WO2019015599A1 - Oxidative cleavage of olefins, epoxides and alcohols - Google Patents

Oxidative cleavage of olefins, epoxides and alcohols Download PDF

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Publication number
WO2019015599A1
WO2019015599A1 PCT/CN2018/096083 CN2018096083W WO2019015599A1 WO 2019015599 A1 WO2019015599 A1 WO 2019015599A1 CN 2018096083 W CN2018096083 W CN 2018096083W WO 2019015599 A1 WO2019015599 A1 WO 2019015599A1
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group
compound
acid
process according
epoxy
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Inventor
Bingyu YANG
Marc Pera Titus
Loic Leclercq
Véronique RATAJ
Armin T. Liebens
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Solvay China Co Ltd
Centre National de la Recherche Scientifique CNRS
Universite Lille 1 Sciences et Technologies
Rhodia Operations SAS
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Solvay China Co Ltd
Centre National de la Recherche Scientifique CNRS
Universite Lille 1 Sciences et Technologies
Rhodia Operations SAS
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group and by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an an oxidant in the presence of solid amphiphilic catalytic particles A and solid amphiphilic catalytic particles B.
  • Carboxylic acids are very important chemicals for industry. Specifically, the adipic acid is widely used in different filed. It is used as an acidulant, an additive used to increase acidity or to give a tart taste, in dry food powders. In addition, adipic acid is used as a gelling agent in “imitation jams and jellies” . In pharmaceuticals, adipic acid has been used in controlled release formulations. Some synthetic lubricants contain adipic acid because of its dicarboxylic properties. Adipic acid is used as a monomer in the production of Nylon and other polymers.
  • WO 2012/010842 reported a method for the oxidation cleavage of unsaturated carbon-carbon bonds into carboxylic acids or ketones by using a manganese catalyst and hydrogen peroxide.
  • the manganese catalyst is not easily available and the yields of desired products, especially the acids are very low.
  • WO 95/00243 reported a catalyst system suitable for use in oxidative cleavage of alkenes with hydrogen peroxide, in which the catalyst system comprise a source of ruthenium, a source of molybdenum and a phase transfer agent.
  • WO2009/109857 discloses a method of oxidative cleavage of an unsaturated carbon-carbon bond, said method comprising contacting a reactant molecule containing a carbon-carbon unsaturated bond with a catalytic system comprising (i) either a mixture of tungstate salt and tungstic acid or a mixture of a molybdate salt and molybdic acid; (ii) an aqueous solution of dihydrogen peroxide; (iii) a phase-transfer catalyst; and (iv) a carboxylic acid.
  • a catalytic system comprising (i) either a mixture of tungstate salt and tungstic acid or a mixture of a molybdate salt and molybdic acid; (ii) an aqueous solution of dihydrogen peroxide; (iii) a phase-transfer catalyst; and (iv) a carboxylic acid.
  • phase transfer agent mention the use of phase transfer agent.
  • a way to help stabilize the emulsion is to use an emulsifier, but even if the quantity involved is quite low compared to the reactants the separation issue is still present after the synthesis and there is then a need of a further chemical step.
  • the present invention then concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group, by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an oxidant in the presence of :
  • - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3 H 2 and -SO 3 H;
  • reaction medium comprises at least :
  • solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
  • the present invention is also related to a composition
  • a composition comprising at least :
  • solvent S comprising at least a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group;
  • an aqueous oxidizing solution comprising at least one oxidant
  • - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3 H 2 and -SO 3 H;
  • solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
  • oxidative cleavage of present invention could be performed under specific Pickering emulsion condition (emulsion stabilized by solid particles which are adsorbed onto the interface between the two phases) .
  • Pickering emulsions stabilized by particles are reported since the early 20 th century since the earlier reports by Pickering, S.U. 1907, J. Chem. Soc. 91 Pages 2001-2021. Aveyard et al. published a comprehensive review in Advances in Colloid and Interface Science 100 –102 (2003) 503–546.
  • Pickering emulsion not only solves the problem of reactants incompatibility such as for example organic/hydrophobic substrates and hydrophilic oxidants, but also makes it possible to recycle and reuse the stabilizer amphiphilic solid particles.
  • Such amphiphilic solid particles can be removed easily after the synthesis, notably by centrifugation, by flocculation of filtration without engaging complex separation of surfactants. Said solid particles can be easily separated furthermore from the liquid system and reused.
  • the process of the present invention notably permits to carry out the deep oxidation cleavage of olefins while increasing the reaction yield and/or the reaction selectivity.
  • hydrocarbon group refers to a group mainly consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
  • alkyl refers to a monovalent saturated aliphatic (i.e. non-aromatic) acyclic hydrocarbon group which may be linear or branched and does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • Representative saturated straight chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like; while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, and the like.
  • alkenyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon double bond while it does not comprise any carbon-to-carbon triple bond.
  • Representative unsaturated straight chain alkenyls include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like.
  • arylalkyl or the term “aralkyl” refers to alkyl substituted with an aryl.
  • arylalkoxy refers to an alkoxy substituted with aryl.
  • cyclic group refers to a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group.
  • alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
  • cycloalkyl refers to cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
  • heterocyclic refers to heterocyclic groups containing up to 6 carbon atoms together with 1 or 2 heteroatoms which are usually selected from O, N and S, such as for example radicals of : oxirane, oxirene, oxetane, oxete, oxetium, oxalane (tetrahydrofurane) , oxole, furane, oxane, pyrane, dioxine, pyranium, oxepane, oxepine, oxocane, oxocinc groups, aziridine, azirine, azirene, azetidine, azetine, azete, azolidine, azoline, azole, azinane, tetrahydropyridine, tetrahydrotetrazine, dihydroazine, azine, azepane,
  • Heterocyclic may also refer to a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.
  • (C n -C m ) refers to to an organic group, wherein n and m are each integers, indicating that the group may contain from n carbon atoms to m carbon atoms per group.
  • epoxy group refers to a functional group that consists of an oxygen atom joined by single bonds to two adjacent carbon atoms, thus forming the three-membered epoxide ring.
  • phase separation occurs as the interfacial tension between the two liquids is high.
  • One way to reduce this interfacial tension is to modify this interface by adsorbing an object.
  • Most commonly used objects are surfactants molecules.
  • Emulsions stabilized by particles rely on the fact that once a particle is adsorbed at the interface it is often difficult to remove it.
  • the necessary energy ⁇ E to remove an adsorbed particle is given by the following expression :
  • r is the particle radius
  • ⁇ he is the interfacial tension between the two liquids
  • ⁇ he is the contact angle of the particle in one of the phase.
  • a “hydrophilic” molecule or portion of a molecule is one that has a tendency to interact with or be dissolved by water and other polar substances.
  • hydrophobic molecule or portion of a molecule is one that is repelled from a mass of water and other polar substances.
  • Amphiphilic is a term describing a chemical compound possessing both hydrophilic and hydrophobic properties. Such a compound is called amphiphilic or amphipathic.
  • An “emulsion” is a suspension made of a first liquid in a phase made of a second liquid with which the first liquid is not miscible with the second liquid. A discontinuous phase within a continuous phase is then obtained.
  • An “emulsifier” is a compound or substance at acts as a stabilizer for emulsions preventing the liquids from separating.
  • the present invention then concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group, by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an oxidant in the presence of :
  • - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3 H 2 and -SO 3 H;
  • reaction medium comprises at least :
  • solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
  • the compound I comprising at least one carbonyl group may notably be a ketone, an aldehyde or a carboxylic acid and preferably carboxylic acid.
  • the said carboxylic acid may be any kind of aliphatic or aryl carboxylic acid including at least one carboxylic acid functional group.
  • the carboxylic acid of present invention may be chosen from saturated alkyl carboxylic acids, unsaturated alkyl carboxylic acids or aryl carboxylic acid, notably be chosen in the group consisting of : myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, ricinolic acid (ricinoleic acid) , tallow acid, coco acid, benzoic acid, substituted benzoic acid, citric acid, malic acid and oxa
  • the carboxylic acid of present invention may notably be a dicarboxylic acid of formula (I) as follows :
  • R 1 represents the skeleton moiety of the dicarboxylic acid.
  • R 1 may represent an alkyl, aryl, alkenyl or alkoxy radical, notably comprising 1 to 3000 carbon atoms.
  • the radical R 1 may comprise one or several heteroatom (s) such as O or N.
  • R 1 may notably be an alkyl radical comprising from 1 to 30 carbon atoms.
  • the alkyl group can be linear, branched or cyclic.
  • the dicarboxylic acid may be preferably chosen in the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
  • the compound I comprising at least one hydroxyl group may notably be an alcohol.
  • the alcohol preferably having 2 to 6 hydroxyl groups and more preferably 2 hydroxyl group may include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane, glycerol, diglycerol, pentaerythritol and sorbitol.
  • the compound I may notably be a diol of formula (II) as follows :
  • R 2 represents the skeleton moiety of the diol.
  • R 2 may represent an alkyl, aryl, alkenyl or alkoxy radical, notably comprising 1 to 3000 carbon atoms. Radical R 2 may comprise one or several heteroatom (s) such as O or N. R 2 may notably be an alkyl radical comprising from 1 to 30 carbon atoms.
  • the alkyl group can be linear, branched or cyclic and preferably cyclic.
