Synthesis of carbonylation catalysts

Abstract

A method comprising contacting a ligand complex, a metallated compound and a metal carbonyl in a mixture to form a catalyst. The ligand complex comprises one or more of a phosphine, imine and / or hydroxyl group attached to one or more cyclic structures. The method comprises isolating the catalyst from the mixture. The step of contacting the ligand complex, the metallated compound and the metal carbonyl in the mixture to form the catalyst is performed without isolating any intermediates, is performed in a single container, and / or is performed in a moisture, oxygen and / or air free environment.

Description

[Technical field]

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 280,385, filed November 17, 2021, which is incorporated by reference herein in its entirety.

[0002] The present disclosure relates to methods of making carbonylation catalysts from ligand complexes, metallated compounds and metal carbonyls. [Background technology]

[0003] Carbonylation is a method that can be used to react carbon monoxide and epoxides to make lactones. In some cases, an additional step is employed to react lactones to make polymers. These lactones or their polymers are often used as plastics and fungicides. In making these lactones, carbonylation catalysts are used to optimize the efficiency of the reaction to produce lactones at a competitive price. Carbonylation catalysts are expensive, and therefore new techniques are needed to synthesize carbonylation catalysts from simple building blocks. Some catalysts have been made using a variety of ligands. See, for example, U.S. Patent No. 6,852,865. However, methods of synthesizing carbonylation catalysts from these ligands may utilize multiple synthesis and purification steps. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 6,852,865 Summary of the Invention [Problem to be solved by the invention]

[0005] What is needed, therefore, is a technique for forming carbonylation catalysts that can be carried out in a short period of time with little waste. [Means for solving the problem]

[0006] Compounds useful as carbonylation catalysts are disclosed herein. The method used to prepare such compounds begins with a ligand complex, a metalated compound and a metal carbonyl to obtain the carbonylation catalyst without isolating any intermediates before obtaining the carbonylation catalyst. The metalated compound and the ligand complex are contacted in a hydrocarbon solvent to form the metalated ligand complex. After the formation of the metalated ligand complex, a metal carbonyl and a polar solvent can be added to the same reaction mixture to obtain the carbonylation catalyst without isolating any intermediate compounds such as the metalated ligand complex. After the formation of the carbonylation catalyst, the reaction mixture of components can be subjected to known methods for separating solids from liquids, such as gravity filtration, to obtain the carbonylation catalyst in a form sufficient to catalyze the carbonylation reaction (i.e., the formation of lactones) or other similar ring-opening reactions (i.e., the formation of lactams).

[0007] The carbonylation catalyst formed by the techniques described herein may contain impurities. The carbonylation catalyst exhibits high catalytic activity in the formation of lactones and / or lactams in the presence of such impurities. Because there is no need to filter or isolate intermediates, the amount of solvent used may be limited to that necessary to carry out the reaction steps until the carbonylation catalyst is formed as a precipitate and separated from the reaction mixture (i.e., slurry). Because there is no need to isolate intermediates and the final product does not need to be further purified, for example, by crystallization, the method requires relatively small amounts of solvent to carry out the synthetic sequence. Without the need for additional steps, solvent waste is reduced and the amount of time spent synthesizing and isolating the compounds is significantly reduced.

[0008] The ligand complex comprises one or more of a phosphine, imine and / or hydroxyl group bound to one or more cyclic structures. The ligand complex may have any structure sufficient to support the formation of lactams and / or lactones when combined with a metal and subsequently becomes a carbonylation catalyst. The metallated compound comprises a metal coordinated to the ligand complex. The metal carbonyl comprises a metal capable of ionically bonding with the metallated ligand complex, the metal being bound to one or more carbonyls. One of the intermediates of the method comprises a metallated ligand complex, the complex being a ligand complex coordinated to one or more metals, which is contacted with a metal carbonyl to ionically bond and form a carbonylation catalyst.

[0009] The carbonylation catalyst is a combination of an anionic compound and a cationic compound. For example, the carbonylation catalyst may be a metallated ligand compound that is cationic, and the metallated ligand compound is ionically bonded to a metal carbonyl that is anionic. In addition, the carbonylation catalyst may include one or more other polar ligands coordinated to the metal of the metallated ligand compound, so that the polar solvent used herein may have a dual purpose (i.e., promoting the reaction and coordinating to the metal). The carbonylation catalyst includes at least two metal compounds that are ionically bonded together. For example, aluminum coordinated to the ligand complex may be ionically bonded to a cobalt carbonyl. The carbonylation catalyst may be any catalyst that contains a metal center and has catalytic activity with one or more of epoxides, lactones, aziridines, lactams, or any combination thereof. The metal of the cationic or anionic component of the carbonylation catalyst may be any metal sufficient to catalyze the carbonylation or effect a ring-opening reaction. In one example, the carbonylation catalyst has a structure according to the following formula:

[0010] [ka] where M may be selected from aluminum, chromium, gallium, indium, zinc, copper, manganese, cobalt, ruthenium, iron, rhenium, nickel, palladium, magnesium, titanium, or any combination thereof. R is hydrogen, halogen, or -OR 4 , -NR y 2, -SR, -CN, -NO2, -SO2R y , -SOR y , -SO2NR y 2;-CNO,-NRSO2R y , -NCO, -N3, -SiR3; or C 1~20 Aliphatic; C having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~20 and optionally substituted groups selected from the group consisting of heteroaliphatic; 6-10 membered aryl; 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur. d The groups may be taken together to form one or more optionally substituted rings, R y are each independently hydrogen or acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1~12 Aliphatic; C having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~12 an optionally substituted group selected from the group consisting of heteroaliphatic; a 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group, ymay be taken together with the nitrogen atom to form an optionally substituted 4-7 membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur. Each R1 may be a group independently selected from one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. Each R2 may be a group independently selected from one or more of hydrogen, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. R 3a1 and / or R 3a2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of the following: an alkyl chain, a cyclohexane or a phenyl group, optionally substituted, in combination, with the substituted groups being aromatic, aliphatic, or both. R 3b1 and / or R 3b2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of a cyclic alkyl group, a cyclic alkyl group, an aryl ... R 3a1 and R 3b1 R may be, in combined form, one or more of a heterocyclic compound, a heterocyclic ring having one or more substitutions, a cyclic structure, any combination thereof. 3a1 and R 3b1 may be an optionally substituted six-membered ring, aromatic, or both, in combination. The heterocyclic ring may include pyridine, pyridine with one or more substitutions, or any combination thereof. R 3a2 and R 3b2R may be, in combined form, one or more of pyridine, pyridine with one or more substitutions, a cyclic structure, or any combination thereof. 3a2 and R 3b2 In combination, R may be an optionally substituted six-membered ring, aromatic, or both. 3a1 and / or R 3a2 may be independently combined to form one or more of the cyclic structures. The cyclic structures may include one or more of heterocyclic compounds, aromatic compounds, or any combination thereof. The cyclic structures may include one or more of cyclohexane, phenyl groups, pyridine, or any combination thereof.

[0011] A method is disclosed that includes contacting a ligand complex, a metallated compound, and a metal carbonyl in a reaction mixture to form a catalyst. The method includes separating the catalyst from the reaction mixture.

[0012] The catalyst may comprise about 90 to about 98 weight percent or more of the metallated ligand complex ionically bound to the metal carbonyl; about 10 to about 2 weight percent or less of the unbound ligand complex, the weight percents being based on the total weight of the catalyst. The polar solvent may be contacted with the reaction mixture in a volume ratio between about 2:1 or less and about 0.5:1 or less. The metallated compound may be contacted with the ligand complex in a molar ratio of about 1:1 or greater.

[0013] The step of contacting the ligand complex with the metallated compound and the metal carbonyl in the reaction mixture to form the catalyst may be carried out without isolating any intermediates. The step of contacting the ligand complex with the metallated compound and the metal carbonyl in the reaction mixture to form the catalyst may be carried out in one or more vessels or in a single vessel. The step of contacting the ligand complex, the metallated compound and the metal carbonyl in the reaction mixture to form the catalyst may be carried out in an environment that is free of moisture, air and / or oxygen.

[0014] The step of contacting the ligand complex, the metallated compound and the metal carbonyl in the reaction mixture to form the catalyst may include mixing the reaction mixture. The amount of time the reaction mixture is mixed to form the metallated ligand complex and / or catalyst may be influenced by the concentration of reactants or solvents in the reaction mixture, the application of heat, and the specific selection and ratio of solvents. The combination of polar and hydrocarbon solvents may precipitate the catalyst while the reaction mixture is mixed to form the catalyst. The reaction mixture containing the ligand complex, the metallated compound and the metal carbonyl may be mixed for about 1.5 hours or more or about 12 hours or more to form the catalyst. The step of contacting the ligand complex, the metallated compound and the metal carbonyl in the reaction mixture to form the catalyst may include mixing the reaction mixture with or without applying heat. The step of contacting the ligand complex, the metallated compound and the metal carbonyl may be discussed as a first mixture and a second mixture without isolating any intermediate between the first mixture and the second mixture. In the first mixture, the ligand complex, the hydrocarbon solvent and the metallated compound can be mixed to form the metallated ligand complex, and in the second mixture, the metallated ligand complex, the hydrocarbon solvent, the polar solvent and the metal carbonyl can be mixed to form the catalyst.

[0015] In the first mixture, the ligand complex and the hydrocarbon solvent may be mixed for any amount of time sufficient to at least partially dissolve the ligand complex. A metallation compound may then be added to the first mixture and mixed for about 0.5 hours or more to about 7 hours or more to form the metallation ligand complex.

[0016] A polar ligand and a metal carbonyl can be added to the first mixture to form a second mixture, and the second mixture can be mixed to form the catalyst. The second mixture to form the catalyst, containing the metallated ligand complex, the metal carbonyl, the polar solvent, and the hydrocarbon solvent, can be mixed for about 1 hour or more, or 2 hours or more. The addition of the polar solvent to the first mixture increases the solubility of the metallated ligand complex such that the polar solvent coordinates to the catalyst after formation of the catalyst. The combination of the polar solvent and the hydrocarbon solvent in the second mixture precipitates the catalyst from the second mixture after the catalyst is formed.

