcohol (10 mmol) is placed in 20 mL of EtOAc under a nitrogen atmosphere. 500 mg of GEE-Mn (IV) catalytic solid is added in one go, and the mixture is stirred under reflux for 3 h. After filtration and concentration of the reaction medium, the medium is analyzed by IR and .sup.1H NMR. The CO=vibration band of the ester function is located at 1713 cm.sup.1 and the aldehyde formed is located at 1673 cm.sup.1. A white product quickly crystallizes.

(76) This reaction can be easily transposed to the controlled oxidation of allyl alcohols under similar conditions.

(77) ##STR00018##

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

(79) ##STR00019##

Example 5.2: Controlled Oxidizing Cleavage of Polyols

(80) ##STR00020##

(81) The reaction is complete after stirring for 5 h in dichloromethane at ambient temperature, without degradation and without competing reaction.

(82) TABLE-US-00010 Catalyst Grevillea gillivrayi Species Mn (IV) diol Number of 0.81 1.0 equivalents

(83) Protocol:

(84) 183 mg of furan derivative (R=OEt, R=Me) is placed in 20 mL of CH.sub.2Cl.sub.2. 500 mg of GEE-Mn (IV) catalytic solid is added in one go, and the mixture is stirred. The reaction is monitored by IR. The CO vibration band of the ester function is located at 1713 cm.sup.1 and the aldehyde formed is located at 2732 and 1687 cm.sup.1. The product crystallizes after filtration on Celite and evaporation. .sup.1H NMR analysis confirms that the aldehyde formed is obtained, by the presence of a singlet at 9.7 ppm, deshielding of the aromatic proton at 7.5 ppm and disappearance of the polyol system.

Example 5.3: Oxidation of Benzamine: Example of Aniline

(85) The Oxidation of Aniline is a Conversion of Industrial Interest

(86) TABLE-US-00011 Catalyst Grevillea gillivrayi Species Mn (IV) aniline Number of 1.5 1.0 equivalents

(87) ##STR00021##

(88) Protocol:

(89) 10 mmol of aniline is placed in 15 mL of ethyl acetate. GER-Mn (IV) (15 mmol of Mn (IV)) is added in one go. The mixture is refluxed and heated for 8 h. The solution gradually turns orange. This colour reflects formation of the required azobenzene. After filtration and concentration of the medium, azobenzene is obtained pure.

Example 5.4: Aromatizing Dehydrogenation of Heterocycles and Carbocycles

(90) ##STR00022##

(91) TABLE-US-00012 Catalyst Grevillea Derivative gillivrayi to be Species Mn (IV) aromatized Number of 1.0 1.0 equivalents

(92) Method:

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

(94) Another Example: Aromatizing Dehydrogenation of Carbocycles

(95) Dehydrogenation of a natural cyclic terpene, alpha-terpinene, to an aromatic derivative, para-methyl cumene, which is a platform molecule of the chemical industry.

(96) ##STR00023##

(97) TABLE-US-00013 Catalyst Grevillea Derivative gillivrayi to be Species Mn (IV) aromatized Number of 2.0 1.0 equivalents

(98) Method:

(99) 10 mmol of terpinene is placed in 15 mL of dichloromethane. GEE-Mn (IV) is added in one go at a rate of 2 molar equivalents of Mn (IV). The mixture is stirred for 12 h at 45 C., then filtered on Celite and concentrated under vacuum. The aromatic structure is easily confirmed by GC MS, IR and .sup.1H NMR.

Example 5.5: Direct Halogenation of Enolizable Compounds

(100) Example of the Iodination of Ethyl Acetoacetate:

(101) ##STR00024##

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

(103) ##STR00025##

(104) The reaction of direct iodination of cyclohexanone was carried out with a yield of 64%. This result is remarkable and constitutes a novel green method allowing the easy iodination of carbonylated derivatives, which are usually of low reactivity. It avoids the use of dangerous and/or toxic reagents (oxone, mercuric chloride) and of diiodine.

(105) TABLE-US-00014 Catalyst Grevillea Substrate gillivrayi to be Sodium Species Mn (IV) iodinated iodide Number of 0.3 1.0 1.0 equivalents

(106) General protocol for the iodination of carbonylated derivatives and carboxylates: the substrate to be iodinated (10 mmol) diluted in 10 mL of dichloromethane, and sodium iodide (1 mmol) are placed in a 25-mL single-necked flask equipped with a condenser. The reagent GER-Mn (IV) (3 mmol of Mn (IV)) is added in one go and the mixture is stirred for 12 h at ambient temperature. The solution is filtered on Celite and the organic solution is washed with a solution of sodium thiosulphate, dried over sodium sulphate, filtered and concentrated under vacuum. The reaction is analyzed by GC-MS and then by .sup.1H NMR.