  • the diol may be preferably chosen in the group consisting of 1, 6-hexylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, 1, 2-cyclooctanediol, 1, 2-cycloheptanediol, 1, 2-cyclohexanediol, 1, 2-cyclopentadiol, 1-methyl-1, 2-cyclohexanediol, 1, 2-dimethyl-1, 2-cyclohexanediol, 4-vinyl-1, 2-cyclohexanediol, 3, 4-diol-1-cyclohexene.
  • 1, 2-cyclooctanediol, 1, 2-cycloheptanediol, 1, 2-cyclohexanediol and 1, 2-cyclopentadiol are more preferable.
  • the compound I or J comprising at least one epoxy group of present invention may notably be epoxide derived from epoxidation of a compound J comprising at least one alkenyl group of present invention.
  • the preferable epoxide could be chosen in the group consisting of 1, 2-epoxy-cyclopentane, 1, 2-epoxy-cyclohexane, 1, 2-epoxy-cycloheptane, 1, 2-epoxy-cyclooctane, 1, 2-epoxy-4-vinylcyclohexane, 3-4-epoxy-1-cyclohexene, 1, 2-epoxy-1-methylcyclohexane, 1, 2-epoxy-1, 2-dimethylcyclohexane, vinyl cyclohexene dioxide and 9, 10-epoxystearic acid.
  • the compound J comprising at least one alkenyl group which can be used as reactant in the process according to the invention, can be of very diverse types. It may notably be an olefin containing one or more alkenyl group, and can be aliphatic, alicyclic or aromatic.
  • the compound can optionally contain, in their main chain, one or more heteroatoms generally chosen from amongst nitrogen, sulphur or oxygen atoms.
  • the alkenyl compound contains from 2 to 40 carbon atoms.
  • R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen or C 1-11 hydrocarbyl.
  • Said hydrocarbyl could be linear, branched or cyclic and is preferably selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, more preferably selected from alkyl, alkenyl, alkynyl, or aryl, and even more preferably selected from alkyl, alkenyl, or aryl.
  • the olefin can be a terminal olefin or an internal olefin.
  • An internal olefin is preferable.
  • terminal olefin refers to an olefin in which the carbon-to-carbon double bond is at the end of the carbon chain.
  • intermediate olefin refers to an olefin in which carbon-to-carbon double bond is not at the end of the carbon chain.
  • olefins of these types are propylene, but-1-ene, but-2-ene, isobutene, butadiene, pentenes, and in particular pent-1-ene, 2-methylbut-1-ene, 3-methylbut-1-ene, 2-methylbut-2-ene, piperylene, hex-1-ene, hex-2-ene and hex-3-ene, hexadienes, 2, 3-dimethyl-but-2-ene, hept-1-ene, 3-ethylpent-2-ene, oct-1-ene, diisobutylene, 2, 4, 4-trimethylpent-1-ene and 2, 4, 4-trimethylpent-2-ene, octadines, non-1-ene, dec-1-ene, undec-1-ene, dodec-1-ene, tridec-1-ene, tetradec-1-ene, pentadec-1-ene, he
  • the compound J comprising at least one alkenyl group may be preferably chosen in the group consisting of cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl cyclohexene and 4-methyl cyclohexene.
  • the compound J comprising at least one hydroxyl group or epoxy group which can be used as reactant in the process according to the invention has the same meaning of compound I comprising at least one hydroxyl group or epoxy group.
  • Particles A of the present invention comprise at least one substituted polyoxometalate. It should be understood the substituted polyoxometalate have both amphiphilic and catalytic characteristics.
  • polyoxometalate is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks.
  • the polyoxometalate is not particularly limited as long as it shows catalytic performance towards oxidative cleavage reactions.
  • POMs Keggin type polyoxometalates
  • Cs 2.5 H 0.5 PW 12 O 40 and H 3 PW 12 O 40 as described in Catalysis Today 149 (2010) 117-121.
  • Preferable polyoxometalate is H 3 PW 12 O 40 .
  • the substituent group is also not particularly limited. It may be straight, branched or cyclic C 2 -C 30 hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N. More preferable substituent group may notably for example C 2 -C 12 straight aliphatic hydrocarbon group, that is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
  • particles A could be alkylpolyoxometalates as disclosed by Chem. Eur. J. 2012, 18, 14352 –14358.
  • the solid amphiphilic catalytic polyoxometalate nanoparticles could not only stabilize the Pickering Emulsion, but also is easy for recycling and reuse.
  • Particles A could be prepared by some well-known ways, such as the method mentioned in Chem. Eur. J. 2012, 18, 14352 –14358.
  • particles B of the present invention may preferably comprise at least one metal compound of at least one metal element, wherein the metal element is chosen from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) titanium, zirconium, cerium and (vi) mixtures thereof.
  • Metal element could be preferably chosen in the group consisting of aluminium, silicon, tin, titanium, zirconium, cerium, magnesium and barium and more preferably chosen in the group consisting of aluminium, silicon and titanium and most preferably silicon.
  • the said metal compound comprised in particles B include, for example, water immiscible metal salts, metal hydroxides, metal oxides, mixed metal oxides or clays. Among these, metal oxide or mixed metal oxides are preferable.
  • the said metal compound comprised in particles B are particularly inorganics such as for example made of an oxide, hydroxide and/or oxy-hydroxyde of at least one metal chosen from aluminium, silicon, titanium. Preferably, it could be silicon dioxide.
  • metal compound examples include bentonite, tin oxide, magnesium aluminum silicate, magnesium oxide, titanium oxide, barium sulphate and/or silica, such as is described in U.S. Pat. No. 4,833,060 at col. 4, lines 54-61, the cited portion of which being incorporated herein by reference, and alumina as described in U.S. application 2005/0156340.
  • the metal compound is in the form of solid particles (hereinafter referred to as “particles C” ) .
  • particles C have a colloidal behaviour, preferably with an interparticule agglomeration rate (number of agglomerated particles/total number of particles) inferior or equal to 5 %, more preferably inferior or equal to 2 %.
  • the solid particles such as silica and/or alumina particles, are introduced in the form of colloidal dispersion, wherein finely divided solid particles are dispersed within a continuous medium in a manner that prevents them from being filtered easily or settled rapidly. Said solid particles are insoluble in the reaction medium of present invention.
  • particles C may show amphiphilic property.
  • particles C could be modified, such as being linked with hydrophilic and hydrophobic functional groups (hereinafter referred to as “modified particles C” ) . Amphiphilic property could therefore be introduced.
  • Particles C linked with hydrophilic and hydrophobic functional groups could display or not amphiphilic property.
  • particles C linked with hydrophilic and hydrophobic functional groups could be inorganics such as for example made of an oxide, hydroxide or oxy-hydroxide of at least one element chosen from aluminium, silicon, titanium.
  • Hydrophilic nature is usually provided by the presence of hydrophilic groups. These groups may be neutral such as -OH, -COOH, -PO 3 H 2 , -SO 3 H as example, or preferentially under their anionic or cationic corresponding forms.
  • Hydrophobic nature is usually provided by the presence of hydrophobic groups such as organic chains having a hydrophobic nature.
  • Said chains are defined as organic chains having a hydrophobic character such as these chains are soluble in a hydrophobic solvent and less soluble, notably insoluble, in water.
  • Organic chains having a hydrophobic nature may have at least 50 %wt, preferentially at least 80 %wt of hydrophobic groups such as alkylated groups, or alkoxylated groups.
  • Hydrophobic groups are preferably alkyl chains comprising 1 to 30 carbon atoms, more preferably from 1 to 8 carbon atoms or alkoxylated groups notably comprising 1 to 10 units of ethylene oxide -CH 2 CH 2 O-groups.
  • link existing between organic chains and the surface of particles C can vary in a large measure and may be for example a covalent bond, or physical adsorption more often including an electrostatic bond, an ionic bond and a hydrogen bond.
  • Covalent bonds can be obtained by grafting or co-condensation or co-precipitation.
  • the grafting rate of the particle surface by hydrophobic groups may be comprised between 5 and 90 %of the original amount of hydroxyl groups, preferably between 30 and 70 %. This grafting rate may be evaluated by a thermal decomposition of the particles and then calculate the amount of water formed during the decomposition. It is then possible to proceed to an extrapolation of the number of hydroxyl group.
  • the bonds between the organic chains of hydrophobic nature and the surface of particles are covalent bonds.
  • these are usually made covalent bonds between atoms of metal particles and organic chains, usually via oxygen atoms initially present in a hydroxyl metal group of the particle surface.
  • the metal atom of these groups hydroxylated metal surface is an atom of silicon, aluminum, or titanium.
  • particles C are formed at least partially of silicon oxide, oxy-hydroxide of aluminum and/or titanium oxide, this or these oxide (s) and/or oxy-hydroxide being at least this (s) on the surface.
  • particles C can then be formed such oxide (s) , hydroxide (s) and/or oxy-hydroxide (s) of chemical nature variable, having a surface layer of silicon oxide oxy -aluminum hydroxide and/or titanium oxide, made for example by after-treatment surface.
  • organic chains covalently linked are generally introduced by this embodiment of the invention by condensation of a silanol group SiOH on the particle, according to the general reaction:
  • M is Si, Al or Ti.
  • the silanol group SiOH usually comes from the acid hydrolysis, neutral, or basic group of a alkoxysilane, for example acid hydrolysis of a compound or trimethoxyalkysilane, triethoxyalkylsilane.
  • Modified particles C may also be obtained by co-precipitation of compounds providing hydrophilic function and compounds providing hydrophobic function.