[0017] The method may include contacting a first mixture containing the metallated ligand complex and a hydrocarbon solvent with a polar solvent to form a second mixture; sparging the second mixture with a gas at a pressure sufficient to support formation of the catalyst; and contacting a metal carbonyl with the second mixture containing the metallated ligand complex, the polar solvent, and the hydrocarbon solvent to form the catalyst. The second mixture may be sparged with the gas at a pressure of about 100 kP or less.

[0018] Separating the catalyst from the reaction mixture may include filtering the catalyst from the final reaction mixture; applying a vacuum to the catalyst to remove any remaining volatiles, such as hydrocarbon solvents and / or polar solvents, from the catalyst; applying heat to the catalyst to remove any remaining volatiles, such as hydrocarbon solvents and / or polar solvents, from the catalyst; and / or applying a nitrogen flow to the catalyst to remove any remaining volatiles, such as hydrocarbon solvents and / or polar solvents, from the catalyst.

[0019] The above steps of forming a catalyst by combining the ligand complex, the metallated compound, and the metal carbonyl in a reaction mixture and separating the catalyst from the reaction mixture result in a catalyst having high purity and high catalytic activity in forming lactones and / or lactams. If even higher purity is desired, the catalyst separated from the reaction mixture can be subjected to a recrystallization step to remove any other impurities mixed with the catalyst. The method may further include the steps of contacting the catalyst removed from the reaction mixture with one or more solvents to form a crystallization mixture; precipitating the catalyst from the crystallization mixture; and separating the catalyst from the one or more solvents. The one or more solvents may include one or more polar solvents and one or more hydrocarbon solvents, and the step of contacting the catalyst removed from the reaction mixture with one or more solvents to form a crystallization mixture may include contacting the catalyst removed from the previous reaction mixture with one or more polar solvents and one or more hydrocarbon solvents to form a crystallization mixture; heating the crystallization mixture to a temperature sufficient to dissolve the catalyst in the one or more polar solvents and one or more hydrocarbon solvents; and cooling the crystallization mixture so that the catalyst crystallizes and precipitates from the one or more polar solvents and one or more hydrocarbon solvents. The step of separating the one or more solvents and / or one or more other compounds from the catalyst may include separating the one or more polar solvents and / or one or more hydrocarbon solvents so that the catalyst is substantially free of other compounds. The method may further include washing the catalyst with one or more hydrocarbon solvents.

[0020] The reaction mixture, the crystallization mixture, the first mixture, the second mixture, or any combination thereof may be a solution and / or a slurry. The ligand complex may include an aromatic group, the ligand complex may include a conjugated, imine or phosphazine group and one or more cyclic structures. The ligand complex may include a macrocycle. The ligand complex may include one or more of a porphyrin ligand, a salen ligand, a salph ligand, a salcy ligand, a phosphasalen ligand, a phosphasalph ligand, a phosphasalcy ligand, a disubstituted bipyridine ligand, a disubstituted phenanthroline ligand, a dibenzotetramethyltetraaza

[14] annulene derivative, a phthalocyanine derivative, a diaminocyclohexane derivative (e.g., a Trost ligand), other derivatives thereof, or any combination thereof. The method may further include dissolving the metallation compound in a hydrocarbon solvent to form a precursor mixture having a molar concentration of about 1.0 or greater, and contacting the precursor mixture with a reaction mixture containing the ligand complex and the hydrocarbon solvent. The method may include adding the metallation compound to the mixture containing the ligand complex and the hydrocarbon solvent without first dissolving the metallation compound in any solvent. The metallation compound may include aluminum or chromium. The metallation compound may include one or more of triethylaluminum, trimethylaluminum, triisobutylaluminum, chromium(II) chloride, diethylaluminum chloride, or any combination thereof. The metallation compound may include a trialkylaluminum compound. The metal carbonyl may include cobalt. The metal carbonyl may include NaCo(CO)4, HCo(CO)4, Co2(CO)8, any Co ... x (CO) yThe solvent may include one or more of the following compounds, and x and y are independently integers between 1 and 12, or combinations thereof. The gas introduced during the blowing step may include one or more of carbon monoxide, synthesis gas, or combinations thereof. Other gases removed by the blowing step may include inert gases, such as one or more of argon, nitrogen, or both. The hydrocarbon solvent may include linear or cyclic structures containing only carbon and hydrogen. The hydrocarbon solvent may be aromatic, aliphatic, or may have both aromatic and aliphatic portions. The hydrocarbon solvent may include one or more of hexane, heptane, pentane, benzene, toluene, xylene, any other hydrocarbon, or any combination thereof. The polar solvent may include polar aprotic solvents. The polar solvent may include one or more of esters, ketones, aldehydes, ethers, nitriles, or any combination thereof. The polar solvent may include one or more of tetrahydrofuran, ethyl acetate, methyl ethyl ketone, acetone, 2-cyclohexanone, 2-methyltetrahydrofuran, butyl acetate, methyl acetate, cyclopentanone, or any combination thereof.

[0021] The present disclosure provides carbonylation catalysts that have high catalytic activity to form lactones or lactams with epoxides or aziridines. The present disclosure provides a method for synthesizing a carbonylation catalyst that reduces the amount of solvent required to purify the carbonylation catalyst by up to about 80% or less, since various purification steps are not required to form a carbonylation catalyst with high catalytic activity. Since intermediates do not need to be isolated, the number of steps utilized to form a carbonylation catalyst with high catalytic activity is reduced, thereby significantly reducing the amount of time required to carry out the reaction, and thus the capital costs of the overall reaction. The present technique provides a final carbonylation catalyst in a molar yield of about 90% or greater. The present technique provides a catalytically active carbonylation catalyst without or prior to a crystallization step. [Brief description of the drawings]

[0022] [Figure 1]1 is a synthetic scheme for forming a carbonylation catalyst. [Figure 2A] 1H NMR spectra of isolated carbonylation catalysts of Examples 1-3 formed by the disclosed method, analyzed in d8-THF. [Figure 2B] 1H NMR spectra of isolated carbonylation catalysts of Examples 4-9, prepared by different methods of preparing the catalyst, analyzed in d8-THF. [Figure 2C] 1H NMR spectrum of the isolated carbonylation catalyst of Example 9, formed by the disclosed method, analyzed in d8-THF. [Figure 2D] 1H NMR spectra of isolated carbonylation catalysts of Examples 10-12, formed by the disclosed method, analyzed in d8-THF. [Diagram 3] 1 is a graph showing the catalytic activity of a carbonylation catalyst made from a method described herein and from another method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Although the present disclosure has been described in connection with certain specific embodiments, it should be understood that the disclosure is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalents that are within the scope of the appended claims, which should be accorded the broadest interpretation so as to encompass all such modifications and equivalent configurations as permitted under law.

[0024] As used herein, one or more means that at least one of the listed components, or more than one, may be used as disclosed. Residue, with respect to a component or reactant used to prepare a polymer or structure disclosed herein, means the portion of the component remaining in the polymer or structure after inclusion as a result of the method disclosed herein. Substantially or substantially, as used herein, means that more than 90% of the reference parameter, composition, structure or compound meets the specified criteria, that more than 95%, more than 99% of the reference parameter, composition or compound meets the specified criteria, or that more than 99.5% of the reference parameter, composition or compound meets the specified criteria. Substantially free, as used herein, means that the reference parameter, composition, structure or compound contains about 10% or less, about 5% or less, about 1% or less, about 0.5% or less, or about 0.1% or less. Portion, as used herein, means less than the total amount or quantity of a component in a composition, stream, or both. Precipitate, as used herein, refers to a solid compound in a slurry or blend of liquid and solid compounds. A component or product can exist in various states, such as solid, liquid, or gas, during the disclosed process. Phase refers to a portion of the reaction mixture that is not dissolved in another portion of the reaction mixture. Dispersions and slurries disclosed herein may include multiple phases. Particular components and products may exist in various states and phases at the same time of the process and at different times of the process. Slurries and dispersions include solid components dispersed in liquid components, products, and / or solvents. Parts by weight refer to parts of the component relative to the total weight of the entire composition. Catalyst component, as used herein, refers to a metallated ligand complex, a metal carbonyl, a Lewis acid, a Lewis acid derivative, a metal carbonyl derivative, or any combination thereof. Catalyst or carbonylation catalyst, as used herein, includes at least a cationic compound and an anionic compound.A 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 can be contained in a single container. In other words, a mixture can include components that are solid, gas (i.e., volatile) and / or liquid at room temperature (i.e., 25 degrees Celsius). Heteroatoms refer to nitrogen, oxygen, sulfur, and phosphorus, with more preferred heteroatoms including nitrogen and oxygen. Hydrocarbyl, as used herein, refers to a group that contains one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. When the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups known to those skilled in the art. The hydrocarbyl group may include cycloaliphatic, aliphatic, aromatic, or any combination of such segments. The aliphatic segments may be linear or branched. The aliphatic and cycloaliphatic segments may contain one or more double bonds and / or triple bonds. Included among the hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic and acyclic moieties. Hydrocarbylene means a hydrocarbyl group or any of the listed subsets having a valency greater than one, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. One or both of the hydrocarbyl groups may consist of one or more carbon atoms and one or more hydrogen atoms.

[0025] Compounds useful as carbonylation catalysts are disclosed herein. The method used to prepare such compounds starts with a ligand complex, a metalated compound, and a metal carbonyl to form a carbonylation catalyst, which can be carried out without isolating any intermediates before obtaining the carbonylation catalyst. The reaction can be completed all in the same reaction vessel. For example, the metalated compound and the ligand complex are contacted in a hydrocarbon solvent to form a metalated ligand complex. After the formation of the metalated ligand complex, the metal carbonyl and a polar solvent can simply be added to the reaction mixture to obtain the carbonylation catalyst without isolating any intermediate compounds such as the metalated ligand complex. After the formation of the carbonylation catalyst, the reaction mixture of components and products can be subjected to known methods for separating solids from liquids, such as gravity filtration, to obtain the carbonylation catalyst in a form sufficient to catalyze the carbonylation reaction (i.e., the formation of lactones) or other similar ring-opening reactions (i.e., the formation of lactams).

