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WO2024259296A1 - Synthèse de catalyseur de carbonylation à partir de sels de cobalt - Google Patents

Synthèse de catalyseur de carbonylation à partir de sels de cobalt Download PDF

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Publication number
WO2024259296A1
WO2024259296A1 PCT/US2024/034094 US2024034094W WO2024259296A1 WO 2024259296 A1 WO2024259296 A1 WO 2024259296A1 US 2024034094 W US2024034094 W US 2024034094W WO 2024259296 A1 WO2024259296 A1 WO 2024259296A1
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Prior art keywords
metal
group
cobalt
alkyl group
occurrence
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PCT/US2024/034094
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English (en)
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Alison M. WILDERS
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Novomer, Inc.
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Publication of WO2024259296A1 publication Critical patent/WO2024259296A1/fr

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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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • 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
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • the present disclosure relates to a method for making carbonylation catalysts from ligand complexes, metalation compounds, and metal carbonyls.
  • Carbonylation is a process that can be used to react carbon monoxide and an epoxide to make a lactone. In some cases, additional steps are taken to react the lactones to make polymers. These lactones or polymers thereof are often used as plastics and disinfectants. When making these lactones, a carbonylation catalyst is used to optimize the efficiency of the reaction to produce lactones at competitive prices. Carbonylation catalysts are expensive, and thus, new techniques to synthesize the carbonylation catalysts from simple components are needed. Some catalysts have been made using a variety of ligands. For example, see US Patent Number 6,852,865. However, the process to synthesize the carbonylation catalyst from these ligands can utilize many synthetic and purification steps.
  • a method including contacting a cobalt salt comprising one or more of a cobalt halide or ester with a reducing metal and a coordinating compound, optionally in the presence of an inert solvent and in the presence of carbon monoxide under conditions to form a cobalt tetracarbonyl salt of the reducing metal; and contacting the cobalt tetracarbonyl salt of the reducing metal with a with a porphyrin metal halide in the presence of a coordinating compound, optionally in the presence of an inert solvent, under conditions such that a complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl is formed.
  • the cobalt salt and the reducing metal may be contacted to form the cobalt tetracarbonyl salt of the reducing metal with before contacting the cobalt tetracarbonyl salt of the reducing metal with the porphyrin metal halide.
  • the cobalt salt and the reducing metal may be contacted with porphyrin metal halide in the presence of carbon monoxide, wherein the cobalt tetracarbonyl salt of the reducing metal is formed and the formed cobalt tetracarbonyl salt of the reducing metal reacts with the porphyrin metal halide under conditions such that a complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl is formed.
  • a metal byproduct of the process may be a metal halide, metal acetate or metal ester.
  • the formed metal byproduct may be separated from the formed complex.
  • the formed complex may be dissolved or suspended in the coordinating compound, and optionally an inert solvent.
  • the partial pressure of CO may be greater than atmospheric pressure to less than 1000 psi.
  • the partial pressure of CO may be about 10 psi to about 500 psi.
  • the temperature of the method may be about 25 °C to about 120 °C.
  • the molar ratio of the reducing metal to cobalt salt may be 1 .5:1.0 to about 10.0:1 .0.
  • the molar ratio of the reducing metal to cobalt salt may be 1 .5:1 .0 to about 3.0 to 1 .0.
  • the molar ratio of the cobalt tetracarbonyl to the porphyrin metal halide may be from about 1 .0:1 .0 to about 2.0:1 .0.
  • the molar ratio of the cobalt tetracarbonyl to the porphyrin metal halide may be about 1 .0: 1 .0 to about 1.1 to 1.0.
  • the complex formed may be contain less than 1 ,000 g/g of the reducing metal and less than 25,000 g/g of the metal halide, metal acetate or metal ester.
  • the reducing metal may be an alkaline metal, an alkali metal or a period 4 transition metal.
  • the reducing metal may be sodium, magnesium, manganese, or zinc.
  • the cobalt salt may be one or more of a cobalt halide or cobalt acetate.
  • the cobalt salt may be one or more of cobalt chloride, cobalt bromide or cobalt iodide.
  • the complex may correspond to the formula; wherein:
  • CS is separately in each occurrence a molecule of a coordinating solvent
  • M 1 is separately in each occurrence a metal:
  • R is separately at each occurrence hydrogen, halogen, -OR 2 , -NR y 2 , -SR, -CN, -NO2, - SO 2 R y , - SOR y , -SO 2 NR y 2 ; -CNO, -NRSO 2 R y , -NCO, -N 3 , -Si R 2 ; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R y is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl
  • R 1 and R 2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,
  • X is separately in each occurrence is a halogen or alkyl group.
  • the complex formed may be contacted with an epoxide and carbon monoxide under conditions to form a beta-lactone.
  • the complex may be dissolved or suspended in the coordinating compound utilized to form the complex.
  • the starting materials and byproducts formed may be separated from the complex formed before being contacted with the epoxide and carbon monoxide.
  • the complex formed may contain less than less than 25,000 p/g of the metal M.
  • compositions including beta lactones that optionally contains about 25,000 p/g of the metal.
  • a porphyrin metal halide is reacted with a simple cobalt sale and a reducing metal under CO pressure to form a complex (e.g., [(TPP)AI(THF)2][Co(CO)4]) having reactivity in a carbonylation reaction.
  • the reducing metal reduces the Co(ll) salt to Co(0) which reacts with CO atmosphere to form a cobalt tetracarbonyl salt (e.g., MnCox(CO)y (dependent on the reducing metal)).
  • the cobalt tetracarbonyl salts made in situ react with porphyrin metal halides to form the same complex (e.g., [(TPP)AI(THF)2][Co(CO)4]) that has been formed using processes that utilize Co2(CO)8 as a starting material.
  • the reaction is filtered to remove starting materials and byproduct metals, and the carbonylation catalyst can be isolated or the THF solution of [(TPP)AI(THF)2][Co(CO)4] can be used directly in carbonylation.
  • FIG. 1 is an illustration of catalytic activity over time and conversion of EO for the catalysts formed according to Examples 1 -5. Detailed Description
  • One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed.
  • Residue with respect to an ingredient or reactant used to prepare the polymers or structures disclosed herein means that portion of the ingredient that remains in the polymers or structures after inclusion as a result of the methods disclosed herein.
