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WO2025238174A1 - Composé diaminotrisphénol, ses complexes métalliques et catalyseur supporté - Google Patents

Composé diaminotrisphénol, ses complexes métalliques et catalyseur supporté

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Publication number
WO2025238174A1
WO2025238174A1 PCT/EP2025/063445 EP2025063445W WO2025238174A1 WO 2025238174 A1 WO2025238174 A1 WO 2025238174A1 EP 2025063445 W EP2025063445 W EP 2025063445W WO 2025238174 A1 WO2025238174 A1 WO 2025238174A1
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WO
WIPO (PCT)
Prior art keywords
compound
group
diaminotrisphenol
immobilised
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/063445
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English (en)
Inventor
Johan BOOTSMA
Joost Nicolaas Hendrik Reek
Frank VERGUNST
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New Green World BV
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New Green World BV
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Filing date
Publication date
Priority claimed from PCT/EP2024/063744 external-priority patent/WO2024240667A1/fr
Application filed by New Green World BV filed Critical New Green World BV
Publication of WO2025238174A1 publication Critical patent/WO2025238174A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/50—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/32—Gallium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group

Definitions

  • the invention is directed to a novel diaminotrisphenol ligand, its metal complexes and a supported catalyst comprising the metal complexes.
  • Organometallics 2023, 42, 2102-2110 describes diaminotrisphenolate aluminium complexes.
  • Organometallics 2023, 42, 2102-2110 describes diaminotrisphenolate aluminium complexes.
  • ChemCatChem 2021 , 13, 4099-4110 describes aminotrisphenolate gallium complexes.
  • the metal complexes of these known diaminotrisphenol ligands are interesting because they can be used as a catalyst in the preparation of cyclic carbonate compounds starting from carbon dioxide and an epoxide.
  • a problem with the prior art ligands and their corresponding metal complexes is that they are difficult to immobilise to a heterogeneous support.
  • Such supported metal complexes are preferred when used as a catalyst. This because it enables a more simple separation of the catalyst and the reactants of the cyclic carbonate synthesis.
  • the object is to provide a ligand which can be simply immobilised on a heterogeneous support.
  • the aliphatic RS group being a hydroxyl group, carboxylic acid group or an ester group can selectively react with anchoring groups such as 3- isocyanatopropyl(trimethoxyilane) or 3-chloropropyltrimethoxy silane or 3- bromopropyltrimethoxysilane.
  • anchoring groups such as 3- isocyanatopropyl(trimethoxyilane) or 3-chloropropyltrimethoxy silane or 3- bromopropyltrimethoxysilane.
  • the thus obtained reaction product is easily immobilised on for example a silica support.
  • RS is a group comprising alkyl(trialkoxy) silane or alkyltrichlorosilane it may be directly immobilised by covalent bonding to for example a silica support.
  • a preferred diaminotrisphenol ligand is where n is 2 or 3, preferably n is 2, to allow for the formation of a 5- or 6-membered metal chelate ring when reacted with a suitable metal compound.
  • the choice for m is less critical as it forms the connection to the heterogeneous support. Good results have been achieved when m is 2 but m may also be higher.
  • the direct chain of atoms connecting the amine of the ligand and the support contains 6 or less carbon atoms. This direct chain of atoms may further comprise of heteroatoms, such as oxygen, nitrogen and sulphur. Preferably one to three of such heteroatoms are present in this chain.
  • R 1 and R 2 may be hydrogen or any hydrocarbon substituent or a functional group substituent and more preferably both are a hydrocarbon substituent or a functional group substituent or a combination of a hydrocarbon substituent and a functional group substituent.
  • hydrocarbon substituents are alkyl groups having 1 to 5 carbon atoms, for example methyl, ethyl, propyl, iso-propyl, butyl, tert-butyl, preferably methyl and tert-butyl.
  • Possible aryl groups are phenyl and methyl-substituted phenyl.
  • the substituent may also be a functional group, for example a nitro (-NO2) group, a halogen like a chloro, bromo or fluoro group, or a methoxy (-OMe) group.
  • a nitro (-NO2) group for example a nitro (-NO2) group, a halogen like a chloro, bromo or fluoro group, or a methoxy (-OMe) group.
  • Examples of compounds prepared and having a catalytic activity are compounds wherein R1 is methyl, tert-butyl or chloro in combination with a R2 group which is methyl or chloro. Homogeneous experiments show a high catalytic activity when R1 or R2 are chloro or when R1 and R2 are both chloro.
  • R 2 is a hydroxyl group, carboxylic acid group or an ester group.
  • the ester group may be an -C(O)OR 4 group wherein R 4 is a hydrocarbon group having from 1 to 5 carbon atoms.
  • Possible groups R 4 are methyl, ethyl, propyl, iso-propyl, butyl and tert, -butyl.
