Novel carbonylation catalyst and method for producing same

Abstract

Disclosed herein are compounds and methods that are useful as carbonylation catalysts that have improved reaction with epoxides, avoided reaction with lactones, improved steric properties such that the polymer bond to the metal center is weakened, thereby promoting faster ring closure; improved stability of the carbonylation catalyst by being less susceptible to hydrolysis, thereby reducing by-products and improving recovery of the carbonylation catalyst after use to make lactones; and improved steric and electronic properties such that release time of the lactone product is minimized, thereby reducing side reactions.

Description

[Technical field]

[0001] The present disclosure relates to novel catalysts for use in the production of lactones from epoxides and methods for making the same. [Background technology]

[0002] Carbonylation is a process that can be used to react carbon monoxide with epoxides to produce lactones. In some cases, additional steps are taken to react the lactones to produce polymers. These lactones or their polymers are often used as plastics and disinfectants. When producing 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 carbonylation catalysts and new techniques to synthesize the carbonylation catalysts from simple components are needed. Furthermore, some current carbonylation catalysts can produce undesirable by-products that must be filtered out later. Some carbonylation catalysts can be found in US Patents US 6,852,865, US 8,481,756 and US 8,633,123. Some of these carbonylation catalysts can result in slow reaction times, can be unstable, and can become deactivated during the course of catalytic carbonylation. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 6,852,865 [Patent Document 2] U.S. Pat. No. 8,481,756 [Patent Document 3] U.S. Pat. No. 8,633,123 Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, there is a need for a catalyst that can be used in the carbonylation reaction, that can be recycled, that has a longer catalyst life, that can increase the rate of formation of the lactone product and / or avoid undesirable by-products. [Means for solving the problem]

[0005] Summary of the Invention Disclosed are compounds having catalytic activity towards one or more of epoxides, succinic anhydrides or lactones according to one of the following formulas:

[0006] [ka] In these compounds, R is, separately for each occurrence, a hydrogen, an alkyl, or an aryl group; R 1 is separately for each occurrence a hydrogen, an alkyl, or an aryl group; R 2 is, separately for each occurrence, an alkyl, aryl, or alkoxide group; R 3 is separately for each occurrence an alkyl or aryl group; R 4 can be an alkyl group or a halogen separately for each occurrence, PL is the residue of a polar ligand, and M is a Lewis acid metal separately for each occurrence.

[0007] The above compound is reacted with the compound having the following formula:

[0008] [ka] with a metallation agent to obtain a compound according to the formula

[0009] [ka] The compound thus formed and the metal carbonyl are reacted with one of the compounds according to the method described below.

[0010] [ka] (In the formula, R, R 1 , R 2 , R 3 , R 4 , PL and M are as described above.) Disclosed herein is a method for preparing a compound comprising the steps of: contacting a metal carbonyl, a polar ligand, or both of the compound with a metal carbonyl under conditions such that one of the compounds is formed. The method may further include contacting the compound formed with a polar ligand, a metal carbonyl, or both of the compound with a polar ligand such that one of the compounds is formed.

[0011] The following formula

[0012] [ka] Disclosed herein is a method for preparing one of the compounds according to one of the formulas by contacting a phenol, which may be substituted at the 2- and / or 4-positions with hydrogen, an alkyl or aryl group, with a halogenating agent under conditions such that a halogen atom is added to the carbon atom at the 6-position to form a halogenated phenol. The method further comprises contacting the halogenated phenol with a halo-di(aryl or alkyl)phosphine in the presence of an alkyllithium under conditions to replace the halogen on the phenol with a di(alkyl or aryl)phosphate to form a dialkyl or diaryl phosphate substituted phenol. The method further comprises contacting the dialkyl or diaryl phosphate substituted phenol with a diamine, orthophenyleneamine or orthocyclohexyldiamine, in the presence of a bromine source and a trialkylamine to form a compound of the formula: The method may further include the steps of first contacting the dialkyl- or diaryl-phosphate-substituted phenol with a bromine source to form an activated dialkyl- or diaryl-phosphate-substituted phenol, and then contacting the activated dialkyl- or diaryl-phosphate-substituted phenol with ethylenediamine, orthophenyleneamine, or cyclohexyldiamine in the presence of a trialkylamine to form a compound of the formula:

[0013] The following formula

[0014] [ka] Disclosed herein is a method for preparing one of the compounds according to one of the formulas by contacting a phenol, which may be substituted at the 2- and / or 4-positions with hydrogen, alkyl, or aryl groups, with a halogenating agent under conditions such that a halogen atom is added to the carbon atom at the 6-position to form a halogenated phenol. The method further includes contacting the formed halogenated phenol with a trialkylborate in the presence of an alkyllithium compound to replace the halogen atom with a boron dihydroxide group. The method further includes contacting the phenol containing the boron dihydroxide group with a bipyridine or phenanthroline having a halogen group on the carbon adjacent to the nitrogen atom in the presence of a palladium catalyst and an alkali metal carbonate under conditions to form one of the compounds according to the formula. The trialkylamine may consume bromate to form an ammonium salt. The method may further include contacting the phenol containing the boron dihydroxide group with hydrochloric acid to quench the reaction.

[0015] The following formula

[0016] [ka] Disclosed herein is a method for preparing one of the compounds according to one of the above by contacting a phenol, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, with a halogenating agent and a silyl halide under conditions such that halogen atoms are added to the 2- and 6-carbon atoms of the aromatic ring, the 1-hydroxyl group is converted to a silyl ether group, and the 4-position is optionally substituted with hydrogen, an alkyl or aryl group. The method further comprises contacting the formed 2,6-halogenated 1-silyl ether substituted benzene with an alkyl lithium compound and dimethylformamide to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, and optionally substituted at the 4-position with hydrogen, an alkyl or aryl group. The method further comprises contacting a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, with one of o-phenylenediamine, ethylenediamine or cyclohexanediamine, optionally in the presence of a Lewis or Bronsted acid catalyst and an alkali metal or ammonium salt, to form one of the compounds corresponding to one of the formulas. The method may further comprise first contacting the optionally substituted phenol with a halogenating agent to form a halogenated phenol, and then contacting the halogenated phenol with the silyl halide under conditions such that the hydroxyl group at the 1-position is converted to a silyl ether group and the 4-position may be optionally substituted with hydrogen, an alkyl or aryl group. The method may further comprise contacting the halogenated phenol and the silyl halide with a tertiary amine to consume any acid by-products, thereby forming a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group.The method may further include contacting the initially formed 2,6-halogenated 1-silyl ether substituted benzene with an alkyl lithium compound to form a phenol having a silyl at the 2- or 6-position, and then contacting the phenol having a silyl at the 2- or 6-position with dimethylformamide to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, with the 4-position optionally being substituted with hydrogen, an alkyl, or an aryl group.

[0017] The present disclosure relates to phosphasalen, phosphasulf, phosphasalci ligands, 6,6'-di(3,5-disubstituted-2-hydroxybenzene)-2,2'-bipyridine ("Pb-2-hydroxyphenyl)-2,2'-bipyridine), and / or phosphasulfonyl esters having catalytic activity toward one or more of ethylene oxide, β-propiolactone, and / or succinic anhydride. R dhbpy(H) 2 " [wherein R is hydrogen, alkyl, or aryl at each occurrence]) or 6,6'-di(3,5-disubstituted-2-hydroxybenzene)-2,2'-phenanthroline (" R dhphen(H) 2 " [wherein R is hydrogen, alkyl, or aryl at each occurrence]) ligand and / or silyl substituted salen, sulfh, or salsi ligand. The present disclosure provides carbonylation catalysts comprising phosphasalen, phosphasulf, phosphasalsi ligands, which have improved steric and electronic quality, improved reaction yields, reduced reaction times, reduced by-products, extended catalyst life, increased catalyst stability, and are more easily recoverable after the carbonylation reaction. R dhbpy(H) 2 or R dhphen(H) 2 Carbonylation catalysts are provided that include ligands and / or silyl substituted salen, sulfh or salsi ligands. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 shows a synthetic scheme for forming a carbonylation catalyst having a Lewis acid containing silyl substituted salen, sulf or salsi ligand. [Diagram 2]FIG. 1 shows a synthetic scheme for forming carbonylation catalysts having Lewis acid containing phosphasalen, phosphasulf, and phosphasalci ligands. [Diagram 3] FIG. 1 shows a synthetic scheme for forming a carbonylation catalyst having a Lewis acid containing Rdhbpy(H)2 or Rdhphen(H)2 ligand. [Figure 4] FIG. 1 shows the 1H NMR spectrum of an isolated carbonylation catalyst with a Lewis acid containing Rdhbpy(H)2 ligand. [Diagram 5] FIG. 1 shows ReactIR spectra demonstrating in situ monitoring of β-propiolactone (bPL) formation from carbonylation catalysts with Lewis acids containing pyridine or phenanthroline ligands. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Although the present disclosure has been described in connection with several embodiments, it should be understood that it should not be limited to the disclosed embodiments, but rather is intended to include various modifications and equivalent arrangements included within the scope of the appended claims, which scope should be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as permitted under law.