  • silica particles may be obtained by co-precipitation of hydrophilic silane compounds and hydrophobic silane compounds. Pavithran et al. (Langmuir, 26 (2010) 730-735) reported bifunctionalized silica spheres carring aminopropyl and vinyl groups by hydrolytic co-condensation.
  • bonds between the chains and hydrophobic particles are inhomogeneously distributed on the surface of said particles, whereby said particles modified surface have a first area to overall hydrophilic nature and a second area to overall hydrophobic character.
  • Particles B of the invention are also catalytic and then comprise at their surface at least one catalytic function, permitting to carry out the oxidation reaction of the present invention.
  • This catalytic function may be obtained by the use of groups directly grafted or supported to particles C. These groups may then act as catalyst in the reaction of the present invention.
  • the functional group is preferably be an acidic group chosen in the group consisting of -COOH, -PO 3 H 2 or -SO 3 H. Sulfonic (-SO 3 H) is particularly efficient as both catalytic and hydrophilic functions for particles B.
  • Particles B of the present invention may notably provide sulfonic acid function containing group (s) .
  • These groups may also comprise alkyl, peralkyl or aryl group, such as for instance :
  • concentration of particles B according to the invention is advantageous to choose the concentration of particles B according to the invention to be greater than 0.1 %by weight, advantageously could be comprised from 0.1 %by weight to 30 %by weight, based on the total weight of the preparations.
  • Particles A and B of the instant invention may notably be particles having an average diameter comprised from 2 to 5000 nm, preferably from 50 to 3000 nm, more preferably from 100 to 1000 nm and most preferably from 100 to 400 nm.
  • the average diameter of particles can be determined by examining a micrograph of a transmission electron microscopy "TEM" image, measuring the diameter of the particles in the image, and calculating the number average particle size of the measured particles based on magnification of the TEM image.
  • TEM transmission electron microscopy
  • One of ordinary skill in the art will understand how to prepare such a TEM image and determine the particle size based on the magnification.
  • silica particles could be characterized by TEM on a JEOL JEM 2100 microscope operated at 200 kV and equipped with Energy Dispersive Spectroscopy (EDS) .
  • EDS Energy Dispersive Spectroscopy
  • the particles to be measured refer to the projection (2D-representation) of the particles on the micrograph. Before performing the measurements, it is necessary to calibrate the image.
  • Size distribution histograms are then plotted as percent silica particles versus silica diameter on the basis of the size measurements obtained from an image processing program, such as ImageJ.
  • the number average is obtained by weighted average method.
  • the measurement should be made on a sufficiently high number of particles, for example at least about 100 particles, preferably at least 300 particles, more preferably at least 1000 particles, still more preferably at least 3000 particles.
  • the shape or morphology of particles A and B can vary.
  • generally spherical morphologies can be used, as well as particles that are cubic, platy, or acicular (elongated or fibrous) , such as sticks or needles.
  • the weight ratio of solid amphiphilic catalytic particles A to solid amphiphilic catalytic particles B at the start of the reaction is preferably comprised from 0.5: 1 to 1: 0.5, more preferably from 0.8: 1 to 1: 0.8.
  • the oxidant of present invention could notably be chosen in the group consisting of organic peroxy acid, such as peracetic acid, organic peroxide, such as t-butyl hydrogen peroxide and inorganic peroxides, such as hydrogen peroxide, a perborate, a persulfate and any combination thereof.
  • organic peroxy acid such as peracetic acid
  • organic peroxide such as t-butyl hydrogen peroxide
  • inorganic peroxides such as hydrogen peroxide, a perborate, a persulfate and any combination thereof.
  • hydrogen peroxide could be more preferable.
  • a typical amount of use of oxidant depends on the starting material and final product. When hydrogen peroxide is employed, it is preferably comprised from 0.5 mol to 10 mol equivalents, more preferably 1.0 mol to 5.0 mol equivalents of the starting material.
  • H 2 O 2 1.0 mol to 1.5 mol equivalents H 2 O 2 could be used to convert an olefin into an epoxide. 3.0 mol to 3.5 mol equivalents H 2 O 2 could be used to convert an epoxide or a diol to a carboxylic acid.
  • Solvent S is typically chosen based on its ability to dissolve compound J and compound I to prevent them from precipitating at the bottom of the reactor so that biphasic system can be well kept. It could be chosen in a group consisting of alcohols, alkane, aromatics, ether, ester, ketone and any combination thereof.
  • Preferable solvent could be aromatics, such as benzene, toluene, xylene and ethyl-benzene, and aliphatics, such as pentane, hexane, heptane, cyclohexane, methyl-cyclohexane and cyclopenyl methyl ether.
  • Some bio-based solvents, such as 2-methyltetrahydrofuranethyl lactate, D-limonene, and methyl soyate could also be used.
  • Solvent S can be used in variable amounts.
  • the reaction mixture contains at most 50 %by weight of solvent and preferably from 20 %to 50 %by weight with respect to total weight of reaction mixture.
  • the reactant concentration could be comprised from 0.2 to 20.0 mol/L and preferably from 0.5 to 2 mol/L.
  • the present invention concerns a process for the conversion of a compound J comprising at least one epoxy group to a compound I comprising one carbonyl group.
  • the present invention concerns a process for the conversion of a compound J comprising at least one alkenyl group to a compound I comprising one carbonyl group.
  • the process according to the invention is particularly suitable for converting olefins containing from 5 to 20 carbon atoms, and more especially cyclic olefins (that is to say cyclic compounds which contain at least one ethylenic double bond in a ring) to dicarboxylic acids. It is particularly suitable for converting cyclic olefins containing not more than 8 carbon atoms per ring to dicarboxylic acids.
  • the selectivity of compound I comprising one carbonyl group obtained in above two embodiments could be at least of 60 %and more preferable comprised from 70 %and 95 %and most preferably from 85 %and 95 %.
  • Emulsification instrument can be any instrument giving high energy such as ultra sound, or high shear such as homogenizer, or other stirring methods.
  • the medium used in the present process of the invention is substantially free or, in some cases, completely free of any surfactant (other than the amphiphilic particles of the invention) , at the start of the reaction.
  • surfactant refers to materials that have an amphiphilic molecular structure, which includes a polar hydrophilic molecular moiety and a nonpolar lipophilic molecular moiety, and which acts to lower the interfacial tension between the dispersed phase and the continuous phase in an emulsion.
  • surfactants can be classified as ionic (anionic, cationic, and amphoteric) or nonionic.
  • the term “substantially free” when used with reference to the absence of surfactant in the medium of the present invention means that the emulsion comprises less than 0.1 %wt of surfactant, based on the total weight of the medium, notably at the beginning of the reaction; and preferably during the reaction.
  • the term “completely free” when used with reference to the absence of surfactant in the medium of the present invention means that the emulsion comprises no surfactant at all.
  • the reaction temperature of present may be generally comprised between 10°C and 250°C, preferably between 20°C and 80°C.
  • reaction may be carried out under atmospheric pressure or under pressure.
  • Said reaction can be made under inert gas or air for example.
  • composition comprising at least :
  • solvent S comprising at least a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group;
  • an aqueous oxidizing solution comprising at least one oxidant
  • - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3 H 2 and -SO 3 H;
  • solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
  • the modified silica particles are noted as X/Y R/C 3 SO 3 H.
  • X and Y stand for the molar ratio between trimethoxyalkylsilane and (3-mercaptopropyl) trimethoxysilane.
  • R stands for the alkyl chain in trimethoxyalkylsilane, which could be varied among propyl (C 3 ) , phenyl (Ph) , octyl (C 8 ) and octadecyl (C 18 ) chains.
  • the following protocol refers to the modification procedure to obtain the 80/20 C 18 /C 3 SO 3 H nanoparticles.
  • the dried powder was then grinded by mortar and pestle, and the thiol groups were oxidized by 60 mL H 2 O 2 (50 %) .
  • a small amount of acetonitrile (3 to 4 mL) was added drop-wise until a homogeneous suspension was obtained.
  • the mixture was heated slowly at 40°C for 24 hours. After the reaction, the residue was filtered, washed and dried.
  • 50/50 C 18 /C 3 SO 3 H, 20/80 C 18 /C 3 SO 3 H, 80/20 C 8 /C 3 SO 3 H, and 50/50 C 8 /C 3 SO 3 H nanoparticles are prepared in the same way as 80/20 C 18 /C 3 SO 3 H nanoparticles.
  • the POM nanoparticles were prepared by ion exchange.
  • An aqueous solution of H 3 [PW 12 O 40 ] (1 equiv) was added dropwise to an aqueous solution of dodecyltrimethylammonium hydroxide (3 equiv) at 25.8°C under vigorous magnetic stirring at 1500 rpm.
  • a colourless precipitate was formed within a few minutes, which was separated and lyophilized, thereby providing spherical and fairly monodisperse [C 12 ] 3 [PW 12 O 40 ] nanoparticles.
  • 0.05 g dodecylpolyoxometalate as prepared in Example 2 0.05 g amphiphilic modified silica nanoparticles as prepared in Example 1, 1.5 mL toluene phase containing 0.5 mol/L cyclohexene oxide and 1.5 mL water phase containing 3.5 eq. H 2 O 2 were mixed.
  • the system was emulsified at 11500 rpm for 2 min, and the reaction was carried out at 80°C, 500 rpm for 12 h. After the reaction, the emulsions were broken by centrifugation at 4000 rpm for 20 min and the particles as well as the products could be separated and collected.