  • R 4 is methyl.
  • R 2 may also comprise a group comprising alkyl(trialkoxy) silane or alkyltrichlorosilane.
  • the alkyl group of the alkyl(trialkoxy) silane or alkyltrichlorosilane has 2 to 6 carbon atoms and the alkoxy group of the alkyl(trialkoxy)silane has 1 to 3 carbon atoms.
  • the diaminotrisphenol ligand of this invention is not only of interest in that it can be easily immobilised, but additionally, it is also advantageous because it can be prepared in a single synthesis step starting from simple starting compounds.
  • the ligand may be prepared by alkylation of a suitable diamine with optionally substituted phenols containing a 2-bromomethyl group, or by a reductive amination employing a suitable diamine with optionally substituted phenols containing a 2-formyl group, or through a Mannich condensation reaction of a suitable diamine with an optionally substituted phenol and (para)formaldehyde.
  • a Mannich condensation is preferred as it does not require functionalisation of the optionally substituted phenol at the 2-position prior to reaction with the amine.
  • the invention is therefore also directed to this reaction where a functionalised diamine having a group R 2 reacts with a corresponding optionally substituted phenol and formaldehyde to form the diaminotrisphenol ligand and water as a byproduct.
  • the formaldehyde may be added to the reaction mixture as such or added as a precursor, such as paraformaldehyde, which forms the formaldehyde in situ.
  • a preferred substituted phenol is ortho substituted with a group R 1 and para substituted with a group R 2 .
  • the functionalised diamine has a primary amine, a secondary amine and a R 2 group and a phenylene or preferably an alkylene group bridging the primary amine and the secondary amine and an alkylene group bridging the secondary amine with the R 2 group.
  • the R 2 group of the functionalised diamine is a hydroxyl group, carboxylic acid group or an ester group.
  • Suitable diamines are 2-((2-aminoethyl) amino)ethan-1 -ol, 3-((2-aminoethyl)amino)propan-1 -ol, 2-((3- aminopropyl)amino)ethan-1 -ol, 3-((2-aminoethyl)amino)propanoic acid or methyl 3-((2-aminoethyl)amino)propanoate.
  • Suitable substituted phenols are 2,4-di-tert-butylphenol 2,4-dimethylphenol, 2-tert-butyl-4- methylphenol, 2-tert-butyl-4-methoxyphenol, 2-tert-butyl-4-chlorophenol, 4- chloro-2-methylphenol, 2,4-dichlorophenoL It is believed that this reaction proceeds according to a so-called Mannich reaction.
  • reaction is preferably presented as:
  • the preparation of the diaminotrisphenol ligand may be performed in a solvent.
  • the preparation is performed under neat conditions in the absence of a solvent.
  • the reactants are preferably mixed in around stoichiometric quantities.
  • the temperature at which the preparation is performed is suitably below the boiling points of the reactants at the chosen pressure and may be between 65 and 1 10 Q C and preferably between 85 and 95 °C.
  • the pressure is suitably ambient pressure.
  • the diaminotrisphenol ligand may be isolated from the reaction mixture by chromatography, precipitation and/or crystallization.
  • the diaminotrisphenol ligand of this invention and the ligand as obtained by the above process may advantageously be combined with a metal to form a complex.
  • a metal Possible metals which can be used are one or more chosen from the group of aluminium, gallium, indium, iron, cobalt, nickel, zinc, titanium and/or bismuth.
  • the metal may be a rare earth metal such as Y, Sm, Nd and La.
  • the metal is one of Ga, Fe and Al and the metal complex may be advantageously used as a catalyst in the preparation of cyclic carbonates.
  • the complex may be used as a homogeneous catalyst and preferably as a supported catalyst comprising the complex. The invention is for this reason also directed to the complex as such as well as to a supported catalyst comprising the complex.
  • Gallium complexes are preferably prepared by contacting a suitable gallium compound with the ligand in a solvent.
  • Suitable gallium compounds may be gallium(lll) ethoxide, gallium(lll) acetylacetonate or gallium(lll) chloride.
  • a suitable solvent is tetrahydrofuran (THF). The reaction may be performed at ambient conditions.
  • Aluminium complexes are preferably prepared by contacting a suitable aluminium compound with the ligand in a solvent.
  • Suitable aluminium compounds may be aluminium(lll) isopropoxide, trimethyl aluminium or aluminium(lll) chloride.
  • a suitable solvent is tetrahydrofuran (THF). The reaction may be performed at ambient conditions.
  • Iron complexes are preferably prepared by contacting a suitable iron compound with the ligand in a solvent.
  • Suitable iron compounds may be iron(lll) chloride or iron(lll) acetylacetonate.
  • Suitable solvents are tetrahydrofuran (THF), ethyl acetate or methanol. The reaction may be performed at ambient conditions.
