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  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
  • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
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  • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
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  • C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides

Definitions

• the present disclosure relates generally to the production of /?ara-xylene and terephthalic acid, and more specifically to the production of /?ara-xylene and terephthalic acid from renewable biomass resources (e.g., cellulose, hemicellulose, starch, sugar) and ethylene.
• renewable biomass resources e.g., cellulose, hemicellulose, starch, sugar
• Terephthalic acid is a precursor of polyethylene terephthalate (PET), which may be used to manufacture polyester fabrics. Terephthalic acid can be produced by oxidation of /?ara-xylene.
• Xylene is an aromatic hydrocarbon that occurs naturally in petroleum and coal tar.
• Commercial production of /?ara-xylene is typically accomplished by catalyic reforming of petroleum derivatives. See e.g., U.S. Patent Application No. 2012/0029257.
• the use of petroleum-based feedstocks to commercially produce /?ara-xylene (and hence terephthalic acid) generates greenhouse gas emissions and perpetuates reliance on petroleum resources.
• the present disclosure addresses this need by providing methods using particular catalysts, solvents, and reaction conditions to produce /?ara-xylene from 2,5-dimethylfuran, 2,5-hexanedione, or a combination thereof.
• the /?ara-xylene produced can then be oxidized to produce terephthalic acid.
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, by:
• the starting material is 2,5-dimethylfuran (DMF), 2,5-hexanedione (HD), or a combination thereof;
• the method further includes isolating /?ara-xylene from the reaction mixture.
• the catalyst is a metal-containing catalyst.
• the catalyst may include a metal cation and counterion(s).
• the metal cation may be selected from, for example, Group 3, Group 9, Group 10, Group 11, or the lanthanide series.
• the catalyst includes a monovalent metal cation, a divalent metal cation or a trivalent metal cation.
• the monovalent metal cation may be, for example, Cu + .
• the divalent metal cation may be, for example, Cu 2+ , Co 2+ , Cr 3+ , Ni 2+ , Mg 2+ , or Zn 2+ .
• the trivalent metal cation may be, for example, Al 3+ , Bi 3+ , Fe 3+ , Gd 3+ , In 3+ , Nd 3+ , La 3+ , Sc 3+ , or Y 3+ .
• Suitable counterion(s) in the catalyst may include, for example, halides (e.g., chloride, bromide), triflates (-OTf), and carboxylates (e.g. formate, acetate, acetylacetonate).
• the catalyst is aluminum chloride, aluminum bromide, aluminum triflate, bismuth chloride, bismuth bromide, bismuth triflate, copper chloride, copper bromide, copper triflate, copper (II) bis(trifluoromethylsulfonyl)imide, cobalt chloride, cobalt bromide, cobalt triflate, chromium chloride, chromium bromide, chromium triflate, iron chloride, iron bromide, iron triflate, gadolinium chloride, gadolinium bromide, gadolinium triflate, indium chloride, indium bromide, indium triflate, nickel chloride, nickel bromide, nickel triflate, neodynium chloride, neodynium bromide, neodynium triflate, magnesium chloride, magnesium bromide, magnesium triflate, lanthanum chloride, lanthanum bromide, lanthanum
• the catalyst is Al(OTf) 3 , Bi(OTf) 3 , Cu(OTf) 2 , Cu(OTf), Cr(OTf) 3 , Fe(OTf) 3 , Gd(OTf) 3 , In(OTf) 3 , Ni(OTf) 2 , Nd(OTf) 3 , Rb(OTf), Cs(OTf), Mg(OTf) 2 , La(OTf) 3 , Sc(OTf) 3 , Ti(OTf) 4 , V(OTf) 5 , Y(OTf) 3 , Zn(OTf) 2 , Pt(OTf) 2 , Pd(OTf) 2 , AgOTf, Au(OTf) 3 , Tl(OTf) 3 , Tl(OTf), Re(OTf) 3 , Hg 2 (OTf) 2 , Hg(OTf) 2 , NH 4 (OTf), Sn(OTf) 4 , Sn(OTf) 4 , Sn(OT
• the catalyst may be a metal salt, including any such salts that may convert in situ into a different catalytic species for the reactions described herein.
• the catalyst used may be copper triflate.
• the copper triflate may yield triflic acid, which may contribute at least in part to the increase in rate of the chemical reaction.
• the catalyst is unsupported.
• the catalyst is solid supported.
• one or more of the metal cations described above may be deposited on a solid support.
• Suitable supports include, for example, silica, alumina, mordenite, carbon (including, for example, activated carbon), and zeolites.
• the catalyst may be copper (II) on mordenite, copper chloride on alumina, or copper chloride on HY zeolite.
• Such solid supported catalysts can more easily be recovered, recycled, and used in a continuous process.
• the catalyst may be an acid, including a Lewis acid or a weak acid.
• the catalyst is a heteropolyacid.
• the catalyst is molybdo silicic acid or molybdophosphoric acid.
• the catalyst may be (a) a sulfonic acid, or a salt, ester, anhydride or resin thereof, (b) a sulfonamide, or a salt thereof, or (c) a sulfonimide, or a salt thereof.
• Suitable examples of such catalyst may include trifluoromethanesulfonic acid (also referred to as triflic acid), 4-methylbenzenesulfonic acid (also referred to as p-toluene- sulfonic acid), and triflimide.
• the solvent system includes an aprotic solvent.
• the solvent may also be water-tolerant.
• the solvent may have one or more functional groups including, for example, ether, ester, ketone, alcohol, and halo.
• the solvent system includes an ether, which may include cyclic ethers, polyethers, glycol ethers, and other copolyethers. Suitable ether solvents may include dioxane, dioxin, glyme, diglyme, triglyme, tetrahydrofuran, and any combinations or mixtures thereof. In one embodiment, the solvent system includes 1,4-dioxane. In another embodiment, the solvent system includes triglyme.
• the solvent system includes dimethylacetamide (e.g., N-methylacetamide),
• ⁇ , ⁇ -dimethylacetamide dimethylformamide (e.g. , ⁇ , ⁇ -dimethylformamide), acetonitrile, sulfolane, dioxane, dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, triacetin,
• N-methylpyrrole N-methylpyrrole
• methylpyrrolidinone e.g. , N-methylpyrrolidinone
• dimethylfuran e.g. , 2,5-dimethylfuran
• dichlorobenzene e.g. , odichlorobenzene
• water /?ara-xylene, mesitylene, dodecylbenzene, pentylbenzene, hexylbenzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, Santovac, diphenyl ether, methyldiphenyl ether, ethyldiphenyl ether, water, or any combinations or mixtures thereof.
• the solvent system includes dioxane, dodecane, hexadecane, mesitylene, 2,5-dimethylfuran, /?ara-xylene, or any combinations or mixtures thereof. In one embodiment, the solvent system includes dioxane, dodecane, /?ara-xylene, or any combinations or mixtures thereof.
• the solvent system includes water, aliphatic solvents (which may be branched or linear), aromatic solvents, or alkyl benzene solvents.
• the solvent system includes diphenyl ether or alkyldiphenyl ether.
• the solvent system includes an ionic liquid. Suitable ionic liquids may include, for example, l-allyl-3-methylimidazolium bromide,
• the catalyst is a metal chloride, metal triflate, metal acetate or metal
• the solvent system includes an ether, a C8+ alkyl solvent (e.g., decane, dodecane), or /?ara-xylene.
• the catalyst is a metal chloride, metal triflate, metal acetate or metal
• the solvent system includes an ether, a C 4+ alkyl solvent (e.g., decane, dodecane), /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is a metal triflate; and the solvent system includes dioxane or dodecane, or a mixture of combination thereof. In other embodiments, the solvent system further includes /?ara-xylene as a solvent. In yet other embodiments, the catalyst is a metal triflate; and the solvent system includes para-xylene.
• the catalyst is a copper chloride, copper triflate, or yttrium triflate
• the solvent system includes an ether, a C 4+ alkyl solvent), para-xylene, or any mixtures or combinations thereof.
• the catalyst is copper (I) triflate. In another embodiment, the catalyst is copper (II) triflate. [0031] In certain embodiments:
• the catalyst is copper chloride, copper triflate, or yttrium triflate
• the solvent system includes dioxane, dodecane, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is copper (I) triflate. In another embodiment, the catalyst is copper (II) triflate. In certain embodiments:
• the catalyst is copper triflate
• the solvent system includes a mixture of /?ara-xylene and a Cg + alkyl solvent.
• the catalyst is copper (I) triflate. In another embodiment, the catalyst is copper (II) triflate. In one embodiment, the C8+ alkyl solvent is dodecane.
• the catalyst is a sulfonic acid
• the solvent system includes an ether, a Cg + alkyl solvent, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is a sulfonic acid
• the solvent system includes dioxane, dodecane, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is triflic acid
• the solvent system includes an ether, a C 4+ alkyl solvent, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is triflic acid; and (ii) the solvent system includes dioxane, dodecane, hexadecane, /?ara-xylene, or any mixtures or combinations thereof.
• the catalytic is triflic acid
• the solvent system includes a C 4+ alkyl solvent.
• the catalytic is triflic acid
• the solvent system include dodecane or hexadecane.
• the catalyst is a metal triflate, triflic acid, or a heteropolyacid
• the solvent includes an ether or n-alkane.
• the catalyst is a metal triflate selected from La(OTf) 3 , Nd(OTf) 3 , Sc(OTf) , Cu[N(Tf) 2 ] 2 , Y(OTf) 3 , [Cu(I)OS0 2 CF 3 ] 2 C 6 H 6 , and any combination thereof.
• the catalyst is triflic acid.
• the heteropolyacid is H 4 [SiMo 12 0 4 o] x H 2 0, H 3 [PMo 12 0 4 o] x H 2 0, or any combination thereof.
• the solvent system includes an ether, such as dioxane or triglyme.
• the solvent system includes an alkane, such as dodecane.
• the catalyst is a heteropolyacid
• the solvent system includes an ether, a Cg + alkyl solvent (e.g. , decane, dodecane), /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is a heteropolyacid; and (ii) the solvent system includes dioxane, dodecane, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is aluminum chloride
• the solvent system includes an ether, a Cg + alkyl solvent (e.g. , decane, dodecane), /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is aluminum chloride
• the solvent system includes dioxane, dodecane, /?ara-xylene, or any mixtures or combinations thereof.