  • Example 3 The reaction was performed in the same way as Example 3 with 80/20 C 18 /C 3 SO 3 H as amphiphilic modified silica nanoparticles. 1.5 ml n-heptane and 1.5 ml dibutylether (containing the same concentration of substrate) are used as solvent in replacement of toluene. The products obtained were indentified by NMR and conversion and selectivity of each product are listed in Table 2.
  • catalyst only amphiphilic silica or only POM NPs
  • 1.5 mL toluene 0.5 mol/L cyclohexene oxide
  • 1.5 mL water containing 3.5 eq. H 2 O 2
  • the reaction was carried out in an oil bath of 80°C, magnetic stir at 500 rpm for 12 hours.
  • the experimental results are shown in Table 4.

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Abstract

Provided is a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group and by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an an oxidant in the presence of solid amphiphilic catalytic particles A and solid amphiphilic catalytic particles B.

Description

Oxidative cleavage of olefins, epoxides and alcohols
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims priority to International Application No. PCT/CN2017/093295 filed on 18 July 2017, the whole content of this application being incorporated herein by reference.
TECHNICAL FIELD
The present invention concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group and by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an an oxidant in the presence of solid amphiphilic catalytic particles A and solid amphiphilic catalytic particles B.
PRIOR ART
The following discussion of the prior art is provided to place the invention in an appropriate technical context and enable the advantages of it to be more fully understood. It should be appreciated, however, that any discussion of the prior art throughout the specification should not be considered as an express or implied admission that such prior art is widely known or forms part of common general knowledge in the field.
Carboxylic acids are very important chemicals for industry. Specifically, the adipic acid is widely used in different filed. It is used as an acidulant, an additive used to increase acidity or to give a tart taste, in dry food powders. In addition, adipic acid is used as a gelling agent in “imitation jams and jellies” . In pharmaceuticals, adipic acid has been used in controlled release formulations. Some synthetic lubricants contain adipic acid because of its dicarboxylic properties. Adipic acid is used as a monomer in the production of Nylon and other polymers. WO 2012/010842 reported a method for the oxidation cleavage of unsaturated carbon-carbon bonds into carboxylic acids or ketones by using a manganese  catalyst and hydrogen peroxide. However, the manganese catalyst is not easily available and the yields of desired products, especially the acids are very low.
WO 95/00243 reported a catalyst system suitable for use in oxidative cleavage of alkenes with hydrogen peroxide, in which the catalyst system comprise a source of ruthenium, a source of molybdenum and a phase transfer agent. WO2009/109857 discloses a method of oxidative cleavage of an unsaturated carbon-carbon bond, said method comprising contacting a reactant molecule containing a carbon-carbon unsaturated bond with a catalytic system comprising (i) either a mixture of tungstate salt and tungstic acid or a mixture of a molybdate salt and molybdic acid; (ii) an aqueous solution of dihydrogen peroxide; (iii) a phase-transfer catalyst; and (iv) a carboxylic acid. Both literatures mention the use of phase transfer agent.
A way to help stabilize the emulsion is to use an emulsifier, but even if the quantity involved is quite low compared to the reactants the separation issue is still present after the synthesis and there is then a need of a further chemical step.
Pickering emulsion stabilized by catalytic polyoxometalate nanoparticles is used as a new effective medium for oxidation reactions according to Chem. Eur. J. 2012, 18, 14352-14358. A great deal of studies regarding catalytic epoxidation of alkene in the presence of polyoxometalates supported by silica are reported, such as US6229028, KR101170486, CN105689002A. However, the final products are epoxy compounds and the catalytic and emulsifying performance is not demonstrated.
There is a need then to develop a new process permitting to carry out an oxidative cleavage reaction involving a medium with a hydrophobic phase and a hydrophilic phase, notably without the presence of surfactant or phase transfer agent. Furthermore, the new process could realize deep oxidative cleavage, which makes it possible to produce diacid compounds with high selectivity and yield.
INVENTION
The present invention then concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group, by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an oxidant in the presence of :
- solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
- solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
wherein the reaction medium comprises at least :
a) a solvent S comprising at least a compound J;
b) an aqueous oxidizing solution comprising at least one oxidant;
wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
The present invention is also related to a composition comprising at least :
- a solvent S comprising at least a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group;
- an aqueous oxidizing solution comprising at least one oxidant;
- solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
- solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
It appears that it is now possible to realize the oxidative cleavage of olefins, epoxides and alcohols, notably comprising at the surface both hydrophilic and hydrophobic functions. Such a synthesis reaction may be made without the presence of surfactant or phase transfer agent. Without wishing to be bound by any theory, it is believed that the catalytic and  emulsifying performance is well improved and the deep oxidative cleavage product diacid could be obtained with the help of synergistic effect brought by particles A and particles B.
It is found that oxidative cleavage of present invention could be performed under specific Pickering emulsion condition (emulsion stabilized by solid particles which are adsorbed onto the interface between the two phases) . Pickering emulsions stabilized by particles are reported since the early 20 th century since the earlier reports by Pickering, S.U. 1907, J. Chem. Soc. 91 Pages 2001-2021. Aveyard et al. published a comprehensive review in Advances in Colloid and Interface Science 100 –102 (2003) 503–546. Pickering emulsion not only solves the problem of reactants incompatibility such as for example organic/hydrophobic substrates and hydrophilic oxidants, but also makes it possible to recycle and reuse the stabilizer amphiphilic solid particles. Such amphiphilic solid particles can be removed easily after the synthesis, notably by centrifugation, by flocculation of filtration without engaging complex separation of surfactants. Said solid particles can be easily separated furthermore from the liquid system and reused.
The process of the present invention notably permits to carry out the deep oxidation cleavage of olefins while increasing the reaction yield and/or the reaction selectivity.
Other characteristics, details and advantages of the invention will emerge even more fully upon reading the description which follows.
DEFINITIONS
Throughout the description, including the claims, the term "comprising one" should be understood as being synonymous with the term "comprising at least one" , unless otherwise specified, and "between" should be understood as being inclusive of the limits.
As used herein, the term "hydrocarbon group" refers to a group mainly consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
As used herein, the term “alkyl” refers to a monovalent saturated aliphatic (i.e. non-aromatic) acyclic hydrocarbon group which may be linear or branched and does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond. Representative saturated straight chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like; while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, and the like.
As used herein, the term "alkenyl" refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon double bond while it does not comprise any carbon-to-carbon triple bond. Representative unsaturated straight chain alkenyls include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl and the like.
As used herein, the term "aryl" refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like. The term "arylalkyl" or the term "aralkyl" refers to alkyl substituted with an aryl. The term "arylalkoxy" refers to an alkoxy substituted with aryl.
As used herein, the term "cyclic group" refers to a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group. The term "alicyclic group" means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
As used herein, the term "cycloalkyl" refers to cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
As used herein, the term “heterocyclic" refers to heterocyclic groups containing up to 6 carbon atoms together with 1 or 2 heteroatoms which are usually selected from O, N and S, such as for example radicals of : oxirane, oxirene, oxetane, oxete, oxetium, oxalane (tetrahydrofurane) , oxole, furane, oxane, pyrane, dioxine, pyranium, oxepane, oxepine, oxocane, oxocinc groups, aziridine, azirine, azirene, azetidine, azetine, azete, azolidine,  azoline, azole, azinane, tetrahydropyridine, tetrahydrotetrazine, dihydroazine, azine, azepane, azepine, azocane, dihydroazocine, azocinic groups and thiirane, thiirene, thiethane, thiirene, thietane, thiete, thietium, thiolane, thiole, thiophene, thiane, thiopyrane, thiine, thiinium, thiepane, thiepine, thiocane, thiocinic groups.
"Heterocyclic" may also refer to a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.
As used herein, the terminology " (C n-C m) " refers to to an organic group, wherein n and m are each integers, indicating that the group may contain from n carbon atoms to m carbon atoms per group.
As used herein, the term “epoxy group” refers to a functional group that consists of an oxygen atom joined by single bonds to two adjacent carbon atoms, thus forming the three-membered epoxide ring.
In a general way, phase separation occurs as the interfacial tension between the two liquids is high. One way to reduce this interfacial tension is to modify this interface by adsorbing an object. Most commonly used objects are surfactants molecules.
Emulsions stabilized by particles rely on the fact that once a particle is adsorbed at the interface it is often difficult to remove it. The necessary energy ΔE to remove an adsorbed particle is given by the following expression :
ΔE=πr 2γ he (1±cosθ he)  2
wherein : r is the particle radius, γ he is the interfacial tension between the two liquids and θ he is the contact angle of the particle in one of the phase.
From this expression, it can be seen that the adsorption energy highly depends on the particle radius and its wettability.
A “hydrophilic” molecule or portion of a molecule is one that has a tendency to interact with or be dissolved by water and other polar substances.
A “hydrophobic” molecule or portion of a molecule is one that is repelled from a mass of water and other polar substances.
“Amphiphilic” is a term describing a chemical compound possessing both hydrophilic and hydrophobic properties. Such a compound is called amphiphilic or amphipathic.
An “emulsion” is a suspension made of a first liquid in a phase made of a second liquid with which the first liquid is not miscible with the second liquid. A discontinuous phase within a continuous phase is then obtained.
An “emulsifier” is a compound or substance at acts as a stabilizer for emulsions preventing the liquids from separating.
Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
DETAILS OF THE INVENTION
The present invention then concerns a process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group, by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an oxidant in the presence of :
- solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
- solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
wherein the reaction medium comprises at least :
a) a solvent S comprising at least a compound J;
b) an aqueous oxidizing solution comprising at least one oxidant;
wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
The compound I comprising at least one carbonyl group may notably be a ketone, an aldehyde or a carboxylic acid and preferably carboxylic acid. The said carboxylic acid may be any kind of aliphatic or aryl carboxylic acid including at least one carboxylic acid functional group.
The carboxylic acid of present invention may be chosen from saturated alkyl carboxylic acids, unsaturated alkyl carboxylic acids or aryl carboxylic acid, notably be chosen in the group consisting of : myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, ricinolic acid (ricinoleic acid) , tallow acid, coco acid, benzoic acid, substituted benzoic acid, citric acid, malic acid and oxalic acid.
The carboxylic acid of present invention may notably be a dicarboxylic acid of formula (I) as follows :
R 1- (COOH)  2 (I)
wherein R 1 represents the skeleton moiety of the dicarboxylic acid.
R 1 may represent an alkyl, aryl, alkenyl or alkoxy radical, notably comprising 1 to 3000 carbon atoms. The radical R 1 may comprise one or several heteroatom (s) such as O or N.
R 1 may notably be an alkyl radical comprising from 1 to 30 carbon atoms. The alkyl group can be linear, branched or cyclic.
The dicarboxylic acid may be preferably chosen in the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
The compound I comprising at least one hydroxyl group may notably be an alcohol. Specific examples of the alcohol preferably having 2 to 6 hydroxyl groups and more preferably 2 hydroxyl group may include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane, glycerol, diglycerol, pentaerythritol and sorbitol.
The compound I may notably be a diol of formula (II) as follows :
R 2- (OH)  2 (II)
wherein R 2 represents the skeleton moiety of the diol.
R 2 may represent an alkyl, aryl, alkenyl or alkoxy radical, notably comprising 1 to 3000 carbon atoms. Radical R 2 may comprise one or several heteroatom (s) such as O or N. R 2 may notably be an alkyl radical comprising from 1 to 30 carbon atoms. The alkyl group can be linear, branched or cyclic and preferably cyclic.
The diol may be preferably chosen in the group consisting of 1, 6-hexylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, 1, 2-cyclooctanediol, 1, 2-cycloheptanediol, 1, 2-cyclohexanediol, 1, 2-cyclopentadiol, 1-methyl-1, 2-cyclohexanediol, 1, 2-dimethyl-1, 2-cyclohexanediol, 4-vinyl-1, 2-cyclohexanediol, 3, 4-diol-1-cyclohexene. Among these, 1, 2-cyclooctanediol, 1, 2-cycloheptanediol, 1, 2-cyclohexanediol and 1, 2-cyclopentadiol are more preferable.
The compound I or J comprising at least one epoxy group of present invention may notably be epoxide derived from epoxidation of a compound J comprising at least one alkenyl group of present invention.
The preferable epoxide could be chosen in the group consisting of 1, 2-epoxy-cyclopentane, 1, 2-epoxy-cyclohexane, 1, 2-epoxy-cycloheptane, 1, 2-epoxy-cyclooctane, 1, 2-epoxy-4-vinylcyclohexane, 3-4-epoxy-1-cyclohexene, 1, 2-epoxy-1-methylcyclohexane, 1, 2-epoxy-1, 2-dimethylcyclohexane, vinyl cyclohexene dioxide and 9, 10-epoxystearic acid.
The compound J comprising at least one alkenyl group, which can be used as reactant in the process according to the invention, can be of very diverse types. It may notably be an olefin containing one or more alkenyl group, and can be aliphatic, alicyclic or aromatic. The compound can optionally contain, in their main chain, one or more heteroatoms generally chosen from amongst nitrogen, sulphur or oxygen atoms. It can also be substituted by various atoms or groups which are stable in the reaction mixture, such as halogens, and more particularly chlorine, fluorine or bromine atoms, or hydroxyl, alkoxy, nitro, amino, carbonyl, nitrile, acid, ester or amide groups, or alternatively by aromatic, aliphatic or alicyclic groups, which might be themselves optionally substituted. In general, the alkenyl compound contains from 2 to 40 carbon atoms.
The process according to the invention is generally applied to olefins corresponding to the general formula (III) :
Figure PCTCN2018096083-appb-000001
wherein R 3, R 4, R 5 and R 6 are each independently selected from hydrogen or C 1-11 hydrocarbyl. Said hydrocarbyl could be linear, branched or cyclic and is preferably selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, more preferably selected from alkyl, alkenyl, alkynyl, or aryl, and even more preferably selected from alkyl, alkenyl, or aryl.
The olefin can be a terminal olefin or an internal olefin. An internal olefin is preferable. As used herein, “terminal olefin” refers to an olefin in which the carbon-to-carbon double bond is at the end of the carbon chain. “Internal olefin” refers to an olefin in which carbon-to-carbon double bond is not at the end of the carbon chain.
Examples which may be mentioned of olefins of these types are propylene, but-1-ene, but-2-ene, isobutene, butadiene, pentenes, and in particular pent-1-ene, 2-methylbut-1-ene, 3-methylbut-1-ene, 2-methylbut-2-ene, piperylene, hex-1-ene, hex-2-ene and hex-3-ene, hexadienes, 2, 3-dimethyl-but-2-ene, hept-1-ene, 3-ethylpent-2-ene, oct-1-ene, diisobutylene,  2, 4, 4-trimethylpent-1-ene and 2, 4, 4-trimethylpent-2-ene, octadines, non-1-ene, dec-1-ene, undec-1-ene, dodec-1-ene, tridec-1-ene, tetradec-1-ene, pentadec-1-ene, hexadec-1-ene, heptadec-1-ene, octadec-1-ene, nonadec-1-ene, eicos-1-ene, propylene trimers and tetramers, polybutadienes, isoprene, terpenes, such as terpinenes, limonene, terpinolene, sabinene, pinene, camphene, myrcene, cadinene, cedrene, santalene, calarene, colophene and polyterpenes and also their derivatives, such as geraniol, linalol and linalyl acetate, methylenecyclopropane, cyclopentene and its derivatives substituted by alkyl or aryl groups, cyclopentadiene, cyclohexene and its derivatives substituted by alkyl and aryl groups, methylenecyclopentane, cyclohexadiene, methylenecyclohexane, norbornene, cyclopheptene, vinylcyclohexane, vinylcyclohexene, styrene, cycloheptene, cyclooctene, cyclooctadienes, vinylnorbornene, substituted or unsubstituted indene, tetrahydroindene, alpha-methylstyrene and alpha-alkylstyrenes optionally substituted on the aromatic nucleus, dicyclopentadiene, divinylbenzene, substituted or unsubstituted dihydronaphthalenes, cyclododecene, cyclododecatriene, stilbene, 2, 3-diphenylbut-2-ene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allyl chloride and bromide, trichloropropylenes, crotyl chloride, methallyl chloride, chlorobutenes, dichlorobutenes, dibromobutadienes, dichlorobutadienes, hexafluorobutadiene, allyl alcohol and methallyl alcohol and also their alkyl or aryl derivatives, but-1-en-4-ol and its 2-alkyl and 4-alkyl derivatives, but-2-en-1-ol, but-2-ene-1, 4-diol, cyclopentenediols, pent-4-enols, 2-methylpent-2-en-1-ol, 1, 2-dihydroxy-4-vinylbenzene, beta-chlorostyrene and alpha-alkyl-beta-chlorostyrenes optionally substituted on the aromatic nucleus, octa-2, 7-dien-1-ol, cyclohexylcarbinol, tridec-2-en-1-ol, 2-and 3-alkoxypropenes and 2-and 3-aryloxypropenes and their substituted derivatives, unsaturated steroids, ethoxyethylene, diallyl ether and its substituted derivatives, isoeugenol, anithole, isosafrole, dihydrofuran and its alkyl derivatives, benzofuran and its substituted derivatives, unsaturated carboxylic acids of all types, such as acrylic acid, methacrylic acid, alpha-and beta-cyanoacrylic acids and their derivatives, crotonic acid, maleic acid and its alkyl derivatives, vinylacetic acid and unsaturated fatty acids, including, more particularly, oleic, linoleic, palmitoleic, linolenic, vaccinic, gadoleic, ricinoleic and eleostearic acids, and natural fats and oils in which they are present, and also esters of all these unsaturated acids, such as alkyl acrylates and methacrylates, diallyl maleate, methyl 7-hydroxyhept-5-enoate and methyl oleate, and esters of unsaturated alcohols, such as allyl carbonate, diallyl phthalate and allyl acetate.
The compound J comprising at least one alkenyl group may be preferably chosen in the group consisting of cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl cyclohexene and 4-methyl cyclohexene.
The compound J comprising at least one hydroxyl group or epoxy group, which can be used as reactant in the process according to the invention has the same meaning of compound I comprising at least one hydroxyl group or epoxy group.
Particles A of the present invention comprise at least one substituted polyoxometalate. It should be understood the substituted polyoxometalate have both amphiphilic and catalytic characteristics.
As used herein, polyoxometalate is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks.
The polyoxometalate is not particularly limited as long as it shows catalytic performance towards oxidative cleavage reactions. Non-limiting examples of polyoxometalate could notably be Keggin type polyoxometalates (POMs) , including H 3PW xMo 12-xO 40 (x = 1, 3 or 6) , Cs 2.5H 0.5PW 12O 40 and H 3PW 12O 40 as described in Catalysis Today 149 (2010) 117-121. Preferable polyoxometalate is H 3PW 12O 40.