[0020] As used herein, one or more means that at least one or more than one of the listed components may be used as disclosed. Residue, in reference to materials or reactants used to prepare the polymers or structures disclosed herein, means that portion of the material remaining in the polymer or structure after inclusion as a result of the methods disclosed herein. Substantially all, as used herein, means that more than 90% of the referenced parameters, compositions, structures or compounds meet the defined criteria, more than 95%, more than 99% of the referenced parameters, compositions or compounds meet the defined criteria, or more than 99.5% of the referenced parameters, compositions or compounds meet the defined criteria. Portion, as used herein, means less than the total amount of a component in a composition, stream or both. Precipitate, as used herein, means a solid compound in a slurry or blend of liquid and solid compounds. Phase, as used herein, means a solid precipitate or a distinct homogenous state of liquid or gas in a system with no visible boundaries separating the phases. Parts by weight, as used herein, means the number of parts of a component relative to the total weight of the entire composition. Catalyst components as used herein refer to metal-centered compounds, metal carbonyls, Lewis acids, Lewis acid derivatives, metal carbonyl derivatives, or any combination thereof. Catalysts as used herein include at least cationic and anionic compounds. Organic compounds as used herein include any compound that does not contain a metal atom. Inorganic compounds as used herein include compounds that contain at least one metal atom. Compositions as used herein include all components in a stream, reactant stream, product stream, slurry, precipitate, liquid, solid, gas, or any combination thereof that may be contained within a single vessel.

[0021] Disclosed herein are compounds and methods useful as carbonylation catalysts that improve reaction with epoxides, avoid reaction with lactones, and improve steric properties such that polymer binding to the metal center is weakened, thereby promoting faster ring closure and improving the stability of the carbonylation catalyst by being less susceptible to hydrolysis, which provides the advantages of reduced by-products, improved recovery of the carbonylation catalyst after use to make lactones, and improved steric and electronic properties such that release time of the lactone product is minimized, thereby reducing side reactions.

[0022] The carbonylation catalyst may be a phosphasalen, phosphasulf or phosphasalci ligand, R dhbpy(H) 2 or R dhphen(H) 2 The ligands may include Lewis acids, including silyl substituted salen, sulfh, or salsi ligands, and may function to catalyze the carbonylation reaction of an epoxide with carbon monoxide to form one or more lactones described herein. The carbonylation catalysts described herein may also be used to react an aziridine with carbon monoxide to form a lactam.

[0023] The phosphasalen, phosphasulf, or phosphasarci ligand can have the structure of compounds 1, 2, and / or 3 below:

[0024] [ka] (In structure, R 1 may be independently at each occurrence a hydrogen, an alkyl, or an aryl group; R 2 may be independently an alkyl, aryl, or alkoxide group at each occurrence.

[0025] After the metallation step described below, a Lewis acid precursor containing a phosphasalen, phosphasulf, or phosphasalci ligand is formed, which can have the structure of compounds 4, 5, and / or 6 below:

[0026] [ka] (In structure, R 1 and R 2 are described for compounds 1, 2 and 3, R 4 may be, separately at each occurrence, an alkyl group or a halogen; M can be a Lewis acid metal for each occurrence separately).

[0027] To form the carbonylation catalyst, a Lewis acid precursor containing a phosphasalen, phosphasulf, or phosphasalci ligand is reacted with a metal carbonyl additive as described below. The final carbonylation catalyst with a Lewis acid precursor containing a phosphasalen, phosphasulf, or phosphasalci ligand can have the structure of compounds 7, 8, and / or 9 below:

[0028] [ka] (In structure, R 1 , R 2 and M are as described for compounds 1 to 6; PL can be the residue of a polar ligand such as diethyl ether, dioxane or tetrahydrofuran).

[0029] R dhbpy(H) 2 or R dhphen(H) 2 The ligand can have the structure of compounds 10 and / or 11 below:

[0030] [ka] (In the structures, R is separately for each occurrence a hydrogen, an alkyl, or an aryl group).

[0031] After the metallation step described below: R dhbpy(H) 2 or R dhphen(H) 2 A Lewis acid precursor is formed that includes a ligand, and the Lewis acid precursor can have the structure of compounds 12 and / or 13 below:

[0032] [ka] (In the structure, R, M and R 4 are described for compounds 1-11).

[0033] To form the carbonylation catalyst, R dhbpy(H) 2 or R dhphen(H) 2 The Lewis acid precursor containing the ligand reacts with the metal carbonyl additive as described below. R dhbpy(H) 2 or R dhphen(H) 2 The final carbonylation catalyst with Lewis acid precursor containing ligand can have the structure of compounds 14 and / or 15 below:

[0034] [ka] (In the structures, R, M and PL are as described for compounds 1 to 13).

[0035] The silyl substituted salen, sulf or salsi ligand can have the structure of compounds 16, 17 and / or 18 below:

[0036] [ka] (In the structure, R is as described in Compounds 1 to 15. R 3 may be independently an alkyl or aryl group at each occurrence.

[0037] After the metallation step described below, a Lewis acid precursor containing a silyl substituted salen, sulf or salsi ligand is formed, which can have the structure of compounds 19, 20 and / or 21 below:

[0038] [ka] (In structure, R, R 3 , R 4 and M are as described for compounds 1-18).

[0039] To form the carbonylation catalyst, a Lewis acid precursor containing a silyl-substituted salen, sulfur or salsi ligand is reacted with a metal carbonyl additive as described below. The final carbonylation catalyst with a Lewis acid precursor containing a silyl-substituted salen, sulfur or salsi ligand can have the structure of compounds 22, 23 and / or 24 below:

[0040] [ka] (In structure, R, R 3 , M and PL are as described for compounds 1 to 21).

[0041] The carbonylation reaction can include contacting one or more epoxides, lactones, or both with carbon monoxide in the presence of a catalyst. This can be carried out in a reactor having one or more inlets, two or more inlets, three or more inlets, or multiple inlets. The one or more epoxides, lactones, carbon monoxide, and catalyst can be added to a single inlet, multiple inlets, or each can be added to a separate inlet as a separate or combined feed stream. The carbonylation reaction can produce one or more product streams or compositions.

[0042] The epoxide used in the carbonylation reaction can be any cyclic alkoxide containing at least two carbon atoms and one oxygen atom. For example, the epoxide can have a structure represented by formula (I): Formula (I):

[0043] [ka] (wherein, in the context of formula (I), R 1 and R 2 is hydrogen; C 1 ~C 15 R is independently selected from the group consisting of an alkyl group; a halogenated alkyl chain; a phenyl group; an optionally substituted aliphatic or aromatic alkyl group; an optionally substituted phenyl; an optionally substituted heteroaliphatic alkyl group; an optionally substituted 3- to 6-membered carbocyclic ring; and an optionally substituted 3- to 6-membered heterocyclic ring; 1 and R 2 can optionally be taken together with intervening atoms to form a 3-10 membered substituted or unsubstituted ring optionally containing one or more heteroatoms, or any combination thereof).

[0044] The lactone formed by 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 acetolactone, propiolactone, butyrolactone, valerolactone, caprolactone, or a combination thereof. Wherever propiolactone or lactone is used or described in this application, another lactone may be applicable or usable in the process, step, or method. When propiolactone is used or produced in the carbonylation reaction, the propiolactone may have a structure corresponding to formula (II): Formula (II):

[0045] [ka] (wherein, in the context of formula (II), R 1 and R 2 is hydrogen; C 1 ~C 15 R is independently selected from the group consisting of an alkyl group; a halogenated alkyl chain; a phenyl group; an optionally substituted aliphatic or aromatic alkyl group; an optionally substituted phenyl; an optionally substituted heteroaliphatic alkyl group; an optionally substituted 3- to 6-membered carbocyclic ring; and an optionally substituted 3- to 6-membered heterocyclic ring; 1 and R 2 can optionally be taken together with intervening atoms to form a 3-10 membered substituted or unsubstituted ring optionally containing one or more heteroatoms, or any combination thereof).

[0046] The product stream or composition may include one or more organic compounds including propiolactone, polypropiolactone, succinic anhydride, polyethylene glycol, poly-3-hydroxypropionate, 3-hydroxypropionic acid, 3-hydroxypropionaldehyde, polyester, polyethylene, polyether, unreacted epoxide, any derivative thereof, any other monomer or polymer derived from the reaction of an epoxide with carbon monoxide, or any combination thereof. The product stream or composition may include one or more inorganic compounds including a catalytic component such as a metal carbonyl, a metal carbonyl derivative, a metal-centered compound, a Lewis acid, a Lewis acid derivative, or any combination thereof. A metal carbonyl derivative is a compound that includes one or more metals and one or more carbonyl groups that can be treated to form an anionic metal carbonyl component for use in carbonylation catalysis. A Lewis acid derivative is a compound that includes one or more metal-centered Lewis acids that are bonded at the metal center to one or more undesirable compounds that can be treated to a cationic Lewis acid for use in carbonylation catalysis. The product stream or composition may include catalyst that was not consumed or used up in the process of forming propiolactone. The product stream or composition may include one or more unreacted epoxides or carbon monoxide.