• the catalyst is copper chloride, copper triflate, yttrium triflate, copper acetate or copper acetylacetonate;
• the solvent system includes dioxane, triglyme, or any mixtures or combinations thereof.
• the catalyst is copper triflate or yttrium triflate
• the solvent system includes dioxane or triglyme.
• the catalyst is copper triflate or yttrium triflate
• the solvent system includes a Cg + alkyl solvent (e.g. , decane, dodecane).
• a Cg + alkyl solvent e.g. , decane, dodecane.
• the catalyst is copper triflate or yttrium triflate; and (ii) the solvent system includes /?ara-xylene.
• the catalyst is copper triflate, and the solvent system includes an ether, such as dioxane or triglyme.
• the catalyst is copper acetate or copper acetylacetonate, and the solvent system includes an ether, such as dioxane or triglyme.
• catalyst/solvent combinations described above may be used for a reaction using HD as the starting material, DMF as the starting material, or both HD and DMF as the starting materials.
• a method for producing /?ara-xylene by: combining a starting material, ethylene, a solvent system and a catalyst to form a reaction mixture, wherein the starting material is 2,5-dimethylfuran, 2,5-hexanedione, or a combination thereof; and producing
• a catalyst wherein the catalyst is a metal chloride, a metal triflate, a metal acetate, a metal acetylacetonate, or a heteropolyacid;
• the catalyst is copper chloride, copper triflate, yttrium triflate, copper acetate or copper acetylacetonate.
• the solvent system includes dioxane, dodecane, decane, /?ara-xylene, diphenyl ether, alkyldiphenyl ether, or any mixtures or combinations thereof.
• the solvent system includes dioxane, dodecane, decane, hexadecane, 2,5-dimethylfuran, /?ara-xylene, diphenyl ether, alkyldiphenyl ether, or any mixtures or combinations thereof.
• At least a portion of the DMF (if present), HD (if present), or a combination thereof is converted to /?ara-xylene at a temperature of at least 150°C, or between 150°C and 300°C.
• the /?ara-xylene produced by any of the methods described above may be used for the manufacture of a plastic or a fuel.
• terephthalic acid from /?ara-xylene by: a) producing /?ara-xylene according to any of the methods described herein; and b) oxidizing the /?ara-xylene to produce terephthalic acid.
• each R and R is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, heteroaryl.
• R and R 2 may be the same or different substituents.
• each R independently hydrogen or alkyl.
• the compound of formula I is para-xylene (PX)
• the compound of formula A is 2,5-dimethylfuran (DMF)
• the compound of formula B is 2,5-hexanedione (HD).
• PX para-xylene
• DMF 2,5-dimethylfuran
• HD 2,5-hexanedione
• a method of producing a compound of formula I by: combining a compound of formula A (e.g. , DMF), a compound of formula B (e.g. , HD), or a combination thereof, with ethylene, a catalyst, and optionally a solvent to form a reaction mixture; and producing para-xylene from at least a portion of the compound of formula A (e.g. , DMF), the compound of formula B (e.g. , HD), or a combination thereof, in the reaction mixture.
• a compound of formula A e.g. , DMF
• a compound of formula B e.g. , HD
• a combination thereof ethylene, a catalyst, and optionally a solvent to form a reaction mixture
• para-xylene from at least a portion of the compound of formula A (e.g. , DMF), the compound of formula B (e.g. , HD), or a combination thereof, in the reaction mixture.
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl. In certain embodiments, each R 1 and R 2 is independently hydrogen or alkyl. In certain embodiments, each R 1 and R 2 is independently a C 1-10 or a C 1-6 or a
• R 1 and R2 are each methyl. In another embodiment, R 1 is methyl, and R is hydrogen.
• the methods involve using a compound of formula A.
• 2,5-dimethylfuran is used in the methods provided herein to produce /?ara-xylene.
• 2-methylfuran is used in the methods provided herein to produce /?ara-xylene.
• the methods involve using a compound of formula B.
• 2,5-hexanedione is used in the methods provided herein to produce toluene.
• 4-oxopentanal is used in the methods provided herein to produce toluene.
• the methods involve using a mixture of compounds of formula A to produce a mixture of compounds of formula I.
• a mixture of compounds of formula A for example, in one embodiment,
• 2,5-dimethylfuran and 2-methylfuran may be used in the methods provided herein to produce a mixture of /?ara-xylene and toluene.
• the methods involve using a mixture of compounds of formula B to produce a mixture of compounds of formula I.
• 2,5-hexanedione and 4-oxopentanal may be used in the methods provided herein to produce a mixture of /?ara-xylene and toluene.
• the methods involve using a mixture of compounds of formula A and compounds of formula B to produce a mixture of compounds of formula I.
• 2,5-dimethylfuran, 2-methylfuran, 2,5-hexanedione and 4-oxopentanal may be used in the methods provided herein to produce a mixture of /?ara-xylene and toluene.
• Alky refers to a monoradical unbranched or branched saturated hydrocarbon chain.
• alkyl as used herein such as in compounds of formula I, (A) or (B), as 1 to
• alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-raethylpentyl.
• butyl can include n-butyl, sec-butyl, isobutyl and t-butyl
• propyl can include n -propyl and isopropyl
• Cycloalkyl refers to a cyclic alkyl group.
• cycloalkyl as used herein, such as in compounds of formula I, (A) or (B) has from 3 to 20 ring carbon atoms (i.e. , C3-20 cycloalkyl), or 3 to 12 ring carbon atoms (i.e. , C3-12 cycloalkyl), or 3 to 8 ring carbon atoms (i.e. , C 3 -8 cycloalkyl),
• Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
• Heterocycloalkyl refers to a cyclic alkyl group, with one or more ring heteroatoms independently selected from nitrogen, oxygen and sulfur. In some embodiments, the
• heterocycloalkyl as used herein, such as in compounds of formula I, (A) or (B), has 2 to 20 ring carbon atoms (i.e. , C2-20 heterocycloalkyl), 2 to 12 ring carbon atoms (i.e. , C 2-12 heterocycloalkyl), or 2 to 8 ring carbon atoms (i.e. , C 2 -8 heterocycloalkyl); and 1 to 5 ring heteroatoms, 1 to 4 ring heteroatoms, 1 to 3 ring heteroatoms, 1 or 2 ring heteroatoms, or 1 ring heteroatom independently selected from nitrogen, sulfur or oxygen.
• ring carbon atoms i.e. , C2-20 heterocycloalkyl
• 2 to 12 ring carbon atoms i.e. , C 2-12 heterocycloalkyl
• 2 to 8 ring carbon atoms i.e. , C 2 -8 heterocycloalkyl
• 1 to 5 ring heteroatoms 1 to 4 ring hetero
• a heterocycloalkyl has 2 to 8 ring carbon atoms, with 1 to 3 ring heteroatoms independently selected from nitrogen, oxygen and sulfur.
• heterocycloalkyl groups may include pyrrolidinyl, piperidinyl, piperazinyl, oxetanyl, dioxolanyl, azetidinyl, and morpholinyl.
• Aryl refers to an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g. , biphenyl), or multiple fused rings (e.g. , naphthyl, fiuorenyl, and anthryl).
• aryl as used herein, such as in compounds of formula I, (A) or (B) has 6 to 20 ring carbon atoms (i.e. , C 6-2 o aryl ), or 6 to 12 carbon ring atoms (i.e. , C -n aryl ).
• Aryl does not encompass or overlap in any way with heteroaryl, separately defined below.
• the resulting ring sy stem is heteroaryl.
• Heteroaryl refers to an aromatic group having a single ring, multiple rings, or multiple fused rings, with one or more ring heteroatoms independently selected from nitrogen, oxygen, and sulfur.
• heteroaryl is an aromatic, monocyclic or bicyclic ring containing one or more heteroatoms independently selected from nitrogen, oxygen and sulfur with the remaining ring atoms being carbon
• heteroaryl as used herein, such as in compounds of formula I, (A) or (B) has 3 to 20 ring carbon atoms (i.e. , C 3 - 20 heteroaryl), 3 to 12 ring carbon atoms (i.e. , C 3-12 heteroaryl), or 3 to 8 carbon ring atoms (i.e. , C 3- s heteroaryl); and 1 to
• heteroaryl has 3 to 8 ring carbon atoms, with 1 to 3 ring heteroatoms independently selected from nitrogen, oxygen and sulfur.
• heteroaryl groups include pyridyi, pyridazinyl, pyrimidinyl, benzothiazolyl, and pyrazolyl. Heteroaryl does not encompass or overlap with aryl as defined above.
• substituted means that any one or more hydrogen atoms on the designated atom or group is replaced with a moiety other than hydrogen, provided that the designated atom' s normal valence is not exceeded.
• C ⁇ alkyl (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or Cl-6 alkyl) is intended to encompass, C 1 ; C 2 , C 3 , C 4 ,
• the compounds of formula A and the compounds of formula B used in the methods described herein can be obtained from any source (including any commercially available sources), or be produced by any methods known in the art. Further, it should be understood that the compound of formula B may be generated in situ from the reaction mixture.
• DMF used in the methods described herein may be commercially available, or be derived from carbonaceous materials.
• suitable carbonaceous materials from which DMF can be derived include agricultural materials (e.g. , corn stover, rice hulls, peanut hulls, spent grains, pine chips), processing waste (e.g. , paper sludge), recycled cellulosic materials (e.g., cardboard, old corrugated containers (OCC), mixed paper, old newspaper (ONP)), as well as fructose (e.g., high fructose corn syrup), sucrose, glucose, or starch.
• cellulose and hemicellulose (if present) or other six-carbon sugars e.g., glucose, fructose
• HD also known as acetonyl acetone
• HD may be commercially available, or be prepared according to methods known in the art.
• HD can be prepared by oxidization of allylacetone. See U.S. Patent No. 3,947,521.
• HD can also be prepared by hydrolysis of the lactone of
• Ethylene is also a starting material for this reaction.