[0026] The carbonylation catalyst formed by the techniques described herein may contain impurities, yet the carbonylation catalyst has such high catalytic activity that it will form lactones and / or lactams without further purification. The process can be carried out by mixing all of the components in a single vessel, which can then be subjected to known methods of separating solids from liquids, such as filtration, to recover the carbonylation catalyst in molar yields of 90% or more. Because there is no need to filter or isolate intermediates, the solvent used can be limited to that needed to carry out just the reaction step until the carbonylation catalyst is formed as a precipitate and separated from the reaction mixture (i.e., slurry), thereby reducing the amount of solvent used in the process and the amount of time spent synthesizing and isolating the compounds.

[0027] The ligand complex may function to bind to the metal, thereby forming a metallated ligand complex. The ligand complex may have any structure sufficient to support the formation of lactams and / or lactones when combined with the metal and subsequently carbonylation catalyst. The ligand complex may be aromatic, such that the ligand complex is fully conjugated and / or the carbonylation catalyst has conjugation in some of its structure. The ligand complex may include aromatic groups. The ligand complex may include one or more of phosphine groups, imine groups, or amine groups bonded to a cyclic structure. The cyclic structure may include atoms bonded together to form a continuous loop of atoms. The ligand complex may include one or more macrocycles. The ligand complex may include one or more substitution moieties configured to improve the steric and / or electronic properties of the carbonylation catalyst formed from the ligand complex. The ligand complexes can be formed by one or more methods contained in co-pending U.S. Provisional Patent Application Nos. 63 / 171,150 (filed April 6, 2021); 63 / 220,126 (filed July 9, 2021); and / or 63 / 171,152 (filed April 6, 2021), U.S. Application No. 2017 / 0225157 (filed July 24, 2017), and / or U.S. Patent Nos. 9,327,280 and 8,921,581, each of which is incorporated herein in its entirety. Exemplary ligand complexes include complexes corresponding to the following formula:

[0028] [ka] It may include, wherein M may be selected from aluminum, chromium, gallium, indium, zinc, copper, manganese, cobalt, ruthenium, iron, rhenium, nickel, palladium, magnesium, titanium, or any combination thereof. R is hydrogen, halogen, or -OR 4 , -NR y 2, -SR, -CN, -NO2, -SO2R y , -SOR y , -SO2NRy 2;-CNO,-NRSO2R y , -NCO, -N3, -SiR3; or C 1~20 Aliphatic; C having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~20 and optionally substituted groups selected from the group consisting of heteroaliphatic; 6-10 membered aryl; 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein two or more R d The groups may be taken together to form one or more optionally substituted rings, R y are each independently hydrogen or acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1~12 Aliphatic; C having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~12 an optionally substituted group selected from the group consisting of heteroaliphatic; a 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group, y may be combined with the nitrogen atom to form an optionally substituted 4-7 membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur. Each R1 may be a group independently selected from one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. Each R2 may be a group independently selected from one or more of hydrogen, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. R 3a1 and / or R 3a2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of the following: an alkyl chain, a cyclohexane or a phenyl group, optionally substituted, in combination, with the substituted groups being aromatic, aliphatic, or both. R 3b1 and / or R 3b2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of a cyclic alkyl group, a cyclic alkyl group, an aryl ... R 3a1 and R 3b1 R may be, in combined form, one or more of a heterocyclic compound, a heterocyclic ring having one or more substitutions, a cyclic structure, any combination thereof. 3a1 and R 3b1 R may be an optionally substituted six-membered ring, aromatic, or both in combination. The heterocyclic ring may include pyridine, pyridine with one or more substitutions, or any combination thereof. 3a2 and R 3b2 R may be, in combined form, one or more of pyridine, pyridine with one or more substitutions, a cyclic structure, or any combination thereof. 3a2 and R 3b2 In combination, R may be an optionally substituted six-membered ring, aromatic, or both. 3a1 and / or R 3a2may be independently combined to form one or more of the cyclic structures. The cyclic structures may include one or more of heterocyclic compounds, aromatic compounds, or any combination thereof. The cyclic structures may include one or more of cyclohexane, phenyl groups, pyridine, or any combination thereof.

[0029] The metal carbonyl of the carbonylation catalyst functions to provide the anionic component of the carbonylation catalyst. The carbonylation catalyst may comprise one or more, two or more metal carbonyls, or a combination. The metal carbonyl may be capable of ring-opening an epoxide and facilitating the insertion of CO into the resulting metal-carbon bond. The metal carbonyl may comprise an anionic metal carbonyl moiety. In another example, the metal carbonyl compound may comprise a neutral metal carbonyl compound. The metal carbonyl may comprise a metal carbonyl hydride compound. The metal carbonyl may be a pre-catalyst that can react in situ with one or more reaction components to provide an active species different from the initially obtained compound. The metal carbonyl comprises an anionic metal carbonyl species. The metal carbonyl may be represented by the general formula Q d [M' e (CO) w ] y and Q may include one or more of hydrogen, an alkali metal, or a combination of both. Q may be optional. M' is a metal atom, d is an integer between 0 and 8 (inclusive), e is an integer between 1 and 6 (inclusive), w is a number that results in a stable anionic metal carbonyl complex, and y is the charge of the anionic metal carbonyl species. y may be positive, negative, or neutral. The metal carbonyl may include a monoionic carbonyl complex of a metal from Group 5, 7, or 9 of the periodic table, or a dianionic carbonyl complex of a metal from Group 4 or 8 of the periodic table. The metal carbonyl may contain titanium, vanadium, iron, chromium, osmium, rhenium, technetium, cobalt, manganese, ruthenium, rhodium, or any combination thereof. An exemplary metal carbonyl is [Co(CO)4] -, [Ti(CO)e] 2- , [V(CO)6] - [Rh(CO)4] - , [Fe(CO)4] 2- , [Ru(CO)4] 2- , [Os(CO)4] 2- , [Cr2(CO) 10 ] 2- , [Fe2(CO)8] 2- , [Tc(CO)] - , [Re(CO)5] - , [Mn(CO)5] - or any combination thereof. The metal carbonyl may comprise a mixture of two or more anionic metal carbonyl complexes in the carbonylation catalyst used in the present process. The metal carbonyl may comprise a salt. The metal carbonyl may comprise NaCo(CO)4, Co2(CO)8, HCo(CO)4, or any combination thereof.

[0030] A metallated compound can function to coordinate to a metal in one or more ligands to form a metallated ligand complex containing halogen and / or alkyl groups. A metallated compound may include any compound containing a metal and / or one or more alkyl and / or halogen groups. A metallated compound may include any compound capable of coordinating one or more metals to a ligand complex. The metal of the metallated compound may include one or more of aluminum, chromium, zinc, zirconium, or any combination thereof. A metallated compound may include any compound having M(L) j where M corresponds to a metal, L corresponds to an alkyl and / or halogen compound, and j is an integer from 1 to 3. The metallated compound may include a metal that is tri- or di-substituted. The metallated compound may include a metal that is tri- or di-substituted with one or more of an alkyl group, a halogen group, hydrogen, or any combination thereof. The metallated compound may include a trialkyl metal compound, a trihalide metal compound, a dihalide metal compound, or any combination thereof. The metallated compound may include CrCl2, (Et)2AlCl, AlEt3, Al iIt may comprise one or more of Bu3, AlMe3, or any combination thereof.

[0031] In some metalated ligand complexes and / or catalysts, one or more polar ligands can coordinate to the metal atom located within the ligand complex and fill the coordination valence of the metal atom. The polar ligand can coordinate to the metalated ligand complex after the metal is bound to the ligand complex. The polar ligand can be a polar solvent that has a dual function of coordinating to the metal complex and dissolving one or more components that are soluble in the polar solvent. The polar ligand can be any compound that has at least two free valence electrons. The polar ligand can be a polar aprotic compound. The polar ligand can include heterocyclic compounds containing ethers, nitrogen, nitriles, esters, ketones, acetates, or any combination thereof. The ether can be a cyclic ether or a dialkyl ether. The polar ligand can be tetrahydrofuran, dioxane, diphenyl ether, methyl tert-butyl-ether, ethyl acetate, 2-butanone, diethyl ether, or a combination thereof.

[0032] The metallated ligand complex can function to be the cationic component of the carbonylation catalyst. The metallated ligand complex can be any compound sufficient to bind with a metal carbonyl and / or a polar ligand to form a carbonylation catalyst. The metallated ligand complex can be any compound containing at least one metal and at least one ligand complex. The metallated ligand complex can be any compound configured to coordinate to a polar ligand, form a cation, and bind with one or more metal carbonyls, thereby forming a catalyst. The metallated ligand complex can contain one or more moieties that aid in solubility in polar and / or hydrocarbon solvents. The metallated ligand complexes may include one or more compounds described in co-pending U.S. Provisional Patent Application Nos. 63 / 171,150 (filed April 6, 2021); 63 / 220,126 (filed July 9, 2021); and / or 63 / 171,152 (filed April 6, 2021), U.S. Application No. 2017 / 0225157 (filed July 24, 2017), and / or U.S. Patent Nos. 9,327,280 and 8,921,581, each of which is incorporated herein in its entirety.

[0033] The polar solvent functions to dissolve one or more compounds having a polar moiety. The polar solvent may include at least one heteroatom. The polar solvent may be a polar aprotic solvent. The polar solvent may be a compound having at least two free valence electrons. For example, the polar solvent may include one or more of an ester solvent, a ketone solvent, an aldehyde solvent, an ether solvent, or any combination thereof. The polar solvent may be configured to dissolve one or more compounds having a polar moiety and / or to coordinate to a metallated ligand complex or a carbonylation catalyst. The polar solvent may include sulfur, nitrogen, oxygen, carbon, hydrogen, halogen, or any combination thereof. The polar solvent may include a heterocyclic compound containing nitrogen, ether, nitrile, ester, ketone, acetate, or any combination thereof. The polar solvent may be tetrahydrofuran, dioxane, diphenyl ether, methyl tert-butyl-ether, ethyl acetate, 2-butanone, diethyl ether, or any combination thereof.