  • Substantially or essentially all of as used herein means that greater than 90 percent of the referenced parameter, composition, structure or compound meet the defined criteria, greater than 95 percent, greater than 99 percent of the referenced parameter, composition or compound meet the defined criteria, or greater than 99.5 percent of the referenced parameter, composition or compound meet the defined criteria.
  • Substantially or essentially free as used herein means that the reference parameter, composition, structure, or compound contains about 10 percent or less, about 5 percent or less, about 1 percent or less, about 0.5 percent or less, about 0.1 percent or less, or about 0.01 percent or less. Portion as used herein means less than the full amount or quantity of the component in the composition, stream, or both.
  • Precipitate as used herein means a solid compound in a slurry or blend of liquid and solid compounds. The ingredients or products may exist in different states during the processes disclosed, such as solid, liquid, or gaseous state. Phase refers to a portion of a reaction mixture that is not soluble in another part of the reaction mixture. Parts per weight means parts of a component relative to the total weight of the overall composition.
  • Composition or mixture as used herein includes all components in a stream, reactant stream, product stream, slurry, precipitate, solution, liquid, solid, gas, or any combination thereof that are containable within a single vessel.
  • the mixture may include components that are solid, gaseous (i.e., volatile), and/or liquid when at room temperature (i.e., 25 degrees Celsius) or when exposed to elevated temperatures.
  • Certain polymers disclosed can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • the polymers and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
  • the polymers disclosed may be enantiopure compounds. Disclosed are mixtures of enantiomers or diastereomers. In certain structures disclosed in this application parts of the structure are connected by a dotted line - which indicates that the connected structures are ionically bonded together.
  • beta lactone refers to a substituted or unsubstituted cyclic ester having a four-membered ring comprising an oxygen atom, a carbonyl group and two optionally substituted methylene groups.
  • the beta lactone is referred to as propiolactone.
  • Substituted beta lactones include monosubstituted, disubstituted, trisubstituted, and tetrasubstituted beta lactones. Such beta lactones may be further optionally substituted as defined herein.
  • the beta lactones comprise a single lactone moiety.
  • the beta lactones may comprise two or more four-membered cyclic ester moieties.
  • epoxide refers to a substituted or unsubstituted oxirane.
  • substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes.
  • epoxides may be further optionally substituted as defined herein.
  • the epoxides may comprise a single oxirane moiety.
  • the epoxides comprise two or more oxirane moieties.
  • halo and “halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).
  • aliphatic or “aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic.
  • Aliphatic groups may contain 1-40 carbon atoms, 1-20 carbon atoms, 2-20 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, 1 -5 carbon atoms, 1 -4 carbon atoms, 1 -3 carbon atoms, or 1 or 2 carbon atoms.
  • Aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
  • heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.
  • unsaturated as used herein, means that a moiety has one or more double or triple bonds.
  • cycloaliphatic refers to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined below and described herein.
  • Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl.
  • a cycloaliphatic group may have 3-6 carbons.
  • cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
  • alkenyl denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom.
  • alkynyl refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom.
  • alkoxy refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.
  • acyloxy refers to an acyl group attached to the parent molecule through an oxygen atom.
  • aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
  • aryl may be used interchangeably with the term “aryl ring” wherein “aryl” refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.
  • aryl is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like, where the radical or point of attachment is on the aryl ring.
  • heteroaryl and “heteroar-”, used alone or as part of a larger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 n electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
  • heteroaryl may be used interchangeably with the terms “heteroaryl ring” and “heteroaryl group”, any of which terms include rings that are optionally substituted.
  • heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
  • a heteroaryl group may be mono- or bicyclic.
  • heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
  • compounds disclosed may contain “optionally substituted” moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • alkoxylated means that one or more functional groups on a molecule (usually the functional group is an alcohol, amine, or carboxylic acid, but is not strictly limited to these) has appended to it a hydroxy-terminated alkyl chain.
  • Alkoxylated compounds may comprise a single alkyl group or they may be oligomeric moieties such as hydroxylterminated polyethers.
  • Alkoxylated materials can be derived from the parent compounds by treatment of the functional groups with epoxides. Unless otherwise specified, “a,” “an,” “the,” and “at least one” are used interchangeably and mean one or more than one.
  • Epoxides of the present disclosure may be any epoxide with or without substitutions such that desirable mixtures of substituted and unsubstituted beta-lactones are formed when contacted with carbon monoxide and an appropriate catalyst system.
  • Epoxides may be described as substituted epoxide compounds when including one or more substitutions at the carbon atom.
  • the substituted epoxide compounds of the present disclosure may be any three membered heterocyclic compounds configured to react with carbon monoxide in the presence of an appropriate catalyst system.
  • the epoxide may be mono or disubstituted at one or both of the carbons of the epoxide.
  • Substitutions at the carbon atom of the epoxide may include one or more of a linear alkyl group, a branched alkyl group, an aryl group, a linear alkyl-aryl group, a branch alkyl-aryl group, a linear aryl-alkyl group, a branched aryl-alkyl group, a linear or branched alkylhalide group, or any combination thereof each of which may optionally include unsaturation.
  • the epoxide compound may have the following structure of:
  • R3 each comprise hydrogen.
  • at least one of R3 independently be may be a carbon containing group which may have one or more hydrogen or fluorine atoms bonded to carbon atoms, the carbon containing groups may contain one or more of unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterion containing groups, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, an ultraviolet active group, a polymer having surfactant properties, and polymerization initiators or reactive heterocyclic rings.
  • the functional groups may be linked to the ring by a linking group (M) which functions to link the functional portion of the groups to the cyclic ring.
  • exemplary linking groups may be carbon containing groups, ethers, thioethers, polyethers (such as polyalkene ether).
  • R3 may be a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group; an alkyl sulfonate alkyloxy group; alkyl ether substituted alkyl group; a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group; an alkenyloxy substituted alkyl group; an aryl ester substituted alkyl group; an alkenyl group; a cyano-substituted alkyl group; an alkenyl ester substituted alkyl group; a cycloalkyl substituted alkyl group; an aryl group; a heteroatom containing cycloalkenyl, alkyl ether substituted alkyl group; a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group; an aryl substituted alkyl group; a haloaryl substituted alkyl group; an
  • Beta propiolactone corresponds to the formula wherein all of the R3 are hydrogen.