• the ethylene provided for the methods described herein may be obtained from any source (including any commercially available sources).
• ethylene can be obtained from fossil fuel sources or renewable sources, such as by dehydration of ethanol (e.g., fermentation-based ethanol).
• Various catalysts may be used in the method to convert compounds of formula A (e.g., DMF) and/or compounds of formula B (e.g., HD) into compounds of formula I (e.g.,para-xylene).
• the catalysts may be selected from one or more classes of catalysts, including (i) metal-containing catalysts, including metal-containing salts that are catalytic or may convert in situ into a catalytic species, and (ii) acids (e.g., Lewis acids, weak acids, sulfonic acids, heteropolyacids) .
• the catalyst may fall into one or more classes listed herein.
• the catalyst may be copper triflate, which is a metal-containing catalyst and also a Lewis acid.
• the catalyst may also be supported or unsupported.
• the catalyst may also be homogeneous or heterogeneous based on the solvent system used in the reaction.
• the catalysts may also be in the form of a solvate, including, for example, a hydrate.
• the catalysts may also be a polymer.
• the catalyst increases the rate of the chemical reaction, and such increase may be caused directly or indirectly (e.g., by conversion in situ into a different catalyst species).
• the catalyst used may be copper triflate.
• the copper triflate may yield triflic acid, which may contribute to the increase in rate of the chemical reaction.
• the catalyst used may be triflimide.
• the triflimide may yield triflic acid in the reaction mixture, which may contribute to the increase in rate of the chemical reaction.
• the catalysts provided for the methods described herein to produce compounds of formula I may be obtained from any sources (including any commercially available sources), or may be prepared by any methods or techniques known in the art. It should also be understood that providing a catalyst includes providing the catalyst itself, or a precursor that forms a catalytic species (e.g., in situ) that may contribute to the increase in rate of the chemical reaction.
• the catalyst is a metal catalyst.
• a metal catalyst can be any catalyst that is a metal or contains a metal ligand.
• the metals may include, for example, alkali metals, alkali earth metals, transition metals or lanthanides. In one embodiment, the metals may include transition metals or lanthanides. In certain embodiments, the metal is selected from Group 3, Group 9, Group 10, Group 11, and the lanthanide series. In certain embodiments, the metal is selected from Group 3, Group 9, Group 11, and the lanthanide series.
• the metal is aluminum, bismuth, copper, chromium, iron, gadolinium, indium, nickel, neodymium, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, lanthanum, scandium, titanium, vanadium, yttrium, zinc, platinum, palladium, silver, gold, thallium, rhenium, mercury, tin, boron, gallium, lead, cobalt, germanium, and cerium.
• the catalytic species in the reactions described herein may also be formed in situ by providing suitable precursors.
• suitable precursors for example, copper metal and chlorine gas may be provided to the reaction to produce copper chloride in situ.
• the catalytic species may be formed in situ by reaction between the metal precursor and the ethylene provided in the reaction.
• copper triflate is provided to the reaction, and may form a catalytic species with ethylene.
• the metal catalyst is a metal-containing catalyst.
• Metal-containing catalysts have one or more metal cations and one or more counterions or ligands.
• the catalyst may be a metal-centered catalyst.
• the metal cation in a metal-containing catalyst may be a transition metal cation or a lanthanide cation.
• the metal cation in a metal-containing catalyst is selected from Group 3, Group 9, Group 10, Group 11, and the lanthanide series.
• the metal cation is selected from Group 3, Group 9, Group 1 land or the lanthanide series.
• the metal cation is a Group 11 cation. It should be understood that the group number used for the metals follow the IUPAC or long-form nomenclature, which is well-known in the art.
• the catalyst may have a monovalent metal cation.
• the monovalent metal cation is Cu + , Li + , Na + , K + , Rb + , Cs + , Ag + , Tl + , or Hg 2 2+ .
• the monovalent metal cation is Cu 1+ .
• the catalyst may have a divalent metal cation or a trivalent metal cation.
• the divalent metal cation is Cu 2+ , Ni 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Pt 2+ , Pd 2+ , Hg 2+ , Sn 2+ , Pb 2+ , Co 2+ , or Ge 2+ .
• the divalent metal cation is Cu 2+ , Co 2+ , Cr 3+ , Ni 2+ , Mg 2+ , or Zn 2+ .
• the divalent metal cation is Cu 2+ , Co 2+ , Ni 2+ , or Zn 2+ . In one embodiment, the divalent metal cation is Cu 2+ , Co 2+ , or Zn 2+ . In one embodiment, the divalent metal cation is Cu .
• the trivalent metal cation is Al 3+ , Bi 3+ , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Nd 3+ , La 3+ , Sc 3+ , Y 3+ , Au 3+ , Tl 3+ , Re 3+ , Sn 3+ , B 3+ , Ga 3+ , Co 3+ , or Ce 3+ .
• the trivalent metal cation is Al 3+ , Bi 3+ , Fe 3+ , Gd 3+ , In 3+ , Nd 3+ , La 3+ , Sc 3+ , or Y 3+ .
• the trivalent metal cation is Al 3+ , Fe 3+ , Gd 3+ , In 3+ , La 3+ , or Y 3+ . In one embodiment, the trivalent metal cation is Al 3+ , Gd 3+ , In 3+ , La 3+ , or Y 3+ . In another embodiment, the trivalent metal cation is Gd 3+ , In 3+ , La 3+ , or Y 3+ .
• the catalyst may have a tetravalent metal ion.
• the metal cations may coordinate with one or more cations.
• the divalent or trivalent metal cation of the catalyst may coordinate with two or three counterions, respectively.
• Each counterion may independently be selected from, for example, halides (e.g. , chloride, bromide), triflates (-OTf), and carboxylates (e.g. formate, acetate, acetylacetonate). It should be understood, however, that any suitable counterion may be used.
• the counterions may be chloride or triflate. It should be understood that the counterions may all be the same, the counterions may all be different, or two counterions may be the same and the third counterion may be different.
• the counterions may be ligands that coordinate with the metal.
• Ligands may be, cationic, anionic or neutral.
• the catalyst may be
• the catalyst is aluminum chloride, aluminum bromide, aluminum triflate, bismuth chloride, bismuth bromide, bismuth triflate, copper chloride, copper bromide, copper triflate, cobalt chloride, cobalt bromide, cobalt triflate, chromium chloride, chromium bromide, chromium triflate, iron chloride, iron bromide, iron triflate, gadolinium chloride, gadolinium bromide, gadolinium triflate, indium chloride, indium bromide, indium triflate, nickel chloride, nickel bromide, nickel triflate, neodynium chloride, neodynium bromide, neodynium triflate, magnesium chloride, magnesium bromide, magnesium triflate, lanthanum chloride, lanthanum bromide, lanthanum triflate, scandium
• the catalyst is copper chloride, copper triflate, yttrium triflate, scandium triflate, lanthanum triflate, neodynium triflate, copper triflimide, or any combinations thereof.
• the catalyst is aluminum chloride, copper chloride, copper triflate, yttrium triflate, or any combination thereof.
• the catalyst is copper chloride or copper triflate, or a combination thereof.
• the catalyst is copper (II) bis(trifluoromethylsulfonyl)imide (i.e., copper triflimide, also referred to as Cu[N(Tf) 2 ] 2 ).
• the catalyst is a metal-containing salt catalyst, including any such salts that may convert in situ into a species that is catalyst for the reactions described herein.
• a metal salt catalyst may include a Group 11 metal with one or more counterion(s).
• the metal of the metal salt catalyst may be a copper cation.
• the catalyst is copper acetate or copper acetylacetonate.
• any suitable counterions may be present in the metal-containing salt catalyst.
• the catalyst comprises copper or a copper ion. In one embodiment, the catalyst comprises a copper (I) ion. In another embodiment, the catalyst comprises a copper (II) ion. In one embodiment, the catalyst is Cu[N(Tf) 2 ] 2 , CuCl 2 ,
• Such catalysts may be obtained from any commercially available source, or prepared by any suitable methods known in the art. Certain catalysts may also be formed in situ.
• copper metal may be provided as a precursor to generate CuCl 2 in situ.
• copper oxide (Cu 2 0) may be provided in combination with HBF 4 and CH CN to generate Cu(I)(BF 4 )(CH 3 CN)4 in situ.
• copper oxide (Cu 2 0) may be provided in combination with CF 3 S0 3 H and CH 3 CN to generate (Cu(I)OS0 2 CF 3 )(CH 3 CN) 4 in situ.
• the catalyst is a Lewis acid.
• a "Lewis acid” refers to an acid substance that can employ an electron lone pair from another molecule in completing the stable group of one of its own atoms.
• one or more of catalysts may be Lewis acids.
• the catalyst may be a Lewis acid, such as aluminum chloride, zinc chloride, indium chloride, divalent transition metal ions of copper, nickel or cobalt or mixtures thereof such as CuCl 2 or CoCl 2 , triflates such as the triflate of indium, copper, gadolinium or yttrium, trivalent metal ions from the lanthanide series of elements or mixtures thereof.
• the catalyst may be a solvate, including hydrate, or anhydrous.
• the catalyst is CuCl 2 x 2H 2 0.
• the catalyst is CuCl 2 , wherein less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% of the catalyst is water.
• the catalysts may also include acetic acid, haloacetic acid (e.g., chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, and difluoroacetic acid, trifluoroacetic acid).
• acetic acid e.g., chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, and difluoroacetic acid, trifluoroacetic acid.
• acetic anhydride may contain a small percentage of acetic acid, which acts as a catalyst for the reaction. Additionally, the acetic anhydride in the reaction mixture may further convert into acetic acid in the reaction.
• the Lewis acid is a heteropolyacid.
• Heteropolyacids is a class of acids that includes a combination of hydrogen and oxygen atoms with certain metals and/or non-metals.
• the heteropolyacid typically includes at least one addenda atom, oxygen, a hetero atom, and acidic hydrogen atoms.
• the addenda atoms may be selected from one or more metals, including for example, tungsten, molybdenum, or vanadium.
• the hetero atom may be selected from p-block elements, such as silicon or phosphorous.
