WO2016122940A1 - Methods of producing anhydrosugar alcohols - Google Patents

Methods of producing anhydrosugar alcohols Download PDF

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Publication number
WO2016122940A1
WO2016122940A1 PCT/US2016/014109 US2016014109W WO2016122940A1 WO 2016122940 A1 WO2016122940 A1 WO 2016122940A1 US 2016014109 W US2016014109 W US 2016014109W WO 2016122940 A1 WO2016122940 A1 WO 2016122940A1
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supported
carbon
acid
catalyst
poly
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PCT/US2016/014109
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French (fr)
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John M. GEREMIA
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Midori Usa, Inc.
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Publication of WO2016122940A1 publication Critical patent/WO2016122940A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Definitions

  • the present disclosure relates generally to methods of producing anhydrosugar alcohols from sugar alcohols. More specifically, the present disclosure relates to the production of anhydrosugar alcohols, such as isosorbide, from sugar alcohols, such as sorbitol, using a catalyst with acidic and ionic groups.
  • anhydrosugar alcohols such as isosorbide
  • sugar alcohols such as sorbitol
  • Anhydrosugar alcohols and their derivatives are commercially used in various applications, such as the production of pharmaceutical compounds, cosmetics, food, and plastics.
  • Isosorbide also referred to as 1,4-3, 6-dianhydro-D- sorbitol
  • isosorbide is used to produce isosorbide dimethyl ether, which may be used as an industrial solvent; and isosorbide dinitrate, which may be used to treat heart-related chest pain.
  • Methods known in the art for producing anhydrosugar alcohols typically involve contacting a sugar alcohol with an acid catalyst at elevated temperatures. See e.g., U.S. Patent Nos. 4,408,061; 7,982,059; 7,439,352; 8,445,705; and 7,728,156.
  • a significant decrease in the activity of the catalyst is often observed over each cycle of recovery and reuse in such known methods, unless costly further processing steps are used to maintain the activity of the catalyst.
  • the catalyst may be washed with an organic solvent between reaction cycles;
  • a method of producing a dianhydrosugar alcohol from a sugar alcohol by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture.
  • a method of producing a dianhydrosugar alcohol from a sugar alcohol by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a dianhydrosugar alcohol.
  • a method of producing a monoanhydrosugar alcohol from a sugar alcohol by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a monoanhydrosugar alcohol from at least a portion of the reaction mixture.
  • a method of producing a monoanhydrosugar alcohol from a sugar alcohol by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a monoanhydrosugar alcohol.
  • a method of producing a dianhydrosugar alcohol from a monoanhydrosugar alcohol by: combining a monoanhydrosugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture.
  • a method of producing a dianhydrosugar alcohol from a monoanhydrosugar alcohol by: combining a sugar alcohol with a catalyst; and dehydrating the monoanhydrosugar alcohol to produce a dianhydrosugar alcohol.
  • the catalyst is a polymeric catalyst.
  • the polymeric catalyst has acidic monomers and ionic monomers connected to form a polymeric backbone.
  • the catalyst is a solid-supported catalyst.
  • the solid-supported catalyst has a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
  • the catalysts used in the methods described herein exhibit a loss of activity of less than 1% per cycle.
  • the dianhydrosugar alcohol produced is isosorbide, and the sugar alcohol is sorbitol.
  • FIG. 1 is an exemplary reaction scheme depicting the production of an anhydrosugar alcohol from a sugar alcohol in the presence of a catalyst.
  • FIG. 2A illustrates a portion of a catalyst with a polymeric backbone and side chains.
  • FIG. 2B illustrates a portion of an exemplary catalyst, in which a side chain with the acidic group is connected to the polymeric backbone by a linker and in which a side chain with the cationic group is connected directly to the polymeric backbone.
  • FIG. 3 depicts a reaction scheme to prepare a dual-functionalized catalyst from an activated carbon support, in which the catalyst has both acidic and ionic moieties.
  • FIG. 4 illustrates a portion of a polymeric catalyst, in which the monomers are arranged in blocks of monomers, and the block of acidic monomers alternates with the block of ionic monomers.
  • FIG. 5A illustrates a portion of a polymeric catalyst with cross-linking within a given polymeric chain.
  • FIG. 5B illustrates a portion of a polymeric catalyst with cross-linking within a given polymeric chain.
  • FIG. 6A illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
  • FIG. 6B illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
  • FIG. 6C illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
  • FIG. 6D illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
  • FIG. 7 illustrates a portion of a polymeric catalyst with a polyethylene backbone.
  • FIG. 8 illustrates a portion of a polymeric catalyst with a polyvinylalcohol backbone.
  • FIG. 9 illustrates a portion of a polymeric catalyst, in which the monomers are randomly arranged in an alternating sequence.
  • FIG. 10 illustrates two side chains in a polymeric catalyst, in which there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 11 illustrates two side chains in a polymeric catalyst, in which there are zero carbons between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 12 illustrates a portion of a polymeric catalyst with an ionomeric backbone.
  • FIG. 13 is an exemplary process diagram depicting the steps of producing
  • anhydrosugar alcohol from sugar alcohol in the presence of a catalyst, in which the catalyst is recovered and reused for one or more reaction cycles.
  • FIG. 14 is a graph depicting the conversion of sorbitol to isosorbide over time using a catalyst loading of 0.1 kg catalyst per kg of sorbitol.
  • FIG. 15 is a high-performance liquid chromatography (HPLC) trace showing the reaction mixture contents after 1.5 hours during the conversion of sorbitol to isosorbide in the presence of a catalyst containing acidic and ionic groups.
  • HPLC high-performance liquid chromatography
  • FIG. 16 is an HPLC trace showing the reaction mixture contents after 5.5 hours during the conversion of sorbitol to isosorbide in the presence of a catalyst containing acidic and ionic groups.
  • FIG. 17 is a graph comparing the catalyst rate constant over four cycles of use of a catalyst during conversion of sorbitol to isosorbide.
  • the sugar alcohols can undergo a dehydration reaction in the presence of the catalysts described herein to produce dianhydrosugar alcohols.
  • sorbitol an example of a sugar alcohol
  • isosorbide an example of a dianhydrosugar alcohol
  • the sugar alcohols can also undergo a dehydration reaction in the presence of the catalysts described herein to produce monanhydrosugar alcohols.
  • xylitol an example of a sugar alcohol
  • 1,4-anhydroxylitol an example of a monoanhydrosugar alcohol
  • the monoanhydrosugar alcohols can undergo a dehydration reaction in the presence of the catalysts described herein to produce dianhydrosugar alcohols.
  • dianhydrosugar alcohols For example, in some aspects, 2-(l,2-dihydroxyethyl)tetrahydrofuran-3,4-diol (an example of a monoanhydrosugar alcohol) may be dehydrated in the presence of the catalysts described herein to produce isosorbide (an example of a dianhydrosugar alcohol).
  • the catalysts used in the methods described herein may be recycled and reused.
  • the catalysts described herein are recycled over multiple reaction cycles, and the catalytic activity of a catalyst in the first reaction cycle may be the same or similar to the catalytic activity of the recycled catalyst used in subsequent reaction cycle(s).
  • the ability of the catalysts described herein to retain catalytic activity over multiple reactions cycles of recovery and reuse presents several commercial advantages, including reducing the need to add fresh catalyst to achieve similar levels of catalytic activity, which can in turn reduce the cost of anhydrosugar alcohol production.
  • provided herein are methods of producing anhydrous sugar alcohols from sugar alcohols using recyclable catalysts, in which the catalytic activity of the recyclable catalysts in the first reaction is same or similar to the catalytic activity of the recyclable catalysts in one or more subsequent reaction cycles.
  • a dianhydrosugar alcohol is produced from a sugar alcohol by:
  • a dianhydrosugar alcohol is produced from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a dianhydrosugar alcohol.