  • the R3 on one carbon atom may both be H while one or both of the selected R3 on the other carbon atom may be an optionally substituted C1-40 aliphatic, optionally substituted C1 - 20 heteroaliphatic, optionally substituted aryl or both of the selected R3 groups may be optionally taken together to form an optionally substituted ring optionally containing one or more heteroatoms.
  • One or two of the R3 on different carbon atoms may be alkyl and the others may be hydrogen.
  • the alkyl groups may be C1 - 20 alkyl groups, C1 -12 alkyl groups, C1 -8 alkyl groups, C1 -4 alkyl groups, wherein the alkyl groups may contain unsaturation, heteroatoms or heteroatom containing functional groups.
  • One or two of the R3 on different carbon atoms may be methyl or ethyl and the others may be hydrogen.
  • Two of R3 on the same carbon atom may be methyl while the other of the selected R3 are hydrogen.
  • the epoxide compound is mono or di substituted at a single carbon and configured to ring open and form either or both of a beta or alpha substituted beta lactone, only one carbon include at least one substitution at R3 that comprises one or more of the other groups described herein.
  • the lactone or beta propiolactone formed from a carbonylation reaction may be any cyclic carboxylic ester having at least one carbon atom and two oxygen atoms.
  • the lactone may be an acetolactone, a beta propiolactone, a butyrolactone, a valerolactone, caprolactone, or a combination thereof. Anywhere in this application where a propiolactone or lactone is used or described, another lactone may be applicable or usable in the process, step, or method.
  • the propiolactone may have a structure corresponding to:
  • the beta-lactones correspond to the general formula: wherein R3 is defined herein.
  • the present disclosure provides for techniques to form complexes, which may be a carbonylation catalysts, that preform carbonylation catalysts before carbonylation processes with little or no side products or deleterious metals present in the complex.
  • the techniques described herein additionally can be completed at lower temperatures (e.g., under 120 degrees Celsius) and pressures (e.g., below 4000 KaPa) such that energy in forming the complexes is conserved.
  • the present techniques utilize a reducing metal and a cobalt salt in the presence of a coordinating compound (or inert solvent) and pressurized carbon monoxide to form the metal carbonyl.
  • a porphyrin metal halide is added to form the complex that is useable as a carbonylation catalyst.
  • the reducing metal forms cobalt tetracarbonyl salts that have no or limited solubility in the inert solvent or coordinating compound.
  • the cobalt tetracarbonyl salts when present undesirable amounts can negatively impact the carbonylation process or form undesirable products, like polymers. Accordingly, the present techniques mitigate presence of the cobalt tetracarbonyl salts.
  • Co2(CO)8 is not needed and the cobalt carbonyl species is formed in situ by a relatively low pressure and low temperature ( ⁇ 100 oC) route.
  • Porphyrin chloride e.g., (TPP)AICI
  • TPP ethylene glycol
  • TPPAIEt ethylene glycol
  • Simple cobalt salts CoCI2, CoBr2, Col2, or Co(OAc)2
  • Mn, Zn, Na, or Mg metal can be used as the reducing metal.
  • the cobalt carbonyl can be formed in the presence of (TPP)AICI to form the catalyst in situ or the cobalt carbonyl intermediate may be formed prior to reaction with (TPP)AICL
  • the cobalt carbonyl intermediates have been identified as NaCo(CO)4, Mn[Co(CO)4]2, or Zn[Co(CO)4]2 depending on the reducing metal used.
  • the final reaction mixture can be filtered and diluted with THF to be used directly in carbonylation or the catalyst can be isolated from the filtrate if desired. The reactions have given up to full conversion of (TPP)AICI to carbonylation catalyst.
  • reaction rates of the formed complexes are comparable to carbonylations using catalyst produced by the existing process using (TPP)AIEt and Co2(CO)8.
  • the methods disclosed herein include contacting a cobalt salt comprising one or more of a cobalt halide or ester with a reducing metal and a coordinating compound in the presence of carbon monoxide under conditions to form a cobalt tetracarbonyl salt of the reducing metal and contacting the cobalt tetracarbonyl salt of the reducing metal with a with a porphyrin metal halide in the presence of the coordinating compound under conditions such that a complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl is formed.
  • steps may be conducted in sequence, with or without isolation in between, or in situ. The steps may be conducted in the same container or in different containers.
  • the step of contacting the cobalt salt and the reducing metal may be conducted before, after, or during addition of the porphyrin metal halide.
  • the step of contacting the cobalt salt and the reducing metal may be conducted in a water or oxygen free environment or may be conducted at the ambient conditions.
  • the step of contacting the cobalt salt and the reducing metal may be conducted in a vacuum that includes carbon monoxide gases.
  • other gases that are inert may be present such as nitrogen, argon, helium, neon, krypton, xenon, radon, or any combination thereof.
  • the step of contacting the cobalt salt and the reducing metal may be conducted at any pressure sufficient to form the cobalt tetracarbonyl salt or the carbonylation catalyst (where the porphyrin metal halide is present). It is believed without being bound by any theory that when the cobalt salt is contacted with carbon monoxide and a reducing agent that a cobalt tetra carbonyl intermediate will form for some period of time before formation of the complex, regardless if the porphyrin metal halide is present or not.
  • the pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more.
  • the pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less.
  • the reaction steps described herein may be conducted in a pressurized reactor, a Schlenk line, a glove box, or any combination thereof.
  • the cobalt salt and the reducing metal may be contacted at a temperature sufficient to form the cobalt tetracarbonyl salt in the coordinating compound.
  • the cobalt salt and the reducing metal may be contacted at a temperature sufficient to phase metal byproducts of the reducing metal.
  • the cobalt salt and the reducing metal may be contacted at a temperature sufficient to form the carbonylation catalyst or the cobalt tetracarbonyl salt.
  • the cobalt salt and the reducing metal may be contacted at a temperature and pressure sufficient to retain the coordinating compound in a liquid state.
  • the cobalt salt and the reducing metal may be contacted at a first temperature that is different than a second temperature in which the porphyrin metal halide is contacted with the cobalt tetracarbonyl salt.