• Suitable heteropolyacids may include, for example, tungsto silicic acid, tungostophosphoric acid, molybdo silicic acid, molybdophosphoric acid.
• a mixture of heteropolyacids may also be used.
• the heteropolyacids may have certain structures that are known in the art.
• the heteropolyacid is a Keggin structure, having the formula ⁇ ⁇ ⁇ 1 2 ⁇ 4 ⁇ , where X is the hetero atom, M is the addenda atom, and n is an integer greater than 0.
• the heteropolyacid is a Dawson structure having the formula H n X 2 M 18 062, where X is the hetero atom, M is the addenda atom, and n in an integer greater than 0.
• the catalyst is a heteropolyacid selected from 12- tungstophosphoric acid, 12-molybdophosphoric acid, 12-tungsto silicic acid, 12-molybdo silicic acid, and any combinations thereof.
• the catalyst may be a solvate of a heteropolyacid. Suitable solvates may include hydrates or alcohol solvates.
• the catalyst that is a heteropolyacid may be unsupported or supported.
• the catalyst is a supported heteropolyacid.
• Suitable solid supports for the heteropolyacids may include, for example, carbon, alumina, silica, ceria, titania, zirconia, niobia, zeolite, magnesia, clays, iron oxide, silicon carbide, aluminosilicates, and any modifications, mixtures or combinations thereof.
• the catalyst is a sulfonic acid, or a salt, ester, anhydride or resin thereof.
• Sulfonic acids used herein may have a structure of formula of R x S0 3 H.
• R x is alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8, or 1 to 5, or 1 to 3 substituents independently selected from alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, -OR', -C(0)OR', -C(0)NR'R" -CHO, -COR', and cyano, and wherein each R' and R" is independently hydrogen, alkyl, or haloal
• R x is a CI -CIO alkyl, or a CI -CIO haloalkyl.
• R x is methyl, ethyl, propyl, CHF 2 , CH 2 F, or CF 3 .
• the alkyl or haloalkyl may be further substituted with an ether moiety.
• the alkyl or haloalkyl may be further substituted with -OR , where R is alkyl or haloalkyl.
• R x is alkyl, haloalkyl, or aryl optionally substituted with alkyl, haloalkyl, or nitro.
• haloalkyl refers to an unbranched or branched chain alkyl group, wherein one or more hydrogen atoms are replaced by a halogen.
• a residue is substituted with more than one halogen, it may be referred to by using a prefix corresponding to the number of halogen moieties attached.
• dihaloalkyl or trihaloalkyl refers to alkyl substituted with two ("di") or three ("tri") halo groups, which may be, but are not necessarily, the same halogen; thus, for example, 2-chloro-2-fluorobutyl is within the scope of dihaloalkyl.
• An alkyl group in which each H is replaced with a halo group is referred to as a "perhaloalkyl.”
• a perhaloalkyl group is trifluoromethyl (-CF ).
• the sulfonic acids used in the methods described herein may include, for example, CF 3 S0 3 H (i.e., triflic acid), HCF 2 CF 2 S0 3 H, C 6 F 5 S0 3 H, 4-methylbenzenesulfonic acid (i.e., /7-toluene-sulfonic acid), or 2,4-dinitrobenzenesulfonic acid.
• the sulfonic acid is triflic acid.
• the sulfonic acid is p-toluene-sulfonic acid.
• Salts of sulfonic acids used herein may have the structure of formula Q r+ [R x S0 3 ⁇ ] r , wherein: Q is a cation; R x is as described above for sulfonic acids; and r is the charge of the cation.
• Q r+ is Al 3+ , Bi 3+ , Cu 2+ , Cu + , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Ni 2+ , Nd 3+ , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ba 2+ , Ca 2+ , La 3+ , Sc 3+ , Ti 4+ , V 5+ , Y 3+ , Zn 2+ , Pt 2+ , Pd 2+ , Ag + , Au 3+ , Tl 3+ , Tl + , Re 3+ , Hg 2 2+ , Hg 2+ , NH 4 + , Sn 4+ , Sn 3+ , Sn 2+ , B 3+ , Ga 3+ , Pb 4+ , Pb 2+ , Co 3+ , Co 2+ , Ge 4+ , Ge 2+ , Ce 4+ , or Ce 3
• the salts of the sulfonic acids used in the methods described herein may include, for example, is Al(OTf) 3 , Bi(OTf) 3 , Cu(OTf) 2 , Cu(OTf), Cr(OTf) 3 , Fe(OTf) 3 , Gd(OTf) 3 , In(OTf) 3 , Ni(OTf) 2 , Nd(OTf) 3 , Rb(OTf), Cs(OTf), Mg(OTf) 2 , La(OTf) 3 , Sc(OTf) 3 , Ti(OTf) 4 , V(OTf) 5 , Y(OTf) 3 , Zn(OTf) 2 , Pt(OTf) 2 , Pd(OTf) 2 , AgOTf, Au(OTf) 3 , Tl(OTf) 3 , Tl(OTf), Re(OTf) 3 , Hg 2 (OTf) 2 , Hg(OTf) 2 , NH 4 (
• the sulfonic acid salt may be in the form of an ionic liquid.
• the sulfonic acid may be a hydrate.
• the sulfonic acid may be anhydrous.
• the catalyst may be triflic anhydride.
• the catalyst is a quaternary amine triflate.
• the sulfonic acid catalyst may be a sulfonic acid polymer, including for example, a sulfonic acid resin.
• the sulfonic acid resin is a halosulfonic acid resin.
• the sulfonic acid resin is a fluoro sulfonic acid resin.
• the sulfonic acid resin is R xl CF 2 S0 3 H, where R xl is alkyl or haloalkyl.
• the sulfonic acid resin is a sulfonated tetrafluoroethylene polymer, such as Nafion.
• the catalyst may, in some embodiments, be a sulfonate having the formula
• R x S0 3 Si(R m ) 3 wherein R x is as defined above for sulfonic acids; and R m at each occurrence is independent alky or haloalykl.
• R x is as defined above for sulfonic acids; and R m at each occurrence is independent alky or haloalykl.
• the salt of thes ulfonic acid is
• the catalyst is a sulfonamide, or a salt thereof.
• Sulfonamides used herein may have a structure of formula of (R yl S0 2 )NH 2 or (R yl S0 2 )NH(R z ).
• R yl and R z are each independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8, or 1 to 5, or 1 to 3 substituents independently selected from alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, -OR', -C(0)OR',
• R yl and R z are each independently alkyl or haloalkyl. In another embodiment, R yl and R z are each independently alkyl. In certain embodiments, R yl and R z are each independently a CI -CIO alkyl, or a CI -CIO haloalkyl. In certain embodiments, R yl and R z are each independently methyl, ethyl, propyl, CHF 2 , CH 2 F, or CF 3 . In certain
• the alkyl or haloalkyl may be further substituted with an ether moiety.
• the alkyl or haloalkyl may be further substituted with -OR , where R is alkyl or haloalkyl.
• R yl and R z are each independently alkyl, haloalkyl, or aryl optionally substituted with alkyl, haloalkyl, or nitro.
• Salts of the sulfonamides used herein may have the structure of formula
• Q r+ is Al 3+ , Bi 3+ , Cu 2+ , Cu + , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Ni 2+ , Nd 3+ , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ba 2+ , Ca 2+ , La 3+ , Sc 3+ , Ti 4+ , V 5+ , Y 3+ , Zn 2+ , Pt 2+ , Pd 2+ , Ag + , Au 3+ , Tl 3+ , Tl + , Re 3+ , Hg 2 2+ , Hg 2+ , NH 4 + , Sn 4+ ,
• the catalyst is a sulfonimide, or a salt thereof.
• Sulfonimides used herein may have a structure of formula of (R yl S0 2 )NH(S0 2 R y2 ).
• R yl and R y2 are each independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8, or 1 to 5, or 1 to 3 substituents independently selected from alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, -OR', -C(0)OR', -C(0)NR'R" -CHO, -COR', and cyano, and wherein each R' and R" is independently hydrogen, alkyl, or haloalkyl.
• R yl and R y2 are each independently alkyl or haloalkyl. In another embodiment, R yl and R y2 are each independently alkyl. In certain embodiments, R yl and R y2 are each independently a CI -CIO alkyl, or a CI -CIO haloalkyl. In certain embodiments, R yl and R y2 are each independently methyl, ethyl, propyl, CHF 2 , CH 2 F, or CF 3 . In certain
• the alkyl or haloalkyl may be further substituted with an ether moiety.
• the alkyl or haloalkyl may be further substituted with -OR , where R is alkyl or haloalkyl.
• R x is alkyl, haloalkyl, or aryl optionally substituted with alkyl, haloalkyl, or nitro.
• the sulfonimides used in the methods described herein may include, for example, NH(Tf) 2 (i.e., triflimide). It should be understood that, as used herein, "-Tf ' refers to triflyl.
• Salts of sulfonimides used herein may have the structure of formula
• Q r+ is Al 3+ , Bi 3+ , Cu 2+ , Cu + , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Ni 2+ , Nd 3+ , Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ba 2+ , Ca 2+ , La 3+ , Sc 3+ , Ti 4+ , V 5+ , Y 3+ , Zn 2+ , Pt 2+ , Pd 2+ , Ag + , Au 3+ , Tl 3+ , Tl + , Re 3+ , Hg 2 2+ , Hg 2+ , NH 4 + , Sn 4+ , Sn 3+ , Sn 2+ , B 3+ , Ga 3+ , Pb 4+ , Pb 2+ , Co 3+ , Co 2+ , Ge 4+ , Ge 2+ , Ce 4+ , or Ce 3
• the salts of sulfonimides used herein may include, for example, Al[N(Tf) 2 ] ,
• the salt of the sulfonimide is bis(pentafluoroethylsulfonyl)imide salt.
• the salt of the sulfonic acid, sulfonamide, or sulfonimide has a cation, wherein the reduction of the cation to its elemental state (i.e., zero oxidation state) has a standard reduction potential greater than -0.2 eV relative to standard hydrogen potential. Any suitable methods or techniques known in the art may be used to measure standard reduction potential.