[0047] To prepare the carbonylation catalyst described herein, the phenol may be halogenated in a halogenation step to form the Lewis acid basis of the carbonylation catalyst. The phenol, polar solvent and halogenating agent may be contacted under conditions such that a halogen atom is added to the 4- and / or 6-position carbon atom to form a halogenated phenol. The phenol and halogenating agent may be added in a molar ratio of about 1:1 or greater, about 2:3 or greater, or about 1:2 or greater. The phenol may be substituted at the 2- and / or 4-position with hydrogen, alkyl or aryl groups. The halogenation step may be carried out in a polar solvent that is aprotic or protic depending on the halogenating agent and the substituents on the phenol. The halogenation step may be carried out at room temperature and in ambient air. After mixing the phenol and halogenating agent, the halogenation reaction may be stirred by known means, such as using a magnetic stir bar. The halogenation reaction may be stirred for about 1 hour or greater, about 1.5 hours or greater, or about 2 hours or greater. The halogenation reaction may be stirred for about 3.5 hours or less, about 3 hours or less, or about 2.5 hours or less. The reaction may be quenched, for example, by the addition of sodium bicarbonate, which separates the aqueous and organic layers. The halogenated phenol may be isolated using any technique described herein or any known technique. For example, the halogenated phenol may be isolated using a simple organic / aqueous extraction, removing the aqueous layer, and the organic layer may be separated using MgSO 4 Or Na 2 SO 4 and stirring with basic alumina and then filtering through a combination of silica gel and diatomaceous earth.

[0048] After producing and isolating the halogenated phenol, the halogenated phenol can be further modified with a silyl group in a silylation step. The halogenated phenol can be contacted with a polar aprotic solvent and a silyl halide under conditions such that the hydroxyl group at the 1-position of the halogenated phenol is converted to a silyl ether group to form a 2,6-halogenated 1-silyl ether substituted benzene. The halogenated phenol and the silyl halide can be added in a molar ratio of about 1:1. This silylation step can be carried out in the presence of a catalyst that functions to promote the conversion of the hydroxyl group to a silyl ether group. This silylation step can be carried out in the presence of a scavenger that can consume any acid formed during the conversion of the hydroxyl to the silyl ether. The scavenger can include one or more of a tertiary amine. The scavenger can include one or more of a triethylamine. The scavenger and the halogenated phenol can be added in a molar ratio of about 1:1, about 1.1:1, or about 1.2:1. Prior to the addition of the silyl halide, the aprotic solvent and halogenated phenol may be cooled to about -10°C or higher, about -5°C or higher, or about 0°C or higher. The aprotic solvent and halogenated phenol may be cooled to about 15°C or lower, about 10°C or lower, or about 5°C or lower. After the addition of the silyl halide, the silylation step may then be allowed to warm to room temperature and stirred. After the addition of the materials, the silylation step may be allowed to stir at room temperature for about 3 hours or less, about 2.5 hours or less, or about 2.0 hours or less. The silylation step may be allowed to stir at room temperature for about 0.5 hours or more, about 1.0 hours or more, or about 1.5 hours or more. After stirring, the 2,6-halogenated 1-silyl ether substituted benzene may be isolated using any means known or described herein. For example, the solvent may be removed by vacuum filtration, the remaining product stream may be dissolved in a non-polar solvent, the product stream may be filtered through a filter bed such as diatomaceous earth, and the non-polar solvent may be removed by vacuum filtration.

[0049] After producing and isolating the halogenated phenol, the halogenated phenol may be subjected to a elimination step to replace the halogen atom on the phenol with a di(aryl or alkyl) phosphate. The halogenated phenol may be contacted with an alkyllithium compound and a halo-di(aryl or alkyl) phosphine in a polar aprotic solvent to form a dialkyl or diaryl phosphate substituted phenol. The halogenated phenol and the halo-di(aryl or alkyl) phosphine may be added in a molar ratio of about 1:1 or greater. The alkyllithium may be added in an amount sufficient to replace the halogen atom on the phenol. Initially, the halogenated phenol may be dissolved in a polar aprotic solvent and cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less. The polar aprotic solvent and the halogenated phenol may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more. After cooling, the halogenated phenol may be contacted with an alkyllithium compound in a polar aprotic solvent to form an intermediate composition. The intermediate composition may be allowed to warm to about room temperature (i.e., about 25° C.) and stirred for about 0.5 hours or more, about 0.75 hours or more, or about 1.0 hours or more. The intermediate composition may be stirred for about 2.25 hours or less, about 1.75 hours or less, or about 1.25 hours or less.

[0050] After stirring, the intermediate composition comprising the halogenated phenol, alkyl lithium compound, or residue thereof in the polar aprotic solvent may be cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less, prior to the addition of the halo-di(aryl or alkyl)phosphine. The intermediate composition may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more. After cooling, the intermediate composition comprising the halogenated phenol, alkyl lithium compound, or residue thereof in the polar aprotic solvent may be contacted with a halo-di(aryl or alkyl)phosphine to form a dialkyl or diaryl phosphate substituted phenol in the product composition, without isolating any of the compounds in the intermediate composition. After contacting with the halo-di(aryl or alkyl)phosphine, the product composition may be warmed to about room temperature (i.e., about 25° C.) and stirred for about 0.5 hours or more, about 1.0 hours or more, or about 1.5 hours or more. The product composition may be stirred for about 3.0 hours or less, about 2.5 hours or less, or about 2.0 hours or less. The product composition can be washed with a buffer and the organic phase can be removed by any means described herein or known to those skilled in the art, such as organic / aqueous extraction. The buffer can be potassium phosphate. Thus, the dialkyl or diaryl phosphate substituted phenol can be removed or isolated from the product stream by any other known isolation or extraction means. The desorption step can be carried out under an inert gas, such as nitrogen, and / or in a dry box or Schlenk line.

[0051] After producing and isolating the halogenated phenol, the halogenated phenol may be subjected to a elimination step to replace the halogen atom on the phenol with a boron dihydroxide group. In this step, the halogenated phenol may be contacted with an alkyllithium compound and a trialkylborate in a polar aprotic solvent to form a phenol containing a boron dihydroxide group at the 6-position. The halogenated phenol, alkyllithium, and trialkylborate may be added in a molar ratio of about 1:2:1 or greater. Initially, the halogenated phenol may be dissolved in a polar aprotic solvent and cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less. The polar aprotic solvent and the halogenated phenol may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more. After cooling, the halogenated phenol may be contacted with an alkyllithium compound in a polar aprotic solvent to form an intermediate composition. The intermediate composition may be warmed to about room temperature (i.e., about 25° C.) and stirred for about 0.5 hours or more, about 0.75 hours or more, or about 1.0 hours or more. The intermediate composition may be stirred for about 2.25 hours or less, about 1.75 hours or less, or about 1.25 hours or less. After stirring, the intermediate composition may be recooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less, prior to the addition of the trialkyl borate. The polar aprotic solvent and halogenated phenol may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more.

[0052] After cooling, the intermediate composition comprising the halogenated phenol, alkyl lithium compound or residue thereof in the polar aprotic solvent may be contacted with a trialkyl borate to form a phenol comprising a borate ester at the 6-position in the product composition. After contacting with the trialkyl borate, the product composition may be warmed to room temperature and stirred for about 30 hours or less, about 24 hours or less, or about 18 hours or less. The product composition may be stirred for about 6 hours or more, about 12 hours or more, or about 18 hours or more. An acid may then be contacted with the product stream comprising the phenol comprising a borate ester at the 6-position in the aprotic solvent to catalyze the hydrolysis and form a phenol comprising a boron dihydroxide group at the 6-position. The acid may include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, boric acid, perchloric acid, or any combination thereof. The acid may have a molar concentration of about 1.6 or more, about 1.8 or more, or about 2.0 or more. The acid may have a molar concentration of about 2.4 or less, about 2.2 or less, or about 2.0 or less. After hydrolysis, the phenol containing a boron dihydroxide group at the 6-position can be isolated using any known technique or those described herein, such as aqueous / organic extraction. The elimination step can be carried out under an inert gas, such as nitrogen, and / or in a dry box or Schlenk line.