  • the preferred metal complex may suitable be prepared by first preparing a diaminotrisphenol compound by a process according to this invention to obtain a reaction mixture containing the diaminotrisphenol compound and wherein without isolation of the diaminotrisphenol compound from the reaction mixture a suitable gallium, aluminium or iron compound is added to the reaction mixture to obtain the corresponding metal complex.
  • the metal complex of this Invention may be used as a homogeneous catalyst and preferably as a supported catalyst comprising the complex.
  • the invention is thus also directed to a homogeneously catalysed process to prepare a cyclic carbonate by reacting an epoxide compound and carbon dioxide in the presence of the metal complex and a quaternary ammonium halogen salt or a quaternary phosphonium halogen salt.
  • a quaternary ammonium halogen salt or a quaternary phosphonium halogen salt may be those described below, except that in this process they are dissolved in the reaction medium.
  • the metal complex is part of a supported catalyst as described below because this avoids the use of dissolved quaternary ammonium halogen salt or a quaternary phosphonium halogen salt.
  • the supported catalyst will comprise a solid support.
  • the complex is covalently bonded to the surface of the solid support.
  • the solid support needs to contain or be derivatized to contain reactive functionalities which can serve for covalently linking an anchoring compound to the surface thereof.
  • suitable reactive functionalities are titanol (Ti-OH), silanol (Si-OH) and aluminol (AI-OH).
  • Materials having such functionalities are for example silicon dioxide supports containing reactive silanol groups, alumina supports containing reactive aluminol groups, amorphous silica-alumina supports having both silanol and aluminol groups and sol-gel materials.
  • Other possible carrier particles may be polyacrylamide supports, polystyrene supports and polyethylene glycol supports.
  • Preferred solid supports are titanium dioxide, silica, alumina and/or silica alumina as present as particles.
  • the silanol groups as present on the surface of the silica or silica-alumina particle and/or the aluminol groups as present on the surface of the alumina or silica-alumina particle or the titanol as present on the surface of the titanium dioxide particle are covalently connected to the complex by an anchoring group.
  • the catalyst particle may be relatively large when used as part of a packed bed in a reactor. In such a bed inert particles may also be present.
  • the supported catalyst may also be present as a suspension in a liquid reaction mixture.
  • the support will then be present as a powder having dimensions which are small enough to create a high active catalytic surface per weight of the support and large enough to be easily separated from the cyclic carbonate in or external of the reactor.
  • Preferably the support powder particles have for at least 90 wt% of the total particles a particle size of above 10 pm and below 2000 pm. The particle size is measured by a Malvern® Mastersizer® 2000.
  • the anchoring group is connected to the hydroxyl group of the ligand.
  • a bi functional compound having a functional group which can react with the hydroxyl group of the ligand and provided with a functional group which can covalently bond with the surface of a solid support is reacted with the ligand or more preferably with the metal complex comprising the ligand.
  • Suitable functional groups which can react with the hydroxyl group R ⁇ are chloro groups, bromo groups and isocyanato groups.
  • Suitable functional groups which can react with the carboxylic acid group or ester RS are amino groups.
  • Suitable functional groups which can covalently bond with the surface of a solid support are alkyl(trialkoxy) silane wherein the alkyl group preferably has 2 to 6 carbon atoms and the alkoxy group has preferably 1 to 3 carbon atoms, and alkyltrichlorosilane wherein the alkyl group preferably has 2 to 6 carbon atoms.
  • the functional groups which can react with the hydroxyl group and the functional groups which can covalently bond with the surface of a solid support are preferably present at either end of an alkylene group having between 2 and 10 carbon atoms, preferably between 3 and 6 and most preferably 4 carbon atoms, for example 3 carbon atoms
  • suitable compounds which are reacted and connected to the hydroxyl group R ⁇ of the ligand are (3-isocyanatopropyl)trimethoxysilane, (4-isocyanatobutyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, and (3- bromopropyl)trimethoxysilane
  • Examples of suitable compounds which are reacted and connected to the carboxylic acid group or ester group R ⁇ of the ligand are 3- aminopropyl(trimethoxysilane), and 4-aminobutyl(trimethoxysilane).
  • reaction product of ligands or metal complexes comprising the ligand and the bi functional compound are subsequently immobilised on a solid support.
  • the preferred trialkoxy groups react with the silanol, titanol or aluminol groups of the solid support to obtain the supported catalyst.
  • the heterogeneous or supported catalyst comprises carrier particles having a carrier surface, to which carrier surface the metal-complex is immobilised.
  • a halogen salt is immobilised such that the metal-complex and the halogen salt are each individually immobilised to the carrier surface.
  • this supported catalyst can be advantageously be used as a catalyst or as part of a catalyst in a chemical process in the presence of an organic halogen compound and in the absence of a non-immobilised halogen ammonium salt.