The substituent group is also not particularly limited. It may be straight, branched or cyclic C 2-C 30 hydrocarbon group that can be an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, eventually comprising one or several heteroatoms such as O, S, F, and N. More preferable substituent group may notably for example C 2-C 12 straight aliphatic hydrocarbon group, that is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
In a particular embodiment, particles A could be alkylpolyoxometalates as disclosed by Chem. Eur. J. 2012, 18, 14352 –14358. The solid amphiphilic catalytic polyoxometalate nanoparticles could not only stabilize the Pickering Emulsion, but also is easy for recycling and reuse.
Particles A could be prepared by some well-known ways, such as the method mentioned in Chem. Eur. J. 2012, 18, 14352 –14358.
As mentioned above, particles B of the present invention may preferably comprise at least one metal compound of at least one metal element, wherein the metal element is chosen from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) titanium, zirconium, cerium and (vi) mixtures thereof. Metal element could be preferably chosen in the group consisting of aluminium, silicon, tin, titanium, zirconium, cerium, magnesium and barium and more preferably chosen in the group consisting of aluminium, silicon and titanium and most preferably silicon.
The said metal compound comprised in particles B include, for example, water immiscible metal salts, metal hydroxides, metal oxides, mixed metal oxides or clays. Among these, metal oxide or mixed metal oxides are preferable.
The said metal compound comprised in particles B are particularly inorganics such as for example made of an oxide, hydroxide and/or oxy-hydroxyde of at least one metal chosen from aluminium, silicon, titanium. Preferably, it could be silicon dioxide.
Specific non-limiting examples of metal compound include bentonite, tin oxide, magnesium aluminum silicate, magnesium oxide, titanium oxide, barium sulphate and/or silica, such as is described in U.S. Pat. No. 4,833,060 at col. 4, lines 54-61, the cited portion of which being incorporated herein by reference, and alumina as described in U.S. application 2005/0156340.
It can be advantageous that the metal compound is in the form of solid particles (hereinafter referred to as “particles C” ) .
It could be preferable that particles C have a colloidal behaviour, preferably with an interparticule agglomeration rate (number of agglomerated particles/total number of  particles) inferior or equal to 5 %, more preferably inferior or equal to 2 %. In certain embodiments, the solid particles, such as silica and/or alumina particles, are introduced in the form of colloidal dispersion, wherein finely divided solid particles are dispersed within a continuous medium in a manner that prevents them from being filtered easily or settled rapidly. Said solid particles are insoluble in the reaction medium of present invention.
In one embodiment, particles C may show amphiphilic property. In another embodiment, particles C could be modified, such as being linked with hydrophilic and hydrophobic functional groups (hereinafter referred to as “modified particles C” ) . Amphiphilic property could therefore be introduced. Particles C linked with hydrophilic and hydrophobic functional groups could display or not amphiphilic property. Preferably, particles C linked with hydrophilic and hydrophobic functional groups could be inorganics such as for example made of an oxide, hydroxide or oxy-hydroxide of at least one element chosen from aluminium, silicon, titanium.
Hydrophilic nature is usually provided by the presence of hydrophilic groups. These groups may be neutral such as -OH, -COOH, -PO 3H 2, -SO 3H as example, or preferentially under their anionic or cationic corresponding forms.
Hydrophobic nature is usually provided by the presence of hydrophobic groups such as organic chains having a hydrophobic nature. Said chains are defined as organic chains having a hydrophobic character such as these chains are soluble in a hydrophobic solvent and less soluble, notably insoluble, in water. Organic chains having a hydrophobic nature may have at least 50 %wt, preferentially at least 80 %wt of hydrophobic groups such as alkylated groups, or alkoxylated groups.
Hydrophobic groups are preferably alkyl chains comprising 1 to 30 carbon atoms, more preferably from 1 to 8 carbon atoms or alkoxylated groups notably comprising 1 to 10 units of ethylene oxide -CH 2CH 2O-groups.
The exact nature of the link existing between organic chains and the surface of particles C can vary in a large measure and may be for example a covalent bond, or physical adsorption  more often including an electrostatic bond, an ionic bond and a hydrogen bond. Covalent bonds can be obtained by grafting or co-condensation or co-precipitation.
The grafting rate of the particle surface by hydrophobic groups may be comprised between 5 and 90 %of the original amount of hydroxyl groups, preferably between 30 and 70 %. This grafting rate may be evaluated by a thermal decomposition of the particles and then calculate the amount of water formed during the decomposition. It is then possible to proceed to an extrapolation of the number of hydroxyl group.
In a preferred embodiment of the invention, the bonds between the organic chains of hydrophobic nature and the surface of particles are covalent bonds. In this case, these are usually made covalent bonds between atoms of metal particles and organic chains, usually via oxygen atoms initially present in a hydroxyl metal group of the particle surface.
Preferably, the metal atom of these groups hydroxylated metal surface is an atom of silicon, aluminum, or titanium. In this case, particles C are formed at least partially of silicon oxide, oxy-hydroxide of aluminum and/or titanium oxide, this or these oxide (s) and/or oxy-hydroxide being at least this (s) on the surface. Thus, particles C can then be formed such oxide (s) , hydroxide (s) and/or oxy-hydroxide (s) of chemical nature variable, having a surface layer of silicon oxide oxy -aluminum hydroxide and/or titanium oxide, made for example by after-treatment surface.
The organic chains covalently linked are generally introduced by this embodiment of the invention by condensation of a silanol group SiOH on the particle, according to the general reaction:
[particle] -M-OH + HO-Si [organic chain] -> [particle] -M-O-Si- [organic chain]
wherein M is Si, Al or Ti.
In this case, the silanol group SiOH usually comes from the acid hydrolysis, neutral, or basic group of a alkoxysilane, for example acid hydrolysis of a compound or trimethoxyalkysilane, triethoxyalkylsilane.
Modified particles C may also be obtained by co-precipitation of compounds providing hydrophilic function and compounds providing hydrophobic function. For examples, silica particles may be obtained by co-precipitation of hydrophilic silane compounds and hydrophobic silane compounds. Pavithran et al. (Langmuir, 26 (2010) 730-735) reported bifunctionalized silica spheres carring aminopropyl and vinyl groups by hydrolytic co-condensation.
Whatever the exact nature of links implemented to ensure cohesion between the hydrophobic chains and the particle surface, it is preferred that the bonds between the chains and hydrophobic particles are inhomogeneously distributed on the surface of said particles, whereby said particles modified surface have a first area to overall hydrophilic nature and a second area to overall hydrophobic character.
Particles B of the invention are also catalytic and then comprise at their surface at least one catalytic function, permitting to carry out the oxidation reaction of the present invention. This catalytic function may be obtained by the use of groups directly grafted or supported to particles C. These groups may then act as catalyst in the reaction of the present invention. The functional group is preferably be an acidic group chosen in the group consisting of -COOH, -PO 3H 2 or -SO 3H. Sulfonic (-SO 3H) is particularly efficient as both catalytic and hydrophilic functions for particles B.
Particles B of the present invention may notably provide sulfonic acid function containing group (s) . These groups may also comprise alkyl, peralkyl or aryl group, such as for instance :
- CH 3-SO 3 -
- CH 2-CH 2-SO 3 -
- CF 3-SO 3 -
- phenyl-SO 3 -
It is advantageous to choose the concentration of particles B according to the invention to be greater than 0.1 %by weight, advantageously could be comprised from 0.1 %by weight to 30 %by weight, based on the total weight of the preparations.
Particles A and B of the instant invention may notably be particles having an average diameter comprised from 2 to 5000 nm, preferably from 50 to 3000 nm, more preferably from 100 to 1000 nm and most preferably from 100 to 400 nm.
The average diameter of particles can be determined by examining a micrograph of a transmission electron microscopy "TEM" image, measuring the diameter of the particles in the image, and calculating the number average particle size of the measured particles based on magnification of the TEM image. One of ordinary skill in the art will understand how to prepare such a TEM image and determine the particle size based on the magnification. For example, silica particles could be characterized by TEM on a JEOL JEM 2100 microscope operated at 200 kV and equipped with Energy Dispersive Spectroscopy (EDS) . The particles to be measured refer to the projection (2D-representation) of the particles on the micrograph. Before performing the measurements, it is necessary to calibrate the image. Size distribution histograms are then plotted as percent silica particles versus silica diameter on the basis of the size measurements obtained from an image processing program, such as ImageJ. The number average is obtained by weighted average method. The measurement should be made on a sufficiently high number of particles, for example at least about 100 particles, preferably at least 300 particles, more preferably at least 1000 particles, still more preferably at least 3000 particles.
The shape or morphology of particles A and B can vary. For example, generally spherical morphologies can be used, as well as particles that are cubic, platy, or acicular (elongated or fibrous) , such as sticks or needles.
The weight ratio of solid amphiphilic catalytic particles A to solid amphiphilic catalytic particles B at the start of the reaction is preferably comprised from 0.5: 1 to 1: 0.5, more preferably from 0.8: 1 to 1: 0.8.