[0053] After producing the 2,6-halogenated 1-silyl ether substituted benzene, the 2,6-halogenated 1-silyl ether substituted benzene may be subjected to an elimination step to rearrange the silyl group, with the 2-position exchanging one halogen with an aldehyde and the 6-position exchanging with the other halogen. In this step, the 2,6-halogenated 1-silyl ether substituted benzene may be contacted with an alkyllithium compound and dimethylformamide in a polar aprotic solvent to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions. The halogenated phenol, alkyllithium, and dimethylformamide may be added in a molar ratio of about 1:4:4. First, the 2,6-halogenated 1-silyl ether substituted benzene may be dissolved in a polar aprotic solvent and cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less. The polar aprotic solvent and the 2,6-halogenated 1-silyl ether substituted benzene may be cooled to about 65° C. or greater, about 70° C. or greater, or about 75° C. or greater. After cooling, the 2,6-halogenated 1-silyl ether substituted benzene may be contacted with an alkyllithium compound in the polar aprotic solvent to form an intermediate composition, which may be warmed to 0° C. and stirred for about 0.5 hours or greater, about 1.0 hours or greater, or about 1.5 hours or greater. In other examples, the intermediate composition may be warmed to room temperature. The intermediate composition may be stirred for about 3.0 hours or less, about 2.5 hours or less, or about 2.0 hours or less.

[0054] After stirring, the intermediate composition may be cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less, without an isolation step. The intermediate composition may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more. After cooling, the intermediate composition comprising 2,6-halogenated 1-silyl ether substituted benzene, alkyl lithium compound and / or residues thereof in a polar aprotic solvent may be contacted with dimethylformamide to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions in the product composition. In addition to dimethylformamide, a quenching agent diluted in a polar aprotic solvent may be added to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions. The quenching agent may be NH 4Cl(aq). After cooling, the product composition may be warmed to about 0° C. and stirred for about 0.5 hours or more, about 0.75 hours or more, or about 1.0 hours or more after addition of dimethylformamide. The product composition may be stirred for about 2.25 hours or less, about 1.75 hours or less, or about 1.25 hours or less. After formation of the phenol having silyl and acetaldehyde groups at the 2- and 6-positions, the phenol having silyl and acetaldehyde groups at the 2- and 6-positions may be purified or isolated using any known technique such as aqueous / organic extraction or any technique described herein. All desorption steps may be performed under an inert gas such as nitrogen and / or in a dry box or Schlenk line.

[0055] After isolating the dialkyl or diaryl phosphate substituted phenol, the dialkyl or diaryl phosphate substituted phenol can be subjected to an addition step to form a phosphasalen, phosphasulf or phosphasalci ligand. For example, the phosphasalen, phosphasulf or phosphasalci ligand can have the structure of compounds 1, 2 and / or 3 above.

[0056] In this step, the dialkyl or diaryl phosphate substituted phenol may be contacted with bromine and a diamine in the presence of a polar aprotic solvent and a trialkylamine to form a phosphasalen, phosphasulf, or phosphasalci ligand. The dialkyl or diaryl phosphate substituted phenol, bromine, and diamine may be added in a molar ratio of about 2:2:1 or greater. First, under a nitrogen flow (i.e., a glove box or a Schlenk line), the dialkyl or diaryl phosphate substituted phenol may be dissolved in an aprotic solvent and cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less. The polar aprotic solvent and the dialkyl or diaryl phosphate substituted phenol may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more. After cooling, the dialkyl or diaryl phosphate substituted phenol may be contacted with bromine in a polar aprotic solvent to form an intermediate composition, which may be warmed to room temperature (i.e., about 25° C.) and stirred for about 0.25 hours or more, about 0.50 hours or more, or about 0.75 hours or more. The intermediate composition may be stirred for about 2.0 hours or less, about 1.50 hours or less, or about 1.25 hours or less. After stirring, the intermediate composition may be cooled to about 90° C. or less, about 85° C. or less, or about 80° C. or less. The intermediate composition may be cooled to about 65° C. or more, about 70° C. or more, or about 75° C. or more.

[0057] After cooling, the intermediate composition comprising bromine, dialkyl or diaryl phosphate substituted phenol and / or their residues in a polar aprotic solvent can be contacted with a diamine in the presence of a trialkylamine to form a phosphasalen, phosphasulf or phosphasalci ligand in the product composition. After contacting, the product composition can be warmed to room temperature (i.e., about 25°C) and stirred overnight. For example, the product composition can be stirred for about 12 hours or more, about 18 hours or more, or about 23 hours or more. The product composition can be stirred for about 36 hours or less, about 30 hours or less, or about 25 hours or less. After stirring, any by-products, such as ammonium bromide, can be precipitated from the composition using any known filtration technique, such as gravity filtration. The phosphasalen, phosphasulf or phosphasalci ligand can be isolated from the product composition by any known technique or any technique described herein. For example, the phosphasalen, phosphasulf, or phosphasarci ligand can be isolated from the product composition by removing the solvent by rotary evaporation and subjecting the phosphasalen, phosphasulf, or phosphasarci to an additional precipitation step and an additional purification step in column chromatography. All additional steps can be performed under an inert gas, such as nitrogen, and / or in a dry box or Schlenk line.

[0058] After isolating the phenol containing a boron dihydroxide group at the 6-position, the phenol containing a boron dihydroxide group at the 6-position is subjected to a Suzuki reaction step to give R dhbpy(H) 2 or R dhphen(H) 2 For example, R dhbpy(H) 2 or R dhphen(H) 2 The ligand can have the structure of compounds 10 and / or 11.

[0059] In this Suzuki reaction step, a phenol containing a boron dihydroxide group at the 6-position can be contacted with a dibromobipyridine or dibromophenanthroline containing one or more halogens adjacent to the nitrogen atom in the presence of one or more polar solvents, an alkali metal carbonate, and a palladium catalyst to form ligands of compounds 10 and / or 11 in the product composition. The one or more polar solvents can be a combination of solvents that dissolve one or more compounds in the reaction. The one or more polar solvents can be protic, aprotic, or a combination of protic and aprotic solvents. The phenol containing a boron dihydroxide group at the 6-position and the dibromobipyridine or dibromophenanthroline containing one or more halogens adjacent to the nitrogen atom can be added in a molar ratio of about 2:1 or greater. Additionally, bromic acid can be added to the combination of the phenol containing a boron dihydroxide group at the 6-position and the dibromobipyridine or dibromophenanthroline in a molar ratio of about 2:2:1 or greater. The palladium catalyst may be added as a solution of about 2 mole percent or more, about 3 mole percent or more, or about 4 mole percent or more. The palladium catalyst may be added as a solution of about 8 mole percent or less, about 7 mole percent or less, or about 6 mole percent or less. The alkali metal carbonate may be added as a solution of about 1.6M or more, about 1.8M or more, or about 2.0M or more. The alkali metal carbonate may be added as a solution of 2.6 or less, about 2.4 or less, or about 2.2 or less. After contacting the materials, the Suzuki reaction step may be carried out at reflux for about 72 hours or less, about 96 hours or less, or about 120 hours or less. The Suzuki reaction step may be carried out at reflux for about 24 hours or more, about 48 hours or more, or about 70 hours or more. After refluxing, the ligands of compounds 10 and / or 11 are removed from the product composition using any known extraction technique described herein or known to one of skill in the art. For example, the ligand of compounds 10 and / or 11 can be removed by adding a solvent that dissolves the ligand, such as a polar aprotic solvent, adding brine (i.e., an aqueous solution), extracting the brine, and evaporating the polar aprotic solvent to leave behind dry ligand. The Suzuki reaction step can be carried out under an inert gas, such as nitrogen, and in a dry box and / or Schlenk line.

[0060] After isolating the phenol having silyl and acetaldehyde groups at the 2- and 6-positions, the phenol having silyl and acetaldehyde groups at the 2- and 6-positions may be subjected to a condensation step to form a silyl-substituted salen, sulfur or salicylic ligand. For example, the silyl-substituted salen, sulfur or salicylic ligand may have the structure of compounds 16, 17 and / or 18. In this step, the phenol having silyl and acetaldehyde groups at the 2- and 6-positions may be contacted with a diamine in the presence of a Lewis acid or Bronsted acid and an alkali metal or ammonium salt in a polar solvent that is forced to form a silyl-substituted salen, sulfur or salicylic ligand in the product composition. In other examples, the reaction may not include a Lewis acid or Bronsted acid so that the diamine and the phenol having silyl and acetaldehyde groups at the 2- and 6-positions may be contacted in a polar solvent. These steps may be completed in ambient air, at room temperature (e.g., about 25°C), or at reflux of the polar solvent. The phenol and diamine having silyl and acetaldehyde groups at the 2- and 6-positions may be added in a molar ratio of about 1:2 or greater. A Lewis acid or Bronsted acid may be added in an amount sufficient to catalyze the condensation reaction. The silyl-substituted salen, sulfh, or salsi ligand may be isolated from the product composition by any known technique or any technique described herein. For example, the silyl-substituted salen, sulfh, or salsi ligand may be recovered as a precipitate by gravity filtration after the product composition has cooled.