  • a dianhydrosugar alcohol is produced from a monoanhydrosugar alcohol by: combining a monoanhydrosugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture.
  • a dianhydrosugar alcohol is produced from a monoanhydrosugar alcohol, by: combining a monoanhydrosugar alcohol with a catalyst; and dehydrating the monoanhydrosugar alcohol to produce a dianhydrosugar alcohol.
  • a monoanhydrosugar alcohol is produced from a sugar alcohol by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a monoanhydrosugar alcohol from at least a portion of the reaction mixture.
  • a monoanhydrosugar alcohol is produced from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a monoanhydrosugar alcohol.
  • sugar alcohol refers to acyclic compounds with the chemical formula (CHOH) n (CH 2 0H) 2 , wherein n is greater than or equal to 1.
  • sugar alcohols include glycerol, erythritol, threitol, arabinitol, xylitol, ribitol, sorbitol, mannitol, galactitol, fucitol, iditol, and inositol.
  • anhydrosugar alcohol refers to both dianhydrosugar alcohols and monoanhydrosugar alcohols.
  • “monoanhydrosugar alcohol” refers to a compound with the chemical formula C(CHOH) n _i(CH 2 OH) 2 , wherein n is greater than or equal to 1.
  • monoanhydrosugar alcohols include 2-(l,2-dihydroxyethyl)tetrahydrofuran-3,4-diol and 2- (hydroxymethyl)tetrahydrofuran-3,4-diol.
  • dianhydrosugar alcohol refers to a compound with the chemical formula C 2 (CHOH) n _2(CH 2 OH)2, wherein n is greater than or equal to 2.
  • dianhydrosugar alcohols include isosorbide, isomannide, and isoidide.
  • process 100 is an exemplary embodiment for producing dianhydrohexitol 110 from hexitol 102 in the presence of catalyst 104.
  • the catalyst 104 contains both acidic and ionic groups.
  • catalyst 104 is a polymeric catalyst or a solid-supported catalyst.
  • hexitol 102 is sorbitol
  • isosorbide is dianhydrohexitol 110 produced.
  • provided herein are methods of producing isosorbide from sorbitol using a catalyst containing both acidic and ionic groups. It should be generally understood that other sugar alcohols, as described herein, may be used to produce their corresponding anhydrosugar alcohols.
  • one or more additional reagents may be used.
  • hexitol 102 may be contacted with catalyst 104 and a solvent.
  • hexitol 102 may be contacted with catalyst 104 and an additional acid.
  • process 100 may include one or more steps.
  • process 100 may further include isolating catalyst 104 from the reaction mixture to recover the catalyst.
  • the isolated catalyst may then be contacted with additional hexitol to produce additional dianhydrohexitol.
  • catalyst 104 may be recycled for use in one or more subsequent reaction cycles.
  • process 200 depicts an exemplary multi-step scheme for producing anhydrosugar alcohol from sugar alcohol in the presence of catalyst, in which the catalyst is recycled for use in one or more subsequent reaction cycles.
  • the sugar alcohol provided in step 202 and the catalyst provided in step 204 are combined in step 206 to produce anhydrosugar alcohol in step 210.
  • the catalyst is isolated from the anhydrosugar alcohol produced, and reused in step 204 to provide catalyst for another reaction cycle. Steps 212, 204, 206, and 210 may be repeated one or more cycles, after which the anhydrosugar alcohol produced is isolated in step 220.
  • step 206 the sugar alcohol and catalyst are combined in step 206 in the further presence of a solvent.
  • the sugar alcohol and catalyst are combined in step 206 in the further presence of additional reactants.
  • process 200 may include one or more steps, or one more steps in process 200 may be omitted.
  • the anhydrosugar alcohol isolated in step 220 of process 200 may undergo further processing, for example, purification.
  • step 220 to isolate the anhydrosugar alcohol may be omitted and the reaction mixture containing anhydrosugar alcohol produced in step 210 may be used in a subsequent chemical transformation.
  • sugar alcohols used in the methods described herein may be obtained from any commercially available sources or produced according to any methods known in the art.
  • the sugar alcohols used may be obtained from biomass.
  • Any suitable sugar alcohol that can be converted into an anhydrosugar alcohol may be used as a starting material in the methods described herein.
  • suitable sugar alcohols include arabinitol, ribitol, sorbitol, mannitol, galactitol, iditol, mannitol, and xylitol. Any mixtures of the sugar alcohols described herein may also be used.
  • the sugar alcohol is a C6 sugar alcohol.
  • a "C6 sugar alcohol” refers to a sugar alcohol with six carbon atoms.
  • a C6 sugar alcohol may also be referred to as a "hexitol”.
  • the sugar alcohol is sorbitol.
  • the sugar alcohol is a C5 sugar alcohol.
  • a "C5 sugar alcohol” refers to a sugar alcohol with five carbon atoms.
  • a C5 sugar alcohol may also be referred to as a "pentitol”.
  • the sugar alcohol is xylitol.
  • the monoanhydrosugar alcohols used in the methods described herein may be obtained from any commercially available sources or produced according to any methods known in the art.
  • the monoanhydrosugar alcohols used may be obtained from biomass.
  • Any suitable monoanhydrosugar alcohol that can be converted into a dianhydrosugar alcohol may be used as a starting material in the methods described herein.
  • suitable sugar alcohols include 1,4-anhydroxylitol and 1,4-anhydrosorbitol. Any mixtures of the monoanhydrosugar alcohols described herein may also be used. Catalysts
  • the catalysts used in the methods described herein include polymeric catalysts and solid-supported catalysts.
  • the catalyst is a polymer made up of acidic monomers and ionic monomers (which are also referred to herein as "ionomers") connected to form a polymeric backbone.
  • Each acidic monomer includes at least one Bronsted-Lowry acid
  • each ionic monomer includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or any combination thereof.
  • at least some of the acidic and ionic monomers may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to a portion of the polymeric backbone.
  • the Bronsted-Lowry acid and the linker together form a side chain.
  • the cationic group and the linker together form a side chain.
  • the side chains are pendant from the polymeric backbone.
  • the catalyst is solid-supported, having acidic moieties and ionic moieties each attached to a solid support.
  • Each acidic moiety independently includes at least one Bronsted-Lowry acid
  • each ionic moiety includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or any combination thereof.
  • at least some of the acidic and ionic moieties may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to the solid support.
  • the produced catalyst is a solid-supported catalyst with acidic and ionic moieties.
  • the polymeric catalysts include a plurality of acidic monomers, where as the solid-supported catalysts include a plurality of acidic moieties attached to a solid support.
  • a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic moieties (e.g., of a solid-supported catalyst) has at least one Bronsted- Lowry acid.
  • a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic moieties (e.g., of a solid-supported catalyst) has one Bronsted- Lowry acid or two Bronsted-Lowry acids.
  • a plurality of the acidic monomers (e.g. , of a polymeric catalyst) or a plurality of the acidic moieties (e.g. , of a solid- supported catalyst) has one Bronsted-Lowry acid, while others have two Bronsted-Lowry acids.
  • each Bronsted-Lowry acids is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, each Bronsted-Lowry acids is independently sulfonic acid or phosphonic acid. In one embodiment, each Bronsted-Lowry acid is sulfonic acid. It should be understood that the Bronsted-Lowry acids in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid- supported catalyst) may be the same at each occurrence or different at one or more occurrences.
  • an acidic monomer e.g. , of a polymeric catalyst
  • an acidic moiety e.g. , of a solid- supported catalyst
  • one or more of the acidic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the acidic moieties of a solid- supported catalyst are directly connected to the solid support.
  • one or more of the acidic monomers (e.g. , of a polymeric catalyst) or one or more acidic moieties (e.g. , of a solid- supported catalyst) each independently further includes a linker connecting the Bronsted-Lowry acid to the polymeric backbone or the solid support (as the case may be).