  • the second temperature may be less or more than the first temperature.
  • the cobalt salt, reducing metal, and/or porphyrin metal halide may all be contacted at the same temperature.
  • the temperature (or first or second temperature) may be about 60 degrees Celsius or more, about 70 degrees Celsius or more, or about 80 degrees Celsius or more.
  • the temperature may be about 110 degrees Celsius or less, about 100 degrees Celsius or less, or about 90 degrees Celsius or less.
  • the step of contacting the cobalt salt and the reducing metal may form a cobalt carbonyl intermediate that is configured to react with the porphyrin metal halide in the coordinating compound.
  • a cobalt tetracarbonyl salt may be formed that at least partially phase separates from the coordinating compound and/or inert solvent.
  • the cobalt tetracarbonyl salt and the cobalt carbonyl intermediate may comprise a residue of the reducing metal and another counterion, such as an anionic cobalt carbonyl and/or one or more halides.
  • the cobalt carbonyl intermediate may be first removed from the coordinating compound or inert solvent where the cobalt salt and the reducing metal were contacted before contacting the porphyrin metal halide and the cobalt carbonyl intermediate in the same type or different coordinating compounds and/or inert solvents. Where the cobalt salt, the reducing metal, and the porphyrin metal halide are contacted together simultaneously, no cobalt carbonyl intermediate is formed. Once the cobalt tetracarbonyl salt is formed, the cobalt tetracarbonyl salt may be separated from the complex (i.e., carbonylation catalyst) through any means sufficient to separate two components, such as decanting, filtering, or any combination thereof.
  • the complex i.e., carbonylation catalyst
  • the cobalt salt, the reducing metal, the cobalt tetracarbonyl salt, and/or porphyrin metal halide in the presence of the coordinating compound (optionally an inert solvent) and reduced carbon monoxide pressure may be agitated by any means and for any period of time in a reaction vessel sufficient to form the complex useable as a carbonylation catalyst.
  • the reaction vessel(s) may contain one or more reaction zones, and may include, a batch reactor, a continuous stirred- tank reactor, a plug flow reactor, semi-batch reactor, a catalytic reactor, a continuous flow reactor, or any combination thereof.
  • the vessel may be equipped with a mechanism for mixing the reaction, such as an agitator, impeller, or a combination of both.
  • the reaction may be mixed by the flow of fluids within a reactor, such as sparging or turbulent flow.
  • the residence time of the reaction may be about 1 minute or more, about 5 minutes or more, or about 30 minutes or more.
  • the residence time may be 240 minutes or less, about 200 minutes or less, or about 100 minutes or less.
  • the cobalt salt and the reducing metal may be contacted in any molar ratio sufficient to form the cobalt tetracarbonyl salt.
  • the cobalt salt and the reducing metal may be contacted in any molar ratio sufficient to form the complex with limited byproducts.
  • the cobalt salt and the reducing metal may be contacted in a molar ratio of about 1 :10 or more, about 1 :5 or more, or about 1 :2 or more.
  • the cobalt salt and the reducing metal may be contacted in a molar ratio of about 1 :1 .5 or less, about 1 :2.5 or less, or about 1 :3 or less.
  • the cobalt salt and/or cobalt tetracarbonyl salt may be contacted with the porphyrin chloride in any ratio sufficient to form the complete (i.e., carbonylation catalyst).
  • the molar ratio of (cobalt salt and/or cobalt tetracarbonyl salt)/porphyrin chloride may be about 1 :1 or more, about 1 :1 .5 or more, or about 1 :2 or more.
  • the molar ratio of (cobalt salt and/or cobalt tetracarbonyl salt)/porphyrin chloride may be about 2:1 or less, about 2:1 .5 or less, or about 1 :1 or less.
  • the cobalt salt may be configured to form a cobalt tetracarbonyl salt when contacted with the reducing metal.
  • the cobalt salt may comprise cobalt and an appropriate counterion.
  • the counterion may be an appropriate anion.
  • the counterion alone or in combination with other counterions may have any charge sufficient to balance the charge of the cobalt.
  • Each of the counterions may have a negative charge of 1 , 2, or 3.
  • the cobalt may have positive charge of 2 or 3.
  • the counterion may include one or more halides, esters, or any combination thereof.
  • the halides may include one or more chloride, fluorine, bromine, and/or iodine.
  • the ester may include one or more ester groups having an anionic end at an oxygen atom and a substituted end attached to a carbon atom of a carbonyl.
  • the substituted end may include one or more of a linear or branched alkyl group, alkyl-aryl group, an aryl-alkyl group, aryl group, cycloalkyl, or any combination thereof including between C1-24 optionally including unsaturation along the chain of carbons.
  • the ester may include one or more of a stearate, acetate, 3-ethylhexanoate, or any combination thereof.
  • the cobalt salt may have a configuration of CoX2 where X comprises a halide, an acetate, an ester, or any combination thereof.
  • the cobalt salt may be soluble or insoluble in the coordinating compound.
  • the reducing metal may function to assist with formation of one or more cobalt tetracarbonyl salts.
  • the reducing metal may include an alkaline metal, an alkali metal and/or a period 4 transition metal.
  • the metals of the reducing metal may include one or more of cobalt, chromium, copper, nickel, vanadium, scandium, iron, manganese, titanium, and/or zinc.
  • the reducing metal may be essentially insoluble (about 5 weight percent, 3 weight percent, 1 weight percent or 0.1 weight percent or less of the reducing metal dissolves based on the total weight of the complex in the inert solvent) in the inert solvent and/or coordinating compound.
  • the reducing metal may be present in small amounts within the coordinating compound and/or inert solvent.
  • the reducing metal being essentially insoluble in the coordinating compound and/or inert solvent, may be present in an amount that does not generate detrimental amounts of polymer in the complex.
  • the reducing metal may be present in about 5,000 p/g or less, about 2,000 p/g or less, about 1 ,000 p/g or less, about 500 p/g or less, or about 100 p/g or less.
  • the cobalt tetracarbonyl salt may function as an intermediate between the cobalt salt and the complex that is configured to be used as a carbonylation catalyst.
  • the cobalt tetracarbonyl salt may comprise residues of the cobalt salt and the reducing metal in combination with carbon monoxide.