[0061] phosphasalen, phosphasulf or phosphasalci ligands, R dhbpy(H) 2 or R dhphen(H) 2After forming the ligand or silyl substituted salen, sulfur or salicylic ligand, the ligand may be subjected to a metallation step to form a Lewis acid containing a halogen or alkyl group. The Lewis acid containing a halogen or alkyl group may have the structure of compounds 4, 5, 6, 12, 13, 19, 20 and / or 21 above. The halogen or alkyl group of the Lewis acid may be bonded to the metal center of the Lewis acid. In the metallation step, the metal alkyl compound is reacted with the phosphasalen, phosphasulf or phosphasalcilic ligand, R dhbpy(H) 2 or R dhphen(H) 2 The metal alkyl compound and the phosphasalen, phosphasulf or phosphasalci ligand, R dhbpy(H) 2 or R dhphen(H) 2The ligand or silyl-substituted salen, sulf or salsi ligand may be added in about a 1:1 molar ratio. The metalation step may be stirred for any time sufficient to form a Lewis acid containing a halogen or alkyl group. For example, the metalation step may be stirred for about 36 hours or less, about 30 hours or less, or about 24 hours or less. The metalation step may be stirred for about 12 hours or more, about 18 hours or more, or about 22 hours or more. The metalation step may be carried out under an inert gas, such as nitrogen, and in a dry box and / or a Schlenk line. The metalation step may be carried out in the open air or in an oxygen- and water-free inert atmosphere, such as a dry box or a Schlenk line. The metalation step may be similar to the metalation step described in U.S. Pat. No. 8,633,123, which is incorporated herein by reference in its entirety. After the metalation step is complete, the Lewis acid containing a halogen or alkyl group may be isolated using any known technique, such as recovery of the Lewis acid containing a halogen or alkyl group by gravity filtration. The step for forming a Lewis acid containing a halogen or alkyl group can be carried out in a dry box or Schlenk line under moisture and oxygen free conditions, for example under an inert gas such as nitrogen.

[0062] After forming and isolating one of the above halogen or alkyl group containing Lewis acids, the halogen or alkyl group containing Lewis acid may be subjected to a catalyst formation step to form a carbonylation catalyst. The carbonylation catalyst may have one of the above structures in compounds 7, 8, 9, 14, 15, 22, 23 and / or 24. The catalyst formation step may include contacting the halogen or alkyl group containing Lewis acid with a polar ligand, a metal carbonyl additive or both to form the carbonylation catalyst. The halogen or alkyl group containing Lewis acid may be added in a molar ratio of about 1:1. The metal carbonyl additive may include at least the metal carbonyl, which is anionic, and a cationic group configured to cleave and bond the alkyl group or halogen of the metal center compound. The cationic group may be an alkali metal, (R 4 ) 3 Si-[wherein, R4 are independently selected from phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.] may be one or more of any counterion or any combination thereof sufficient to ionically bind and / or maintain the ionic balance of the metal carbonyl. In examples where the metal carbonyl additive cleaves or decouples the alkyl group, the alkyl group may be coupled with a cationic group, and the alkyl group and cationic group may be removed via any filtering or removal means described herein. In examples where the metal carbonyl additive cleaves the halogen from the metal center compound and is contacted with a polar compound, the halogen combines with the cationic group of the metal carbonyl additive, and a Lewis acid containing polar compound is formed. Any by-products may be removed by any other removal or separation step described herein. After the metal carbonyl additive cleaves or decouples the alkyl group, the Lewis acid may combine with a polar ligand to form a cationic species. The Lewis acid containing a polar ligand is then contacted with the anionic metal carbonyl of the metal carbonyl additive to form a regenerated carbonylation catalyst.

[0063] The steps for forming the carbonylation catalyst may be carried out under moisture- and oxygen-free conditions. For example, the catalyst formation step may be carried out under an inert atmosphere (i.e., nitrogen) in a dry glove box, a Schlenk line, or a reactor. The catalyst formation step may be carried out under nitrogen, argon, or any other inert gas. During the catalyst formation step, the Lewis acid, polar ligand, metal carbonyl, or any combination thereof may be contacted and stirred by stirring for a sufficient time to form the carbonylation catalyst. The time for stirring the ingredients may be about 5 minutes or more, about 30 minutes or more, about 60 minutes or more. The time for stirring the ingredients may be about 24 hours or less, about 12 hours or less, or about 6 hours or less. The ingredients in the catalyst formation step may be completed at ambient temperature and / or pressure. Additional steps for producing regenerated catalysts may be found in US 6,852,865 B2 and US 8,481,756 B1, each of which is incorporated herein by reference in their entirety.

[0064] The filtering, isolating or removing steps taught herein function to remove from the composition any undesirable components that may interfere with the formation of the carbonylation catalyst or any precursor of the carbonylation catalyst. For example, one or more of the solvent, polymer, unreacted acid compound, inorganic compound, organic compound or any combination thereof may be removed from the composition such that the carbonylation catalyst may be regenerated from the Lewis acid containing halogen or alkyl compound and have catalytic activity with respect to one or more of succinic anhydride, propiolactone or epoxide. The filtering, isolating or removing steps may include one or more of vacuum filtration, gravity filtration, centrifugation, decantation, precipitation, phase layer extraction or any combination thereof. The filtering, isolating or removing steps may utilize any method sufficient to separate one or more of the solvent, polymer, unreacted acid compound, inorganic compound, organic compound or any combination thereof and the Lewis acid containing halogen or alkyl group, ligand or any combination thereof. The filtering, isolating or removing step 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 components dissolved in a solvent. The filtering or removing 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 or removal steps / methods 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 ligands, Lewis acids including halogens or alkyl groups, or any combination thereof.

[0065] The carbonylation catalysts described herein function to catalyze the reaction of an epoxide with carbon monoxide to produce one or more propiolactone and other products. The carbonylation catalyst comprises at least a metal carbonyl, which is anionic, and a Lewis acid, which is cationic.

[0066] 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, or a mixture of metal carbonyls. The metal carbonyl may be capable of ring opening an epoxide and facilitating the insertion of CO into the resulting metal carbon bond. In some embodiments, the metal carbonyl may comprise an anionic metal carbonyl moiety. In other embodiments, the metal carbonyl compound may comprise a neutral metal carbonyl compound. The metal carbonyl may comprise a metal carbonyl hydride or a hydride metal carbonyl compound. The metal carbonyl may be a pre-catalyst that reacts in situ with one or more reaction components to provide an active species different from the initially provided compound. The metal carbonyl comprises an anionic metal carbonyl species. In some embodiments, the metal carbonyl may be a metal carbonyl having the general formula [Q d M' e (CO) w ] y+ where Q is an optional ligand, 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, for example, and y is the charge of the anionic metal carbonyl species. The metal carbonyl can include a monoanionic carbonyl complex of a metal in Groups 5, 7, or 9 of the Periodic Table, or a dianionic carbonyl complex of a metal in Groups 4 or 8 of the Periodic Table. The metal carbonyl can include cobalt, manganese, ruthenium, or rhodium. Exemplary metal carbonyls include [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- , [Cr 2 (CO) 10 ] 2-, [Fe 2 (CO) 8 ] 2- , [Tc(CO) 5 ] - , [Re(CO) 5 ] - and [Mn(CO) 5 ] - The metal carbonyl may be a mixture of two or more anionic metal carbonyl complexes in the carbonylation catalyst used in the process.

[0067] The halogenating agent can function to couple a halogen atom to the phenol. The halogenating agent can be any compound that contains one or more halogens that can be coupled to the phenol. Halogenating agents include N-bromosuccinimide, bromine (i.e., Br 2 ), dibromoisocyanuric acid, or any combination thereof.

[0068] The alkyllithium compound may function to replace the halogen group on the phenol with another compound. The alkyllithium compound may be n-butyllithium, t-butyllithium, or any combination thereof. When n-butyllithium is used, an additive to activate n-butyllithium may be used, such as tetramethylethylenediamine, hexamethylphosphoramide, N,N'-dimethylpropyleneurea, or any combination thereof.

[0069] The halo-di(aryl or alkyl)phosphines may function to form disubstituted phosphine groups on phenolic compounds. The halo-di(aryl or alkyl)phosphines include one or more of chloro-di(aryl)phosphines, chloro-di(alkyl)phosphines, or both.

[0070] The silyl halide may function to form a silyl ether on a phenol group. The silyl halide may contain one or more of fluorine, chlorine, bromine and / or iodine. The silyl halide may be, for example, Si(R 3 )3 Structure of [R 3 is described above with respect to compounds 1-24.

[0071] The trialkylborate may function to form a compound suitable for Suzuki coupling reactions. The trialkylborate may be trimethyl borate or any combination thereof.

[0072] As used herein, a diamine may function to form a ligand by connecting two substituted phenol groups. The diamine may be any substituted compound that contains at least two amine groups separated by at least two carbon atoms. The diamine may be one or more of ethylenediamine, orthophenyleneamine, orthocyclohexyldiamine, or any combination thereof.