Example 6: Synthesis of Pyridines by Hantzsch Reaction-Oxidation in Situ

(107) Applying the following reaction diagram:

(108) ##STR00026##

(109) TABLE-US-00015 Catalyst Grevillea beta- exul dicarbonylated Ammonium Species rubiginosa aldehyde compound acetate Number of 0.10 1.0 2.0 1.5 equivalents
and the following procedure:

(110) 1 mmol of aldehyde, 2 mmol of ethyl acetoacetate, 1.5 mol of ammonium acetate and 0.1 mmol (manganese equivalent) of catalyst supported on SiO.sub.2 (1:1 mass equivalent) are introduced into a scintillation tube. The mixture is placed in a 600 W microwave oven for 5 min (stirring after 1 min);

(111) The following structures were obtained:

(112) TABLE-US-00016 Pyridine/yield (%) Yield (%) 81 98 92 0 99 69 98 96 98 48 98 98 98 97 0 98 95 80 80 98

Example 7: Epoxidation of Alkenes

(113) Using the following standard conditions:

(114) TABLE-US-00017 Catalyst Hydrogen Grevillea peroxide Species exul exul alkene NaHCO.sub.3 30% Number of 0.05 1.0 0.2 3.2 equivalents

(115) 1 mL of DMF, and the volume of water indicated for each alkene, are introduced into a haemolysis tube. The alkene (0.25 mmol) is added and the mixture is cooled to 0 C. in an ice bath, under stirring. The catalyst K10/Grevillea exul exul is then added in one go (m.sub.(catalyst, in mg)/n.sub.(alkene, in mmol)=144). Stirring is continued for 5 minutes, then a mixture of 30% H.sub.2O.sub.2 (85 L; 0.8 mmol) and 0.2 M NaHCO.sub.3 (250 L; 0.05 mmol) previously stirred for 5 minutes, is added in 3 portions over 30 minutes. Stirring is continued at 0 C. for 4 h, then a sample is taken for extraction with ether and GC-MS analysis.

(116) The following alkenes were thus epoxidized, with yields often greater than those described:

(117) TABLE-US-00018 Volume of Yield of water epoxide Alkene.sup.1 (L).sup.3 t(h) T( C.) (%) 0 4 0 99 100 4 0 43 0 4 0 75 0 4 0 63 600 4 0 72 0 600 4 0 27 100 4 0 74 300 4 0 78 600 4 0 74 0 4 0 42 0 4 0 23 600 4 0 98 0 4 0 55 0 4 0 89
The addition of a small quantity of water proved beneficial, leading to a marked increase in yield in most cases.

Example 8: Synthesis of Vanillin

(118) Procedure:

(119) TABLE-US-00019 Catalyst Grevillea Hydrogen exul peroxide Acetic Species rubiginosa isoeugenol 30% acid Number of 0.10 5.0 1.0 9.5 equivalents

(120) 5 mL of acetonitrile, 30.5 L (0.2 mmol) of isoeugenol, the appropriate weight of biosourced Mn catalyst, calculated so as to react 10% (in mol of limiting reagent) of the specific metallic species of the catalyst selected, 4.1 L (0.04 mmol) of 30% hydrogen peroxide, 22 L (0.38 mmol) of acetic acid and 4.66 L (0.04 mmol) of acetophenone, which serves as internal standard, are introduced into a 25-mL flask. The mixture is stirred at AT for 48 h, and then analyzed by GC-MS. The yield of vanillin is 81%, based on the internal standard introduced.

Example 9: Ene Reactions

(121) Summary of the operating conditions:

(122) TABLE-US-00020 catalyst/citronellal/ % % solvent solvent duration isopulegol p-cymene 100 mg GER/ CH.sub.2Cl.sub.2 1 h 95 0 154 mg (1 mmol, 1 equiv)/10 mL 100 mg GER + 1 h 5 80 SiO.sub.21 g/154 mg (1 mmol, 1 equiv)

(123) TABLE-US-00021 Catalyst Grevillea exul Species rubiginosa aldehyde Number of 0.05 1.0 equivalents

(124) Description of the Preparation of Isopulegol:

(125) 1 mmol of citronellal diluted in 10 mL of dichloromethane is added to a 25 mL four-necked flask equipped with a CaCl.sub.2 trap, a thermometer, a magnetic stirring bar, a condenser and a dropping funnel. The GER catalyst (100 mg of catalyst, activated by heating at 150 C. for 15 min) is suspended in the solvent. The mixture is stirred for 60 minutes at 40 C. (the reaction is monitored by TLC (eluent: hexane/ether 4/1, development I.sub.2)). The reaction mixture is filtered, the organic phase is washed with a hydrogen carbonate solution, dried and concentrated. The yield and stereoselectivity are determined by NMR and GC MS.

(126) Description of the Preparation of P-Cymene:

(127) The method is similar to the preceding method with 100 mg of catalyst supported on 1 g of silica, but the reaction is carried out without solvent at 90 C. for 1 hour. The conversion of isopulegol to p-cymene is easily monitored by GC MS.