• the acid has a pKa that is lower than the pKa of sulfuric acid. In other embodiments, the acid is HC10 4 or H 2 S0 4 .
• the catalysts may also be water-tolerant catalysts.
• a water-tolerant catalyst refers to a catalyst that is not deactivated by the presence of water in a given reaction.
• a given catalyst may show water stability for the purposes of one reaction, but not toward another.
• Water-tolerant catalyst can improve recyclability of the catalyst used in the reaction on industrial scale, since water can often be produced as a by-product in the reaction.
• the water-tolerant catalyst may have a p3 ⁇ 4 between 4.3 and 10.08.
• K h is the hydrolysis constant.
• the water-tolerant catalyst may have a water exchange rate constant of at least 3.2 x 10 6 M ' V 1 . See generally Kobayashi et al., J. Am. Chem. Soc. 1998, 120, 8287-8288.
• Examples of water-tolerant catalysts may include those with a metal cation selected from Sc(III), Y(III), Ln(III), Fe(II), Cu(II), Zn(II), Cd(II), Pb(II), La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III).
• the catalyst may include Fe(II), Cu(II), Zn(II), Cd(II), Pb(II) Sc(III), Y(III), Ln(III), Mn(II), or Ag(I).
• Water-tolerant catalysts may include, for example, ScCl 3 , Sc(C10 4 ) 3 ,
• any of the catalysts described above may be unsupported or supported.
• the catalyst is unsupported.
• the catalyst is supported by a solid support.
• Suitable supports may include, for example, carbon, alumina, silica, ceria, titania, zirconia, niobia, zeolite, magnesia, clays, iron oxide, silicon carbide, aluminosilicates, and any modifications, mixtures or combinations thereof.
• the support is silica, alumina, mordenite, carbon (including, for example, activated carbon), or zeolites (e.g., HY zeolite).
• Examples of supported catalyst may include copper on mordenite, alumina or zeolite.
• the catalyst is copper (II) on mordenite, copper chloride on silica, copper chloride on alumina, or copper chloride on HY zeolite.
• the support is activated carbon.
• the activated carbon may also be further treated, for example, acid treated (e.g., H 3 P0 4 treated).
• Solid supported catalysts can more easily be recovered, recycled, and used in a continuous process. When a catalyst support is used, the metals may be deposited using any procedures known in the art. See e.g., Schwarz et al., Chem. Rev. 95, 477-510, (1995).
• the catalyst is homogeneous in the reaction mixture.
• a "homogeneous catalyst” refers to a catalyst that substantially dissolves in the reaction mixture under the reaction conditions.
• acetic acid as the catalyst substantially dissolves in dioxane.
• copper triflate substantially dissolves in dodecane under the reaction conditions, but not at all conditions (e.g., at standard, temperature and pressure).
• a catalyst is "substantially dissolved” when the amount of dissolved catalyst exceeds the quantity of undissolved catalyst at the reaction conditions.
• the catalyst is substantially dissolved when the ratio of amount of undissolved catalyst to the amount of dissolved catalyst is between 0 : 1 and 1 : 1 at the reaction conditions. In one embodiment, the ratio of amount of undissolved catalyst to the amount of dissolved catalyst is about 0 at the reaction conditions. Any suitable methods may be used to determine or quantify the solubility of catalyst.
• the homogeneous catalyst is a sulfonic acid, or a salt, ester, anhydride or resin thereof, a sulfonamide, or a salt thereof, or a sulfonimide, or a salt thereof.
• the catalyst is heterogeneous in the reaction.
• a heterogeneous catalyst refers to any catalyst that is not a homogeneous catalyst as described above.
• homogeneity or heterogeneity of a catalyst may depend on the solvent or solvent mixtures used, as well as the reaction conditions.
• the amount of catalyst used may vary depending on the catalyst, starting materials, solvent, and reaction conditions.
• catalyst loading refers to the amount of catalyst used in relation to the amount of DMF used, expressed as a weight ratio of DMF (as the starting material) to the catalyst used.
• the catalyst loading is between 10 to 500, or between 10 to 300, or between 50 to 500, or between 100 to 500, or between 100 to 300, or between 200 to 500. Under certain conditions, it was surprisingly observed that lowering the amount of catalyst used relative to the amount of DMF used increased selectivity of PX produced.
• a solvent, or a combination or mixture of solvents may also be optionally added to the reaction mixture.
• the solvent(s) used in the methods described herein dissolve(s) at least a portion of ethylene, compounds of formula A and/or compounds of formula B (if present).
• the solvents used in the methods described herein may be obtained from any source, including any
• the methods described herein use certain solvents to convert DMF, HD, or a combination thereof, into /?ara-xylene with yields of at least 50%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% on a molar basis.
• the particular solvents used in the methods described herein typically can solubilize, or at least partially solubilize, the starting materials (e.g. , DMF, HD or a combination thereof, ethylene) and/or catalysts, which can help to enhance the solvation effect and improve the reaction rate.
• the solvent system has an ethylene solubility between about 0 mol/L and about 0.82 mol/L, between about 0.82 mol/L and about 1.2 mol/L, or between about 1.2 mol/L and about 4.0 mol/L, when ethylene solubility is measured a temperature of about 23°C.
• the solvents used may also be selected based on their boiling points.
• the solvents may be selected based on their boiling points at standard pressure or operating pressure.
• the solvent may have a boiling point of between 80°C and 400°C, or between 150°C and 350°C, or between 350°C and 450°C .
• the solvent, or the combination or mixture of solvents, selected may have a boiling point higher than /?ara-xylene. This would allow
• the solvents are typically stable to the process conditions, and preferably can be recycled for use again in the reaction. The recyclability of the solvent is particularly useful for performing the methods described herein on a commercial scale.
• the solvents used herein may be aliphatic or aromatic.
• the solvents may also have one or more functional groups such as halo, ester, ether, ketone, and alcohol, or any combinations or mixtures thereof.
• the solvent may also be non-cyclic (including linear or branched) or cyclic.
• solvents e.g. , aprotic solvents, aliphatic solvents, aromatic solvents, alkyl phenyl solvents, ether solvents, alcohol solvents, ketone solvents, haloginated solvents, or ionic liquids
• dioxane is an ether that is aprotic.
• the solvent system includes dimethylacetamide (e.g. , dimethylacetamide, e.g. , dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, dimethylacetamide, e.g. , N-(2-aminoethyl)-2-methylacetamide
• ⁇ , ⁇ -dimethylacetamide dimethylformamide (e.g. , ⁇ , ⁇ -dimethylformamide), acetonitrile, sulfolane, dioxane, dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether (monoglyme), ethylene glycol diethyl ether (ethyl glyme), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl digylme), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (butyl diglyme), tetraethylene glycol dimethyl ether (tetraglyme), polygyme, proglyme, higlyme, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclobutanone, cyclopentanone, cyclohexanone,
• methylpyrrolidinone e.g. , N-methylpyrrolidinone
• dimethylfuran e.g. , 2,5-dimethylfuran
• dichlorobenzene e.g. , o-dichlorobenzene
• /?ara-xylene mesitylene, dodecylbenzene, pentylbenzene, hexylbenzene
• the solvent system includes dioxane, tetrahydrofuran, sulfolane, triglyme, or any combinations or mixtures thereof.
• the solvent system includes 1,4-dioxane.
• the solvent system includes a glyme.
• the solvent system includes triglyme. Any of the above indicated solvents which have these same properties as dioxane or triglyme may be used as a solvent in the methods described herein.
• the solvent system includes an aprotic solvent.
• the aprotic solvent may have a dipole moment above 0.1.
• the dipole moment is a measure of polarity of a solvent.
• the dipole moment of a liquid can be measured with a dipole meter.
• Suitable aprotic solvents may include, for example,
• dimethylacetamide dimethylformamide (including, for example, N,N-dimethylformamide), methylpyrrolidinone (e.g., N-methylpyrrolidinone), dioxane, polyethers (including, for example, glyme, diglyme, triglyme, tetraglyme), acetonitrile, sulfolane, ethers (including, for example, tetrahydrofuran, dialkylether (e.g., dimethylether, diethylether), nitromethane, anisole, nitrobenzene, bromobenzene, chlorobenzene, or any combinations or mixtures thereof.
• polyethers including, for example, glyme, diglyme, triglyme, tetraglyme
• acetonitrile acetonitrile
• sulfolane ethers
• ethers including, for example, tetrahydrofuran, dialkylether (e.
• the solvent system includes an aliphatic solvent.
• the aliphatic solvent may be linear, branched, or cyclic.
• the aliphatic solvent may also be saturated (e.g., alkane) or unsaturated (e.g., alkene or alkyne).
• the solvent system includes a C1-C20 aliphatic solvent, a CI -CIO, aliphatic solvent, or a C1-C6 aliphatic solvent.
• the solvent system includes a C4-C30 aliphatic solvent, a C6-C30 aliphatic solvent, a C6-C24 aliphatic solvent, or a C6-C20 aliphatic solvent.
• the solvent system includes C8+ alkyl solvent, or a C8-C50 alkyl solvent, a C8-C40 alkyl solvent, a C8-C30 alkyl solvent, a C8-C20 alkyl solvent, or a C8-C16 alkyl solvent.
• Suitable aliphatic solvents may include, for example, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, cycloheptane, octane, cyclooctane, nonane, decane, undecane, dodecane, hexadecane, or any combinations or mixtures thereof.
• the aliphatic solvent is linear.
• the aliphatic solvent may be obtained from petroleum refining aliphatic fractions, including any isomers of the aliphatic solvents, and any mixtures thereof.
• alkane solvents may be obtained from petroleum refining alkane fractions, including any isomers of the alkane solvents, and any mixtures thereof.
• the solvent system includes petroleum refining alkane fractions.
• the solvent system includes an aromatic solvent.
• the solvent system includes a C6-C20 aromatic solvent, a C6-C12 aromatic solvent, or a C13-C20 aromatic solvent.
• the aromatic solvent may be optionally substituted. Suitable aromatic solvents may include, for example, toluene, anisole, nitrobenzene, bromobenzene, chlorobenzene (including, for example, dichlorobenzene), dimethylfuran (including, for example,
• the solvent system includes /?ara-xylene (which may be produced in the reaction or provided to the reaction system).