  • some of the Bronsted-Lowry acids are directly connected to the polymeric backbone or the solid support (as the case may be), while other the Bronsted-Lowry acids are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
  • each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.
  • each linker in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid-supported catalyst) is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1
  • the acidic monomers e.g. , of a polymeric catalyst
  • one or more acidic moieties e.g. , of a solid-supported catalyst
  • linker may have the same linker, or independently have different linkers.
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each Z is independently C(R 2 )(R 3 ), N(R 4 ), S, S(R 5 )(R 6 ), S(0)(R 5 )(R 6 ), S0 2 , or O, wherein any two adjacent Z can (to the extent chemically feasible) be joined by a double bond, or taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl;
  • each m is independently selected from 0, 1, 2, and 3;
  • each n is independently selected from 0, 1, 2, and 3;
  • each R , R , and R is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl;
  • each R 5 and R 6 is independently alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl.
  • each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas IA, IB, IVA, or IVB.
  • each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas IA, IB, IVA, or IVB.
  • each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may
  • each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas IIIA, MB, or IIIC.
  • each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas VA, VB, or VC.
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • Z can be chosen from C(R 2 )(R 3 ), N(R 4 ), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl, and heteroaryl.
  • any two adjacent Z can be joined by a double bond. Any combination of these embodiments is also contemplated (as chemically feasible).
  • m is 2 or 3. In other embodiments, n is 1, 2, or 3.
  • R 1 can be hydrogen, alkyl or heteroalkyl. In some embodiments, R 1 can be
  • each R , R and R can independently be
  • each R , R and R can independently be heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl.
  • each R 5 and R 6 can independently be alkyl, heterocyclyl, aryl, or heteroaryl.
  • any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the polymeric catalysts and solid-supported catalysts described herein contain monomers or moieties, respectively, that have at least one Bronsted- Lowry acid and at least one cationic group.
  • the Bronsted-Lowry acid and the cationic group can be on different monomers/moieties or on the same monomer/moiety.
  • the acidic monomers of the polymeric catalyst may have a side chain with a Bronsted-Lowry acid that is connected to the polymeric backbone by a linker.
  • the acidic moieties of the solid-supported catalyst may have a Bronsted- Lowry acid that is attached to the solid support by a linker.
  • Side chains (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid- supported catalyst) with one or more Bronsted-Lowry acids connected by a linker can include, for example,
  • L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; and r is an integer.
  • L is an alkyl linker.
  • L is methyl, ethyl, propyl, or butyl.
  • the linker is ethanoyl, propanoyl, or benzoyl.
  • r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be: wherein: s is 1 to 10; each r is independently 1 , 2, 3, 4, or 5 (as applicable or chemically feasible); and w is 0 to 10.
  • s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1.
  • w is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • the acidic monomers e.g. , of a polymeric catalyst
  • the acidic moieties e.g. , of a solid-supported catalyst
  • Side chains directly connect to the polymeric backbone (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid-supported catalyst) directly attached to the solid support may can include, for example,
  • the polymeric catalysts include a plurality of ionic monomers, where as the solid-supported catalysts includes a plurality of ionic moieties attached to a solid support.
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • a plurality of ionic monomers e.g.
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • the ionic monomers e.g. , of a polymeric catalyst
  • ionic moieties e.g. , of a solid-supported catalyst
  • the cationic groups can be the same or different.
  • each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is a nitrogen-containing cationic group.
  • each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is a phosphorous-containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is imidazolium, while the cationic group in other monomers (e.g.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a substituted phosphonium.
  • the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is triphenyl phosphonium, while the cationic group in other monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is imidazolium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from imidazolium, pyridinium, pyrimidinium, morpholinium, piperidinium, and piperizinium.
  • the nitrogen-containing cationic group can be imidazolium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous -containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, and triethyl phosphonium.
  • the phosphorous-containing cationic group can be triphenyl phosphonium.
  • one or more of the ionic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the ionic moieties of a solid- supported catalyst are directly connected to the solid support.
  • one or more of the ionic monomers (e.g. , of a polymeric catalyst) or one or more ionic moieties (e.g. , of a solid-supported catalyst) each independently further includes a linker connecting the cationic group to the polymeric backbone or the solid support (as the case may be).
  • some of the cationic groups are directly connected to the polymeric backbone or the solid support (as the case may be), while other the cationic groups are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
  • each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker.
  • the linker is a phenyl linker.
  • the linker is a hydroxyl-substituted phenyl linker.
  • a solid-supported catalyst is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
  • ionic monomers e.g. , of a polymeric catalyst
  • one or more ionic moieties e.g. , of a solid-supported catalyst
  • linker may have the same linker, or independently have different linkers.
  • each ionic monomer e.g. , of a polymeric catalyst
  • each ionic moiety e.g. , of a solid-supported catalyst
  • each R is independently hydrogen, Ci_ 4 alkyl, or Ci_ 4 heteroalkyl.
  • Z can be chosen from C(R")(R J ), N(R ), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl and heteroaryl. In other embodiments, any two adjacent Z can be joined
  • each X can be CI “ , N0 3 ⁇ , S0 4 , R'S0 4 ⁇ , or R'C0 2 ⁇ , where R can be hydrogen or Ci_ 4 alkyl.
  • each X can be CI " , B ⁇ , HS0 4 " , HC0 2 " , CH 3 C0 2 " , or N0 3 " .
  • X is acetate.
  • X is bisulfate.
  • X is chloride.
  • X is nitrate.
  • n is 1, 2, or 3. In some embodiments, m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some
  • each R , R , and R can be independently hydrogen, alkyl, heterocyclyl, aryl, or
  • each R , R and R can be independently heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl.
  • each R 5 and R 6 can be independently alkyl, heterocyclyl, aryl, or heteroaryl.
  • any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the ionic monomers of the polymeric catalyst may have a side chain with a cationic group that is connected to the polymeric backbone by a linker.
  • the ionic moieties of the solid-supported catalyst may have a cationic group that is attached to the solid support by a linker.
  • Side chains (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid-supported catalyst) with one or more cationic groups connected by a linker can include, for example, ⁇ ⁇
  • L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; each R la , R lb and R lc are independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heterocycloalkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R lc is absent; r is an integer; and
  • X is as described above for Formulas VIIA-XIB .
  • L is methyl, ethyl, propyl, butyl.
  • the linker is ethanoyl, propanoyl, benzoyl.
  • r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • each linker is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
  • each linker is an unsubstituted alkyl linker or an alkyl linker with an oxo substituent.
  • r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • at least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
  • each R la , R lb and R lc are independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R a and R 1D are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R c is absent; s is an integer; v is 0 to 10; and
  • X is as described above for Formulas VIIA-XIB .
  • s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1.
  • v is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
  • At least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
  • the ionic monomers e.g. , of a polymeric catalyst
  • the ionic monomers can have a side chain with a cationic group that is directly connected to the polymeric backbone.
  • the ionic moieties e.g. , of a solid- supported catalyst
  • Side chains e.g. , of a polymeric catalyst directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid- supported catalyst) directly attached to the solid support may can include, for example,
  • the nitrogen-containing cationic group can be an N-oxide, where the negatively charged oxide (0-) is not readily dissociable from the nitrogen cation.
  • Non- limiting examples of such groups include, for example,
  • the phosphorous-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the ionic monomers e.g. , of a polymeric catalyst
  • the ionic monomers can have a side chain with a cationic group that is directly connected to the polymeric backbone.