  • This halogen compound enhances the activity of the catalyst and enhances the activity when the catalyst is reused in for example subsequent batch or semi-batch operations to prepare the cyclic carbonate.
  • this catalyst allows one to use this catalyst in chemical processes which are up to now catalysed by metal complexes and in the presence of a non-immobilised halogen ammonium salt.
  • this catalyst in the presence of an organic halogen compound one does not require the presence of the unwanted non-immobilised halogen ammonium salt. It is especially found that this supported catalyst can be used in a process to prepare a cyclic carbonate by reacting an epoxide compound and carbon dioxide without leaching of a halogen ammonium salt.
  • the halogen salt is preferably an ammonium or phosphonium halogen salt.
  • the choice of the halogen will also decide the choice of any other halogen compound used as part of the catalyst system as they are preferably the same.
  • This halogen is also referred to as the catalyst system halogen.
  • Preferred halogen salts are iodide salts and bromide salts.
  • the iodide salt which is immobilised is preferably a quaternary phosphonium iodide salt and more preferably a quaternary ammonium iodide salt.
  • the bromide salt which is immobilised is preferably a quaternary phosphonium bromide salt and more preferably a quaternary ammonium bromide salt.
  • the immobilised halogen salt is preferably a quaternary ammonium halogen salt or a phosphonium salt having the following general formula R5R6R7R8ZX, wherein X is an iodide anion and preferably a bromide, Z may be N or P, R5 is an anchoring group which covalently binds the quaternary ammonium halogen salt or quaternary phosphonium halogen salt to the carrier surface and R® , R 7 and R ⁇ are the same or different alkyl groups having between 1 and 20 carbon atoms.
  • the anchoring group preferably comprises a functional group which can covalently bond with the surface of a solid support such as described above for immobilising the ligand or the complex.
  • These functional groups are preferably alkyl(trialkoxy) silane wherein the alkyl group preferably has 2 to 6 carbon atoms and the alkoxy group has preferably 1 to 3 carbon atoms and alkyltrichlorosilane wherein the alkyl group preferably has 2 to 6 carbon atoms.
  • the metal-complex and the halogen salt are each individually immobilised enables one to influence the relative presence of the halogen salt with respect to the metal complex in the catalyst. It has been found that after immobilisation also immobilised amine is found on the carrier surface. It is believed that part of the halogen salt converts to an amine by means of the reversed Menshutkin reaction as illustrated below in more detail.
  • An amine may also be individually immobilised to the carrier surface next to the metal complex.
  • an amine is individually immobilised to the carrier surface next to the metal complex and the halogen salt, although good results are achieved when no amine is immobilised next to the metal complex and the halogen salt.
  • the amine may be a tertiary amine.
  • the tertiary amine may be presented as R9R10R11 N and wherein R9 is an anchoring group which covalently binds the tertiary amine to the carrier surface and R ⁇ 0 and R ⁇ 1 are the same or different alkyl group having from 1 to 20 carbon atoms or wherein R 1 0 and R 1 1 are part of a ring structure forming a 5- or 6 membered ring or R10 or R11 are amino alkyl groups.
  • the anchoring group R ⁇ preferably comprises a functional group which can covalently bond with the surface of a solid support such as described above for immobilising the ligand or the complex.
  • These functional groups are preferably alkyl(trialkoxy) silane wherein the alkyl group preferably has 2 to 6 carbon atoms and the alkoxy group has preferably 1 to 3 carbon atoms and alkyltrichlorosilane wherein the alkyl group preferably has 2 to 6 carbon atoms.
  • the molar ratio of the separately immobilised halogen salt and the metal complex is preferably higher than 2:1 , more preferably higher than 3:1 and below 10:1 .
  • the molar ratio between the separately immobilised amine and the metal complex is preferably between 0:1 and 10:1 and more preferably between 0:1 and 5:1 .
  • the metal-complex, the halogen salt and the optional tertiary amine are thus suitably individually immobilised to the carrier surface of the heterogeneous catalyst as presented below:
  • S is the carrier surface
  • Z may be N or P
  • R$- R ⁇ are as above.
  • R9 and R ⁇ 2 are the anchoring group which covalently binds the metal complex to the carrier surface S and wherein k:m:n is the molar ratio of the amine, the halogen salt and the metal-complex as individually immobilised to the carrier surface S.
  • a halogen salt such as a bromide salt
  • a halogen compound such as a bromide compound
  • a liquid and/or gaseous reaction mixture as the corresponding halogen compound.
  • This halogen compound is thus non-immobilised.
  • the halogen compound can in-situ repair any deactivated immobilised halogen salt by reaction of the halogen compound with immobilised amine compound. This is illustrated below for 1 ,4 dibromobutane as the bromide compound and for an illustrative individually immobilised bromide salt and an illustrative individually immobilised tertiary amine compound.