• an alkyl phenyl solvent refers to a class of solvents that may have one or more alkyl chains and one or more phenyl or phenyl-containing ring systems.
• the alkyl phenyl solvent may be referred to as an alkylbenzene or a phenylalkane.
• phenylalkanes may also be interchangeably referred to as an alkylbenzene.
• (l-phenyl)pentane and pentylbenzene refer to the same solvent.
• the solvent system includes an alkylbenzene.
• alkylbenzene examples may include (monoalkyl)benzenes, (dialkyl)benzenes, and (polyalkyl)benzenes.
• the alkylbenzene has one alkyl chain attached to one benzene ring.
• the alkyl chain may have one or two points of attachment to the benzene ring.
• alkylbenzenes with one alkyl chain having one point of attachment to the benzene ring include pentylbenzene, hexylbenzene and dodecylbenzene.
• the alkyl chain may form a fused cycloalkyl ring to the benzene.
• alkylbenzenes with one alkyl having two points of attachment to the benzene ring include tetralin. It should be understood that the fused cycloalkyl ring may be further substituted with one or more alkyl rings.
• the alkylbenzene has two or more alkyl chains (e.g., 2, 3, 4, 5, or 6 alkyl chains) attached to one benzene ring.
• the alkylbenzene is an alkyl- substituted fused benzene ring system.
• the fused benzene ring system may include benzene fused with one or more heterocyclic rings.
• the fused benzene ring system may be two or more fused benzene rings, such as naphthalene.
• the fused benzene ring system may be optionally substituted by one or more alkyl chains.
• the solvent system includes phenylalkane. Examples may include (monophenyl)alkanes, (diphenyl)alkanes, and (polyphenyl)alkanes. In certain
• the phenylalkane has one phenyl ring attached to one alkyl chain.
• the phenyl ring may be attached to any carbon along the alkyl chain.
• the phenyl alkyl having one alkyl chain may be (l-phenyl)pentane, (2-phenyl)pentane, (l-phenyl)hexane, (2-phenyl)hexane,
• the phenylalkane has two or more phenyl rings attached to one alkyl chain.
• the solvent system includes Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, or any combinations or mixtures thereof.
• the alkyl chain of a solvent may be 1 to 20 carbon atoms (e.g., Ci-20 alkyl). In one embodiment, the alkyl chain may be 4 to 15 carbons (e.g., C 4 _ 1 5 alkyl), or 10 to 13 carbons (e.g., Qo-13 alkyl).
• the alkyl chain may be linear or branched. Linear alkyl chains may include, for example, n-propyl, n-butyl, n-hexyl, n-heptyl, n-octyl, n-nonanyl, n-decyl, n-undecyl, and n-dodecyl.
• Branched alkyl chains may include, for example, isopropyl, sec -butyl, isobutyl, tert-butyl, and neopentyl.
• certain alkyl chains may be linear, whereas other alkyl chains may be branched.
• all the alkyl chains may be linear or all the alkyl chains may be branched.
• the solvent system includes a linear alkylbenzene ("LAB").
• Linear alkylbenzenes are a class of solvents having the formula C 6 H 5 C n H 2n+1 .
• the linear alkylbenzene is dodecylbenzene.
• Dodecylbenzene is commercially available, and may be "hard type” or "soft type”. Hard type dodecylbenzene is a mixture of branched chain isomers. Soft type dodecylbenzene is a mixture of linear chain isomers.
• the solvent system includes a hard type dodecylbenzene.
• the solvent system includes any of the alkyl phenyl solvents described above, in which the phenyl ring is substituted with one or more halogen atoms.
• the solvent system includes an alkyl (halobenzene).
• the alkyl(halobenzene) may include alkyl (chlorobenzene).
• the halo substituent for the phenyl ring may be, for example, chloro, bromo, or any combination thereof.
• the solvent system includes naphthalene, naphthenic oil, alkylated naphthalene, diphenyl, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, or haloginated hydrocarbons.
• the solvent system includes an ether solvent, which refers to a solvent having at least one ether group.
• the solvent system includes a C2-C20 ether, or a C2-C10 ether.
• the ether solvent can be non-cyclic or cyclic.
• the ether solvent may be alkyl ether ⁇ e.g., diethyl ether, glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), or triethylene glycol dimethyl ether (triglyme)).
• the ether solvent may be cyclic, such as dioxane ⁇ e.g., 1,4-dioxane), dioxin, tetrahydrofuran, or a cycloalkyl alkyl ether ⁇ e.g., cyclopentyl methyl ether).
• the solvent system may include an acetal such as dioxolane ⁇ e.g., 1,3-dioxolane).
• the solvent system may also include a polyether with two or more oxygen atoms.
• the ether solvent has a formula as follows: where each R a and R b are independently aliphatic moieties, and n and m are integers equal to or greater than 1.
• each R a and R b are independently alkyl.
• each R a and R b are independently CI -CIO alkyl, or C1-C6 alkyl.
• R a and R b may be the same or different.
• each n and m are independently 1 to 10, or 1 to 6, where n and m may be the same or different.
• the formula above includes proglymes (such as dipropylene glycol dimethylether), or glymes (such as glycol diethers based on ethylene oxide).
• the solvent system includes glyme, diglyme, triglyme, or tetraglyme.
• a solvent having an ether group may also have one or more other functional groups. It should be understood, however, that the solvent may have an ether functional group in combination with one or more additional functional groups, such as alcohols.
• the solvent system includes alkylene glycols ⁇ e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol), phenyl ethers (e.g., diphenyl ether, polyphenyl ethers), or alkylphenylethers (e.g., alkyldiphenyl ether).
• the solvent system includes a polyphenyl ether that includes at least one phenoxy or at least one thiophenoxy moiety as the repeating group in ether linkages.
• the solvent system includes Santovac.
• the solvent system includes an ester solvent, which refers to a solvent having at least one ester group.
• the solvent system includes a C2-C20 ester, or a C2-C10 ester.
• the ester solvent can be non-cyclic (linear or branched) or cyclic.
• non-cyclic ester solvents may include alkyl acetate (e.g., methyl acetate, ethyl acetate, propyl acetate, butyl acetate), triacetin, and dibutylphthalate.
• An example of cyclic ester is, for example, propylene carbonate.
• a solvent having an ester group may also have one or more other functional groups.
• the ester solvent may also include alkyl lactate (e.g., methyl lactate, ethyl lactate, propyl lactate, butyl lactate), which has both an ester group as well as a hydroxyl group.
• the solvent system includes an alcohol, which refers to a solvent having at least hydroxyl group.
• the solvent can be a C1-C20 alcohol, a CI -CIO alcohol, or a C1-C6 alcohol.
• Alcohol solvents may include, for example, methanol, ethanol and propanol.
• the solvent may also be an alkanediol, such as 1,3-propanediol or propylene glycol.
• the solvent system includes a ketone.
• the solvent can be a C2-C20 ketone, a C2-C10 ketone, or a C2-C6 ketone.
• the ketone solvent can be non-cyclic (linear or branched) or cyclic.
• the solvent system includes
• cyclobutanone cyclopentanone, cyclohexanone, cycloheptanone, or cyclooctanone.
• the solvent system includes haloginated solvents.
• the solvent can be a chlorinated solvent.
• Suitable chlorinated solvents may include, for example, carbon tetrachloride, chloroform, methylene chloride, bromobenzene and dichlorobenzene .
• the solvent may also be an ionic liquid.
• Suitable ionic liquids may include, for example, l-allyl-3-methylimidazolium bromide and l-benzyl-3-methylimidazolium
• a combination or mixture of solvents may also used in the methods described herein.
• an ether solvent may be combined with one or more other types of solvents listed above, including for example an aliphatic solvent.
• the solvent combination or mixture is dioxane and an aliphatic solvent.
• the solvent combination is dioxane and dodecane, or /?ara-xylene and dodecane.
• the two or more solvents may be used in any suitable combination to convert DMF and/or HD into PX.
• the two solvents may be present in a weight ratio of about 1 to about 1, or about 1 to about 2, or about 1 to about 3, or about 1 to about 4, or about 1 to about 5.
• the solvent system includes dioxane and dodecane, or /?ara-xylene and dodecane, the two solvents are used in a weight ratio of about 1 to about 1.
• the amount of solvent used may vary depending on the starting materials, catalyst used, and reaction conditions.
• the concentration of the DMF and/or HD in the reaction mixture is from about 1 to about 75% by weight in the solvent, or from about 3 to about 50% by weight in the solvent.
• the amount of solvent used may vary depending on whether the reaction is as a batch or a continuous system. For example in a batch operation, the concentration of the DMF and/or HD in the reaction mixture may start at 50% by weight and end up to be 0.01% by weight.
• ethylene used in the methods described herein may be added using any suitable methods or techniques to the reactor.
• ethylene may be added as a gas into the reactor.
• the initial ethylene pressure refers to the pressure at which ethylene (as a gas) is added to the reactor.
• the ethylene may be added at an initial pressure such that the concentration of this reactant is sufficiently high in the solvent for optimal reaction rates.
• the initial ethylene pressure is at least 10 psi, at least 50 psi, at least 75 psi, at least 100 psi, at least 200 psi, at least 250 psi, at least 300 psi, or at least 400 psi.
• the initial ethylene pressure is between 50 psi and 20,000 psi, or between 100 psi and 20,000 psi, or between 300 psi to 20,000 psi, or between 400 psi and 1 ,000 psi, or between 400 psi and 800 psi, between 600 psi and 1000 psi, between 600 and 6000 psi, or between, between 760 psi and 6000 psi, or between 1000 psi to 6000 psi.
• ethylene may be dissolved, or at least partially dissolved, in one or more solvents described herein and added to the reactor.
• the ethylene solubility in the solvent system is between about 0 mol/L and about 0.82 mol/L, between about 0.82 mol/L and about 1.2 mol/L, or between about 1.2 mol/L and about 4.0 mol/L, when ethylene solubility is measured at temperature of about 23 °C.
• the ethylene may also be provided at supercritical pressures and/or supercritical temperatures.