  • the ionic moieties e.g. , of a solid- supported catalyst
  • Side chains e.g. , of a polymeric catalyst directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid- supported catalyst) directly attached to the solid support may can include, for example,
  • the ionic monomers (e.g., of a polymeric catalyst) or ionic moieties (e.g., of a solid-supported catalyst) can either all have the same cationic group, or can have different cationic groups.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a nitrogen-containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a phosphorous-containing cationic group.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst, respectively is a nitrogen-containing cationic group, whereas the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst, respectively, is a phosphorous -containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is pyridinium.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a substituted phosphonium.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst is triphenyl phosphonium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the monomers in the polymeric catalyst contain both the Bronsted-Lowry acid and the cationic group in the same monomer. Such monomers are referred to as "acidic- ionic monomers”.
  • some of the moieties in the solid-supported catalyst contain both the Bronsted-Lowry acid and the cationic group in the same moieties. Such moieties are referred to as "acidic-ionic moieties”.
  • the acidic-ionic monomer e.g., of a polymeric catalyst
  • an acidic-ionic moiety e.g., of a solid-supported catalyst
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) include both Bronsted-Lowry acid(s) and cationic group(s), where either the Bronsted-Lowry acid is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or solid support (e.g. , of a solid-supported catalyst) by a linker, and/or the cationic group is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or is attached to the solid support (e.g. , of a solid- supported catalyst) by a linker.
  • the polymeric backbone e.g. , of a polymeric catalyst
  • solid support e.g. , of a solid-supported catalyst
  • any of the Bronsted-Lowry acids, cationic groups and linkers (if present) suitable for the acidic monomers/moieties and/or ionic monomers/moieties may be used in the acidic-ionic monomers/moieties.
  • the Bronsted-Lowry acid at each occurrence in the acidic- ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently sulfonic acid or phosphonic acid.
  • the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is sulfonic acid.
  • the nitrogen-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen- containing cationic group is imidazolium.
  • the phosphorous-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous -containing cationic group is triphenyl phosphonium.
  • the polymeric catalyst or solid-supported catalyst can include at least one acidic-ionic monomer or moiety, respectively, connected to the polymeric backbone or solid support, wherein at least one acidic-ionic monomer or moiety includes at least one Bronsted-Lowry acid and at least one cationic group, and wherein at least one of the acidic-ionic monomers or moieties includes a linker connecting the acidic-ionic monomer to the polymeric backbone or solid support.
  • the cationic group can be a nitrogen-containing cationic group or a phosphorous-containing cationic group as described herein.
  • the linker can also be as described herein for either the acidic or ionic moieties.
  • the linker can be selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.
  • Monomers of a polymeric catalyst that have side chains containing both a Bronsted- Lowry acid and a cationic group can also be called "acidic ionomers”.
  • Acidic-ionic side chains (e.g. , of a polymeric catalyst) or acidic-ionic moieties (e.g. , of a solid-supported catalyst) that are connected by a linker can include, for example,
  • each X is independently selected from F, CI “ , Br “ , ⁇ , N0 2 “ ,N0 3 " , S0 4 2” , R 7 S0 4 “ , R 7 C0 2 “ ,
  • R 1 can be selected from hydrogen, alkyl, and heteroalkyl. In some embodiments, R 1 can be selected from hydrogen, methyl, or ethyl. In some embodiments,
  • each X can be selected from CI “ , N0 3 “ , S0 4 “ , R S0 4 “ , and R C0 2 " , where R can be selected from hydrogen and Ci_ 4 alkyl.
  • each X can be selected from CI “ , Br “ , ⁇ , HS0 4 “ , HC0 2 “ , CH 3 C0 2 “ , and N0 3 " .
  • X is acetate.
  • X is bisulfate.
  • X is chloride.
  • X is nitrate.
  • the acidic-ionic side chain e.g. , of a polymeric catalyst
  • the acidic-ionic moiety e.g. , of a solid-supported catalyst
  • the acidic-ionic side chain e.g. , of a polymeric catalyst
  • the acidic-ionic moiety e.g. , of a solid-supported catalyst
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) can have both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support.
  • Such side chains in acidic-ionic monomers (e.g., of a polymeric catalyst) or moieties (e.g., of a solid-supported catalyst) can include, for example,
  • the polymeric catalyst further includes hydrophobic monomers connected to form the polymeric backbone.
  • the solid-supported catalyst further includes hydrophobic moieties attached to the solid support.
  • each hydrophobic monomer or moiety has at least one hydrophobic group.
  • each hydrophobic monomer or moiety, respectively has one hydrophobic group.
  • each hydrophobic monomer or moiety has two hydrophobic groups.
  • some of the hydrophobic monomers or moieties have one hydrophobic group, while others have two hydrophobic groups.
  • each hydrophobic group is independently selected from an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
  • each hydrophobic group is an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl.
  • each hydrophobic group is phenyl. Further, it should be understood that the hydrophobic monomers may either all have the same hydrophobic group, or may have different hydrophobic groups.
  • the hydrophobic group is directly connected to form the polymeric backbone. In some embodiments of the solid-supported catalyst, the hydrophobic group is directly attached to the solid support.
  • the acidic and ionic monomers make up a substantial portion of the polymeric catalyst. In some embodiments, the acidic and ionic moieties make up a substantial portion solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers or moieties of the catalyst, based on the ratio of the number of acidic and ionic monomers/moieties to the total number of monomers/moieties present in the catalyst.
  • the polymeric catalyst or solid-supported catalyst has a total amount of Bronsted-Lowry acid of between about 0.1 and about 20 mmol, between about 0.1 and about 15 mmol, between about 0.01 and about 12 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 7 mmol, between about 3 and about 6 mmol, between about 1 and about 5, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid- supported catalyst.
  • each ionic monomer further includes a counterion for each nitrogen-containing cationic group or phosphorous-containing cationic group.
  • each counterion is independently selected from halide, nitrate, sulfate, formate, acetate, or organo sulfonate.
  • the counterion is fluoride, chloride, bromide, or iodide.
  • the counterion is chloride.
  • the counterion is sulfate.
  • the counterion is acetate.
  • the polymeric catalyst or solid-supported catalyst has a total amount of nitrogen-containing cationic groups and counterions or a total amount of
  • phosphorous-containing cationic groups and counterions of between about 0.01 and about 10 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 6 mmol, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the acidic and ionic monomers make up a substantial portion of the polymeric catalyst or solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers of the polymeric catalyst or solid-supported catalyst, based on the ratio of the number of acidic and ionic monomers or moieties to the total number of monomers or moieties present in the polymeric catalyst or solid-supported catalyst.
  • the ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties can be varied to tune the strength of the catalyst.
  • the total number of acidic monomers or moieties exceeds the total number of ionic monomers or moieties in the polymer or solid support.
  • the total number of acidic monomers or moieties is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of ionic monomers or moieties in the polymeric catalyst or solid-supported catalyst.
  • the ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1 or about 10: 1.
  • the total number of ionic monomers or moieties exceeds the total number of acidic monomers or moieties in the catalyst. In other embodiments, the total number of ionic monomers or moieties is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of acidic monomers or moieties in the polymeric catalyst or solid-supported catalyst.
  • the ratio of the total number of ionic monomers or moieties to the total number of acidic monomers or moieties is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1 or about 10: 1.
  • the acidic monomers, the ionic monomers, the acidic-ionic monomers and the hydrophobic monomers, where present can be arranged in alternating sequence or in a random order as blocks of monomers. In some embodiments, each block has not more than twenty, fifteen, ten, six, or three monomers.
  • the monomers of the polymeric catalyst are randomly arranged in an alternating sequence. With reference to the portion of the polymeric catalyst depicted in FIG. 9, the monomers are randomly arranged in an alternating sequence.
  • the monomers of the polymeric catalyst are randomly arranged as blocks of monomers. With reference to the portion of the polymeric catalyst depicted in FIG. 4, the monomers are arranged in blocks of monomers. In certain embodiments where the acidic monomers and the ionic monomers are arranged in blocks of monomers, each block has no more than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, or 3 monomers.