[0073] The trialkylamine may be a compound sufficient to consume the generated HBr in the form of an ammonium salt, such as tributylammonium bromide. The trialkylamine may be one or more of tributylamine, triethylamine, trimethylamine, or any combination thereof.

[0074] A Lewis or Bronsted acid catalyst may function to catalyze the condensation reaction. The Lewis or Bronsted acid catalyst may be one or more of formic acid, acetic acid, aluminum chloride, or any combination thereof.

[0075] The alkali metal carbonate can function to decompose boron dihydroxide. 2 CO 3 or any combination thereof. Instead of an alkali metal carbonate, an alkali metal alkoxide and / or an alkali metal hydroxide may be used to decompose boron dihydroxide.

[0076] Metal alkyl compounds may function to coordinate a metal to one or more ligands to form Lewis acids that contain halogen or alkyl groups. Metal alkyl compounds may be any compound that contains a metal and / or one or more alkyl and / or halogen groups. The metal of the metal alkyl compound may be one or more of aluminum, chromium, or any combination thereof. Metal alkyl compounds include CrCl 2 , (Et)2AlCl or (Et)3Al or any combination thereof.

[0077] The metal carbonyl additive functions to deliver the metal carbonyl to a suitable Lewis acid for combination to form a carbonylation catalyst. The metal carbonyl additive may function to dissociate a halogen or alkyl group from the Lewis acid to form a carbonylation catalyst comprising a combination of the Lewis acid and the metal carbonyl. The metal carbonyl additive comprises at least a metal carbonyl and a cationic compound as described herein. The cationic compound may include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof. The metal carbonyl additive may be a salt. The metal carbonyl additive may be a metal carbonyl additive comprising R 3 The metal carbonyl additive may be a silicon salt of the form Si-, where R is independently selected from phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof. The metal carbonyl additive may be NaCo(CO) 4 , Co 2 (CO) 8 , HCo(CO) 4 or any combination thereof. If a Lewis acid containing a halogen is formed after the metallation step, NaCo(CO) 4 can be used to form the carbonylation catalyst. When a Lewis acid containing an alkyl group is formed, Co 2 (CO) 8 or HCo(CO) 4 may be used to form the carbonylation catalyst.

[0078] In some Lewis acids, one or more polar ligands may coordinate to M or a combination thereof to satisfy the coordination valence of the metal atom. The polar ligand may be a solvent. The polar ligand may be any compound having at least two free valence electrons. The polar ligand may be aprotic. The compound may be tetrahydrofuran, dioxane, diethyl ether, acetonitrile, carbon disulfide, pyridine, epoxides, esters, lactones, or combinations thereof.

[0079] The solvent may be a polar aprotic solvent, a polar protic solvent, or a non-polar solvent that functions to dissolve one or more compounds described herein. One solvent may be soluble in one or more other solvents that enhance the solubility of one or more compounds described herein. A first solvent may be combined with a second solvent that is miscible with the first solvent to precipitate components that are insoluble in the second solvent. The solvent may be selected to form a distinct organic or aqueous phase layer, a separate aqueous phase layer, a precipitate, or some combination of any. The solvent may be one or more of water, methanol, ethanol, propanol, hexane, heptane, nonane, decane, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, sulfolane, toluene, pyridine, diethyl ether, 1,4-dioxane, acetonitrile, ethyl acetate, dimethoxyethane, acetone, chloroform, dichloromethane, or any combination thereof.

[0080] Several techniques have been theorized to illustrate the teachings of this disclosure. Each teaching is merely an example of the present disclosure and is not intended to limit the teachings to any single technique.

[0081] FIG. 1 is a synthetic scheme for forming a carbonylation catalyst having a Lewis acid containing silyl-substituted salen, sulfur or salicylic ligand. For one equivalent of the appropriate 4-substituted phenol, two equivalents of Br 2After isolating, a reaction vessel equipped with a stir bar is charged with the appropriate previously isolated 2,6-dibromophenol in an amount of 0.01 mol in 10 mL of THF solvent. The solution is cooled in an ice bath (0° C.) and a slight excess of triethylamine (0.012 mol) is added, followed by a slight excess of the appropriate trisubstituted chlorosilane. The mixture is stirred at room temperature for 2 hours, and then the solvent is removed by vacuum method. The residue is dissolved in hexane, filtered through diatomaceous earth, and the solvent is removed once more to obtain the desired product. In a reaction vessel equipped with a stir bar, the appropriate 2,6-dibromophenol silyl ether (0.0015 mol) in diethyl ether (3.0 mL) is cooled to −78° C. and treated with 4 equivalents of t-butyllithium (0.006 mol). The reaction is stirred at 0° C. for 1.5 hours. In the same reaction vessel, the reaction mixture is cooled to -78 °C, 0.006 mol of DMF is added, and stirred at 0 °C for 1 h. The reaction is then quenched with 5.0 mL of saturated NH 4 The mixture is quenched with Cl solution and diluted with 75 mL of diethyl ether. The organic and aqueous phases are separated and the organic phase is dried to obtain the desired product. The ligand synthesis is completed by reacting silyl salicylaldehyde with ortho-phenylenediamine in a ratio of 2.2 to 1. A quantity of 0.004 mol of salicylaldehyde is dissolved in 30 mL of ethanol (EtOH) and added to 0.00176 mol of ortho-phenylenediamine and refluxed overnight. Using standard methods of condensation reaction between aldehydes and diamines of salicylaldehyde precursors containing silyl groups, the temperature is subsequently reduced and the product is isolated by gravity filtration after precipitation of the ligand from EtOH. After the ligand is formed, 0.1 mol of the ligand (1.0 M) in 100 mL of toluene solvent is charged to a reaction vessel under an inert atmosphere. One equivalent of Et 2 AlCl is slowly added to the solution and left to stir at room temperature overnight. After precipitating from the solution, the product is collected by filtration. To form the carbonylation catalyst, a reaction vessel under an inert atmosphere is charged with 0.1 mol of the metalated ligand (1.0 M) in 100 mL of THF solvent. 1 equivalent of NaCo(CO) 4is slowly added to the solution and allowed to stir at room temperature overnight. The product is filtered to remove the NaCl by-product. The product is recovered by precipitating the catalyst from the THF solvent by addition of anti-solvent hexane, and the product is then recovered by filtration.

[0082] FIG. 2 is a synthetic scheme for forming a carbonylation catalyst with a Lewis acid containing phosphasalen, phosphasulf, or phosphasalci ligand. A reaction vessel is charged with the appropriate 2,4-disubstituted phenol (0.1 mol) in 300 mL of acetonitrile. The reaction is cooled to 0° C., 0.1 mol of N-bromosuccinimide is added, and the reaction is stirred overnight at room temperature. The reaction mixture is diluted with Na 2 SO 3 The mixture is washed with ethyl acetate and the phases are separated. The organic layer is then collected and the solvent is removed by rotary evaporation. After isolation, the appropriate 2-bromo-4,6-disubstituted phenol (0.014 mol) in 50 mL of diethyl ether is added to the reaction vessel under an inert atmosphere and the temperature is reduced to -78°C. A slight excess of 0.0295 mol of n-butyllithium is slowly added to the cooled solution. The reaction mixture is allowed to warm to room temperature for 1 h. The reaction mixture is then cooled to -78°C and 0.014 mol of the appropriate chlorophosphine (R 2 PCl) and stir at room temperature overnight. 2 PO 4 The layers are separated, the organic layer is dried, and the solvent is removed by rotary evaporation. In an inert atmosphere reaction vessel, 60 mL of the appropriate 2,4-disubstituted-6-(R 2Add 0.00512 mol of phosphanyl)phenol. Reduce the temperature to -78°C and slowly add liquid bromine (0.00512 mol) and then stir at room temperature for 2 hours. Reduce the temperature of the reaction mixture again to -78°C and slowly add 0.00256 mol of tributylamine and 0.00256 mol of ethylenediamine and stir at room temperature overnight. Filter the mixture and dry the filtrate under reduced pressure. Stir the oil in THF to obtain a white solid which is further purified by column chromatography. After the ligand is formed, 0.1 mol of the ligand (1.0M) in 100 mL of toluene solvent is charged to the reaction vessel under inert atmosphere. Add 1 equivalent of Et 2 AlCl is slowly added to the solution and left to stir at room temperature overnight. After precipitating from the solution, the product is collected by filtration. To form the carbonylation catalyst, a reaction vessel under an inert atmosphere is charged with 0.1 mol of the metalated ligand (1.0 M) in 100 mL of THF solvent. 1 equivalent of NaCo(CO) 4 is slowly added to the solution and allowed to stir at room temperature overnight. The product is filtered to remove the NaCl by-product. The product is recovered by precipitating the catalyst from the THF solvent by addition of anti-solvent hexane, and the product is then recovered by filtration.