• the operating temperature refers to the average temperature of the reaction mixture in the vessel.
• the operating temperature may be at least 150°C, or at least 200°C.
• the operating temperature may be between 100°C and 300°C, between 150°C and 400°C, between 150°C and 300°C, between 125°C and 175°C, between 200°C to 350°C, between 200°C to 250°C, between 200°C and 400°C, between 270°C to 400°C, between 220°C to 230°C, between 250°C to 300°C, or between 150°C and 220°C.
• the operating temperature is between room temperature (e.g. , 18°C-22°C) and 300°C.
• the operating pressure refers to the average absolute internal pressure of the vessel.
• the reaction may proceed at an operating pressure between 1 bar and 1000 bar, between 10 bar to 1000 bar, between 20 bar to 1000 bar, between 50 bar to 1000 bar, between 100 bar to 1000 bar, between 150 bar to 500 bar, between 35 and 38 bar, between 1 bar and 50 bar, between 1 bar and 40 bar, between 1 bar and 30 bar, between 1 bar and 20 bar, between 1 bar and
• the operating pressure is between 50 psi and 1 ,000 psi, or between 50 psi and 800 psi, between 50 psi and 700 psi, between 50 psi and 600 psi, or between 600 psi and 1000 psi.
• the ethylene i s near critical where the temperature is between about 270K and about 290 . and the partial operating pressure of ethylene is between about 45 bar and about 65bar.
• the ethylene is supercritical, where the temperature is greater than or equal to about 282 . and the partial operating pressure of ethylene is greater than about 734 psi.
• the ethylene is supercritical, wherein the temperature is greater than or equal to about 282K and the partial operating pressure of ethylene is greater than or equal to about 734 psi.
• the operating temperature and operating pressure may be the same as if each and every combination were individually listed.
• the method is carried out at an operating temperature of about 225 °C and an operating pressure of about 34 bar (equivalent to about 500 psi).
• the methods described herein may also be carried out under supercritical conditions (e.g. , supercritical pressures and/or supercritical temperatures).
• supercritical conditions may be used if a solvent is not used in the reaction.
• the method is carried out at or above 50 bar and/or at or above 9°C (i.e. , 282 K).
• temperature may be expressed as degrees Celsius (°C) or Kelvin (K).
• K Kelvin
• pressure may also be expressed as gauge pressure (barg), which refers to the pressure in bars above ambient or atmospheric pressure. Pressure may also be expressed as bar, atmosphere (atm), pascal (Pa) or pound-force per square inch (psi).
• barg gauge pressure
• Pa pascal
• psi pound-force per square inch
• the method may be performed with or without stirring. In certain preferred embodiments, the method is performed with stirring to increase conversion and/or selectivity.
• the method may be carried out batch-wise or continuously.
• the reaction time (in a batch- wise process) or residence time (in a continuous process) will also vary with the reaction conditions and desired yield, but is generally about 1 to 72 hours.
• the reaction time or residence time is determined by the rate of conversion of the starting material.
• the reaction mixture is reacted for 1 to 24 hours.
• the reaction mixture is reacted for I to 10 hours.
• the reaction mixture is reacted for 1 to 5 hours.
• the reaction mixture is reacted for 1 to 3 hours.
• the reaction mixture is reacted for less than 2 hours.
• the methods described herein may further include isolating the compound of formula I from the reaction mixture.
• the methods described herein further includes isolating /?ara-xylene from the reaction mixture. Any methods known in the art may be employed to isolate the product.
• the compound of formula I e.g. , /?ara-xylene
• the reaction mixture can be first filtered to remove any solid catalysts and desiccants (if present). The filtered mixture may then be transferred to a distillation column.
• One of skill in the art would know how to recover the compound of formula I (e.g. , para-xylene) by distillation since the boiling points of the various components of the reaction mixture are known, including the boiling points of the solvents used.
• the solvent has a boiling point of 101°C. It is known in the art that /?ara-xylene has a boiling point of 138°C; HD has a boiling point of 191°C; and DMF has a boiling point of 94°C.
• the methods described herein may also include purifying the isolated compound of formula I (e.g. , /?ara-xylene). Any suitable methods known in the art may be employed to purify the isolated compound of formula I (e.g., isolated /?ara-xylene), including for example column chromatography or recrystallization.
• the yield of a product takes into account the conversion of the starting materials into the product, and the selectivity for the product over other byproducts that may be formed.
• reaction With respect to the conversion of DMF into /?ara-xylene, the reaction can be generalized as follows, where "A” represents the moles of DMF; “B” represents the moles of ethylene; “C” represents the moles of /?ara-xylene; “D” represents the moles of water produced; and “a”, “b”, “c” and “d” are stoichiometric coefficients.
• the reaction can be generalized as follows, where "A” represents the total moles of HD and DMF; “B” represents the moles of ethylene; “C” represents the mole of /?ara-xylene; “D” represents the moles of water produced; and "a”, “b”, “c” and “d” are stoichiometric coefficients. aA + bB— cC + dD,
• % Conversion Ao * 100%, where A 0 is the initial number of moles of reactant A; and A f is the final number of moles of reactant A.
• the yield of product C is the percentage of reactant A that is converted into product C, as expressed by the following equation:
• selectivity is calculated based on the amount of the molar sum of DMF and HD.
• the methods described herein have a yield of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% by weight.
• the yield is between 10% to 100%, between 10% to 90%, between 20% to 80%, between 30% to 80%, between 40% to 80%, between 50%-80%, or between 60%-80% by weight.
• the methods described herein have a selectivity of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 99%.
• the selectivity is between 40% to 99%, between 40% to 95%, between 40% to 90%, between 40% to 80%, between 50% to 99%, between 50% to 95%, between 50% to 90%, between 50% to 80%, between 60% to 99%, between 60% to 95%, between 60% to 90%, between 60% to 80%, between 70% to 99%, between 70% to 95%, between 70% to 90%, or between 70% to 80%.
• the compounds of formula I including /?ara-xylene (PX or p-xylene) for example, produced according to the methods described herein may be suitable for manufacture of one or more plastics, solvents or fuels.
• /?ara-xylene can also be further oxidized to produce terephthalic acid.
• the terephthalic acid can be further processed to manufacture one or more plastics.
• a method for producing /?ara-xylene comprising:
• the solvent system comprises an ether solvent.
• the solvent system comprises a C1-C20 aliphatic solvent, a C6-C20 aromatic solvent, an alkyl phenyl solvent, a C2-C20 ether, a C2-C20 ester, a C1-C20 alcohol, a C2-C20 ketone, or any combinations or mixtures thereof.
• the solvent system comprises dimethylacetamide, acetonitrile, sulfolane, dioxane, dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether (monoglyme), ethylene glycol diethyl ether (ethyl glyme), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl digylme), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (butyl diglyme), tetraethylene glycol dimethyl ether (tetraglyme), polygyme, proglyme, higlyme, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone,
• the solvent system comprises dioxane, glyme, diglyme, triglyme, decane, dodecane, /?ara-xylene, or any combinations or mixtures thereof.
• the catalyst comprises a Group 3 metal cation, a Group 9 metal cation, a Group 10 metal cation, a Group 11 metal cation, or a metal cation from the lanthanide series.
• the catalyst comprises a metal cation selected from the group consisting of Zn 2+ , Cu 2+ , Ni 2+ , Co 2+ , Al 3+ , In 3+ , Fe 3+ , La 3+ , Gd 3+ , and Y 3+ . 13.
• the catalyst is aluminum chloride, aluminum bromide, aluminum triflate, bismuth chloride, bismuth bromide, bismuth triflate, copper chloride, copper bromide, copper triflate, cobalt chloride, cobalt bromide, cobalt triflate, chromium chloride, chromium bromide, chromium triflate, iron chloride, iron bromide, iron triflate, gadolinium chloride, gadolinium bromide, gadolinium triflate, indium chloride, indium bromide, indium triflate, nickel chloride, nickel bromide, nickel triflate, neodynium chloride, neodynium bromide, neodynium triflate, magnesium chloride, magnesium bromide, magnesium triflate, lanthanum chloride, lanthanum bromide, lanthanum triflate, scandium chloride, scandium bromide, scandium triflate, tin
• a method for producing terephthalic acid comprising:
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, comprising: a) combining one or more compounds of formula A, one or more compounds of formula B:
• R x S0 3 H wherein R x is alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 8 substituents independently selected from the group consisting alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro, -OR', -C(0)OR',
• each R' and R" is independently hydrogen, alkyl, or haloalkyl.
• R x is alkyl, haloalkyl, or aryl optionally substituted with alkyl, haloalkyl, or nitro.
• sulfonic acid is CF 3 S0 3 H (i.e., triflic acid), HCF 2 CF 2 S0 3 H, C 6 FsS0 3 H, 4-methylbenzenesulfonic acid (i.e., /?-toluene-sulfonic acid), or 2,4-dinitrobenzenesulfonic acid.
• R x is alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 5 substituents independently selected from the group consisting alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro,
• the salt of the sulfonic acid is Al(OTf) 3 , Bi(OTf) 3 , Cu(OTf) 2 , Cu(OTf), Cr(OTf) 3 , Fe(OTf) 3 , Gd(OTf) 3 , In(OTf) 3 , Ni(OTf) 2 , Nd(OTf) 3 , Mg(OTf) 2 , La(OTf) 3 , Sc(OTf) 3 , Ti(OTf) 4 , V(OTf) 5 , Y(OTf) 3 , Zn(OTf) 2 , Pt(OTf) 2 , Pd(OTf) 2 , Ag(OTf), Au(OTf) 3 , NH (OTf), Sn(OTf) 4 , Sn(OTf) 3 , Sn(OTf) 2 , B(OTf) 3 , or any combinations thereof.
• the sulfonimide has a structure of formula (R yl S0 2 )NH(S0 2 R y2 ), wherein R yl and R y2 are each independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 5 substituents independently selected from the group consisting alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl.