  • the polymeric catalysts described herein can also be cross-linked.
  • Such cross-linked polymeric catalysts can be prepared by introducing cross-linking groups.
  • cross-linking can occur within a given polymeric chain, with reference to the portion of the polymeric catalysts depicted in FIGS. 5A and 5B.
  • cross-linking can occur between two or more polymeric chains, with reference to the portion of the polymeric catalysts in FIGS. 6A, 6B, 6C and 6D.
  • R 1 , R 2 and R 3 are exemplary cross linking groups.
  • Suitable cross-linking groups that can be used to form a cross-linked polymeric catalyst with the polymers described herein include, for example, substituted or unsubstituted divinyl alkanes, substituted or unsubstituted divinyl cycloalkanes, substituted or unsubstituted divinyl aryls, substituted or unsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, and dihaloalkynes, where the substituents are those as defined herein.
  • cross-linking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane, divinylpropane, dichloropropane, divinylbutane, dichlorobutane, ethylene glycol, and resorcinol.
  • the crosslinking group is divinyl benzene.
  • the polymer is cross-linked. In certain embodiments, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% of the polymer is cross-linked.
  • the polymers described herein are not substantially cross-linked, such as less than about 0.9% cross-linked, less than about 0.5% cross-linked, less than about 0.1% cross-linked, less than about 0.01% cross-linked, or less than 0.001% cross-linked.
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers.
  • Polymerization processes using a wide variety of monomers are well known in the art ⁇ see, e.g., International Union of Pure and Applied
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers selected from ethylene, propylene, hydroxyethylene, acetaldehyde, styrene, divinyl benzene, isocyanates, vinyl chloride, vinyl phenols,
  • tetrafluoroethylene butylene, terephthalic acid, caprolactam, acrylonitrile, butadiene, ammonias, diammonias, pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyrazine, pyradizimine, thiazine, morpholine, piperidine, piperizines, pyrollizine, triphenylphosphonate, trimethylphosphonate, triethylphosphonate, tripropylphosphonate, tributylphosphonate, trichlorophosphonate, trifluorophosphonate, and diazole.
  • the polymeric backbone of the polymeric catalysts described herein can include, for example, polyalkylenes, polyalkenyl alcohols, polycarbonates, polyarylenes,
  • the polymeric backbone can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly(acrylonitrile butadiene styrene).
  • the polymeric backbone is polyethyelene or polypropylene.
  • the polymeric backbone is polyethylene.
  • the polymeric backbone is polyvinyl alcohol.
  • the polymeric backbone is polystyrene.
  • the polymeric backbone is any polymeric backbone.
  • polyethylene With reference to FIG. 8, in another embodiment, the polymeric backbone is polyvinyl alcohol.
  • polymeric backbone described herein can also include an ionic group integrated as part of the polymeric backbone.
  • Such polymeric backbones can also be called "ionomeric backbones".
  • the polymeric backbone can be selected from:
  • polyalkyleneammonium polyalkylenediammonium, polyalkylenepyrrolium,
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyridazinium, polyalkylenethiazinium,
  • polyalkylenemorpholinium polyalkylenepiperidinium, polyalkylenepiperizinium,
  • polyalkylenepyrollizinium polyalkylenetriphenylphosphonium
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium
  • polyalkylenediazolium polyarylalkyleneammonium, polyarylalkylenediammonium,
  • polyarylalkylenepyrrolium polyarylalkyleneimidazolium, polyarylalkylenepyrazolium, polyarylalkyleneoxazolium, polyarylalkylenethiazolium, polyarylalkylenepyridinium, polyarylalkylenepyrimidinium, polyarylalkylenepyrazinium, polyarylalkylenepyridazinium, polyarylalkylenethiazinium, polyarylalkylenemorpholinium, polyarylalkylenepiperidinium, polyarylalkylenepiperizinium, polyarylalkylenepyrollizinium,
  • polyarylalkylenetriethylphosphonium polyarylalkylenetripropylphosphonium
  • Cationic polymeric backbones can be associated with one or more anions, including for example F, CI “ , Br “ , ⁇ , N0 2 “ ,N0 3 " , S0 4 2” , R 7 S0 4 " , R 7 C0 2 " , P0 4 2” , R 7 P0 3 " , and R 7 P0 2 " ' where R is selected from hydrogen, Ci_ 4 alkyl, and Ci_ 4 heteroalkyl.
  • each anion can be selected from CI “ , Br “ , ⁇ , HS0 4 “ , HC0 2 “ , CH 3 C0 2 “ , and N0 3 " .
  • each anion is acetate.
  • each anion is bisulfate.
  • each anion is chloride.
  • X is nitrate.
  • the polymeric backbone is alkyleneimidazolium, which refers to an alkylene moiety, in which one or more of the methylene units of the alkylene moiety has been replaced with imidazolium.
  • the polymeric backbone is selected from polyethyleneimidazolium, polyprolyeneimidazolium, and polybutyleneimidazolium.
  • monomers having heteroatoms can be combined with one or more difunctionalized compounds, such as dihaloalkanes, di(alkylsulfonyloxy)alkanes, and di(arylsulfonyloxy)alkanes to form polymers.
  • the monomers have at least two heteroatoms to link with the difunctionalized alkane to create the polymeric chain.
  • difunctionalized compounds can be further substituted as described herein.
  • the difunctionalized compound(s) can be selected from 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2-dichlorobutane, l,3-dichlorobutane,l,4-dichlorobutane, 1,2- dichloropentane, l,3-dichloropentane,l,4-dichloropentane, 1,5-dichloropentane, 1,2- dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,2-dibromobutane, 1,3- dibromobutane, 1 ,4-dibromobutane, 1 ,2-dibromopentane, 1 ,3-dibromopentane, 1 ,4- dibromopentane, 1,5-dibromopentane, 1,2-diiododo
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone.
  • the polymer can be a homopolymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer in the same manner.
  • the polymer can be a heteropolymer having at least two monomer units, and where at least one monomeric unit contained within the polymer that differs from the other monomeric units in the polymer.
  • the different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers.
  • exemplary polymers include, for example, polyalkylene backbones that are substituted with one or more groups selected from hydroxyl, carboxylic acid, unsubstituted and substituted phenyl, halides, unsubstituted and substituted amines, unsubstituted and substituted ammonias, unsubstituted and substituted pyrroles, unsubstituted and substituted imidazoles, unsubstituted and substituted pyrazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted pyridines, unsubstituted and substituted pyrimidines, unsubstituted and substituted pyrazines, unsubstituted and substituted pyradizines, unsubstituted and substituted thiazines, unsubstituted and substituted morpholines, unsubstituted and substituted and substituted
  • unsubstituted phenyl group (-CH 2 -CH(phenyl)-CH 2 -CH(phenyl)-) is also known as polystyrene. Should that phenyl group be substituted with an ethenyl group, the polymer can be named a polydivinylbenzene (-CH 2 -CH(4-vinylphenyl)-CH 2 -CH(4-vinylphenyl)-). Further examples of heteropolymers may include those that are functionalized after polymerization.
  • polystyrene-co-divinylbenzene (-CH 2 -CH(phenyl)- CH 2 -CH(4-ethylenephenyl)-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-).
  • the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
  • the polymeric backbone is a polyalkyleneimidazolium.
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, or zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone. With reference to FIG. 10, in one embodiment, there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group. In another example, with reference to FIG. 11, there are zero atoms between the side chain with the acidic moiety and the side chain with the ionic moiety.
  • the polymeric catalysts described herein can form solid particles.
  • a solid particle can be formed through the procedures of emulsion or dispersion polymerization, which are known to one of skill in the art.
  • the solid particles can be formed by grinding or breaking the polymer into particles, which are also techniques and methods that are known to one of skill in the art.
  • Solid particles include coating the polymers described herein on the surface of a solid core.
  • Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • Polymeric coated core particles can be made by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • Other methods known in the art to prepare solid particles include coating the polymers described herein on the surface of a solid core.
  • the solid core can be a non-catalytic support.
  • Suitable materials for the solid core can include an inert material (e.g. , aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • the solid core is made up of iron.
  • Polymeric coated core particles can be made by techniques and methods that are known to one of skill in the art, for example, by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • the solid supported polymer catalyst particle can have a solid core where the polymer is coated on the surface of the solid core. In some embodiments, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50% of the catalytic activity of the solid particle can be present on or near the exterior surface of the solid particle.
  • the solid core can have an inert material or a magnetic material. In one embodiment, the solid core is made up of iron.
  • the solid particles coated with the polymer described herein have one or more catalytic properties. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80% or at least about 90% of the catalytic activity of the solid particle is present on or near the exterior surface of the solid particle.
  • the solid particle is substantially free of pores, for example, having no more than about 50%, no more than about 40%, no more than about 30%, no more than about 20%, no more than about 15%, no more than about 10%, no more than about 5%, or no more than about 1% of pores.
  • Porosity can be measured by methods well known in the art, such as determining the Brunauer-Emmett-Teller (BET) surface area using the absorption of nitrogen gas on the internal and external surfaces of a material (Brunauer, S. et al., J. Am.
  • Other methods include measuring solvent retention by exposing the material to a suitable solvent (such as water), then removing it thermally to measure the volume of interior pores.
  • suitable solvent such as water
  • Other solvents suitable for porosity measurement of the polymeric catalysts include, for example, polar solvents such as DMF, DMSO, acetone, and alcohols.
  • the solid particles include a microporous gel resin. In yet other embodiments, the solid particles include a macroporous gel resin. Support of the Solid-Supported Catalysts
  • the support may be selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g., mordenite), ceramics, and any combinations thereof.
  • the support is carbon.
  • the support for carbon support can be biochar, amorphous carbon, or activated carbon.
  • the support is activated carbon.
  • the carbon support can have a surface area from 0.01 to 50 m /g of dry material.
  • the carbon support can have a density from 0.5 to 2.5 kg/L.
  • the support can be characterized using any suitable instrumental analysis methods or techniques known in the art, including for example scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy, and Fourier Transform infrared spectroscopy (FTIR).
  • SEM scanning electron microscopy
  • XRD powder X-ray diffraction
  • Raman spectroscopy Raman spectroscopy
  • FTIR Fourier Transform infrared spectroscopy
  • the carbon support can be prepared from carbonaceous materials, including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • carbonaceous materials including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • suitable methods to prepare the carbon supports used herein See e.g., M. Inagaki, L.R. Radovic, Carbon, vol. 40, p. 2263 (2002), or A.G. Pandolfo and A.F. Hollenkamp, "Review: Carbon Properties and their role in supercapacitors," Journal of Power Sources, vol.
  • the support is silica, silica gel, alumina, or silica-alumina.
  • silica- or alumina-based solid supports used herein. See e.g., Catalyst supports and supported catalysts, by A.B. Stiles, Butterworth Publishers, Stoneham MA, 1987.
  • the support is a combination of a carbon support, with one or more other supports selected from silica, silica gel, alumina, magnesia, titania, zirconia, clays ⁇ e.g., kaolinite), magnesium silicate, silicon carbide, zeolites ⁇ e.g., mordenite), and ceramics.
  • “Bronsted-Lowry acid” refers to a molecule, or substituent thereof, in neutral or ionic form that is capable of donating a proton (hydrogen cation, H + ).
  • Homopolymer refers to a polymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer.
  • One suitable example is polyethylene, where ethylene monomers are linked to form a uniform repeating chain (-CH 2 -CH 2 -CH 2 -).
  • Heteropolymer refers to a polymer having at least two monomer units, and where at least one monomeric unit differs from the other monomeric units in the polymer. Heteropolymer also refers to polymers having difunctionalized or trifunctionalized monomer units that can be incorporated in the polymer in different ways. The different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers. One suitable example is polyethyleneimidazolium, where if in an alternating sequence, would be the polymer depicted in FIG. 12.
  • polystyrene - co-divinylbenzene where if in an alternating sequence, could be (-CH 2 -CH(phenyl)-CH 2 -CH(4- ethylenephenyl)-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-).
  • the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
  • . w ⁇ denotes the attachment point of a moiety to the parent structure.
  • Ci_6 alkyl (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C l-6 alkyl) is intended to encompass, Ci, C 2 , C 3 , C 4 , C5, C 6 , Ci_ 6 , Ci_5, Ci ⁇ , Q_ 3, C]_2, C2-6, C2-5, C2- , C2-3, C 3 _6, C 3 _5, C 3 ⁇ , C 4 _6, C4_5, and Cs_ 6 alkyl.
  • alkyl includes saturated straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted.
  • alkyl as used herein may have 1 to 10 carbon atoms (e.g. , Ci_io alkyl), 1 to 6 carbon atoms (e.g. , Ci_ 6 alkyl), or 1 to 3 carbon atoms (e.g. , Ci_ 3 alkyl).
  • Representative straight-chained alkyls include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.
  • Representative branched alkyls include, for example, isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylbutyl, 3- methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4- methylhexyl, 5-methylhexyl, and 2,3-dimethylbutyl.
  • alkyl residue having a specific number of carbons When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butyl” is meant to include n-butyl, sec- butyl, z ' so-butyl, and tert-butyl; “propyl” includes n-propyl, and z ' so-propyl.
  • Alkoxy refers to the group -O-alkyl, which is attached to the parent structure through an oxygen atom. Examples of alkoxy may include methoxy, ethoxy, propoxy, and isopropoxy.
  • alkoxy as used herein has 1 to 6 carbon atoms (e.g. , 0-(Ci_ 6 alkyl)), or 1 to 4 carbon atoms (e.g. , 0-(Ci_ 4 alkyl)).
  • alkenyl refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one double bond.
  • alkenyl has 2 to 10 carbon atoms (e.g. , C 2-1 o alkenyl), or 2 to 5 carbon atoms (e.g. , C 2 _5 alkenyl).
  • alkenyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butenyl” is meant to include n-butenyl, sec-butenyl, and z ' so-butenyl.
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl).
  • Examples of C 2 _ 4 alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2- propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), and butadienyl (C4).
  • C 2 _ 6 alkenyl groups include the aforementioned C 2 _ 4 alkenyl groups as well as pentenyl (C5), pentadienyl (C5), and hexenyl (C6). Additional examples of alkenyl include heptenyl (C7), octenyl (C8), and octatrienyl (C8).
  • Alkynyl refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one triple bond.
  • alkynyl has 2 to 10 carbon atoms (e.g. , C 2 _io alkynyl), or 2 to 5 carbon atoms (e.g. , C 2 -5 alkynyl).
  • alkynyl residue having a specific number of carbons all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "pentynyl” is meant to include n-pentynyl, sec-pentynyl, z ' so-pentynyl, and ieri-pentynyl.
  • alkynyl may include -C ⁇ CH or -C ⁇ C-CH 3 .
  • alkyl, alkoxy, alkenyl, and alkynyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents.
  • substituted alkyl, substituted alkoxy, substituted alkenyl, and substituted alkynyl at each occurrence may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • the one or more substituents of substituted alkyl, alkoxy, alkenyl, and alkynyl is independently selected from cycloalkyl, aryl, heteroalkyl (e.g.
  • each R a is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl (e.g. , bonded through a ring carbon), -C(0)R' and -S(0) t R' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl.
  • R a is independently hydrogen, alkyl, haloalkyl, cycloalkyl, aryl, aralkyl (e.g. , alkyl substituted with aryl, bonded to parent structure through the alkyl group),
  • heterocycloalkyl or heteroaryl.