  • the pressure may be about 50 kPa or more, about 400 kPa or more, or about 1000 kPa or more.
  • the pressure may be about 4000 kPa or less, about 3000 kPa or less, or about 2000 kPa or less.
  • the cobalt tetracarbonyl salt may have a negative charge and ionically bound to a residue of the reducing metal.
  • the cobalt tetracarbonyl salt of the reducing metal a corresponds to the formula Mn(Cox(CO)y; wherein,
  • M is separately in each occurrence an alkaline metal, an alkali metal or a period 4 transition metal; n is an integer of from 1 to 8;
  • x is an integer of from 1 to 8; and y an integer of from 1 to 8.
  • the porphyrin metal halide may function as precursor ligand to the complex that is used as a carbonylation catalyst.
  • the porphyrin metal halide may include a porphyrin ligan that is coordinated to a metal center and a halide coordinated to the metal center.
  • the metal center may be any metal configured to form a cation when coordinated to the coordinating compound and the ligand.
  • the metal center may include one or more of aluminum, chromium, iron, cobalt, titanium, gallium, manganese, indium, or any combination thereof.
  • the porphyrin metal halide may be soluble or insoluble in one or more of the coordinating compounds and/or inert solvents.
  • the complex may be formed having a cationic porphyrin portion containing a coordinating compound and an anionic cobalt carbonyl.
  • the porphyrin metal halide may include one or more substitutions along the porphyrin complex.
  • the substitutions may include one or more hydrogen, phenyl groups, alkyl groups, alkyl-aryl groups, aryl alkyl groups, alkoxy groups, chlorine groups, fluorine groups, or any combination thereof.
  • the substitutions may be positioned at symmetrical locations along porphyrin ring.
  • the porphyrin metal halide may have the following structure:
  • M 1 is separately in each occurrence a metal:
  • R is separately at each occurrence hydrogen, halogen, -OR 2 , -NR y 2, -SR, -CN, -NO2, - SO2R y , - SOR y , -SO 2 NR y 2 ; -CNO, -NRSO2R y , -NCO, -N 3 , -SiR 2 ; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R y is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamoyl,
  • R 1 and R 2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,
  • Xi is separately in each occurrence is a halogen or alkyl group.
  • the complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl.
  • complex may be interchangeable with carbonylation catalyst.
  • the carbonylation catalyst may be a combination of an anionic compound and a cationic compound.
  • the porphyrin metal halide once integrated into the complex may be described as a metalated ligand complex that is free of halides.
  • the carbonylation catalyst may include one or more other coordinating compounds coordinated to the metal of the metalated ligand compound so that the coordinating compounds used herein may have a dual purpose (i.e., facilitating the reaction and coordinating to the metal).
  • the carbonylation catalyst may include at least two metal compounds that are ionically affiliated with each other.
  • an aluminum integrated with a ligand complex may be ionically affiliated with a cobalt carbonyl.
  • the carbonylation catalyst may include any metal that is contained within the metalated ligand complex, the metal carbonyl, or both.
  • the carbonylation catalyst may be any catalyst containing a metal center and having catalytic activity with one or more of an epoxide, succinic anhydride, a lactone, an aziridine, a lactam or any combination thereof.
  • the metal of the cationic or anionic component of the carbonylation catalyst may be any metal sufficient to catalyze a carbonylation or ring opening reaction.
  • the carbonylation catalyst may have one or more structures shown in US Provisional Application Nos. 63/171 ,150 (filed on April 6, 2021 ); 63/220,126 (filed on July 9, 2021 ); and/or 63/171 ,152 (filed on April 6, 2021 ), US Publication No. 2017/0225157 (filed on July 24, 2017), and/or US Patent Nos. 9,327,280 and 8,921 ,581 , which are each incorporated herein by reference in their entirety.
  • the complex useable as a carbonylation complex may have the following structure:
  • CS is separately in each occurrence a molecule of a coordinating solvent
  • M 1 is separately in each occurrence a metal
  • R is separately at each occurrence hydrogen, halogen, -OR 2 , -NR y 2 , -SR, -CN, -NO 2 , - SO 2 R y , - SOR y , -SO 2 NR y 2 ; -CNO, -NRSO 2 R y , -NCO, -N 3 , -Si R 2 ; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R y is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamo
  • the metal byproduct may include anionic residues of the cobalt salt and cationic residues of the reducing metal.
  • the metal byproduct may include at least a cationic and an anionic component ionically bound together.
  • the metal byproduct may include one or more metal halides, metal esters, and/or metal acetates.
  • the metal byproduct may have the following structure: M x A y where M may be a metal selected from a period 4 transition metal, an alkaline earth metal, and/or an alkali metal, where A may be an acetate, a halide, and/or an ester, where x and y are integers from 1 to 4 that in combination form a neutral metal byproduct.
  • the metal byproduct may be insoluble or essentially insoluble (about 5 weight percent, 3 weight percent, 1 weight percent or 0.1 weight percent or less of the reducing metal dissolves based on the total weight of the complex in the inert solvent) in the inert solvent and/or coordinating compound.
  • the metal byproduct may be present in an amount of about 100,000 /g or less, about 50,000 p/g or less, or about 25,000 p/g or less.
  • the metal byproduct may be present in an amount of about 1 ,000 p/g or more, about 5,000 p/g or more, or about 10,000 p/g or more.
  • the complex Before using the complex as a carbonylation catalyst, the complex may be removed from the reaction mixture by any separation means sufficient to yield a complex with catalytic activity to form a lactone. Any technique known by the skilled artisan may be used as a separation means to separate solids and liquids and yield the complex as a solid in a form that has catalytic activity and yield the other components as a liquid or solid separate from the complex.
  • the single vessel used in the first and second steps may be subjected to a filtering means that collects the complex in a form of a precipitate, and a container of any form may be positioned under the separation means to collect the components of the reaction mixture having a form that is liquid.
  • the third step may be performed under conditions that are free of air, moisture, and/or oxygen so that the stability of the complex is not affected and undesirable side reactions do not occur.
  • the separation means may utilize any technique or device sufficient to collect a precipitate and allow a liquid to drain through the filter.
  • the separation means may include one or more of a vacuum filters, gravity filters, centrifugation means, decantation means, surface filters, depth filters, hot filtration, cold filtration, or any combination thereof.