[0083] Figure 3 shows R dhbpy(H) 2 or R dhphen(H) 2 A synthetic scheme for forming a carbonylation catalyst with a Lewis acid containing ligand. A reaction vessel under an inert atmosphere is charged with 0.10 mol of 2,4-disubstituted phenol (1.0 M reaction) in 100 mL of solvent. 1 equivalent (0.10 mol) of Br 2 is added at -78 °C and stirred at room temperature for 2 h. The reaction mixture is then diluted with 50 mL of saturated NaHCO 3 Quench with a solution of MgSO and separate the organic and aqueous layers. 4 Or Na 2 SO 4The organic phase, after drying at 30° C., is slurried with basic alumina and then filtered through a combination of silica gel and diatomaceous earth. After isolation, the reaction vessel under inert atmosphere is charged with 2-bromo-4,6-disubstituted phenol (0.0175 mol) in 200 mL of diethyl ether solvent (approximately 0.1 M). The temperature of the solution is reduced to −78° C. and a slight excess of n-butyl lithium (n-BuLi) (0.042 mol) is slowly added to the reaction vessel. After the addition, the reaction is stirred at room temperature for 2 hours. The temperature of the reaction mixture is then reduced again to −78° C. and 0.0282 mol of trimethyl borate is added. The reaction is allowed to reach room temperature and stirred for 18 hours. The temperature of the reaction is then reduced to 0° C. and quenched with 2M HCl solution. The organic and aqueous phases are separated and the product is recovered by evaporation of the solvent under reduced pressure. Next, a reaction vessel under an inert atmosphere was charged with 0.00637 mol of the dibromopyridine linker ligand (6,6'-dibromobipyridine or 2,9-dibromo-1,10-phenanthroline), 0.0127 mol of the previously synthesized 3,5-disubstituted-2-hydroxy-phenyl)boronic acid in 250 mL of toluene, 30 mL of MeOH, 60 mL of 2M Na 2 CO 3 and 5 mol% Pd(PPh 3 ) 4 The mixture is refluxed under inert atmosphere for 72 hours. After cooling, the organic and aqueous phases are separated and the organic solvent is removed under reduced pressure to obtain the desired ligand. After the ligand is formed, the reaction vessel under inert atmosphere is charged with 0.1 mol of the ligand (1.0 M) in 100 mL of toluene solvent. 1 equivalent of Et 2 AlCl is slowly added to the solution and left to stir at room temperature overnight. After precipitating from the solution, the product is collected by filtration. To form the carbonylation catalyst, a reaction vessel under an inert atmosphere is charged with 0.1 mol of the metalated ligand (1.0 M) in 100 mL of THF solvent. 1 equivalent of NaCo(CO) 4 is slowly added to the solution and allowed to stir at room temperature overnight. The product is filtered to remove the NaCl by-product. The product is recovered by precipitating the catalyst from the THF solvent by addition of anti-solvent hexane, and the product is then recovered by filtration.

[0084] Enumerated embodiments The following examples are included to illustrate the invention, but not to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0085] Embodiment 1. A compound according to one of the following formulas:

[0086] [ka] (In the formula, R is, separately for each occurrence, a hydrogen, an alkyl, or an aryl group; R 1 is separately for each occurrence a hydrogen, an aryl, or an alkyl group; R 2 is separately for each occurrence an alkyl, aryl, or alkoxide group; R 3 is separately for each occurrence an alkyl or aryl group; PL is a residue of a polar ligand; M is a Lewis acid metal separately for each occurrence.

[0087] Embodiment 2. R is, separately for each occurrence, an alkyl or aryl group; R 1 is separately for each occurrence an alkyl group; R 2 is separately for each occurrence an alkyl group; R 3 is separately for each occurrence an alkyl group; PL is a residue of tetrahydrofuran, diethyl ether, or a combination thereof; M is, separately for each occurrence, aluminum or chromium; The compound of embodiment 1.

[0088] Embodiment 3. A method for preparing a compound according to embodiment 1 or 2, comprising the steps of: The following formula

[0089] [ka] with a metallation agent to obtain a compound according to the formula

[0090] [ka] forming one of the compounds according to The compounds formed and the metal carbonyls are shown below.

[0091] [ka] contacting under conditions such that one of Including, During the ceremony, R is, separately for each occurrence, a hydrogen, an alkyl, or an aryl group; R 1 is separately for each occurrence a hydrogen, an aryl, or an alkyl group; R 2 is separately for each occurrence an alkyl, aryl, or alkoxide group; R 3 is separately for each occurrence an alkyl or aryl group; R 4 is separately for each occurrence an alkyl group or a halogen; PL is a residue of a polar ligand; M is, separately for each occurrence, a Lewis acid metal; method.

[0092] Embodiment 4. R is, separately for each occurrence, an alkyl or aryl group; R 1 is separately for each occurrence an alkyl group; R 2 is separately for each occurrence an alkyl group; R 3 is separately for each occurrence an alkyl group; R 4is separately for each occurrence an alkyl group or a halogen; PL is a residue of tetrahydrofuran, diethyl ether, or a combination thereof; M is, separately for each occurrence, aluminum or chromium; 4. The method of embodiment 3.

[0093] Embodiment 5. The following formula

[0094] [ka] one of the compounds according to one of contacting a phenol, which may be substituted at the 2- and / or 4-positions with hydrogen, alkyl, or aryl groups, with a halogenating agent under conditions such that a halogen atom is attached to the 6-carbon atom to form a halogenated phenol; contacting a halogenated phenol with a halo-di(aryl or alkyl)phosphine in the presence of an alkyllithium under conditions to replace the halogen on the phenol with the di(alkyl or aryl)phosphate to form a dialkyl or diaryl phosphate substituted phenol; and contacting a dialkyl or diaryl phosphate substituted phenol with a diamine, orthophenyleneamine or orthocyclohexyldiamine, in the presence of bromine and a trialkylamine to form a compound of the formula 5. The method of claim 3 or 4, comprising preparing the compound by

[0095] Embodiment 6. The following formula

[0096] [ka] one of the compounds according to one of contacting a phenol, which may be substituted at the 2- and / or 4-positions with hydrogen, alkyl, or aryl groups, with a halogenating agent under conditions such that a halogen atom is attached to the 6-carbon atom to form a halogenated phenol; contacting the formed halogenated phenol with a trialkylborate in the presence of an alkyllithium compound to replace the halogen atoms with boron dihydroxide groups; and contacting a phenol containing a boron dihydroxide group with a bipyridine or phenanthroline having a halogen group on the carbon adjacent to the nitrogen atom in the presence of a palladium catalyst and an alkali metal carbonate under conditions to form one of the compounds of the formula: 5. The method of claim 3 or 4, comprising preparing the compound by

[0097] Embodiment 7. The following formula

[0098] [ka] one of the compounds according to one of contacting a phenol, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, with a halogenating agent and a silyl halide under conditions such that halogen atoms are added to the 2- and 6-carbon atoms of the aromatic ring and the 1-hydroxyl group is converted to a silyl ether group, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group; contacting the formed 2,6-halogenated 1-silyl ether substituted benzene with an alkyllithium compound and dimethylformamide to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, the 4-position optionally being substituted with hydrogen, an alkyl or aryl group; and contacting a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, with one of o-phenylenediamine, ethylenediamine or cyclohexanediamine, optionally in the presence of a Lewis or Bronsted acid catalyst and an alkali metal or ammonium salt, to form one of the compounds corresponding to one of the formulas: 5. The method of claim 3 or 4, comprising preparing the compound by

[0099] Embodiment 8. The step of contacting a dialkyl or diaryl phosphate substituted phenol with a diamine, orthophenyleneamine or orthocyclohexyldiamine, in the presence of bromine and a trialkylamine to form a compound of the formula: contacting a dialkyl or diaryl phosphate substituted phenol with bromine to form an activated dialkyl or diaryl phosphate substituted phenol; and contacting an activated dialkyl or diaryl phosphate substituted phenol with an orthophenyleneamine or an orthocyclohexyldiamine in the presence of a trialkylamine to form a compound of the formula 6. The method of embodiment 5, comprising:

[0100] Embodiment 9. The method of embodiment 5 or 8, wherein the halo-di(aryl or alkyl)phosphine is one or more of chloro-di(aryl)phosphines, chloro-di(alkyl)phosphines, chloro-di(alkoxide)phosphines, or any combination.

[0101] Embodiment 10. The method of any one of embodiments 5 or 8-9, wherein the trialkylamine is configured to consume bromic acid to form an ammonium salt.

[0102] Embodiment 11. The method of any one of embodiments 5 or 8-10, wherein the trialkylamine comprises one or more tributylamines.

[0103] Embodiment 12. The step of contacting the formed halogenated phenol with a trialkylborate in the presence of an alkyllithium compound to replace the halogen atom with a boron dihydroxide group comprises: contacting the phenol containing the boron dihydroxide group with hydrochloric acid to quench the reaction. 7. The method of embodiment 6, comprising:

[0104] Embodiment 13. The method of embodiment 6 or 12, wherein the trialkyl borate comprises one or more of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, or any combination thereof.