[0034] The hydrocarbon solvent functions to dissolve one or more compounds having a non-polar element. The hydrocarbon solvent may not include any heteroatoms and / or may not include free valence electrons. In other words, the hydrocarbon solvent may include only a combination of carbon and hydrogen. The hydrocarbon solvent may include one or more cyclic and / or linear moieties. The hydrocarbon solvent may include alkyl and / or aryl moieties. The hydrocarbon solvent may include unsaturated moieties or may be fully saturated. The hydrocarbon solvent may include saturated or unsaturated cyclic carbon compounds, saturated or unsaturated linear carbon compounds. The hydrocarbon solvent may include from about 3 to about 20 carbons. For example, the hydrocarbon solvent may include one or more of pentane, hexane, heptane, cycloheptane, cyclohexane, benzene, xylene, toluene, or any combination thereof.

[0035] Hydrocarbon solvents and / or polar solvents may be used in combinations where the solvents are miscible with each other. For example, one solvent may be soluble in one or more other solvents to increase the solubility of one or more compounds described herein. Specifically, a first solvent may be combined with a second solvent that is miscible with the first solvent, and heat may be applied to dissolve the solid compound. The first and second solvents with the dissolved solid compound may then be cooled (e.g., using an ice bath) to crystallize and precipitate the dissolved compound in a higher purity than when originally dissolved. In this example, the combination of the first and second solvents may result in a method of separating the carbonylation catalyst from undesired impurities. The reaction steps disclosed herein may be carried out under conditions such that one or more of the components, unrecovered intermediates, or products saturate a portion of the reaction mixture where the described reaction occurs and the rate-limiting characteristic of the reaction is related to the solubility of the particular component, unrecovered intermediate, or product in such reaction medium. The amount of heat, choice of solvent and ratio of solvents can be adjusted to increase or decrease the solubility of the components, unrecovered intermediates or products in the reaction medium, up to the solubility of the components, unrecovered intermediates or products, to help move the reaction toward the desired intermediates and products of each reaction step.

[0036] The impurities associated with the carbonylation catalyst described herein may include a number of compounds that are separated from the metalated ligand complex bound to the metal carbonyl. The impurities may be any compounds formed by side reactions and / or unreacted starting reagents. The impurities may be any compounds that contain one or more polar ligands and are excluding the catalyst, which is a metalated ligand complex bound to the metal carbonyl. For example, the impurities may include one or more of a polar solvent, a hydrocarbon solvent, a metal carbonyl, a metalated compound, a ligand complex, an alkyl compound (e.g., butene and / or butane), a carbonyl (e.g., 3-pentanone), any unbound metalated ligand complex, or any combination thereof. The impurities may be removed if one or more impurities interfere with or slow down the reactivity of the carbonylation catalyst or interact undesirably with one or more components in the reaction. The impurities may be removed by additional separation steps, if desired, as known by those skilled in the art.

[0037] The carbonylation catalyst may be a combination of an anionic compound and a cationic compound. For example, the carbonylation catalyst may be the metallated ligand compound described above, which is cationic, and is ionically bonded to a metal carbonyl, which is anionic. The carbonylation catalyst may include one or more other polar ligands coordinated to the metal of the metallated ligand compound, so that the polar solvents used herein may have a dual purpose (i.e., promoting the reaction and coordinating to the metal). The carbonylation catalyst may include at least two metal compounds ionically bonded together. For example, aluminum associated with the ligand complex may be ionically bonded to a cobalt carbonyl. The carbonylation catalyst may include any metal contained in the metallated ligand complex, the metal carbonyl, or both. The carbonylation catalyst may be any catalyst that contains a metal center and has catalytic activity with one or more of epoxides, lactones, aziridines, lactams, 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 U.S. Provisional Application No. 63 / 171,150 (filed April 6, 2021); No. 63 / 220,126 (filed July 9, 2021); and / or No. 63 / 171,152 (filed April 6, 2021), U.S. Publication No. 2017 / 0225157 (filed July 24, 2017), and / or U.S. Patent Nos. 9,327,280 and 8,921,581, each of which is incorporated herein by reference in its entirety. For example, the carbonylation catalyst may have a structure according to the following formula:

[0038] [ka] wherein M may be selected from aluminum, chromium, gallium, indium, zinc, copper, manganese, cobalt, ruthenium, iron, rhenium, nickel, palladium, magnesium, titanium, or any combination thereof. R is hydrogen, halogen, or -OR 4 , -NR y 2, -SR, -CN, -NO2, -SO2R y , -SOR y , -SO2NR y 2;-CNO,-NRSO2R y , -NCO, -N3, -SiR3; or C 1~20 Aliphatic; C having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~20 and optionally substituted groups selected from the group consisting of heteroaliphatic; 6-10 membered aryl; 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein two or more R d The groups may be taken together to form one or more optionally substituted rings, R y are each independently hydrogen or acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1~12 Aliphatic; C having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~12 an optionally substituted group selected from the group consisting of heteroaliphatic; a 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; a 4-7 membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group, y may be combined with the nitrogen atom to form an optionally substituted 4-7 membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur. Each R1 may be a group independently selected from one or more of hydrogen, halogen, heteroaliphatic, heterocyclic, heteroaromatic, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. Each R2 may be a group independently selected from one or more of hydrogen, alkyl, alkoxide, aryl, silylalkyl, alkyl-aryl, amine, trifluoromethyl, nitro, hydrocarbyloxy, derivatives thereof, substituted groups thereof, or any combination thereof. R 3a1 and / or R 3a2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of the following: an alkyl chain, a cyclohexane or a phenyl group, optionally substituted, in combination, with the substituted groups being aromatic, aliphatic, or both. R 3b1 and / or R 3b2 is hydrogen, methyl, C 2~10 The alkyl group may be independently selected from one or more of a cyclic alkyl group, a cyclic alkyl group, an aryl ... R 3a1 and R 3b1 R may be, in combined form, one or more of a heterocyclic compound, a heterocyclic ring having one or more substitutions, a cyclic structure, any combination thereof. 3a1 and R 3b1 may be an optionally substituted six-membered ring, aromatic, or both, in combination. The heterocyclic ring may include pyridine, pyridine with one or more substitutions, or any combination thereof. R 3a2 and R 3b2 R may be, in combined form, one or more of pyridine, pyridine with one or more substitutions, a cyclic structure, or any combination thereof. 3a2 and R 3b2In combination, R may be an optionally substituted six-membered ring, aromatic, or both. 3a1 and / or R 3a2 may be independently combined to form one or more of the cyclic structures. The cyclic structures may include one or more of heterocyclic compounds, aromatic compounds, or any combination thereof. The cyclic structures may include one or more of cyclohexane, phenyl groups, pyridine, or any combination thereof.

[0039] The carbonylation catalyst may be any catalyst that contains a metal center and has catalytic activity with one or more of epoxides, lactones, aziridines, lactams, or any combination thereof. The catalyst may be utilized to form lactones in the carbonylation reaction. The carbonylation reaction may include contacting carbon monoxide with one or more epoxides, lactones, or both in the presence of a catalyst. This process may be carried out in a reactor having one or more inlets, two or more inlets, three or more inlets, or more than one inlet. The one or more epoxides, lactones, carbon monoxide, and catalyst may be added to a single inlet, multiple inlets, or each may be added to a separate inlet as a separate or combined feedstream. The carbonylation reaction may produce one or more product streams or compositions from one or more outlets.

[0040] The epoxide used in the carbonylation reaction may be any cyclic alkoxide containing at least two carbon atoms and one oxygen atom. For example, the epoxide may have the structure represented by formula (VII):

[0041] [ka] and wherein R5 and R6 are each independently selected from the group consisting of a hydrocarbyl group or hydrogen, and the hydrocarbyl group may contain one or more heteroatoms, provided that the hydrocarbyl group does not negatively affect the catalytic activity of the ligand complex formed. The hydrocarbyl may be an alkyl group or an aryl group. R5 and R6 may optionally be joined together with the intervening atoms to form a 3-10 membered substituted or unsubstituted ring, optionally containing one or more heteroatoms; or any combination thereof.

[0042] The lactone formed from the carbonylation reaction may be any cyclic carboxylic acid ester having at least one carbon atom and two oxygen atoms. For example, the lactone may be β-propiolactone, β-butyrolactone and β-valerolactone or combinations thereof. Anywhere in this application where propiolactone or lactone is used or described, another lactone may be applicable or usable in the process, step or method. When propiolactone is used or produced in the carbonylation reaction, it has the structure corresponding to Formula V:

[0043] [ka] wherein R5 and R6 are each independently selected from the group consisting of a hydrocarbyl group or hydrogen, and the hydrocarbyl group may contain one or more heteroatoms, provided that the hydrocarbyl group does not negatively affect the catalytic activity of the ligand complex formed. The hydrocarbyl may be an alkyl or aryl group. R5 and R6 may optionally be joined together with the intervening atoms to form a 3-10 membered substituted or unsubstituted ring, optionally containing one or more heteroatoms; or any combination thereof.

[0044] The product stream from the carbonylation reaction may include one or more of propiolactone, polypropiolactone, succinic anhydride, polyethylene glycol, poly-3-hydroxypropionate, 3-hydroxypropionic acid, 3-hydroxypropionaldehyde, polyester, polyethylene, polyether, unreacted epoxide, any derivatives thereof, any other monomer or polymer derived from the reaction of the epoxide and carbon monoxide, any initiating reagent of the catalyst formation, any by-product of the catalyst formation, any derivatives thereof, or any combination thereof. The product stream may include one or more inorganic compounds, including catalyst components such as metal carbonyls, metallated ligand complexes, ligand complexes, or any combination thereof. The product stream may include unconsumed or exhausted carbonylation catalyst in the process of forming the lactone. The product stream may include one or more of unreacted epoxide or carbon monoxide.