  • Heteroalkyl includes alkyl, alkenyl and alkynyl groups, respectively, wherein one or more skeletal chain atoms are selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus, or any combinations thereof.
  • heteroalkyl may be an ether where at least one of the carbon atoms in the alkyl group is replaced with an oxygen atom.
  • Ci_ 4 heteroalkyl which refers to the chain length in total, which in this example is 4 atoms long.
  • heteroalkyl which includes the heteroatom center in the atom chain length description. Connection to the rest of the parent structure can be through, in one embodiment, a heteroatom, or, in another embodiment, a carbon atom in the heteroalkyl chain.
  • Heteroalkyl groups may include, for example, ethers such as methoxyethanyl (- CH 2 CH 2 OCH 3 ), ethoxymethanyl (-CH 2 OCH 2 CH 3 ), (methoxymethoxy)ethanyl (- CH 2 CH 2 OCH 2 OCH 3 ), (methoxymethoxy)methanyl (-CH 2 OCH 2 OCH 3 ) and
  • heteroalkyl, heteroalkenyl, or heteroalkynyl may be unsubstituted or substituted by one or more of substituents.
  • heteroalkynyl may have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • Examples for heteroalkyl, heteroalkenyl, or heteroalkynyl substituents may include the substituents described above for alkyl.
  • Carbocyclyl may include cycloalkyl, cycloalkenyl or cycloalkynyl.
  • Cycloalkyl refers to a monocyclic or polycyclic alkyl group.
  • Cycloalkenyl refers to a monocyclic or polycyclic alkenyl group (e.g. , containing at least one double bond).
  • Cycloalkynyl refers to a monocyclic or polycyclic alkynyl group (e.g. , containing at least one triple bond).
  • the cycloalkyl, cycloalkenyl, or cycloalkynyl can consist of one ring, such as cyclohexyl, or multiple rings, such as adamantyl.
  • a cycloalkyl, cycloalkenyl, or cycloalkynyl with more than one ring can be fused, spiro or bridged, or combinations thereof.
  • cycloalkyl, cycloalkenyl, and cycloalkynyl has 3 to 10 ring atoms (i.e., C 3 -C 10 cycloalkyl, C 3 -C 10
  • cycloalkyl, cycloalkenyl, or cycloalkynyl includes bridged and spiro-fused cyclic structures containing no heteroatoms.
  • cycloalkyl, cycloalkenyl, or cycloalkynyl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
  • C 3 _6 carbocyclyl groups may include, for example, cyclopropyl (C 3 ), cyclobutyl (C 4 ), cyclopentyl (C 5 ), cyclopentenyl (C 5 ), cyclohexyl (C 6 ), cyclohexenyl (C 6 ), and cyclohexadienyl (C 6 ).
  • C 3 _ 8 carbocyclyl groups may include, for example, the aforementioned C 3 _6 carbocyclyl groups as well as cycloheptyl (C 7 ), cycloheptadienyl (C 7 ), cycloheptatrienyl (C 7 ), cyclooctyl (C 8 ), bicyclo[2.2.1]heptanyl, and bicyclo[2.2.2]octanyl.
  • C 3 _io carbocyclyl groups may include, for example, the aforementioned C 3 _ 8 carbocyclyl groups as well as octahydro-lH-indenyl, decahydronaphthalenyl, and spiro [4.5] decanyl .
  • Heterocyclyl refers to carbocyclyl as described above, with one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorous, and sulfur.
  • Heterocyclyl may include, for example, heterocycloalkyl, heterocycloalkenyl, and
  • heterocyclyl is a 3- to 18-membered non-aromatic monocyclic or polycyclic moiety that has at least one heteroatom selected from nitrogen, oxygen, phosphorous and sulfur.
  • the heterocyclyl can be a monocyclic or polycyclic (e.g. , bicyclic, tricyclic or tetracyclic), wherein polycyclic ring systems can be a fused, bridged or spiro ring system.
  • Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • N-containing heterocyclyl moiety refers to an non-aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • heterocyclyl group is optionally oxidized. One or more nitrogen atoms, if present, are optionally quatemized.
  • heterocyclyl may also include ring systems substituted with one or more oxide (-0-) substituents, such as piperidinyl N-oxides. The heterocyclyl is attached to the parent molecular structure through any atom of the ring(s). [0177]
  • heterocyclyl also includes ring systems with one or more fused carbocyclyl, aryl or heteroaryl groups, wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring.
  • heterocyclyl is a 5- 10 membered non- aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5- 10 membered heterocyclyl).
  • a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-8 membered heterocyclyl).
  • a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-6 membered heterocyclyl).
  • the 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen and sulfur.
  • Aryl refers to an aromatic group having a single ring (e.g. , phenyl), multiple rings (e.g. , biphenyl), or multiple fused rings (e.g. , naphthyl, fluorenyl, and anthryl).
  • aryl as used herein has 6 to 10 ring atoms (e.g., C 6 -Cio aromatic or C 6 -Cio aryl) which has at least one ring having a conjugated pi electron system.
  • ring atoms e.g., C 6 -Cio aromatic or C 6 -Cio aryl
  • bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals.
  • aryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position.
  • aryl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
  • 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, phosphorous, 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 is a 5- to 18-membered monocyclic or polycyclic (e.g., bicyclic or tricyclic) aromatic ring system (e.g., having 6, 10 or 14 pi electrons shared in a cyclic array) having ring carbon atoms and 1 to 6 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous and sulfur (e.g. , 5-18 membered heteroaryl).
  • heteroaryl may have a single ring (e.g. , pyridyl, pyridinyl, imidazolyl) or multiple condensed rings (e.g.
  • heteroaryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position. In one embodiment, heteroaryl may have more than one ring where at least one ring is non-aromatic is connected to the parent structure at an aromatic ring position.
  • Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • an N-containing "heteroaryl” refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • One or more heteroatom(s) in the heteroaryl group can be optionally oxidized.
  • One or more nitrogen atoms, if present, are optionally quaternized.
  • heteroaryl may include ring systems substituted with one or more oxide (-0-) substituents, such as pyridinyl N-oxides. The heteroaryl may be attached to the parent molecular structure through any atom of the ring(s).
  • heteroaryl may include ring systems with one or more fused aryl groups, wherein the point of attachment is either on the aryl or on the heteroaryl ring.
  • heteroaryl may include ring systems with one or more carbocycyl or heterocycyl groups wherein the point of attachment is on the heteroaryl ring.
  • a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5- 10 membered heteroaryl).
  • a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-8 membered heteroaryl).
  • a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-6 membered heteroaryl).
  • the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, phosphorous, and sulfur.
  • carbocyclyl including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl
  • aryl, heteroaryl, and heterocyclyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents.
  • a substituted carbocyclyl including, for example, substituted cycloalkyl, substituted cycloalkenyl or substituted cycloalkynyl
  • substituted aryl, substituted heteroaryl, substituted heterocyclyl at each occurrence may be independently may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • carbocyclyl including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl
  • aryl, heteroaryl, heterocyclyl substituents may include alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g.
  • any moiety referred to as a "linker” refers to the moiety has having bivalency.
  • “alkyl linker” refers to the same residues as alkyl, but having bivalency. Examples of alkyl linkers
  • Alkynyl linker refers to the same residues as alkynyl, but having bivalency. Examples alkynyl linkers include -C ⁇ C- or -C ⁇ C-CH 2 -.
  • Carbocyclyl linker refers to the same residues as carbocyclyl, aryl, heteroaryl, and heterocyclyl, respectively, but having bivalency.
  • Amino refers to -N(R a )(R b ), where each R a and R b is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g.
  • amino includes amido (e.g. , -NR a C(0)R b ).
  • the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of R a and R b may be further substituted as described herein.
  • R a and R b may be the same or different.
  • amino is -NH 2 (where R a and R b are each hydrogen).
