# US 12,459,960 B2 · Carbonylation catalysts and methods of making the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,459,960 B2 - Document ID: US12459960B2 - Status: Granted - Kind: B2 - Application number: 18/285,803 - Filed: 2022-03-30 - Published: 2024-11-07 - Granted: 2025-11-04 - Earliest claimed: 2021-04-06 - Assignees: Novomer, Inc. - Applicants: Novomer, Inc. - Inventors: Jonathan D. Tedder; Alison M. Wilders; Geoffrey W. Coates; Catherine A. Falkner - Web page: https://patentgrep.com/patent/US12459960B2 ## CPC - B01J 31/2243: {At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand} - C07F 5/069: {without C-aluminium linkages} - B01J 31/1805: {the ligands containing nitrogen} - B01J 31/20: Carbonyls - B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation - B01J 2531/0252: Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde - B01J 2531/31: Aluminium - B01J 2531/845: Cobalt - Y02A 30/30: in transportation, e.g. on roads, waterways or railways - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - Y02A: TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE ## Abstract Disclosed herein are compounds and methods useful as carbonylation catalysts that improve steric properties so that reaction with epoxide is improved, reaction with lactones is avoided, and polymer bonds to the metal centers are weakened, which facilitates faster ring closure, that improve stability of the carbonylation catalyst by not being susceptible to hydrolysis, which reduces side products and improves recovery yields of the carbonylation catalyst after using to make lactones, and that have improved steric and electron properties so that release time of a lactone product is minimized, which reduces side reactions. ## Claims ### Claim 1 A compound according to one of a following formulas: wherein R is separately in each occurrence hydrogen, alkyl, or aryl group; PL is selected from a group consisting of tetrahydrofuran, dioxane, diethyl ether, acetonitrile, carbon disulfide, pyridine, epoxide, ester, lactone, or a combination thereof; and M is separately in each occurrence aluminum and chromium. ### Claim 2 (depends on 1) The compound according to claim 1 wherein: R is separately in each occurrence an alkyl or aryl group; and PL is selected from a group consisting of, dioxane, diethyl ether, or a combination thereof. ### Claim 3 (depends on 1) A method for preparing a compound according to claim 1 comprising: contacting of a compound according to one of a formulas: with a metalating agent to form one of the compounds according to a formula of: and contacting the formed compounds with a metal carbonyl under condition such that one of the following compounds are formed: wherein R is separately in each occurrence hydrogen, alkyl, or aryl group; PL is selected from a group consisting of tetrahydrofuran, dioxane, diethyl ether, acetonitrile, carbon disulfide, pyridine, epoxide, ester, lactone, or a combination thereof; and M is separately in each occurrence aluminum or chromium. ### Claim 4 (depends on 3) The method according to claim 3 wherein: R is separately in each occurrence an alkyl or aryl group; and PL is selected from a group consisting of tetrahydrofuran, dioxane, diethyl ether, or a combination thereof. ### Claim 5 (depends on 3) The method according to claim 3 comprising preparing one of the compounds according to one of the formulas: by: contacting a phenol which may be substituted at a 2 and/or 4 position with hydrogen, alkyl, or aryl group with a halogenating agent under conditions such that a halogen atom is added at a 6 carbon atom to form a halogenated phenol; contacting the formed halogenated phenol with a trialkyl borate in presence of an alkyl lithium compound to replace the halogen atom with a boron dihydroxide group; and contacting phenol containing a boron dihydroxide group with bipyridine or phenanthroline having halogen groups on carbons adjacent to nitrogen atoms in the presence of a palladium catalyst and an alkali metal carbonate under conditions to form one of the compounds of the formulas. ### Claim 6 (depends on 5) The method of claim 5, wherein contacting the formed halogenated phenol with the trialkyl borate in the presence of an alkyl lithium compound to replace the halogen atom with a boron dihydroxide group further comprises: contacting the phenol containing a boron dihydroxide group with hydrochloric acid to quench a reaction. ### Claim 7 (depends on 5) The method of claim 5, wherein the trialkyl borate selected from a group consisting of trimethyl borate, triethyl borate, tripropyl borate, trisiopropyl borate, or any combination thereof. ### Claim 8 (depends on 5) The method of claim 5, wherein the alkali metal carbonate is sodium carbonate. ### Claim 9 (depends on 5) The method of claim 5, wherein contacting the formed compounds with the metal carbonyl under condition such that one of the compounds are formed includes: contacting the formed compounds, the metal carbonyl, or both with a polar ligand so that that one of the compounds are formed. ### Claim 10 (depends on 5) The method of claim 5, wherein the alkyl lithium compound is selected from a group consisting of one or more of n-butyllithium, t-butyllithium, or any combination thereof. ### Claim 11 (depends on 5) The method of claim 5, wherein the halogenating agent is selected from a group consisting of one or more of bromine, N-bromosuccinimde, dibromoisocyanuric acid, or any combination thereof. ### Claim 12 (depends on 5) The method of claim 5, wherein the metal carbonyl is selected from a group consisting of NaCo(CO)4, Co2(CO)8, HCo(CO)4, or any combination thereof. ### Claim 13 (depends on 5) The method of claim 5, wherein the PL is selected from a group consisting of one or more of tetrahydrofuran, diethyl ether, or any combination thereof. ### Claim 14 (depends on 5) The method of claim 5, wherein the metalating agent is selected from a group consisting of one or more of (Et)2AlCl, (Et)3Al, CrCl2, or any combination thereof. ### Claim 15 (depends on 1) The compound of claim 1, wherein the PL is selected from a group consisting of the tetrahydrofuran. ### Claim 16 (depends on 5) The method of claim 5, wherein the PL is selected from a group consisting of of the tetrahydrofuran.