[0045] To initiate the formation of the carbonylation catalyst from the ligand complex, the reaction may include three steps, which may be carried out in a single vessel or multiple vessels using a minimal amount of solvent and an isolation step. As used herein, a reaction mixture includes a first mixture associated with the first step and a second mixture associated with the second step. In the first step, the ligand complex and the metallated compound may be contacted with or dissolved in a hydrocarbon solvent to form a first mixture. The first step may result in a metallated ligand complex from the reaction of the metallated compound and the ligand complex, which does not need to be isolated prior to the second step. After mixing for a period of time, a polar solvent and a metal carbonyl may be contacted with the first mixture from the first step in a second step that includes mixing for a sufficient time to form a second mixture. In the second step, the carbonylation catalyst may include a combination of a metal carbonyl and a metallated ligand complex. The carbonylation catalyst formed may precipitate from the second mixture in the second step to form a slurry. In a third step, the carbonylation catalyst may be separated from the slurry or suspension by any known means to obtain a solid carbonylation catalyst, and the remaining components (e.g., unreacted starting components, by-products, solvent, etc.) may remain in the second mixture along with the hydrocarbon solvent and / or polar solvent. Carbonylation catalysts using this method may be formed in high molar yields, with minimal interfering impurities, and have desirable catalytic activity without further purification or isolation techniques. The carbonylation catalyst may be subjected to additional steps if desired to remove substantially all impurities that may be present.

[0046] In the first step, the ligand complex and the metalated compound are contacted in a hydrocarbon solvent to form a metalated ligand complex in a first mixture. The entire reaction in the first step may be carried out without any isolation of intermediates or isolation before proceeding to the second step. The entire reaction in the first step may be carried out in a moisture, air and / or oxygen free vessel, so that oxygen and / or moisture do not have undesirable interactions with the ligand complex, the metalated compound, the metalated ligand complex or the carbonylation catalyst. For example, the reaction may be carried out under an inert atmosphere in a dry box and / or in a Schlenk line. The reaction vessel may include one or more reaction zones and may include a batch reactor, a continuous stirred tank reactor, a plug flow reactor, a 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 a shaker, an impeller, or a combination of both. In other examples, the reaction may be mixed by fluid flow within the reactor, such as by sparging or turbulence.

[0047] The ligand complex and the metallated compound may be contacted in any molar ratio sufficient to form a metalated ligand complex. Excess metallated compound may reduce the amount of unreacted ligand complex after formation of the metalated ligand complex. The metallated compound and the ligand may be contacted in a molar ratio of about 1:1 or more, about 1.1:1 or more, or about 1.2:1 or more. The molar ratio may be about 1.5:1 or less, about 1.4:1 or less, or about 1.3:1 or less. The ligand complex and / or the metallated compound may be added to a single vessel in any form sufficient to form a first mixture in which the metalated ligand compound is formed. For example, the ligand complex and / or the metallated compound may be in a solid (i.e., if not mixed with a hydrocarbon prior to being charged to the reaction vessel), liquid (i.e., if initially dissolved in a hydrocarbon prior to being introduced into the reaction vessel), or undiluted form. When the ligand complex and / or metallation compound are added in solid form, the ligand complex and / or metallation compound may simply be added to the vessel in solid form and by adding a sufficient amount to react to form the metallated ligand compound. In other instances where the ligand complex and / or metallation compound are initially in liquid form before being added to the vessel, the ligand complex and / or metallation compound may be added to the vessel via a feed line, pipe, tube, or any combination thereof. The metallation compound and / or ligand complex may be added using techniques that avoid oxygen, air, and / or moisture from the first mixture.

[0048] The ligand complex may be first dissolved by a hydrocarbon solvent to form a first mixture, and the metallated compound may then be dissolved in the first mixture so that the reaction can proceed to form a metallated ligand complex. The ligand complex may be mixed for any amount of time sufficient to partially dissolve the ligand complex in the hydrocarbon solvent. For example, the ligand complex may be mixed with the hydrocarbon solvent for about 30 seconds or more, about 3 minutes or more, or about 5 minutes or more. The ligand complex may be mixed with the hydrocarbon solvent for about 20 minutes or less, about 15 minutes or less, or about 10 minutes or less.

[0049] The metallated compound can be contacted with a hydrocarbon solvent to form a first mixture, and the ligand complex can then be contacted with the first mixture so that the reaction can proceed to form the metallated ligand complex. The metallated compound can be mixed for any amount of time sufficient to dissolve some or all of the metallated compound in the polar solvent and / or hydrocarbon solvent. For example, the metallated compound can be mixed for about 30 seconds or more, about 3 minutes or more, or about 5 minutes or more. The metallated compound can be mixed for about 20 minutes or less, about 15 minutes or less, or about 10 minutes or less.

[0050] The first mixture of the hydrocarbon solvent, the metallated compound and / or the ligand complex may be mixed for any time sufficient to form the metallated ligand complex. For example, the first mixture may be mixed for about 0.5 hours or more, about 1.5 hours or more, or about 3.5 hours or more. The first mixture may be mixed for about 7 hours or less, about 6 hours or less, or about 5 hours or less. While mixing the reactants, the first mixture may be heated at any temperature sufficient to form the metallated ligand complex and without affecting the stability of the metallated ligand complex. For example, the first mixture may be heated at about 40 degrees Celsius or more, about 60 degrees Celsius or more, or about 80 degrees Celsius or more. The first mixture may be heated at about 140 degrees Celsius or less, about 120 degrees Celsius or less, or about 100 degrees Celsius or less.

[0051] After contacting the ligand complex and the metallated compound with the hydrocarbon solvent, the first mixture formed may be a slurry, suspension, and / or solution. After contacting the ligand complex and the metallated compound with the hydrocarbon solvent to form the first mixture, a polar solvent may be contacted with the mixture. The metallated ligand complex may be fully formed prior to the addition of the polar solvent. The addition of the polar solvent may cause any solid components (e.g., the metallated compound, the ligand complex, and / or the metallated ligand complex) to partially dissolve in the second mixture (i.e., in the case of a slurry). The polar solvent may have moieties that coordinate to the metallated ligand complex, such that the metal of the metallated ligand complex includes two or more molecules of the polar solvent in the form of a polar ligand.

[0052] The polar solvent and the first mixture containing the metallated ligand complex and the hydrocarbon solvent may be contacted in any volume ratio sufficient to partially dissolve one or more components of the first mixture to form a second mixture in the second step. For example, the hydrocarbon solvent and the first mixture containing the metallated ligand complex and the polar solvent may be contacted in a volume ratio of about 2:1 or less, about 1.9:1 or less, or about 1.7:1 or less. The polar solvent and the first mixture may be contacted in a volume ratio of about 1.1:1 or more, about 1.3:1 or more, or about 1.5:1 or more. To form the metallated ligand complex, the polar solvent, the hydrocarbon solvent, or both may be selected based on time considerations, the solubility of any of the components of the mixture, the reaction temperature, the boiling point of the solvent, or for a combination of reasons. The second mixture of polar and hydrocarbon solvents, metallated compound, ligand complex and / or metallated ligand complex may be mixed for any amount of time sufficient to partially dissolve one or more components of the mixture and / or to improve formation of the metallated ligand complex.

[0053] Prior to and / or during the second step, the second mixture may be sparged with a gas at a pressure sufficient to support the formation of the carbonylation catalyst. Sparging may introduce gases into the second mixture that support the stability or formation of the metal carbonyl and / or the carbonylation catalyst. Sparging may displace other gases (e.g., argon, nitrogen, etc.) in the second mixture. The gas may be carbon monoxide, synthesis gas (i.e., hydrogen and CO), or both. The partial pressure of the sparging gas may be any partial pressure that enhances the formation of the carbonylation catalyst. The sparging pressure may be about 200 kPa or less, about 150 kPa or less, or about 100 kPa or less. The sparging pressure may be about 10 kPa or more, about 40 kPa or more, or about 70 kPa or more. The single vessel may be equipped with any device sufficient to sparge the second mixture and / or the reaction mixture.

[0054] In the second step, the metallated ligand complex may be contacted with a metal carbonyl, such that the carbonylation catalyst is formed in the second mixture. The second step may be carried out in a second vessel without isolating any compound during the transfer of the mixture from the first step to the second step. The second vessel may be a different vessel from the first solution and may include any of the components or features described within the context of the first component. The second step may be carried out in the same single vessel as the first step, and the single vessel of the second step may have any of the features, configurations or fittings as the single vessel of the first reaction. The second reaction may be carried out in an environment free of moisture, air and / or oxygen, such that the formation and / or stability of the carbonylation catalyst is not negatively affected. For example, the second reaction may be carried out in an inert atmosphere, such as using a Schlenk line and / or a dry box containing an atmosphere of inert gas.

[0055] Prior to the second step, the metal carbonyl may be first contacted with a polar solvent to improve the formation of the carbonylation catalyst and / or improve the solubility of the metal carbonyl in the second mixture. The metal carbonyl may be contacted with the polar solvent and mixed for a time sufficient to form a precursor mixture containing the polar solvent. For example, the metal carbonyl and the polar solvent may be mixed for about 1 hour or less, about 30 minutes or less, or about 15 minutes or less. The metal carbonyl and the polar solvent may be mixed for about 30 seconds or more, about 5 minutes or more, or about 10 minutes or more. The metal carbonyl and the polar solvent may be mixed in any container and by any means sufficient to form a precursor mixture that can be combined with the first mixture of the first step or the second mixture containing the polar solvent, the hydrocarbon solvent, and the metallated ligand complex. The metal carbonyl may be free of the hydrocarbon solvent prior to contacting the metal carbonyl with the second mixture containing the metallated ligand complex, the polar solvent, and the hydrocarbon solvent. In some cases, the metal carbonyl may contain an amount of a hydrocarbon solvent to stabilize the metal carbonyl prior to addition to the reaction mixture, such as between about 1-5% by weight based on the total weight of the metal carbonyl prior to addition to the reaction mixture.

[0056] In the second step, the metal carbonyl may be contacted with a first mixture containing a hydrocarbon solvent and a metalated ligand complex to form a second mixture before adding a polar solvent to the first mixture. The metal carbonyl may be contacted with the already formed second mixture containing a metalated ligand complex and a hydrocarbon solvent and a polar solvent. The metal carbonyl may be contacted with the first mixture or the second mixture in any molar ratio with the metalated ligand complex sufficient to form a carbonylation catalyst. For example, the metal carbonyl and the metalated ligand complex may be contacted in a molar ratio of about 1.5:1 or less, about 1.25:1 or less, or about 1:1 or less. The metal carbonyl and the metalated ligand complex may be contacted in a molar ratio of about 0.25:1 or more, about 0.5:1 or more, 0.75:1 or more, or 1:1 or more. The molar ratio of the metal carbonyl and the metallated ligand complex may be selected such that the molar ratio of the metal in the metal carbonyl to the metal in the ligand complex is about 1:1 or greater, about 1.25:1 or greater, or about 1.5:1 or greater.