The oxidant of present invention could notably be chosen in the group consisting of organic peroxy acid, such as peracetic acid, organic peroxide, such as t-butyl hydrogen peroxide and inorganic peroxides, such as hydrogen peroxide, a perborate, a persulfate and any combination thereof. Among these oxidants, hydrogen peroxide could be more preferable. A typical amount of use of oxidant depends on the starting material and final product. When hydrogen peroxide is employed, it is preferably comprised from 0.5 mol to 10 mol equivalents, more preferably 1.0 mol to 5.0 mol equivalents of the starting material. For example, 1.0 mol to 1.5 mol equivalents H 2O 2 could be used to convert an olefin into an epoxide. 3.0 mol to 3.5 mol equivalents H 2O 2 could be used to convert an epoxide or a diol to a carboxylic acid.
Solvent S is typically chosen based on its ability to dissolve compound J and compound I to prevent them from precipitating at the bottom of the reactor so that biphasic system can be well kept. It could be chosen in a group consisting of alcohols, alkane, aromatics, ether, ester, ketone and any combination thereof. Preferable solvent could be aromatics, such as benzene, toluene, xylene and ethyl-benzene, and aliphatics, such as pentane, hexane, heptane, cyclohexane, methyl-cyclohexane and cyclopenyl methyl ether. Some bio-based solvents, such as 2-methyltetrahydrofuranethyl lactate, D-limonene, and methyl soyate could also be used.
Solvent S can be used in variable amounts. In general, the reaction mixture contains at most 50 %by weight of solvent and preferably from 20 %to 50 %by weight with respect to total weight of reaction mixture.
The reactant concentration could be comprised from 0.2 to 20.0 mol/L and preferably from 0.5 to 2 mol/L.
In a preferred embodiment, the present invention concerns a process for the conversion of a compound J comprising at least one epoxy group to a compound I comprising one carbonyl group.
In another preferred embodiment, the present invention concerns a process for the conversion of a compound J comprising at least one alkenyl group to a compound I comprising one carbonyl group.
The process according to the invention is particularly suitable for converting olefins containing from 5 to 20 carbon atoms, and more especially cyclic olefins (that is to say cyclic compounds which contain at least one ethylenic double bond in a ring) to dicarboxylic acids. It is particularly suitable for converting cyclic olefins containing not more than 8 carbon atoms per ring to dicarboxylic acids.
In a very preferred embodiment, the selectivity of compound I comprising one carbonyl group obtained in above two embodiments could be at least of 60 %and more preferable comprised from 70 %and 95 %and most preferably from 85 %and 95 %.
Emulsification instrument can be any instrument giving high energy such as ultra sound, or high shear such as homogenizer, or other stirring methods.
Preferably, the medium used in the present process of the invention is substantially free or, in some cases, completely free of any surfactant (other than the amphiphilic particles of the invention) , at the start of the reaction. As used herein, the term "surfactant" refers to materials that have an amphiphilic molecular structure, which includes a polar hydrophilic molecular moiety and a nonpolar lipophilic molecular moiety, and which acts to lower the interfacial tension between the dispersed phase and the continuous phase in an emulsion. As will be appreciated, surfactants can be classified as ionic (anionic, cationic, and amphoteric) or nonionic. As used herein, the term "substantially free" when used with reference to the absence of surfactant in the medium of the present invention, means that the emulsion comprises less than 0.1 %wt of surfactant, based on the total weight of the medium, notably at the beginning of the reaction; and preferably during the reaction. As used herein, the term "completely free" when used with reference to the absence of surfactant in the medium of the present invention, means that the emulsion comprises no surfactant at all.
The reaction temperature of present may be generally comprised between 10℃ and 250℃, preferably between 20℃ and 80℃.
Several stirring methods may be used during the reaction; preferably a continuous stirring is maintained in the reaction to form emulsion. During this step, the reaction may be carried out under atmospheric pressure or under pressure. Said reaction can be made under inert gas or air for example.
Several known methods of purification of the resulting compounds at the end of the reaction, such as for example extraction, distillation, and/or crystallisation.
This invention also concerns the composition comprising at least :
- a solvent S comprising at least a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group;
- an aqueous oxidizing solution comprising at least one oxidant;
- solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
- solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
Illustrating the invention are the following examples that are not to be considered as limiting the invention to their details.
EXPERIMENTAL PART
Example 1:
Preparation of functionalized silica particles
The modified silica particles are noted as X/Y R/C 3SO 3H. X and Y stand for the molar ratio between trimethoxyalkylsilane and (3-mercaptopropyl) trimethoxysilane. R stands for the alkyl chain in trimethoxyalkylsilane, which could be varied among propyl (C 3) , phenyl (Ph) ,  octyl (C 8) and octadecyl (C 18) chains. The following protocol refers to the modification procedure to obtain the 80/20 C 18/C 3SO 3H nanoparticles.
16 mmol trimethoxyoctadecylsilane and 4 mmol (3-mercaptopropyl) trimethoxysilane were hydrolyzed in 100 mL water/ethanol solution (pH = 9.6) at room temperature overnight. Then the hydrolyzed mixture was added drop-wise to suspension of 1 g 
Figure PCTCN2018096083-appb-000002
 200 in 100 mL of same ethanol solution mentioned above under reflux for 24 h. After the reaction, the suspension was cooled down, and the product was filtered and washed with ethanol (3x30mL) and acetone (1x30 mL) . A white powder recovered and dried in oven overnight at 80℃.
The dried powder was then grinded by mortar and pestle, and the thiol groups were oxidized by 60 mL H 2O 2 (50 %) . A small amount of acetonitrile (3 to 4 mL) was added drop-wise until a homogeneous suspension was obtained. The mixture was heated slowly at 40℃ for 24 hours. After the reaction, the residue was filtered, washed and dried.
50/50 C 18/C 3SO 3H, 20/80 C 18/C 3SO 3H, 80/20 C 8/C 3SO 3H, and 50/50 C 8/C 3SO 3H nanoparticles are prepared in the same way as 80/20 C 18/C 3SO 3H nanoparticles.
Example 2:
Preparation of alkylpolyoxometalate
The POM nanoparticles were prepared by ion exchange. An aqueous solution of H 3 [PW 12O 40] (1 equiv) was added dropwise to an aqueous solution of dodecyltrimethylammonium hydroxide (3 equiv) at 25.8℃ under vigorous magnetic stirring at 1500 rpm. A colourless precipitate was formed within a few minutes, which was separated and lyophilized, thereby providing spherical and fairly monodisperse [C 12]  3 [PW 12O 40] nanoparticles.
Example 3:
Cyclohexene oxide as starting material
In a typical reaction, 0.05 g dodecylpolyoxometalate as prepared in Example 2, 0.05 g amphiphilic modified silica nanoparticles as prepared in Example 1, 1.5 mL toluene phase  containing 0.5 mol/L cyclohexene oxide and 1.5 mL water phase containing 3.5 eq. H 2O 2 were mixed. The system was emulsified at 11500 rpm for 2 min, and the reaction was carried out at 80℃, 500 rpm for 12 h. After the reaction, the emulsions were broken by centrifugation at 4000 rpm for 20 min and the particles as well as the products could be separated and collected.
We observed total conversion from cyclohexene oxide to adipic acid for emulsions using 80/20 C 18/C 3SO 3H, 50/50 C 18/C 3SO 3H, 20/80 C 18/C 3SO 3H, 80/20 C 8/C 3SO 3H, and 50/50 C 8/C 3SO 3H particles. The reaction products were identified using combined NMR and HPLC. Overall, five products could be identified, where the adipic acid, with a yield between 85 %to 93 %was the major product. Between 3 %to 7 %of 1, 2-cyclohexane diol was detected. Less than 3 %of glutaric acid and succinic acid resulting from the degradation of adipic acid were observed. The conversion and selectivity of each product are listed in Table 1. Furthermore, the toluene phase contained neither starting material nor product according to the NMR spectra and could be reused as such.
Table 1
Figure PCTCN2018096083-appb-000003
Example 4:
Cyclohexene oxide as starting material (n-heptane and dibutylether as solvent)
The reaction was performed in the same way as Example 3 with 80/20 C 18/C 3SO 3H as amphiphilic modified silica nanoparticles. 1.5 ml n-heptane and 1.5 ml dibutylether (containing the same concentration of substrate) are used as solvent in replacement of toluene. The products obtained were indentified by NMR and conversion and selectivity of each product are listed in Table 2.
Table 2
Figure PCTCN2018096083-appb-000004
Example 5:
Olefin as starting material
In a typical reaction, 0.75 mL toluene containing 2 mol/L cyclohexene, 2 mol/L 1-methyl cyclohexene or 2 mol/L 4-methyl cyclohexene is separately mixed with 2.25 mL water containing 1.2 eq. H 2O 2, 0.05 g dodecylpolyoxometalate of Example 2 and 0.01 g dodecyl phosphoric acid (buffer solution) . The system was emulsified at 11500 rpm for 1 min and heated at 60℃ for 12 h. 0.05 g 80/20 C 18/C 3SO 3H amphiphilic silica nanoparticles and another 3.5 eq. H 2O 2 batch were added to the system which was re-emulsified at 11500 rpm for 2 min, and the reaction was continued at 80℃, 500 rpm for 12 h. The products obtained were identified by NMR and HPLC and conversion. The selectivity of each product are listed in Table 3.
Table 3
Figure PCTCN2018096083-appb-000005
Comparative Example 1:
In this example, 50 mg catalyst (only amphiphilic silica or only POM NPs) , 1.5 mL toluene (0.5 mol/L cyclohexene oxide) , 1.5 mL water (containing 3.5 eq. H 2O 2) , pre-emulsify with Ultra-Turrax (R) at 11, 500 rpm for 2 min. The reaction was carried out in an oil bath of 80℃, magnetic stir at 500 rpm for 12 hours. The experimental results are shown in Table 4.