• each R yl and R y2 is independently alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl is optionally substituted with 1 to 5 substituents independently selected from the group consisting alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, nitro,
• Q r+ is Al 3+ , Bi 3+ , Cu 2+ , Cu + , Cr 3+ , Fe 3+ , Gd 3+ , In 3+ , Ni 2+ , Nd 3+ , Mg 2+ , Ba 2+ , Ca 2+ , La 3+ , Sc 3+ , Ti 4+ , V 5+ , Y 3+ , Zn 2+ , Pt 2+ , Pd 2+ , Ag + , Au 3+ , NH 4 + , Sn 4+ , Sn 3+ , Sn 2+ , or B 3+ .
• bis(trifluoromethylsulfonyl)imide triethylsulfonium bis(trifluoromethylsulfonyl)imide, or any combinations thereof.
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, comprising: a) combining one or more compounds of formula A, one or more compounds of formula B:
• reaction mixture b) producing one or more compounds of formula I from at least a portion of the one or more compounds of formula A, the one or more compounds of formula B, or any combinations thereof, and at least a portion of the ethylene in the reaction mixture.
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, comprising: a) combining one or more compounds of formula A, one or more compounds of formula B:
• each R 1 and R 2 is independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, comprising: a) combining one or more compounds of formula A, one or more compounds of formula B:
• the solvent system comprises an aliphatic solvent, an aromatic solvent, an alkyl phenyl solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, an ionic liquid, or any combinations or mixtures thereof.
• the solvent system comprises dimethylacetamide, acetonitrile, sulfolane, dioxane, dioxane, dimethyl ether, diethyl ether, glycol dimethyl ether (monoglyme), ethylene glycol diethyl ether (ethyl glyme), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl digylme), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (butyl diglyme), tetraethylene glycol dimethyl ether (tetraglyme), polygyme, proglyme, higlyme, tetrahydrofuran, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooct
• R 1 and R2" are each methyl; or R 1 is methyl and R 2 is hydrogen; and
• sulfonic acid or a salt, ester, anhydride or polymer thereof.
• R 1 and R 2" are each methyl
• sulfonic acid or a salt, ester, anhydride or polymer thereof.
• the sulfonic acid or a salt thereof is triflic acid or a salt thereof.
• R 1 and R2" are each methyl; or R 1 is methyl and R 2 is hydrogen; and
• the solvent system comprises /?ara-xylene, a C4-C30 alkyl solvent, or any mixture thereof.
• R 1 and R 2" are each methyl
• the solvent system comprises /?ara-xylene, a C4-C30 alkyl solvent, or any mixture thereof.
• a mixture of 5.0 g of DMF, 0.025 g of copper triflate, and 100 mL of dioxane were charged to a high pressure autoclave fitted with a gas entrainment impeller.
• the autoclave was purged 3 times with nitrogen, once with ethylene, and then pressurized to 500 psig (3,447 kpas) with ethylene.
• the autoclave was heated to 250°C at which point the pressure increased to 2250 psig (15,513 kpas).
• the reactor remained pressurized at 250°C for 7 hours whereby the heater was turned off and the reactor was allowed to cool at RT The pressure was vented and the reaction solution was decanted into a storage bottle.
• the reaction mixture was a light yellow solution with a slight amount of black precipitate.
• the solution phase was analyzed by 1 H and 1 1 3 J C NMR spectroscopy, identifying residual DMF, PX, ethylene and HD as the major components together with dioxane as solvent. These components were quantified by 1H NMR spectroscopy, the values being given in Table 1 below. Ethylene was observed in this sample at about 0.3 mole by NMR.
• a mixture of 8.0 g of DMF, 2.0 g of HD, 0.5g of yttrium inflate, and 200 g of dioxane were charged to a high pressure autoclave fitted with a gas entrainment impeller.
• the autoclave was purged 3 times with nitrogen, once with ethylene, and then pressurized to 500 psig (3,447 kpas) with ethylene.
• the autoclave was heated to 250°C at which point the pressure increased to 2,000 psig (13,790 kpas).
• the reactor remained pressurized at 250°C for 7 hours. Samples were taken at hour intervals and analyzed by NMR spectroscopy for conversion and selectivity.
• Mol% refers to mol% in dioxane, except for the HD which is calculated as the mol% of initial DMF
• ND refers to "no data"
• This example compares the rate of reaction in converting DMF into PX using supported catalysts (e.g. , CuCl 2 on alumina, CuCl 2 on HY Zeolite) versus unsupported catalysts (e.g. , CuCl 2 , Cu(OTf) 2 , Y(OTf) 3 ).
• supported catalysts e.g. , CuCl 2 on alumina, CuCl 2 on HY Zeolite
• unsupported catalysts e.g. , CuCl 2 , Cu(OTf) 2 , Y(OTf) 3 .
• the autoclave was heated to 250°C.
• the reactor remained pressurized at 250°C for 7 hours. Samples were taken at hour intervals and analyzed by NMR spectroscopy for conversion and selectivity. After 7 hours, the heater was turned off and the reactor was allowed to cool to RT. The pressure was vented and the reaction solution was decanted into a storage bottle. Conversion, molar selectivity, and yield for each catalyst are summarized in Table 3 below.
• This example compares the rate of reaction in converting DMF into PX using varying amounts of catalyst.
• This examples compares the rate of reaction in converting DMF into PX using different solvents, including dioxane, triglyme, triethylene glycol (TEG), N-methylpyrrole (NMP), sulfolane, propylene carbonate, and dimethylsulf oxide (DMSO).
• solvents including dioxane, triglyme, triethylene glycol (TEG), N-methylpyrrole (NMP), sulfolane, propylene carbonate, and dimethylsulf oxide (DMSO).
• ND refers to "no data"
• This examples compares the rate of reaction in converting DMF into PX using different solvents and catalysts s.
• the solvents used include triglyme and triethylene glycol (TEG).
• the catalysts s include Cu(OTf) 2 and Y(OTf) 3 .
• This example compares the rate of reaction in converting DMF into PX at different temperatures.
• the protocol described in Example 5 above for converting DMF into PX was used according to the temperatures set forth in Table 11 below.
• the reactions in this example used 10 g DMF, 1.0 g Q1CI 2 , 200g dioxane, and 500 psig C 2 H 4 . Conversion and molar selectivity, and yield are summarized in Table 11 below.
• This example compares the rate of reaction in converting DMF into PX at different pressures.
• the protocol described in Example 5 above for converting DMF into PX was used according to the conditions set forth in Tables 12 and 13 below.
• the solvent used in this example was dioxane, and the catalysts used were Q1O 2 and Y(OTf) 3 .
• Conversion, molar selectivity, and yield for each catalyst for each catalyst /pressure combination is summarized in the tables below. Table 12. Summary of Y(OTf) 3 /pressure data (0.5 g Y(OTf) 3 , 10 g DMF, 200 g dioxane, 250°C
• This example compares the rate of reaction in converting DMF into PX using metal-containing salt catalysts, such as copper acetate and copper acetylacetonate.
• metal-containing salt catalysts such as copper acetate and copper acetylacetonate.
• the protocol described in Example 5 was used in for each catalyst and solvent along with the reaction conditions as summarized in Table 18 below.
• PX yield for each reaction is also provided in Table 18 below.
• Parr reactor was subjected to a nitrogen flow to enable cooling. Once the reactor was brought to room temperature the excess ethylene was slowly released through the gas release valve and the reaction mixture was transferred in a sample container and submitted to analysis by NMR and
• This example demonstrates the effect of various concentrations of DMF and Cu(OTf) 2 (as the catalyst) in converting DMF into PX.
• Dodecane alone or a mixture of dodecane and dioxane was used as the solvent.
• the protocol described in Example 16 was used in for each reagent along with the reaction conditions as summarized in Table 20 below. PX conversion and selectivity for each reaction is also provided in Table 20 below.
• This example demonstrates the effect of a mixture of solvents in converting DMF into PX.
• the solvents used in this Example include /?ara-xylene, dodecane and dioxane.
• the protocol described in Example 16 was used in for each reagent along with the reaction conditions as summarized in Table 21 below. PX conversion and selectivity for each reaction is also provided in Table 21 below. Table 21. Summary of solvent mixture data
• 12-Molybdophosphoric acid monohydrate were observed to convert PX with conversions of about 98% and selectivity of about 80% when dioxane was used as solvent. Additionally, it was surprisingly observed that triflic acid alone catalyzed the conversion of DMF into PX.
• the pressure was readjusted to 500 psig by adding more ethylene, so that the total ethylene introduced was 655 psi.
• the reaction mixture was heated to 250 °C and maintained at this temperature for 7 hours. At the end of the reaction time, the heating mantle was removed and the exterior of the Parr reactor was subjected to a nitrogen flow to enable cooling. Once the reactor was brought to room temperature the excess ethylene was slowly released through the gas release valve and the reaction mixture was transferred into a sample container and submitted to analysis by NMR and GC-MS.
• the reaction mixture was heated to 250 °C and maintained at this temperature for 7 hours. At the end of the reaction time, the heating mantle was removed and the exterior of the Parr reactor was subjected to a nitrogen flow to enable cooling. Once the reactor was brought to room temperature the excess ethylene was slowly released through the gas release valve and the reaction mixture was transferred into a sample container and submitted to analysis by NMR and GC-MS.
• n-Heptane (52.3 g), dodecane (7.82g), 2,5-dimethylfuran (11.54g, 0.120 mol) (1.2 M solution of 2,5-dimethylfuran in the mixture of n-heptane and dodecane) and 0.45 g calcined ?-zeolite (Zeolyst CP 814 E) were charged in the Parr vessel and the reactor was sealed, placed in the heating mantle and attached to the nitrogen line, ethylene cylinder, temperature controller and a waste container (through the gas release valve).
• the reaction mixture was flushed three times with nitrogen (nitrogen pressure ⁇ 80 psig) and three times with ethylene (ethylene pressure ⁇ 100 psig) then 200 psig ethylene was introduced in the reaction mixture under stirring at 1020 Hz.
• the reaction mixture was heated to 250 °C and maintained at this temperature for 24 hours.
• the heating mantle was removed and the exterior of the Parr reactor was subjected to a nitrogen flow to enable cooling. Once the reactor was brought to room temperature the excess ethylene was slowly released through the gas release valve.

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