[0057] The reaction mixture containing the metal carbonyl and the metalated ligand complex may be mixed for any time sufficient to form the carbonylation catalyst. For example, the reaction mixture containing the metal carbonyl and the metalated ligand complex may be mixed for about 15 minutes or more, about 30 minutes or more, or about 1 hour or more. The reaction mixture containing the metal carbonyl and the metalated ligand complex may be mixed for about 24 hours or less, about 5 hours or less, or about 2 hours or less. The addition of the metal carbonyl and mixing of the reaction mixture may result in a precipitate containing the carbonylation catalyst. The reaction mixture may become substantially free of any dissolved carbonylation catalyst.

[0058] In the third step, the carbonylation catalyst may be removed from the reaction mixture by any separation means sufficient to yield a carbonylation catalyst having catalytic activity to form lactones. Any technique known by a person skilled in the art may be used as the separation means for separating solids and liquids to obtain the carbonylation catalyst as a solid in catalytically active form and obtain other components as liquid or solid separates from the carbonylation catalyst. For example, a single vessel used in the first and second steps may be provided with a filtering means for collecting the carbonylation catalyst in the form of a precipitate, and a vessel of any form may be placed under a separation means for collecting the components of the reaction mixture having the form of a liquid. The third step may be carried out under air, moisture and / or oxygen free conditions, so that the stability of the carbonylation catalyst is not affected and no undesirable side reactions occur. The separation means may utilize any technique or device sufficient to collect the precipitate and allow the liquid to be drained through a filter. For example, the separation means may include one or more of a vacuum filter, a gravity filter, a centrifugation means, a decantation means, a surface filter, a depth filter, a hot filter, a cold filter, or any combination thereof. The third step may include pouring or contacting additional hydrocarbon solvent and / or polar solvent onto the precipitate containing the carbonylation catalyst to wash the precipitate of further undesirable impurities soluble in the hydrocarbon solvent and / or polar solvent contained within the precipitate, which may be referred to as a washing step within the third step. The washing step may include adding or contacting any amount of hydrocarbon solvent and / or polar solvent sufficient to wash away any undesirable impurities contained within the precipitate and subjecting the catalyst containing precipitate to the separation means. The third step may further include a separation step to separate any remaining hydrocarbon solvent and / or polar solvent from the precipitate. The separation step may include any technique sufficient to separate the hydrocarbon solvent and / or polar solvent from the precipitate, such as subjecting the precipitate to one or more separation means described herein.For example, the separating step may include applying a vacuum to the precipitate to remove the hydrocarbon solvent and / or the polar solvent from the precipitate to obtain a catalyst. The separating step may include applying heat to the precipitate to remove the hydrocarbon solvent and / or the polar solvent from the precipitate to obtain a catalyst. Any amount of heat may be applied as long as the heat is not so high as to affect the stability of the carbonylation catalyst. For example, heat may be applied to raise the temperature of the separating step to about 110 degrees Celsius or less, about 90 degrees Celsius or less, or about 70 degrees Celsius or less. Heat may be applied to raise the temperature of the separating step to about 40 degrees Celsius or more, about 50 degrees Celsius or more, or about 60 degrees Celsius or more. The separating step may include applying a nitrogen flow to the precipitate to remove the hydrocarbon solvent and / or the polar solvent from the precipitate.

[0059] After the third step, the carbonylation catalyst may be subjected to further purification methods so that less impurities are present in the final carbonylation catalyst used to carry out the carbonylation. The carbonylation catalyst may be subjected to a crystallization step to separate the carbonylation catalyst from one or more other undesirable impurities, such as ligand complexes, metallated compounds and / or metallated ligand complexes. For example, the precipitate containing the carbonylation catalyst and other impurities from the third step may be contacted with one or more hydrocarbon solvents and / or polar solvents, and the one or more hydrocarbon solvents and / or polar solvents may be heated to a temperature sufficient to dissolve the precipitate into a crystallization mixture. The one or more polar solvents and / or hydrocarbon solvents may be combined at an elevated temperature in any volume ratio sufficient to dissolve the precipitate containing the carbonylation catalyst. For example, the one or more hydrocarbon solvents and polar solvents may be combined in a volume ratio of about 1:1 or more, about 1.3:1 or more, or about 1.5:1 or more. The one or more hydrocarbon solvents and the polar solvent may be combined in a volume ratio of about 2:1 or less, about 1.9:1 or less, or about 1.7:1 or less. After heating, the crystallization mixture may be cooled to a temperature sufficient to crystallize, i.e., precipitate the carbonylation catalyst from the one or more polar solvents and / or the hydrocarbon solvent. For example, an ice bath may be used to cool the crystallization mixture at a fast rate. After this crystallization step, the carbonylation catalyst may be substantially free of impurities.

[0060] The precipitate containing the carbonylation catalyst from the third step may be contacted with a minimum amount of a hydrocarbon solvent and / or a polar solvent, such that the precipitate dissolves in the combination of solvents. The precipitate containing the carbonylation catalyst may have a higher solubility in the polar solvent. The minimum amount of the hydrocarbon solvent and / or the polar solvent may be any amount sufficient to dissolve substantially all of the precipitate. Over a period of time, the hydrocarbon solvent and / or the polar solvent may have high volatility, so that the hydrocarbon solvent and / or the polar solvent may begin to evaporate. As the hydrocarbon solvent and / or the polar solvent evaporates, the carbonylation catalyst may precipitate out of the crystallization mixture, such that the carbonylation catalyst is substantially free of impurities.

[0061] The carbonylation catalyst may have any purity sufficient to catalyze the reaction between an epoxide and carbon monoxide to form a lactone. For example, the carbonylation catalyst may have a purity of about 90% or more, about 92% or more, or about 95% or more. The carbonylation catalyst may have a purity of about 100% or less, about 98% or less, or about 96% or less. The carbonylation catalyst may be formed by utilizing a first, second, and third step to obtain a carbonylation catalyst having a purity of less than 100%, and the carbonylation catalyst may be subjected to further purification or separation steps as described herein to improve the purity of the carbonylation catalyst. When the carbonylation catalyst has a purity of less than 100%, the carbonylation catalyst may contain one or more other impurities including by-products, residual reactants or starting materials, solvents, and the like. The carbonylation catalyst may contain any amount of impurities such that the carbonylation catalyst still has desirable catalytic properties upon forming the lactone. For example, the carbonylation catalyst may contain impurities in an amount of about 10% or less, about 8% or less, or about 5% or less. The carbonylation catalyst may contain impurities in an amount of about 9.9% or less, about 8% or less, or about 7% or less. The carbonylation catalyst may be substantially free of impurities.

[0062] The separation process taught herein serves to remove any undesirable components from the composition that may interfere with the formation or function of the carbonylation catalyst or any precursor of the carbonylation catalyst. For example, one or more of the solvent, inorganic compounds, organic compounds, or any combination thereof, may be removed from the composition, resulting in the carbonylation catalyst being isolated in a purer form. The separation process may include one or more of vacuum filtration, gravity filtration, centrifugation, decantation, precipitation, phase layer extraction, another technique described herein, or any combination thereof. The separation process may utilize any method sufficient to separate one or more of the solvent, inorganic compounds, organic compounds, or any combination thereof to form the carbonylation catalyst. The separation process may remove a single type of compound at a time, such as a precipitate, or may remove a collection of compounds at a time, such as all of the components dissolved in the solvent. The separation step may include forming multiple phases, including one or more of an organic phase, an aqueous phase, a solid phase (i.e., a precipitate), one or more gas or vapor phases, or any combination thereof. The one or more separation steps described herein may be performed at any temperature, pressure, agitation rate, time, or any combination thereof sufficient to separate or remove any undesirable components from the composition, including the ligand complex, the metallated ligand complex, the metallated compound, the hydrocarbon solvent and / or the polar solvent, their by-products, their derivatives, or any combination thereof.

[0063] The carbonylation catalysts described herein function to catalyze the reaction of an epoxide with carbon monoxide to produce propiolactone and one or more other products. The carbonylation catalyst comprises at least a metal carbonyl, which is anionic, and a cationic metallated ligand complex. The carbonylation catalyst may be stored in an oxygen- and water-free environment.

[0064] Several techniques have been theorized to illustrate the teachings of the present disclosure. One such technique is found below and represented by Figure 1. Each teaching is merely an example of the present disclosure and is not intended to limit the present teachings to any single technique.

[0065] FIG. 1 is a synthesis scheme for forming a carbonylation catalyst. A 500 mL media bottle is charged with 25.00 g of tetraphenylporphyrin (TPPH2) and 75 mL of hexane. Triethylaluminum in the amount of 41.0 mL (1.0 M in hexane) is added to the reaction mixture via syringe. The reaction mixture is mixed for 20 hours. The reaction mixture is charged with 120 mL of tetrahydrofuran. The reaction mixture is sparged with carbon monoxide at a pressure of about 35 KPa to about 50 kPa for 10 minutes. To this slurry is added 7.09 g of metal carbonyl (Co2(CO)8) in solid form containing 1 to 5 wt.% hexane. The reaction is mixed for 5 hours at room temperature. After the reaction, the reaction mixture is filtered through a frit and the resulting purple precipitate is collected, washed with hexane and dried under vacuum. The yield of carbonylation catalyst was 37.3 g, which has a purity of about 95.1% as determined by proton NMR.

[0066] Enumeration of embodiments The following examples are presented to illustrate the invention but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0067] Embodiment 1. a. contacting a ligand complex, a metallated compound, and a metal carbonyl in a reaction mixture to form a catalyst, wherein the ligand complex comprises one or more of a phosphine, imine, and / or hydroxyl group attached to one or more cyclic structures; and b. Separating the catalyst from the reaction mixture A method comprising:

[0068] Embodiment 2. The method of embodiment 1, wherein the step of contacting the ligand complex, the metallated compound, and the metal carbonyl in the reaction mixture is carried out without isolating or separating any intermediates.