[0105] Embodiment 14 The method of any one of embodiments 6, 12, or 13, wherein the alkali metal carbonate comprises sodium carbonate.

[0106] Embodiment 15. The step of contacting a phenol, optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, with a halogenating agent and a silyl halide under conditions such that halogen atoms are added to the 2- and 6-carbon atoms of the aromatic ring, the hydroxyl group at the 1-position is converted to a silyl ether group, and the 4-position is optionally substituted with hydrogen, an alkyl or aryl group, comprises: contacting the optionally substituted phenol with a halogenating agent to form a halogenated phenol; and contacting a halogenated phenol with a silyl halide under conditions such that the hydroxyl group at position 1 is converted to a silyl ether group, which may be optionally substituted at position 4 with hydrogen, an alkyl or aryl group; 8. The method of embodiment 7, comprising:

[0107] Embodiment 16. The step of contacting a halogenated phenol with a silyl halide under conditions such that the hydroxyl group at the 1-position is converted to a silyl ether group, the silyl ether group being optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, comprises: contacting the halogenated phenol and silyl halide with a tertiary amine to consume any acid by-products and result in the formation of a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, and optionally substituted at the 4-position with hydrogen, an alkyl, or an aryl group. 16. The method of embodiment 7 or 15, comprising:

[0108] Embodiment 17. The step of contacting the formed 2,6-halogenated 1-silyl ether substituted benzene with an alkyllithium compound to form a phenol having silyl and acetaldehyde groups at the 2- and 6-positions, and optionally substituted at the 4-position with hydrogen, an alkyl or aryl group, comprises: contacting the formed 2,6-halogenated 1-silyl ether substituted benzene with an alkyllithium compound to form a phenol having a silyl at the 2- or 6-position; and contacting a phenol having a silyl at the 2-position or the 6-position with dimethylformamide to form a phenol having silyl and acetaldehyde groups at the 2-position and the 6-position, the 4-position being optionally substituted with hydrogen, an alkyl or an aryl group. 17. The method according to any one of embodiments 7 or 15-16, comprising:

[0109] Embodiment 18. The method of any one of embodiments 7 or 15-17, wherein the silyl halide is tri-substituted with one or more aryl groups, alkyl groups, or both.

[0110] Embodiment 19. The method of any one of embodiments 7 or 15-19, wherein the silyl halide comprises one or more of fluorine, chlorine, bromine, iodine, or any combination thereof.

[0111] Embodiment 20. The step of contacting the formed compound with a metal carbonyl under conditions such that one of the compounds is formed comprises: contacting the formed compound, the metal carbonyl, or both with a polar ligand, resulting in the formation of one of the compounds. 20. The method according to any one of embodiments 1 to 19, comprising:

[0112] Embodiment 21. The method of any one of embodiments 1-20, wherein the alkyllithium compound comprises one or more of n-butyllithium, t-butyllithium, or any combination thereof.

[0113] Embodiment 22. The method of any one of embodiments 1-21, wherein the halogenating agent comprises one or more of bromine, N-bromosuccinimide, dibromoisocyanuric acid, or any combination thereof.

[0114] Embodiment 23. The metal carbonyl is NaCo(CO) 4 , Co 2 (CO) 8 , HCo(CO) 4 23. The method according to any one of the preceding embodiments, comprising:

[0115] Embodiment 24. The method of any one of embodiments 1 to 23, wherein the polar ligand comprises one or more of tetrahydrofuran, diethyl ether, or any combination thereof.

[0116] Embodiment 25. The metallation agent is (Et) 2 AlCl, (Et) 3 Al, CrCl 2 , 25. The method according to any one of the preceding embodiments, wherein the compound is one or more of the compounds, or any combination thereof. EXAMPLES

[0117] The following examples are included to illustrate the invention, but not to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0118] NMR analysis is performed on a Bruker Advance III-HD spectrometer operating at 400.3 MHz. Prior to testing, samples are dissolved in THF-d8.

[0119] In situ FTIR analysis to track the catalytic activity of the regenerated catalyst is performed on a Mettler Toledo ReatIR 45m equipped with a silicone tipped Sentinel attached directly to the bottom of the reactor.

[0120] FIG. 4 shows the 1H NMR spectra of isolated carbonylation catalysts with Lewis acids containing bipyridine or phenanthroline ligands. 2 Metallized with AlCl, NaCo(CO) 4 and successfully isolated it. tbu dhbpy(H) 2 The desired catalyst derived from the ligand. The inlet image shows Et 2 Metallized with AlCl tbu dhbpy(H) 2 This is expanded to take into account the aromatic region of the ligand.

[0121] 5 is a ReactIR spectrum showing in situ monitoring of β-propiolactone (BPL) formation with carbonylation catalysts having Lewis acids containing pyridine or phenanthroline ligands. The carbonylation catalysts are shown to have good catalytic activity with BPL (top line), some catalytic activity with ethylene oxide (middle line), and minimal activity with succinic anhydride (bottom line).

Claims

1. A catalyst compound according to one of the following formulas: 【Chemistry 1】 (In the formula, R is, separately for each occurrence, a hydrogen, an alkyl, or an aryl group; PL is a residue of tetrahydrofuran, dioxane, diethyl ether, acetonitrile, carbon disulfide, pyridine, an epoxide, an ester, a lactone, or a combination thereof; M is aluminum or chromium separately for each occurrence.

2. R is, separately for each occurrence, an alkyl or aryl group; PL is a residue of tetrahydrofuran, diethyl ether, dioxane, or a combination thereof; The catalyst compound of claim 1.

3. A method for preparing the catalyst compound according to claim 1 or 2, comprising the steps of: The following formula 【Chemistry 2】 with a metalating agent to obtain a precursor compound according to one of the formulas 【Chemistry 3】 forming one of the compounds formed by The compound thus formed and a metal carbonyl are reacted with the following catalyst compound: 【Chemistry 4】 contacting under conditions such that one of Including, During the ceremony, R is, separately for each occurrence, a hydrogen, an alkyl, or an aryl group; PL is a residue of tetrahydrofuran, dioxane, diethyl ether, acetonitrile, carbon disulfide, pyridine, an epoxide, an ester, a lactone, or a combination thereof; M is aluminum or chromium separately for each occurrence; method.

4. R is, separately for each occurrence, an alkyl or aryl group; PL is a residue of tetrahydrofuran, diethyl ether, dioxane, or a combination thereof; The method according to claim 3.

5. The following formula 【Chemistry 5】 one of the precursor compounds according to one of contacting a phenol, which may be substituted at the 2- and / or 4-positions with hydrogen, alkyl, or aryl groups, with a halogenating agent under conditions such that a halogen atom is attached to the 6-carbon atom to form a halogenated phenol; contacting the formed halogenated phenol with a trialkylborate in the presence of an alkyllithium compound to replace the halogen atoms with boron dihydroxide groups; and contacting a phenol containing a boron dihydroxide group with a bipyridine or phenanthroline having a halogen group on the carbon adjacent to the nitrogen atom in the presence of a palladium catalyst and an alkali metal carbonate under conditions to form one of the precursor compounds of the formula above.

5. The method of claim 3 or 4, comprising preparing the compound by:

6. 6. The method of claim 5, wherein the trialkylamine is configured to consume bromic acid to form an ammonium salt.

7. 6. The method of claim 5, wherein the trialkylamine comprises one or more tributylamines.

8. contacting the formed halogenated phenol with a trialkylborate in the presence of an alkyllithium compound to replace the halogen atoms with boron dihydroxide groups; contacting the phenol containing the boron dihydroxide group with hydrochloric acid to quench the reaction. The method of claim 5 , comprising:

9. 9. The method of claim 5 or 8, wherein the trialkyl borate comprises one or more of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, or any combination thereof, and the alkali metal carbonate comprises sodium carbonate.

10. said step of contacting the formed compound with a metal carbonyl under conditions such that one of said catalyst compounds is formed, contacting the formed compound, the metal carbonyl, or both with a polar ligand, resulting in the formation of one of said compounds. The method according to any one of claims 3 to 9, comprising:

11. 11. The method of any one of claims 3 to 10, wherein the alkyllithium compound comprises one or more of n-butyllithium, t-butyllithium, or any combination thereof, and the halogenating agent comprises one or more of bromine, N-bromosuccinimide, dibromoisocyanuric acid, or any combination thereof.

12. The metal carbonyl is NaCo(CO) ４ , Co ２ (CO) ８ , HCo(CO) ４ or any combination thereof.

13. The method of any one of claims 3 to 12, wherein the polar ligand comprises one or more of tetrahydrofuran, dioxane, diethyl ether, or any combination thereof.

14. The metallation agent is (Et) ２ AlCl, (Et) ３ Al, CrCl ２ or any combination thereof.

15. The method of claim 1 or 3, wherein PL is a residue of tetrahydrofuran.

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