  • the above equilibrium reactions also known as the Menshutkin reaction and the reversed Menshutkin reaction, shows that the immobilised bromide salt and the immobilised tertiary amine are in an equilibrium in the presence of the non-immobilised halogen compound.
  • a fresh catalyst is at least immobilised with the halogen salt because this will also result in that immobilised tertiary amine compounds are formed on the carrier surface.
  • the tertiary amine compound may also be individually immobilised.
  • the catalyst will, in use, in a process to prepare a cyclic carbonate by reacting an epoxide compound and carbon dioxide in the presence of a halogen compound be enriched in immobilised amine halogen salt compounds. This as a result of the Menshutkin reaction between the halogen compound and the immobilised tertiary amine compound.
  • the process is preferably performed in the presence of an aryl bromide and/or an alkyl bromide.
  • a tetra-n-butylammonium bromide (TBAB) as in the process of W02009/109765 can be omitted.
  • a suitable aryl bromide is benzyl bromide. Because benzyl bromide is corrosive for some metals it may be preferred to perform the process in glass or glass lined process apparatuses.
  • alkyl bromide such as C3-C10 alkyl bromide compounds, for example propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide and octyl bromide.
  • alkyl bromide such as C3-C10 alkyl bromide compounds, for example propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide and octyl bromide.
  • alkyl bromides such as 1 ,2-dibromoethane, 1 ,3-dibromopropane, 1 ,4-dibromobutane, 1 ,5 dibromopentane and 1 ,6-dibromohexane.
  • the starting epoxide compound suitably has 2 to 8 carbon atoms.
  • Suitable epoxide compounds are ethylene oxide, propylene oxide, butylene oxide, pentene oxide, glycidol, styrene oxide, epichlorohydrin or fluoroethylene oxide.
  • the process may be performed as a continuous process wherein the heterogeneous catalyst is present as part of a fixed bed in a fixed bed reactor.
  • the halogen compound may then be co-fed to the fixed bed reactor together with the epoxide and carbon dioxide.
  • the reaction in the fixed bed may be performed in the gas or liquid phase or combinations of gas and liquid phases.
  • the temperature may be between 20 and 150 °C, more preferably between 40 and 120 °C, and the absolute pressure is suitably between 0.1 and 0.5 mPa, more preferably between 0.1 and 0.3 mPa.
  • the carbon dioxide is suitably contacted with the epoxide compound in a suspension of liquid cyclic carbonate and the heterogeneous catalyst.
  • the temperature and pressure conditions are chosen such that the cyclic carbonate is in its liquid state.
  • the temperature and pressure conditions are further chosen such that carbon dioxide and epoxide easily dissolve in the liquid cyclic carbonate reaction medium.
  • the temperature may be between 0 and 200 °C and the pressure between 0 and 5.0 mPa (absolute) and wherein temperature is below the boiling temperature of the cyclic carbonate product at the chosen pressure. At the high end of these temperature and pressure ranges complex reactor vessels will be required.
  • the temperature is between 20 and 150 °C, more preferably between 40 and 120 °C, and the absolute pressure is between 0.1 and 0.5 mPa, more preferably between 0.1 and 0.4 mPa.
  • the process may be performed as for example described in WO2021/094447.
  • the product can be purified directly after the reaction by column chromatography on silica by eluting with heptane /ethyl acetate/ triethylamine (80:20:2) until a yellow band comes off followed by eluting with heptane:isopropanol:triethyl amine (90:10:2).
  • reaction mixture was cooled to room temperature, resulting in the formation of and aqueous layer on top of a viscous yellow liquid.
  • the aqueous layer was decanted, after which the reaction mixture was diluted with 125 mL toluene.
  • a total of 350 mL pentane was added slowly, resulting in the formation of a voluminous precipitate.
  • This suspension was filtered and washed twice with 350 mL of 20% toluene in pentane (v/v), resulting in a white residue and a slightly yellow filtrate.
  • the residue was subsequently washed with 350 and 200 mL pentane, resulting in a white residue and a clear filtrate.
  • the resulting liquid was purified by column chromatography on silica by eluting using a gradient from heptane I ethyl acetate I toluene I triethylamine 85 : 5 : 10 : 1 (v/v/v/v) to heptane I ethyl acetate I toluene I triethylamine 65 : 30 : 10 : 1 (v/v/v/v).
  • the product was obtained as a white powder (8.51 g, 67.2%).
  • the product was characterised by 1 H NMR: 1 H NMR (400 MHz, CDCh): 5 7.01 (s, 2H), 6.98 (s, 1 H), 6.71 (s, 2H), 6.60 (s, 1 H), 3.73 - 3.58 (m, 8H), 2.76 (s, 4H), 2.58 (s, 2H), 2.23 (s, 9H), 1.40 (s, 18H), 1.34 (s, 9H).
  • the NMR data indicates that the desired product was formed.