  • the third step may include pouring or contacting additional hydrocarbon and/or polar solvents over the precipitate containing the complex to rinse the precipitate of additional undesirable impurities that are contained within the precipitate and are soluble in the hydrocarbon and/or polar solvents, which may be referred to as a rinsing step within the third step.
  • the rinsing step may include adding or contacting of any amount of hydrocarbon and/or polar solvent sufficient to wash away any undesirable impurities contained within the precipitate and subjecting the precipitate that contains complex to a separation means.
  • the third step may additionally include a separation step to separate any remaining hydrocarbon and/or polar solvent from the precipitate.
  • the separation step may include any technique sufficient to separate the hydrocarbon and/or polar solvent from the precipitate, such as subjecting the precipitate to one or more of the separation means described herein.
  • the separation step may include applying a vacuum to the precipitate to remove the hydrocarbon and/or polar solvent from the precipitate to yield the catalyst.
  • the separation step may include applying heat to the precipitate to remove the hydrocarbon and/or polar solvent from the precipitate to yield the catalyst. Any amount of heat may be applied so long as the heat is not so high that the heat affects the stability of the carbonylation catalyst.
  • the heat may be applied to raise the temperature of separation step to about 110 degrees Celsius or less, about 90 degrees Celsius or less, or about 70 degrees Celsius or less.
  • the heat may be applied to raise the temperature of separation step to may be about 40 degrees Celsius or more, about 50 degrees Celsius or more, or about 60 degrees Celsius or more.
  • the separation step may include applying a nitrogen stream to the precipitate to remove the hydrocarbon and/or polar solvent from the precipitate.
  • the present disclosure discusses certain compositions and methods that use the described complexes.
  • the present complexes described may further be used in formation of lactones (e.g., beta propiolactone).
  • lactones e.g., beta propiolactone
  • the complexes may be contacted with an epoxide compound and carbon monoxide, optionally in the presence of a solvent, under such conditions such that a lactone is formed.
  • Methods for forming lactones using complexes i.e., carbonylation catalysts that include porphyrin ligands
  • WO2024049975 WO2022221086A1
  • US10927091 B2 which are incorporated herein by reference in their entirety.
  • compositions described herein may include components of a carbonylation reaction at the start, in the middle of, or at completion of the reaction.
  • the compositions of the current disclosure may include minimal reducing metal and/or metal byproduct after or without separation steps applied to the complex.
  • the metal byproduct may be present in an amount of about 100,000 p/g or less, about 50,000 p/g or less, or about 25,000 p/g or less.
  • the metal byproduct may be present in an amount of about 1 ,000 p/g or more, about 5,000 p/g or more, or about 10,000 p/g or more.
  • the coordinating compound functions to coordinate to the complex such that the complex is useable as a carbonylation catalyst.
  • the coordinate compound additionally may function to dissolve one or more compounds in the disclosed methods, such as the cobalt salts, cobalt tetracarbonyl salts, the porphyrin metal halide, and/or the complex (i.e., carbonylation catalyst).
  • the coordinating compound may include at least one heteroatom.
  • the coordinating compound may be a polar aprotic solvent.
  • the coordinating compound may be a compound with at least two free valence electrons.
  • the coordinating compound may include one or more ester solvents, ketone solvents, aldehyde solvents, ether solvents, or any combination thereof.
  • the coordinating compound may be configured to dissolve one or more compounds with polar portions and/or coordinate to a porphyrin metal halide or a carbonylation catalyst.
  • the coordinating compound may include sulfur, nitrogen, oxygen, carbon, hydrogen, a halogen, or any combination thereof.
  • the coordinating compound may include heterocyclic compounds containing nitrogen, ethers, nitriles, esters, ketones, acetates, or any combination thereof.
  • the coordinating compound may be tetrahydrofuran, 2,5-dimethyl tetrahydrofuran, sulfolane, N-methyl pyrrolidone, 1 ,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ethers, methyl tertbutyl ether, diethylether, diphenyl ether, 1 ,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxy ethane, acetone, methylethyl ketone, or mixture thereof.
  • the coordinating compound
  • the inert solvent may function to dissolve one or more of the cobalt salts, cobalt tetracarbonyl salts, the porphyrin metal halide, and/or the complex (i.e., carbonylation catalyst).
  • the inert solvent may either not coordinate to porphyrin metal halide or a carbonylation catalyst or the inert solvent may have a lesser affinity to the metal of the porphyrin metal halide or a carbonylation catalyst compared to the coordinating compound.
  • the inert solvent may be different than the coordinating compound.
  • the inert solvent may have a polarity sufficient to phase separate from the complex or one or more of the starting components.
  • the inert solvent may be a nonpolar solvent.
  • the inert solvent may be present relative to the coordinating compound in a volumetric ratio sufficient to allow formation of the cobalt carbonyl, porphyrin metal halide or alkyl, and/or complex in the solution.
  • the volumetric ratio may be about 1 :1 or more, about 2:1 or more, or about 4:1 or more.
  • the volumetric ratio may be about 1 :4 or less, about 1 :2 or less, or about 1 :1 or less.
  • the inert solvent may be an alkyl and/or aromatic solvent.
  • the inert solvent may be an alkane.
  • the inert solvent may be a non-polar cyclic ether.
  • the inert solvent may be a solvent that is free of oxygen or nitrogen atoms.
  • the inert solvent may include one or more of pentane, hexane, benzene, heptane, and/or toluene.
  • the inert solvent may be contacted with the porphyrin metal halide, the cobalt salt, the trialkyl or halodialkyl aluminum, or coordinating compound in excess.
  • process 1 illustrates an alternative process
  • processes 2A and 2B illustrate an example of the processes described herein.
  • CoX 2 represents the cobalt salt
  • THF represents tetrahydrofuran
  • Reducing agent represents the reducing metal
  • MCo x (CO)y represents the cobalt tetracarbonyl salt
  • TPP porphyrin metal halide
  • MX n the metal byproduct
  • [(TPP)AI(THF) 2 ][CO(CO)4] represents the complex useable as a carbonylation catalyst.
  • process 1 one of the reducing agents/metals as described herein is not used.