[0069] Embodiment 3. The method of embodiment 1 or 2, wherein step (a) is carried out in a single container.

[0070] Embodiment 4. The method of any one of embodiments 1-3, wherein step (a) is carried out in an environment free of moisture, air and / or oxygen.

[0071] Embodiment 5. a. contacting the ligand complex with one or more hydrocarbon solvents and a metallated compound prior to contacting with the metal carbonyl to form a reaction mixture. 5. The method of any one of embodiments 1 to 4, further comprising:

[0072] Embodiment 6. The step of contacting a ligand complex, a metallated compound and a metal carbonyl in a reaction mixture to form a catalyst comprises: a. mixing the reaction mixture for about 2 hours or more The method of any one of embodiments 1 to 5, comprising:

[0073] Embodiment 7. The step of contacting a ligand complex, a metallated compound and a metal carbonyl in a reaction mixture to form a catalyst comprises: a. mixing the reaction mixture with the application of heat for about 1.5 hours or more. The method of any one of embodiments 1 to 5, comprising:

[0074] Embodiment 8. The step of contacting a ligand complex, a metallated compound, and a metal carbonyl in a reaction mixture to form a catalyst comprises: a. mixing the reaction mixture for about 5 hours or more without the application of heat. The method of any one of embodiments 1 to 5, comprising:

[0075] Embodiment 9. The step of contacting a ligand complex, a metallated compound, and a metal carbonyl in a reaction mixture to form a catalyst comprises: a. contacting a ligand complex and a hydrocarbon solvent to form a first mixture; b. contacting the first mixture and a metallated compound to form a metallated ligand complex in the first mixture; and c. contacting the first mixture, a polar solvent, and a metal carbonyl in a second mixture to form a catalyst. The method of any one of embodiments 1 to 8, comprising:

[0076] Embodiment 10. The step of contacting the first mixture and the metallated compound to form a metallated ligand complex in the first mixture comprises: a. mixing the first mixture for about 3 hours or more without the application of heat or for about 0.25 hours or more with the application of heat; Including, contacting the first mixture, a polar solvent, and a metal carbonyl in a second mixture to form a catalyst, the step comprising: b. mixing the first mixture, a polar solvent, and a metal carbonyl in a second mixture for about one hour or more. 10. The method of embodiment 9, comprising:

[0077] Embodiment 11. The step of contacting a first mixture, a polar solvent, and a metal carbonyl to form a catalyst comprises: a. contacting a first mixture and a polar solvent to form a second mixture; b. blowing a gas through the second mixture at a pressure sufficient to support the formation of the catalyst; and c. contacting the second mixture and a metal carbonyl to form a catalyst. The method of any one of embodiments 1 to 10, comprising:

[0078] Embodiment 12. The step of blowing a gas through the second mixture at a pressure sufficient to form a catalyst comprises: a. blowing a gas at a pressure of about 100 kPa or less onto the second mixture; 12. The method of embodiment 11, comprising:

[0079] Embodiment 13. The step of separating the catalyst from the reaction mixture comprises: a. filtering the catalyst in the form of a precipitate from the reaction mixture. The method of any one of embodiments 1 to 12, comprising:

[0080] Embodiment 14. The step of separating the catalyst from the reaction mixture comprises: a. applying a vacuum to the catalyst to remove the hydrocarbon solvent and / or the polar solvent from the catalyst, such that the catalyst has a solid form; b. applying heat to the catalyst to remove the hydrocarbon solvent and / or the polar solvent from the catalyst, such that the catalyst has a solid form; and / or c. applying a nitrogen flow to the catalyst to remove the hydrocarbon solvent and / or the polar solvent from the catalyst, so that the catalyst has a solid form; The method of any one of the preceding embodiments, comprising:

[0081] Embodiment 15. The method of any one of embodiments 1-14, wherein the polar solvent is contacted with the reaction mixture in a volume ratio of between about 1:1 or less and about 1:2 or less.

[0082] Embodiment 16 The method of any one of embodiments 1-15, wherein the metallated compound is contacted with the ligand complex in a molar ratio of about 0.25:1 or greater.

[0083] EMBODIMENT 17. a. contacting one or more solvents with the catalyst removed from the reaction mixture to form a crystallization mixture; b. precipitating the catalyst from the crystallization mixture; and c. Separating the catalyst from the one or more solvents. 20. The method of any one of the preceding embodiments, further comprising:

[0084] Embodiment 18. The one or more solvents include one or more polar solvents and one or more hydrocarbon solvents; contacting one or more solvents with the catalyst removed from the reaction mixture to form a reaction mixture, a. contacting the catalyst removed from the reaction mixture with one or more polar solvents and one or more hydrocarbon solvents to form a crystallization mixture; b. heating the crystallization mixture to a temperature sufficient to dissolve the catalyst in one or more polar solvents and one or more hydrocarbon solvents; and c. cooling the crystallization mixture so that the catalyst crystallizes and precipitates from the one or more polar solvents and the one or more hydrocarbon solvents. 18. The method of embodiment 17, comprising:

[0085] Embodiment 19. The step of separating one or more solvents and / or one or more other compounds from the catalyst comprises: a. separating the one or more polar solvents and / or the one or more hydrocarbon solvents so that the catalyst is substantially free of other compounds; 19. The method of embodiment 18, comprising:

[0086] EMBODIMENT 20. a. washing the catalyst with one or more hydrocarbon solvents 20. The method of any one of the preceding embodiments, further comprising:

[0087] Embodiment 21. The catalyst comprises: a. a metallated ligand complex ionically bonded to a metal carbonyl in an amount of about 90% by weight or greater; and b. an amount of unbound ligand complex of about 10% by weight or less Including, The method of any one of the preceding embodiments, wherein the weight percent is based on the total weight of the catalyst.

[0088] Embodiment 22. The catalyst comprises: a. a metallated ligand complex ionically bonded to a metal carbonyl in an amount of about 95% or more by weight; and b. an amount of unbound ligand complex of about 5% by weight or less Including, The method of any one of the preceding embodiments, wherein the weight percent is based on the total weight of the catalyst.

[0089] Embodiment 23. The catalyst comprises: a. a metallated ligand complex ionically bonded to a metal carbonyl in an amount of about 98% or greater by weight; and b. Unbound ligand complex in an amount of about 2% by weight or less Including, The method of any one of the preceding embodiments, wherein the weight percent is based on the total weight of the catalyst.

[0090] Embodiment 24. The method of any one of the previous embodiments, wherein the reaction mixture, the crystallization mixture, the first mixture and / or the second mixture have the form of a solution, a slurry and / or a suspension.

[0091] Embodiment 25. The method of any one of the previous embodiments, wherein the catalyst has catalytic activity with carbon monoxide and epoxides to form lactones, succinic anhydride, or both.

[0092] Embodiment 26 The method of any one of the previous embodiments, wherein the catalyst has catalytic activity with carbon monoxide and aziridine to form a lactam.

[0093] Embodiment 27. The method of any one of the previous embodiments, wherein the ligand complex comprises one or more aromatic groups, and the ligand complex comprises one or more imine groups and one or more cyclic structures.

[0094] Embodiment 28 The method of any one of the preceding embodiments, wherein the ligand complex comprises a macrocycle.

[0095] Embodiment 29. The method of any one of the preceding embodiments, wherein the ligand complex comprises one or more of a porphyrin ligand, a salen ligand, a sulfur ligand, a salsi ligand, a phosphasalen ligand, a phosphasulfur ligand, a phosphasalsi ligand, a disubstituted bipyridine ligand, a disubstituted phenanthroline ligand, a dibenzotetramethyltetraaza

[14] annulene derivative, a phthalocyanine derivative, a diaminocyclohexane derivative, other derivatives thereof, or any combination thereof.

[0096] EMBODIMENT 30. a. dissolving a metallated compound in a hydrocarbon solvent to form a precursor mixture having a molar concentration of about 1.0 or greater prior to contacting the ligand complex, the metallated compound, and the metal carbonyl. 20. The method of any one of the preceding embodiments, further comprising:

[0097] Embodiment 31 The method of any one of the previous embodiments, wherein the metallated compound comprises aluminum or chromium.

[0098] Embodiment 32 The method of any one of the preceding embodiments, wherein the metallated compound comprises aluminum.

[0099] Embodiment 33 The method of any one of the previous embodiments, wherein the metallated compound comprises one or more of triethylaluminum, trimethylaluminum, triisobutylaluminum, chromium(II) chloride, diethylaluminum chloride, or any combination thereof.

[0100] Embodiment 34. The method of any one of the preceding embodiments, wherein the metallated compound comprises a trialkylmetal compound.

[0101] Embodiment 35. The method of any one of the previous embodiments, wherein the metal carbonyl comprises a hydrocarbon solvent in an amount of about 1% to about 5% by weight, the weight percentage being based on the total weight of the metal carbonyl.

[0102] Embodiment 36 The method of any one of the preceding embodiments, wherein the metal carbonyl comprises cobalt.

[0103] Embodiment 37. The metal carbonyl is NaCo(CO)4, HCo(CO)4, Co2(CO)8, any Co x (CO) y The method of any one of the preceding embodiments, comprising one or more of the following compounds or combinations thereof:

[0104] Embodiment 38. The method of any one of the preceding embodiments, wherein the gas comprises one or more of carbon monoxide, synthesis gas, an inert gas, or a combination thereof.

[0105] Embodiment 39. The method of any one of the preceding embodiments, wherein the other gases include one or more of argon, nitrogen, or both.

[0106] Embodiment 40. The method of any one of the previous embodiments, wherein the hydrocarbon solvent comprises one or more of hexane, heptane, pentane, benzene, toluene, xylene, any other hydrocarbon, or any combination thereof.

[0107] Embodiment 41 The method of any one of the preceding embodiments, wherein the polar solvent comprises a polar aprotic solvent.

[0108] Embodiment 42. The method of any one of the preceding embodiments, wherein the polar solvent comprises one or more of an ester solvent, a ketone solvent, an aldehyde solvent, an ether solvent, or any combination thereof.