  • the resulting liquid was purified by column chromatography on silica by eluting using a gradient from heptane / ethyl acetate / toluene / triethylamine 60 : 30 : 10 : 1 (v/v/v/v) to heptane I ethyl acetate I toluene I triethylamine 20 : 70 : 10 : 1 (v/v/v/v).
  • the desired product was obtained as a white powder (4.22 g, 37.2%).
  • the NMR data indicates that the desired product was formed.
  • the resulting liquid was purified by column chromatography on silica by eluting using a gradient from heptane / ethyl acetate / toluene / triethylamine 70 : 20 : 10 : 1 (v/v/v/v) to heptane I ethyl acetate I toluene I triethylamine 30 : 60 : 10 : 1 (v/v/v/v).
  • the desired product was obtained as a yellowish powder (5.14 g, 49.4%).
  • the NMR data indicates that the desired product was formed.
  • the resulting liquid was purified by column chromatography on silica by eluting using a gradient from heptane I ethyl acetate I toluene I triethylamine 70 : 20 : 10 : 1 (v/v/v/v) to heptane / ethyl acetate / toluene / triethylamine 30 : 60 : 10 : 1 (v/v/v/v).
  • the desired product was obtained as a yellowish powder (7.17 g, 68.8%).
  • the product was characterised by 1 H NMR: 1 H NMR (400 MHz, CDCh): 5 6.86 (s, 3H), 6.71 (s, 2H), 6.60 (s, 1 H), 3.74 - 3.65 (m, 8H), 2.67 - 2.61 (m, 2H), 2.59 - 2.50 (m, 4H), 2.24 - 2.16 (m, 18H), 1 .91 - 1 .81 (m, 2H).
  • the NMR data indicates that the desired product was formed.
  • the THF was evaporated off under reduced pressure and further dried under reduced pressure at room temperature for 2 hours.
  • the Ga(diaminotrisphenolate) complex was isolated as the THF-adduct being an off-white powder (6.30 g, 99.7 %).
  • the reaction mixture was then filtered over Celite filter aid and washed with THF (2 x 30 mL) resulting in a clear slightly pink solution as the filtrate. Afterwards, the filtrate volume was reduced to approximately 60 mL under reduced pressure. Addition of diethyl ether (240 mL) under stirring resulted in the formation of a white precipitate. This suspension was filtered and washed using diethyl ether (2 x 30 mL) resulting in a white residue and a clear filtrate. The residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at 40 °C for 6 hours. The Al(diaminotrisphenolate) complex was isolated as a white powder (7.04 g, 66.3 %).
  • the residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at 40 °C for 16 hours.
  • the Fe(diaminotrisphenolate) complex was isolated as a red-violet powder (72.18 g, 64.5 %).
  • the dark suspension was filtered, and the material on the filter washed with MeOH (2 x 20 mL), resulting in a dark violet residue and a brown filtrate.
  • the residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at room temperature for 2 hours.
  • the Fe(diaminotrisphenolate) complex was isolated as a dark violet powder (2.02 g, 29.5 %).
  • Example 14 (compound B-4) The preparation of compound B-4 of Example 10 in a one pot, two step procedure according to the below scheme is described. This procedure allows for the preparation of a [Fe(diamonotrisphenolate)] complex without isolation of the ligand from the reaction mixture.
  • Fe(acac)3 (6.71 g, 19.0 mmol, 1 .0 equiv.) was added, resulting in a strong darkening of the reaction mixture.
  • the reaction was allowed to proceed at room temperature for 16 hours.
  • the dark suspension was filtered, and the material on the filter washed with MeOH (2 x 30 mL), resulting in a red-violet residue and a brown filtrate.
  • the residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at room temperature for 2 hours.
  • the Fe(diaminotrisphenolate) complex was isolated as a red-violet powder (6.06 g, 57.0 %).
  • Fe(acac)3 (6.71 g, 19.0 mmol, 1 .0 equiv.) was added, resulting in a strong darkening of the reaction mixture.
  • the reaction was allowed to proceed at room temperature for 16 hours.
  • the dark suspension was filtered, and the material on the filter washed with MeOH (2 x 30 mL), resulting in a violet residue and a brown filtrate.
  • the residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at room temperature for 2 hours.
  • the Fe(diaminotrisphenolate) complex was isolated as a violet powder (8.76 g, 74.3 %).
  • Fe(acac)3 (6.71 g, 19.0 mmol, 1 .0 equiv.) was added, resulting in a strong darkening of the reaction mixture.
  • the reaction was allowed to proceed at room temperature for 16 hours.
  • the dark suspension was filtered, and the material on the filter washed with MeOH (2 x 30 mL), resulting in a dark red residue and a brown filtrate.
  • the residue was air-dried on the filter for 2 hours, and further dried under reduced pressure at room temperature for 2 hours.