  • the porphyrin metal halide is contacted with the cobalt salt, the reducing metal in the coordinating compound (optionally an inert solvent) under a pressure of 10-450 psi and at a temperature of 70-100 degrees Celsius to form the complex in situ.
  • the complex may be optionally separated from the other components in the solution, such as at least some of the metal byproduct.
  • a cobalt salt is contacted with reducing metal in the coordinating compound (optionally an inert solvent) under a pressure of 10-450 psi and at a temperature of 70-100 degrees Celsius to form the cobalt tetracarbonyl salt.
  • the cobalt tetracarbonyl is optionally separated and then contacted with the porphyrin metal halide in the coordinating compound (and optionally an inert solvent) to form the complex.
  • the complex may be optionally separated from the other components in the solution, such as at least some of the metal byproduct.
  • a method comprising: a) contacting a cobalt salt comprising one or more of a cobalt halide or ester with a reducing metal and a coordinating compound, optionally in the presence of an inert solvent and in the presence of carbon monoxide under conditions to form a cobalt tetracarbonyl salt of the reducing metal; and b) contacting the cobalt tetracarbonyl salt of the reducing metal with a with a porphyrin metal halide in the presence of a coordinating compound, optionally in the presence of an inert solvent, under conditions such that a complex comprising a cation of a porphyrin metal wherein the coordinating compound is coordinated to the metal and an anion comprising a cobalt tetracarbonyl is formed.
  • a metal byproduct of the process is a metal halide, metal acetate or metal ester.
  • the cobalt salt comprises one or more of a cobalt halide or cobalt acetate.
  • cobalt salt comprises one or more of cobalt chloride, cobalt bromide or cobalt iodide.
  • cobalt salt comprises cobalt chloride. 22. The method of any of the preceding embodiments, wherein the cobalt tetracarbonyl salt of the reducing metal a corresponds to the formula M n (C0x(CO) y ; wherein,
  • M is separately in each occurrence an alkaline metal, an alkali metal or a period 4 transition metal; n is an integer of from 1 to 8; x is an integer of from 1 to 8; and y an integer of from 1 to 8 .
  • CS is separately in each occurrence a molecule of a coordinating solvent
  • M 1 is separately in each occurrence a metal:
  • R is separately at each occurrence hydrogen, halogen, -OR 2 , -NR y 2 , -SR, -CN, -NO 2 , - SO 2 R y , - SOR y , -SO 2 NR y 2 ; -CNO, -NRSO 2 R y , -NCO, -N 3 , -Si R 2 ; or an optionally substituted group selected from the group consisting of C1-20 aliphatic; C1-20 heteroaliphatic having 1 -4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6 to 10 membered aryl; 5 to 10 membered heteroaryl having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4 to 7 membered heterocyclic having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; R y is separately at each occurrence hydrogen, or an optionally substituted group selected the group consisting of: acyl; carbamo
  • R 1 and R 2 are separately in each occurrence one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silyl alkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyl oxy, and may be optionally substituted; and,
  • X is separately in each occurrence is a halogen or alkyl group.
  • CS is separately in each occurrence a molecule of a dihydrocarbyl ether, alkylene ether or cyclic ether.
  • M 1 is separately in each occurrence a transition metal selected from the periodic table groups 4, 6, 1 1 , 12 and 13:
  • R is separately at each occurrence a hydrogen or an alkyl group
  • R 1 and R 2 are separately in each occurrence a phenyl group, a substituted aryl group; and, X is separately in each occurrence is alkyl, chlorine or bromine.
  • CS is separately in each occurrence a molecule of a cyclic ether.
  • M 1 is separately in each occurrence chromium or aluminum
  • R is separately at each occurrence a hydrogen
  • R 1 is separately in each occurrence an optionally substituted phenyl group or an optionally substituted alkyl group;
  • X is separately in each occurrence is ethyl, chlorine or bromine.
  • R 3 is independently in each occurrence hydrogen or a carbon containing group which may have one or more hydrogen or fluorine atoms attached to the carbon atoms which may optionally contain one or more heteroatoms and/or substituents.
  • R 3 is hydrogen, a halogen substituted alkyl group, a sulfonic acid substituted alkyloxy group; an alkyl sulfonate alkyloxy group; alkyl ether substituted alkyl group; a polyalkylene oxide substituted alkyl group, an alkyl ester substituted alkyl group; an alkenyloxy substituted alkyl group; an aryl ester substituted alkyl group; an alkenyl group; a cyano substituted alkyl group; an alkenyl ester substituted alkyl group; a cycloalkyl substituted alkyl group; an aryl group; a heteroatom containing cycloalkenyl, alkyl ether substituted alkyl group; a hydroxyl substituted alkyl group, a cycloaliphatic substituted alkenyl group; an aryl substituted alkyl group; a
  • composition prepared according to anyone of Embodiments 31 to 41 A composition prepared according to anyone of Embodiments 31 to 41 .
  • composition according to Embodiment 42 comprising a beta-lactone containing less than 25,000 p/g of the metal.
  • Example 1 A 2-dram vial with stir bar is charged with 0.198 g (TPP)AICI, 39 mg CoCI2, and 30 mg Mn powder. Cold THF (4 mL) is added to the vial which is placed in a pressure reactor and sealed. The reaction is pressurized with 450 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The mixture is filtered, and the filtrate is concentrated to dryness to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 . [0067] Example 2.
  • a 2-dram vial with stir bar is charged with 152.6 mg CoCI2, and 1 10.5 mg Mn powder.
  • Cold THE (4 ml_) is added to the vial which is placed in a pressure reactor and sealed.
  • the reaction is pressurized with 450 psi CO then heated to 100 oC for 2 h.
  • the reaction is cooled to room temperature and the pressure is released before opening the reactor.
  • 1 mL of the reaction mixture is added to a vial charged with 0.198 g (TPP)AICI and 2 mL THF.
  • the reaction is allowed to stir at room temperature for 2 h.
  • the mixture is filtered, and the filtrate is concentrated to dryness to afford a purple solid.
  • the solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1.
  • Example 3 A 2-dram vial with stir bar is charged with 0.198 g (TPP)AICI, 38.7 mg CoCI2, and 48 mg Mn powder. Cold THF (4 mL) is added to the vial which is placed in a pressure reactor and sealed. The reaction is pressurized with 180 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The mixture is filtered, and the filtrate is layered with 4 mL heptane. The resulting solid is collected, washed with 1 :1 THF:heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .
  • Example 4 A 2-dram vial with stir bar is charged with 0.200 g (TPP)AICI, 38.7 mg CoCI2, and 48 mg Mn powder. Cold THF (4 mL) is added to the vial which is placed in a pressure reactor and sealed. The reaction is pressurized with 180 psi CO then heated to 100 oC for 2 h. The reaction is cooled to room temperature and the pressure is released before opening the reactor. The mixture is filtered, and the filtrate is layered with 4 mL heptane. The resulting solid is collected, washed with 1 :1 THF:heptane, and dried under vacuum to afford a purple solid. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .
  • Example 5 A 100 mL media bottle with stir bar is charged with 0.205 g (TPP)AICI and 0.071 g CoBr2. THF (50 mL) is added to the media bottle and the resulting solution is sparged with CO (10 psi). 0.072 g Na piece is added to the reaction mixture. The reaction is heated to 60 oC for 2 h. Conversion to [(TPP)AI(THF)2][Co(CO)4] was confirmed by FTIR (1885 cm-1 ). The reaction mixture was filtered and an aliquot of the filtrate was used directly in carbonylation of EO. The solid, useable as a catalyst, is tested for EO conversion, which is illustrated in FIG. 1 .
  • FIG. 1 is an illustration of catalytic activity over time and conversion of EO for the catalysts formed according to Examples 1 -5.

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Abstract

La présente invention concerne un procédé comprenant les étapes consistant à : mettre en contact un sel de cobalt comprenant un ou plusieurs éléments parmi un halogénure ou un ester de cobalt avec un métal réducteur et un composé de coordination, éventuellement en présence d'un solvant inerte et en présence de monoxyde de carbone dans des conditions pour former un sel tétracarbonyle de cobalt du métal réducteur ; et b) mettre en contact le sel de tétracarbonyle de cobalt du métal réducteur avec un halogénure de métal de porphyrine en présence d'un composé de coordination, éventuellement en présence d'un solvant inerte, dans des conditions telles qu'un complexe comprenant un cation d'un métal de porphyrine dans lequel le composé de coordination est coordonné au métal et un anion comprenant un tétracarbonyle de cobalt est formé.
PCT/US2024/034094 2023-06-16 2024-06-14 Synthèse de catalyseur de carbonylation à partir de sels de cobalt WO2024259296A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1167087A (zh) * 1997-01-09 1997-12-10 华中理工大学 常温常压下催化合成羰基钴的方法
US6852865B2 (en) 2001-12-06 2005-02-08 Cornell Research Foundation, Inc. Catalytic carbonylation of three and four membered heterocycles
WO2011123558A1 (fr) * 2010-04-01 2011-10-06 Novomer, Inc. Synthèse de complexes métalliques
US8921581B1 (en) 2007-09-04 2014-12-30 Cornell Research Foundation, Inc. Succinic anhydrides from epoxides
US9327280B2 (en) 2011-05-13 2016-05-03 Novomer, Inc. Catalytic carbonylation catalysts and methods
US20170225157A1 (en) 2014-07-25 2017-08-10 Novomer, Inc. Synthesis of metal complexes and uses thereof
US10927091B2 (en) 2015-02-13 2021-02-23 Novomer, Inc. Continuous carbonylation processes
WO2022221086A1 (fr) 2021-04-16 2022-10-20 Novomer, Inc. Procédé amélioré pour la carbonylation d'un époxyde
WO2024049975A1 (fr) 2022-09-02 2024-03-07 Novomer, Inc. Procédé de préparation de bêta-lactones

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1167087A (zh) * 1997-01-09 1997-12-10 华中理工大学 常温常压下催化合成羰基钴的方法
US6852865B2 (en) 2001-12-06 2005-02-08 Cornell Research Foundation, Inc. Catalytic carbonylation of three and four membered heterocycles
US8921581B1 (en) 2007-09-04 2014-12-30 Cornell Research Foundation, Inc. Succinic anhydrides from epoxides
WO2011123558A1 (fr) * 2010-04-01 2011-10-06 Novomer, Inc. Synthèse de complexes métalliques
US9327280B2 (en) 2011-05-13 2016-05-03 Novomer, Inc. Catalytic carbonylation catalysts and methods
US20170225157A1 (en) 2014-07-25 2017-08-10 Novomer, Inc. Synthesis of metal complexes and uses thereof
US10927091B2 (en) 2015-02-13 2021-02-23 Novomer, Inc. Continuous carbonylation processes
WO2022221086A1 (fr) 2021-04-16 2022-10-20 Novomer, Inc. Procédé amélioré pour la carbonylation d'un époxyde
WO2024049975A1 (fr) 2022-09-02 2024-03-07 Novomer, Inc. Procédé de préparation de bêta-lactones

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CARRUTHERS: "Some Modern Methods of Organic Synthesis", 1987, CAMBRIDGE UNIVERSITY PRESS
EUR. J. INORG. CHEM
HE L. ET AL: "Carbonylative Ring Expansion of Epoxides to [beta]-Lactones Using Inorganic Salt as Catalytic Species Precursor", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, vol. 2022, no. 35, 11 October 2022 (2022-10-11), DE, XP093189408, ISSN: 1434-1948, Retrieved from the Internet <URL:https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejic.202200496> DOI: 10.1002/ejic.202200496 *
JOHN M. ROWLEY ET AL: "Catalytic Double Carbonylation of Epoxides to Succinic Anhydrides: Catalyst Discovery, Reaction Scope, and Mechanism", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 129, no. 16, 1 April 2007 (2007-04-01), pages 4948 - 4960, XP055076024, ISSN: 0002-7863, DOI: 10.1021/ja066901a *
L, HEJ.-C. YANGT.-T. SONGY. LIUX.-B. LU, EUR. J. INORG. CHEM, 2022
LAROCK: "Comprehensive Organic Transformations", 1989, VCH PUBLISHERS, INC.
SMITH: "March March's Advanced Organic Chemistry", 2001, JOHN WILEY & SONS, INC
THOMAS SORRELL: "Periodic Table of the Elements, CAS version", 1999, HANDBOOK OF CHEMISTRY AND PHYSICS

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