[0109] Embodiment 43. The method of any one of the preceding embodiments, wherein the polar solvent comprises one or more of tetrahydrofuran, ethyl acetate, methyl ethyl ketone, acetone, 2-cyclohexanone, 2-methyltetrahydrofuran, butyl acetate, methyl acetate, cyclopentanone, an ester solvent, a ketone solvent, or any combination thereof. EXAMPLES

[0110] The following examples are presented to illustrate the present disclosure but are not intended to limit its scope.

[0111] NMR analysis is performed on a Varian Mercury spectrometer operating at 300.1 MHz. Prior to testing, samples are dissolved in THF-d8.

[0112] In situ FTIR analysis to follow the catalytic activity of the carbonylation catalyst is performed on a Mettler Toledo ReactIR 45m equipped with a silicone tipped sentinel mounted directly at the bottom of the reactor.

[0113] FIG. 2A is a 1H NMR spectrum of the isolated carbonylation catalysts of Examples 1-3 formed by the following method and analyzed in d8-THF: A 1 L media bottle is charged with 75.00 g of tetraphenylporphyrin (TPPH2) and 225 mL of hexane. A quantity of 122.0 mL (1.0 M in hexane) of triethylaluminum is added to the reaction mixture via syringe. The reaction mixture is mixed for 20 hours. The reaction mixture is charged with 360 mL of tetrahydrofuran. The reaction mixture is sparged with carbon monoxide at a pressure of about 35 KPa to about 50 kPa for 30 minutes. To this slurry is added 21.28 g of metal carbonyl (Co2(CO)8) in solid form containing 1-5 wt % hexane. The reaction is mixed for 5 hours at room temperature. After reaction, the reaction mixture is filtered through a frit and the resulting purple precipitate is collected, washed with hexane and dried under vacuum. The yield of carbonylation catalyst was 112.1 g, which was 1 It is approximately 96.4% pure by H NMR.

[0114] FIG. 2B is a 1H NMR spectrum of an isolated carbonylation catalyst of another method of forming the catalyst as a comparative example. It is analyzed in d8-THF. The comparative method of the catalyst shown in FIG. 2 involves charging a 1 L 3-neck flask with 68.4 grams of TPPH2 and 220 ml of anhydrous toluene. A thermocouple is placed on the side of the neck and a 250 ml dropping funnel is placed over the center of the neck of the flask. The dropping funnel is charged with 85 mL of AlEt3 (25 wt % in toluene). The above solution is added dropwise to the reaction mixture over approximately 30 minutes. The reaction is stirred at room temperature for a total of 3 hours. The reaction mixture is filtered through a 600 ml medium fritted funnel over a 2 L Erlenmeyer flask. (TPP)AlEt is collected as a solid and washed with 6×30 ml of hexane. The (TPP)AlEt is transferred to a 1 L round bottom flask and dried under vacuum overnight. 60.0 g of (TPP)AlEt is dissolved in 1120 mL of THF in a 2 L flask. To this solution, 16.2 g of Co2(CO)8 containing 1-5 wt% hexane is added. The reaction is stirred for 16 hours at room temperature under 7 psi gauge pressure of CO. After the reaction between (TPP)AlEt and Co2(CO)8, the reaction mixture is filtered through a frit. The filtrate is then transferred to a 5 L flask. With stirring, 2240 mL of anhydrous hexane is added to the filtrate. The mixture is allowed to stand for 24-72 hours. The resulting purple precipitate is filtered through a frit, washed with fresh hexane, and dried under vacuum. The yield of carbonylation catalyst is 79.2 g of carbonylation catalyst, which is about 93.7% pure based on 1H NMR. From the 1H-NMR in THF-d-8 in Figure 2B, the product is confirmed to be [(TPP)Al(THF)2][Co(CO)4].

[0115] FIG. 2C is a 1H NMR spectrum of the isolated carbonylation catalyst of Example 10 formed by the following method and analyzed in d8-THF: A 1 L 3-neck flask is charged with 125.00 g of tetraphenylporphyrin (TPPH2) and 240 mL of heptane. A 31.0 mL amount of triethylaluminum is added to the reaction mixture via syringe while stirring. The reaction mixture is heated to 70° C. and mixed for 3 hours. The reaction mixture is charged with a solution of 38.1 g of Co2(CO)8 (stabilized with 1-5% hexane) in 325 mL of tetrahydrofuran. The reaction is mixed at room temperature for 2 hours. After the reaction, the reaction mixture is filtered through a frit and the resulting purple precipitate is collected, washed with hexane and dried under vacuum. The yield of carbonylation catalyst is 190.7 g, which is about 96.6% pure based on 1H NMR. From the 1H-NMR in THF-d-8 in Figure 2C, the product is confirmed to be [(TPP)Al(THF)2][Co(CO)4].

[0116] FIG. 2D is a 1H NMR spectrum of the isolated carbonylation catalyst of Examples 11-12 formed by the following method and analyzed in d8-THF. A 100 mL round bottom flask is charged with 4.00 g of tetraphenylporphyrin (TPPH2) and 8 mL of heptane. With stirring, 0.90 mL of diethylaluminum chloride is added to the reaction mixture via syringe. The reaction mixture is heated to 90° C. and mixed for 3 hours. The reaction mixture is cooled to 50° C. and then a solution of 1.26 g of NaCo(CO)4 in 10 mL of tetrahydrofuran is charged. The reaction is mixed at 50° C. for 2 hours. After the reaction, the reaction mixture is cooled to room temperature and filtered through a frit to collect the resulting purple precipitate. The solid is washed with hexane and dried under vacuum. The yield of carbonylation catalyst is 6.72 g, which is about 95.3% pure based on 1H NMR (0.38 g of NaCl also remains in the precipitated solid). 1H-NMR in THF d-8, FIG. 2D, confirms the product as [(TPP)Al(THF)2][Co(CO)4].

[0117] Comparing Figures 2A and 2C-2D with 2B, Examples 1, 10 and 11-12 have similar purity by NMR to the carbonylation catalyst of Figure 2B utilizing the additional isolation step.

[0118] FIG. 3 is a graph showing the catalytic activity of the carbonylation catalysts for producing beta-propiolactone of Examples 1-12.

[0119] Examples 1-3, and 10-12 show carbonylation catalysts made from the method described with respect to Figures 2A and 2C-2D, respectively. Examples 4-9 are made by other methods described with respect to Figure 2B, which utilize additional isolation steps to obtain the carbonylation catalyst. As shown by Figures 2A and 2C-2D, the carbonylation catalysts of Examples 1-3 and 10-12 have similar purity profiles by NMR without additional purification steps when compared to the carbonylation catalyst of Figure 2B, and the activity profile of the carbonylation catalysts formed by the novel method in Figures 2A and 2C-2D is similar to that of the carbonylation catalysts of Examples 4-9 made by the standard method described with respect to Figure 2B. Thus, Examples 1-3 and 10-12 demonstrate carbonylation catalysts that require fewer steps to produce a carbonylation catalyst with high purity, and have catalytic activity to form lactones similar to other methods.

Claims

1. a. contacting a ligand complex, a metallated compound, and a metal carbonyl in a reaction mixture to form a catalyst, wherein the ligand complex comprises one or more of a phosphine, imine, and / or hydroxyl group attached to one or more cyclic structures; i. contacting a ligand complex and a hydrocarbon solvent to form a first mixture; ii. contacting the first mixture and a metallated compound to form a metallated ligand complex in the first mixture; and iii. Contacting the first mixture, a polar solvent, and a metal carbonyl in a second mixture to form a catalyst. and b. Separating the catalyst from the second mixture. A method comprising:

2. 10. The method of claim 1, wherein the step of contacting the ligand complex, the metallated compound, and the metal carbonyl in the reaction mixture is carried out without isolating or separating any intermediates.

3. 3. The method of claim 1 or 2, wherein step (a) is carried out in a single vessel.

4. 3. The method of claim 1 or 2, wherein step (a) is carried out in a moisture-, air- and / or oxygen-free environment.

5. contacting the first mixture and the metallated compound to form a metallated ligand complex in the first mixture; 1. Mixing the first mixture for at least 5 hours without the application of heat or for at least 0.25 hours with the application of heat. Including, contacting the first mixture, a polar solvent, and a metal carbonyl in a second mixture to form a catalyst, the step comprising:

2. Mixing the first mixture, the polar solvent, and the metal carbonyl in a second mixture for at least 1 hour.

3. The method of claim 1 or 2, comprising:

6. Step (b.) separating the catalyst from the second mixture comprises: i. filtering the catalyst in the form of a precipitate from the second reaction mixture; 3. The method of claim 1 or 2, comprising:

7. a. washing the catalyst with one or more hydrocarbon solvents The method of claim 1 or 2, further comprising:

8. The catalyst is a metallated ligand complex in an amount of 90% by weight or greater, ionically bonded to a metal carbonyl; and containing no more than 10% by weight of unbound ligand complex; 3. The method of claim 1 or 2, wherein the weight percentages are based on the total weight of the catalyst.

9. 3. The process of claim 1 or 2, wherein the catalyst has catalytic activity with carbon monoxide and epoxide to form a lactone, succinic anhydride, or both, or the catalyst has catalytic activity with carbon monoxide and aziridine to form a lactam.

10. 3. The method of claim 1 or 2, wherein the ligand complex comprises one or more of a porphyrin ligand, a salen ligand, a sulfur ligand, a salsi ligand, a phosphasalen ligand, a phosphasulfur ligand, a phosphasalsi ligand, a disubstituted bipyridine ligand, a disubstituted phenanthroline ligand, a dibenzotetramethyltetraaza[14]annulene derivative, a phthalocyanine derivative, a diaminocyclohexane derivative, other derivatives thereof, or any combination thereof.

11. 3. The method of claim 1 or 2, wherein the metallated compound comprises aluminum or chromium.

12. 3. The method of claim 1 or 2, wherein the metallated compound comprises a trialkylmetal compound.

13. 3. The method of claim 1 or 2, wherein the metal carbonyl comprises cobalt.

14. 3. The method of claim 1 or 2, wherein the polar solvent comprises a polar aprotic solvent.

15. 3. The method of claim 1 or 2, wherein the ligand complex comprises a porphyrin ligand, a salen ligand, or both.

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