  • the Fe(diaminotrisphenolate) complex was isolated as a dark red powder (1 .95 g, 15.0 %).
  • the activity of the compounds B-4, B-5, B-6 and B-7 was tested as homogeneous catalyst in the below reaction of styrene oxide and carbon dioxide to prepare 4-phenyl-1 ,3-dioxolan-2-one.
  • the reactions were carried out in a mixture of styrene oxide (0.42 mL) and propylene carbonate (1 .40 mL), using 0.8 mol% of compound B-4, B-5, B-6 or B-7 with respect to styrene oxide and 1 .6 mol% of a halogen salt with respect to styrene oxide.
  • This example shows the higher catalytic activity of a homogeneous catalyst wherein R1 or R2 or R1 and R2 of the diaminotrisphenol compound are chloro groups and wherein the metal is iron.
  • the reaction is performed in the presence of a halogen salt, namely a quaternary ammonium halogen salt or a quaternary phosphonium halogen salt.
  • Ga:N:N+ is the molar ratio of the gallium diaminotrisphenolate complex (Ga), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure
  • silica (10 g, SP 540-11508, Grace GmbH, 35 A, 40-60 pm) was dispersed in propylene carbonate (75 mL) and heated to 130 °C over a period of 45 minutes.
  • Example 20 was repeated except that also 1 ,4-dibromobutane (DBB) was added to the flask. After 20 hours the conversion was measured and listed for the different catalysts and amounts of DBB relative to styrene oxide (StO) in Table 3. The main product was 4-phenyl-1 ,3-dioxolan-2-one.
  • DBB 1,4-dibromobutane
  • the catalytic activity of the heterogeneous catalysts used in example 20 and 21 was tested for its recyclability in the reaction of styrene oxide and carbon dioxide to prepare 4-phenyl-1 ,3-dioxolan-2-one.
  • the stirring was stopped, and the solid catalyst allowed to settle to the bottom of the Schlenk reaction flask. Thereafter, the solvent phase of the reaction mixture was removed.
  • ethyl acetate (4 mL) was added, the reaction mixture was stirred for 15 minutes before letting the solid catalyst to settle to the bottom of the Schlenk reaction flask. The solvent phase of the reaction mixture was removed. This washing procedure using ethyl acetate was performed twice in total.
  • the Schlenk reaction flask was heated to 100 °C and put on vacuum.
  • the flask was refilled with CO2 gas after which the propylene carbonate (3.30 mL), styrene oxide (1 mL) and 1 ,4-dibromobutane (DBB, 20.92 pL) were added.
  • the flask was purged with CO2 and the stirring was started. After 20 hours the conversion was measured and listed for the different catalysts in Table 4 as Run 2.
  • the main product was 4-phenyl-1 ,3-dioxolan-2-one.
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Al(diaminotrisphenolate) from Example 8 with (3- isocyanatopropyl)trimethoxysilane , in propylene carbonate/THF at 60 °C.
  • Example 24
  • AI:N:N+ is the molar ratio of the aluminium diaminotrisphenolate complex (Al), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure
  • Example 24 the catalytic activity of the heterogeneous aluminium catalyst 24a-24b obtained in Example 24 were tested in the below reaction of styrene oxide and carbon dioxide to prepare 4-phenyl-1 ,3-dioxolan-2-one, similar to Example 20. See Table 6 below.
  • Example 25 was repeated except that also 1 ,4-dibromobutane (DBB) was added to the flask. After 20 hours the conversion was measured and listed for the different catalysts and amounts of DBB relative to styrene oxide (StO) in Table 6. The main product was 4-phenyl-1 ,3-dioxolan-2-one. Table 6.
  • DBB 1,4-dibromobutane
  • Example 27 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 9 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Example 28 Immobilisation of the material from Example 27 was performed in a similar fashion as described in Example 19 resulting in catalyst 28a and 28b having a composition as presented in Table 7.
  • the immobilised iron complex is represented by the following formula:
  • Fe:N:N+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure
  • Table 8 shows the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as immobilised on the carrier surface.
  • the results of catalyst 28b show that after immobilisation also amine is found on the carrier surface. It is believed that part of the halogen salt converts to an amine by means of the reversed Menshutkin reaction. The same is seen in the ICP-MS analysis of different catalysts as reported in tables 12, 16, 20, 24 and 28.
  • Example 22 was repeated with iron catalysts 28a and 28b. The results are presented in Table 10. Table 10
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 10 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Fe:N:N+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure ICP-MS analysis of the immobilised Fe(diaminotrisphenolate) complex as prepared in this example is provided in Table 12 below. Table 12
  • Example 22 was repeated with iron catalysts 32a and 32b. The results are presented in Table 14. Table 14
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 14 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Fe:N:N+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure ICP-MS analysis of the immobilised Fe(diaminotrisphenolate) complex as prepared in this example is provided in Table 16 below. Table 16
  • Example 22 was repeated with iron catalysts 36a and 36b. The results are presented in Table 18.