Table 4
  Only [C 12]  3 [PW 12O 40]  e Only 80/20 C 18/C 3SO 3H f
Conversion (%)  a 99.8 98.0
Yield of diol (%)  b 30.8 81.3
Yield of adipic acid (%)  c 61.9 12.9
Selectivity on adipic acid (%)  d 62.0 13.2
a Measured by analyzing oil phase by 1H-NMR and CDCl 3 as solvent (dodecane as reference) ; b Measured by analyzing aqueous phase by 1H-NMR DMSO as solvent (dodecanol as reference) ; c Measured after fully extraction of cleavage product, with 1H-NMR (DMSO as solvent dodecanol as reference) ; d Calculated by (yield of diacid/conversion) x 100 %; e 50 mg alkyl POM as catalyst; f 50 mg amphiphilic silica as catalyst.
Example 6:
In a typical reaction, 0.05 g dodecylpolyoxometalate as prepared in Example 2, 0.05 g 80/20 C 18/C 3SO 3H amphiphilic modified silica nanoparticles as prepared in Example 1, 1.5 mL THF containing 1.5mmol 9, 10-epoxystearic acid and 1.5 ml water containing 5.25mmol H 2O 2 were mixed. The system was homogenized at 11, 500 rpm for 2 min, and the reaction was carried out at 80 ℃ for 24 h under stirring (500 rpm) . After the reaction, the emulsions were centrifuged at 4,000 rpm for 20 min and the particles as well as the products were separated and collected. The reaction products were identified by combining  1H NMR and HPLC. Only azelaic acid and 9, 10-dihydroxystearic acid were observed. The conversion of 9, 10-epoxystearic acid and selectivity of azelaic acid are shown as Entry 4 in Table 5.
Comparative Example 2:
The reactions were performed in the same way as Example 6 but in the absence of dodecylpolyoxometalate as prepared in Example 2 and/or amphiphilic modified silica nanoparticles as prepared in Example 1. The experimental results are shown as Entries 1, 2 and 3 in Table 5.
Table 5
Figure PCTCN2018096083-appb-000006

Claims (28)

  1. A process for producing a compound I comprising at least one functional group chosen in the group consisting of epoxy group, hydroxyl group and carbonyl group, by reacting a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group with an oxidant in the presence of:
    - solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
    - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
    wherein the reaction medium comprises at least:
    a) a solvent S comprising at least a compound J;
    b) an aqueous oxidizing solution comprising at least one oxidant;
    wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
  2. The process according to claim 1, wherein solid amphiphilic catalytic particles B comprise at least one metal compound of at least one metal element, wherein the metal element is chosen from (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) titanium, zirconium, cerium and (vi) mixtures thereof.
  3. The process according to claim 2, wherein metal compound is in the form of solid particles.
  4. The process according to any one of claims 1 to 3, wherein solid amphiphilic catalytic particles B comprise hydrophilic and hydrophobic functional groups.
  5. The process according to any one of claims 1 to 4, wherein compound I is a dicarboxylic acid of formula (I) as follows :
    R 1- (COOH)  2 (I)
    wherein R 1 represents an alkyl, aryl, alkenyl or alkoxy radical comprising 1 to 3000 carbon atoms.
  6. The process according to claim 5, wherein compound I is chosen in the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
  7. The process according to any one of claims 1 to 6, wherein compound I or compound J is a compound comprising at least one hydroxyl group.
  8. The process according to claim 7, wherein compound I or compound J is a diol of formula (II) as follows :
    R 2- (OH)  2 (II)
    wherein R 2 represents an alkyl, aryl, alkenyl or alkoxy radical comprising 1 to 3000 carbon atoms.
  9. The process according to claim 8, wherein compound I or compound J is chosen in the group consisting of 1, 6-hexylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, 1, 2-cyclooctanediol, 1, 2-cycloheptanediol, 1, 2-cyclohexanediol, 1, 2-cyclopentadiol, 1-methyl-1, 2-cyclohexanediol, 1, 2-dimethyl-1, 2-cyclohexanediol, 4-vinyl-1, 2-cyclohexanediol, 3, 4-diol-1-cyclohexene.
  10. The process according to any one of claims 1 to 9, wherein compound J is a compound comprising at least one alkenyl group.
  11. The process according to claim 10, wherein compound J is chosen in the group consisting of cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl cyclohexene, 4-methyl cyclohexene.
  12. The process according to claim 10, wherein compound J is an olefin having general formula (III) :
    Figure PCTCN2018096083-appb-100001
    wherein R 3, R 4, R 5 and R 6 are each independently selected from hydrogen or C 1-11 hydrocarbyl.
  13. The process according to claim 12, wherein compound J is an internal olefin.
  14. The process according to any one of claims 1 to 13, wherein compound I or compound J is a compound comprising at least one epoxy group.
  15. The process according to claim 14, wherein compound I or compound J is chosen in the group consisting of 1, 2-epoxy-cyclopentane, 1, 2-epoxy-cyclohexane, 1, 2-epoxy-cycloheptane, 1, 2-epoxy-cyclooctane, 1, 2-epoxy-4-vinylcyclohexane, 3-4-epoxy-1-cyclohexene, 1, 2-epoxy-1-methylcyclohexane, 1, 2-epoxy-1, 2-dimethylcyclohexane and vinyl cyclohexene dioxide.
  16. The process according to claim 14, wherein compound J is a compound comprising at least one epoxy group.
  17. The process according to claim 16, wherein the compound comprising at least one epoxy group is derived from epoxidation of an internal olefin.
  18. The process according to claim 17, wherein the internal olefin is chosen in the group consisting of oleic acid, linoleic acid, palmitoleic acid, linolenic acid, vaccinic acid, gadoleic acid, ricinoleic acid and eleostearic acid.
  19. The process according to claim 18, wherein the internal olefin is oleic acid.
  20. The process according to claim 16, wherein compound J is 9, 10-epoxystearic acid.
  21. The process according to any one of claims 16 to 20, wherein compound I is a dicarboxylic acid of formula (I) as follows:
    R 1- (COOH)  2 (I)
    wherein R 1 represents an alkyl radical comprising from 1 to 30 carbon atoms.
  22. The process according to claim 21, wherein compound I is azelaic acid.
  23. The process according to any one of claims 1 to 22, wherein substituent group of polyoxometalate is straight, branched or cyclic C 2-C 30 hydrocarbon group.
  24. The process according to any one of claims 1 to 23, wherein substituent group of polyoxometalate is chose in the group consisting of ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
  25. The process according to any one of claims 1 to 24, wherein solid amphiphilic catalytic particles A or solid amphiphilic catalytic particles B have an average diameter comprised from 100 to 400 nm.
  26. The process according to any one of claims 1 to 25, wherein the concentration of solid amphiphilic catalytic particles B is comprised from 0.1 %by weight to 30 %by weight based on the total weight of the preparations.
  27. The process according to any one of claims 1 to 26, wherein the weight ratio of solid amphiphilic catalytic particles A to solid amphiphilic catalytic particles B at the start of the reaction is comprised from 0.5: 1 to 1: 0.5.
  28. A composition comprising at least :
    - a solvent S comprising at least a compound J comprising at least one functional group chosen in the group consisting of alkenyl group, epoxy group and hydroxyl group;
    - an aqueous oxidizing solution comprising at least one oxidant;
    - solid amphiphilic catalytic particles A comprising at least one substituted polyoxometalate;
    - solid amphiphilic catalytic particles B comprising at least one functional group chosen in the group consisting of -COOH, -PO 3H 2 and -SO 3H;
    wherein solvent S and aqueous oxidizing solution form a biphasic liquid system when mixed together.
PCT/CN2018/096083 2017-07-18 2018-07-18 Oxidative cleavage of olefins, epoxides and alcohols Ceased WO2019015599A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110090662B (en) * 2019-05-27 2020-07-24 北京化工大学 A kind of preparation method of sulfonic acid group covalently modified vacancy polyacid composite material and its catalytic application

Citations (4)

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WO1995000243A1 (en) * 1993-06-25 1995-01-05 Solvay Interox Limited Oxidative cleavage of alkenes
WO2000043122A1 (en) * 1999-01-24 2000-07-27 Yissum Research Development Company Of The Hebrew University Of Jerusalem Polyoxofluorometallates and use thereof as catalysts for the epoxidation of alkenes
WO2012010842A1 (en) * 2010-07-21 2012-01-26 Unilever Plc Method for the oxidation of unsaturated organic compounds
CN105689002A (en) * 2016-01-18 2016-06-22 浙江大学 Supported tungsten-gallium polyoxometallate catalyst and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995000243A1 (en) * 1993-06-25 1995-01-05 Solvay Interox Limited Oxidative cleavage of alkenes
WO2000043122A1 (en) * 1999-01-24 2000-07-27 Yissum Research Development Company Of The Hebrew University Of Jerusalem Polyoxofluorometallates and use thereof as catalysts for the epoxidation of alkenes
WO2012010842A1 (en) * 2010-07-21 2012-01-26 Unilever Plc Method for the oxidation of unsaturated organic compounds
CN105689002A (en) * 2016-01-18 2016-06-22 浙江大学 Supported tungsten-gallium polyoxometallate catalyst and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110090662B (en) * 2019-05-27 2020-07-24 北京化工大学 A kind of preparation method of sulfonic acid group covalently modified vacancy polyacid composite material and its catalytic application

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