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 12 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Fe:N:N+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure ICP-MS analysis of the immobilised Fe(diaminotrisphenolate) complex as prepared in this example is provided in Table 20 below.
  • Example 22 was repeated with iron catalysts 40a and 40b. The results are presented in Table 22. Table 22
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 13 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Fe:N:N+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and ammonium salt (N+) as applied during the immobilisation procedure
  • Example 22 was repeated with iron catalysts 44a and 44b. The results are presented in Table 26. Table 26
  • Example 18 The so-called ‘click’ reaction’ of Example 18 was repeated starting with the Fe(diaminotrisphenolate) from Example 10 with (3- isocyanatopropyl)trimethoxysilane, in propylene carbonate/THF at 25 °C.
  • Fe(diaminotrisphenolate) of Example 10 (1 .12 g, 2.00 mmol, 1 .00 equiv.), 5 mL pre-dried THF, 10 mL propylene carbonate and (3-isocyanatopropyl)trimethoxysilane (0.38 mL, 2.00 mmol, 1 .00 equiv.) were added to a 50 mL Schlenk flask resulting in a purple solution. The reaction was allowed to proceed at 25 °C for 16 h resulting in a purple-brown solution. The reaction mixture was directly used for immobilisation.
  • Fe:N:P+ is the molar ratio of the iron diaminotrisphenolate complex (Fe), amine (N) and phosphonium salt (P+) as applied during the immobilisation procedure
  • 3-(tripropyl)phosphoniumpropyltrimethoxysilane bromide was prepared by stirring (3-bromopropyl)trimethoxysilane (4.86 g, 20.0 mmol, 1.00 equiv.) and tri-n-butylphosphine (3.20 g, 20.0 mmol, 1 .00 equiv.) under a nitrogen atmosphere in a 50 mL Schlenk flask at 25 °C for 7 days. The resulting clear, thick liquid was washed with 15 mL pre-dried diethyl ether in the Schlenk flask, and subsequently dried under vacuum at 25 °C for 30 minutes.
  • the product was stored under a nitrogen atmosphere at 25 °C until use. Immediately before use, the compound was dissolved in propylene carbonate resulting in a 0.50 M solution.
  • silica 5.0 g, SP 540-11508, Grace GmbH, 35 A, 40-60 pm
  • propylene carbonate 35 mL
  • the just prepared 15 mL immobilisation mixture was added over 3 hours using a syringe pump.
  • the reaction mixture was allowed to stir for an additional 18 hours at 130 °C after which the reaction mixture was cooled to room temperature.
  • Example 22 was repeated with iron catalysts 44a and 44b. The results are presented in Table 30.

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Abstract

L'invention concerne un composé diaminotrisphénol selon la formule suivante : dans laquelle R1 et R2 représentent l'hydrogène ou un substituant, R3 représente un groupe hydroxyle, un groupe acide carboxylique, un groupe ester ou un groupe comprenant un alkyle(trialcoxy)silane ou un alkyltrichlorosilane et dans laquelle n vaut 2 ou 3 et m vaut 2 ou plus.
PCT/EP2025/063445 2024-05-17 2025-05-15 Composé diaminotrisphénol, ses complexes métalliques et catalyseur supporté Pending WO2025238174A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009109765A1 (fr) 2008-03-07 2009-09-11 University Of Newcastle Upon Tyne Synthèse de carbonates cycliques
WO2021094447A1 (fr) 2019-11-15 2021-05-20 New Green World B.V. Procédé de préparation en continu un carbonate cyclique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009109765A1 (fr) 2008-03-07 2009-09-11 University Of Newcastle Upon Tyne Synthèse de carbonates cycliques
WO2021094447A1 (fr) 2019-11-15 2021-05-20 New Green World B.V. Procédé de préparation en continu un carbonate cyclique

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ACS SUSTAINABLE CHEM. ENG., vol. 8, 2020, pages 13185 - 13194
CHEMCATCHEM, vol. 13, 2021, pages 4099 - 4110
CHIN. J. CHEM., vol. 42, 2024, pages 1571 - 1581
ORGANOMETALLICS, vol. 42, 2023, pages 2102 - 2110
QING YUTING ET AL: "Synthesis of Aluminum Complexes Stabilized by Amine-Bridged Tris(phenolato) Ligands and Their Applications in the Cycloaddition Reaction of CO 2 and Epoxides", ORGANOMETALLICS, vol. 42, no. 15, 1 August 2023 (2023-08-01), pages 2102 - 2110, XP093285392, ISSN: 0276-7333, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.3c00255> DOI: 10.1021/acs.organomet.3c00255 *

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