  • R a and R b are other than hydrogen
  • R a and R b can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7- membered ring.
  • Such examples may include 1-pyrrolidinyl and 4-morpholinyl.
  • Ammonium refers to -N(R a )(R b )(R c ) + , where each R a , R b and R c is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g.
  • R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl; or any two of R a , R b and R c may be taken together with the atom to which they are attached to form a cycloalkyl, heterocycloalkyl; or any three of R a , R b and R c may be taken together with the atom to which they are attached to form aryl or heteroaryl.
  • the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of any one or more of R a , R b and R c may be further substituted as described herein.
  • R a , R b and R c may be the same or different.
  • amino also refers to N-oxides of the groups -N + (H)(R a )0 " , and -N + (R a )(R b )0-, where R a and R b are as described herein, where the N-oxide is bonded to the parent structure through the N atom.
  • N-oxides can be prepared by treatment of the
  • amido refers to a chemical moiety with formula -C(O) N(R a )(R b ) or - NR a C(0)R b , where R a and R b at each occurrence are as described herein.
  • amido is a Ci_ 4 amido, which includes the amide carbonyl in the total number of carbons in the group.
  • Carbonyl refers to -C(0)R a , where R a is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, -N(R') 2i -S(0) t R', where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl, and t is 1 or 2.
  • each R' are other than hydrogen
  • the two R' moieties can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7-membered ring.
  • carbonyl includes amido (e.g. , -C(O) N(R a )(R b ))-
  • Cyano refers to a -CN group.
  • Halo means fluoro, chloro, bromo or iodo.
  • haloalkyl means alkyl, alkenyl, alkynyl and alkoxy moieties as described above, wherein one or more hydrogen atoms are replaced by halo.
  • a residue is substituted with more than one halo groups, it may be referred to by using a prefix corresponding to the number of halo groups attached.
  • dihaloaryl, dihaloalkyl, and trihaloaryl refer to aryl and alkyl substituted with two ("di") or three ("tri") halo groups, which may be, but are not necessarily, the same halogen; thus, for example, 3,5-difluorophenyl, 3-chloro-5-fluorophenyl, 4-chloro-3-fluorophenyl, and 3,5- difluoro-4-chlorophenyl is within the scope of dihaloaryl.
  • a haloalkyl group include difluoromethyl (-CHF 2 ), trifluoromethyl (-CF 3 ), 2,2,2-trifluoroethyl, and
  • Perhaloalkyl refers to an alkyl or alkylene group in which all of the hydrogen atoms have been replaced with a halogen (e.g. , fluoro, chloro, bromo, or iodo). In some embodiments, all of the hydrogen atoms are each replaced with fluoro. In some embodiments, all of the hydrogen atoms are each replaced with chloro. Examples of perhaloalkyl groups include -CF 3 , - CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CC1 3 , -CFC1 2 , and -CF 2 C1.
  • Thio refers to -SR a , wherein R a is as described herein.
  • Thiol refers to the group - R a SH, wherein R a is as described herein.
  • Sulfinyl refers to -S(0)R a . In some embodiments, sulfinyl is -S(0)N(R a )(R b ). “Sulfonyl” refers to the -S(0 2 )R a . In some embodiments, sulfonyl is -S(0 2 ) N(R a )(R b ) or - S(0 2 )OH. For each of these moieties, it should be understood that R a and R b are as described herein. [0194] "Moiety” refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
  • the term "unsubstituted" means that for carbon atoms, only hydrogen atoms are present besides those valencies linking the atom to the parent molecular group.
  • One example is propyl (-CH 2 -CH 2 -CH 3 ).
  • valencies not linking the atom to the parent molecular group are either hydrogen or an electron pair.
  • sulfur atoms valencies not linking the atom to the parent molecular group are either hydrogen, oxygen or electron pair(s).
  • substituted group can have a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position.
  • Substituents include one or more group(s) individually and independently selected from alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g.
  • substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH 2 0- is equivalent to -OCH 2 -.
  • Reference to "between” two values or parameters herein includes (and describes) embodiments that include those two values or parameters per se.
  • description referring to "between x and y” includes description of "x" and "y" per se.
  • the polymeric catalysts and the solid-supported catalysts can include any of the Bronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobic groups, cross-linking groups, and polymeric backbones or solid supports (as the case may be) described herein, as if each and every combination were listed separately.
  • the catalyst can include benzenesulfonic acid (i.e., a sulfonic acid with a phenyl linker) connected to a polystyrene backbone or attached to the solid support, and an imidazolium chloride connected directly to the polystyrene backbone or attached directly to the solid support.
  • the polymeric catalyst can include boronyl-benzyl-pyridinium chloride (i.e., a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker) connected to a polystyrene backbone or attached to the solid support.
  • boronyl-benzyl-pyridinium chloride i.e., a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker
  • the catalyst can include benzenesulfonic acid and imidazolium sulfate each individually connected to a polyvinyl alcohol backbone or individually attached to the solid support.
  • the polymeric catalyst is selected from: poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
  • the solid-supported catalyst is selected from: amorphous carbon-supported pyrrolium chloride sulfonic acid;
  • amorphous carbon-supported pyrazolium chloride sulfonic acid amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported
  • amorphous carbon-supported triphenyl phosphonium bromide sulfonic acid amorphous carbon-supported trimethyl phosphonium bromide sulfonic acid; amorphous carbon-supported triethyl phosphonium bromide sulfonic acid; amorphous carbon-supported tripropyl phosphonium bromide sulfonic acid; amorphous carbon-supported tributyl phosphonium bromide sulfonic acid; amorphous carbon- supported trifluoro phosphonium bromide sulfonic acid; amorphous carbon- supported pyrrolium bisulfate sulfonic acid;
  • amorphous carbon-supported triphenyl phosphonium bisulfate sulfonic acid amorphous carbon-supported trimethyl phosphonium bisulfate sulfonic acid; amorphous carbon-supported triethyl phosphonium bisulfate sulfonic acid; amorphous carbon-supported tripropyl phosphonium bisulfate sulfonic acid; amorphous carbon- supported tributyl phosphonium bisulfate sulfonic acid; amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇
  • amorphous carbon-supported triphenyl phosphonium acetate sulfonic acid amorphous carbon-supported trimethyl phosphonium acetate sulfonic acid; amorphous carbon-supported triethyl phosphonium acetate sulfonic acid;
  • amorphous carbon-supported triphenyl phosphonium chloride phosphonic acid amorphous carbon-supported trimethyl phosphonium chloride phosphonic acid; amorphous carbon-supported triethyl phosphonium chloride phosphonic acid; amorphous carbon-supported tripropyl phosphonium chloride phosphonic acid; amorphous carbon- supported tributyl phosphonium chloride phosphonic acid; amorphous carbon- supported trifluoro phosphonium chloride phosphonic acid; amorphous carbon- supported pyrrolium bromide phosphonic acid;
  • amorphous carbon-supported triphenyl phosphonium bromide phosphonic acid amorphous carbon-supported trimethyl phosphonium bromide phosphonic acid; amorphous carbon-supported triethyl phosphonium bromide phosphonic acid; amorphous carbon-supported tripropyl phosphonium bromide phosphonic acid; amorphous carbon-supported tributyl phosphonium bromide phosphonic acid; amorphous carbon- supported trifluoro phosphonium bromide phosphonic acid; amorphous carbon- supported pyrrolium bisulfate phosphonic acid;
  • amorphous carbon-supported triphenyl phosphonium bisulfate phosphonic acid amorphous carbon-supported trimethyl phosphonium bisulfate phosphonic acid; amorphous carbon-supported triethyl phosphonium bisulfate phosphonic acid; amorphous carbon-supported tripropyl phosphonium bisulfate phosphonic acid; amorphous carbon-supported tributyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported trifluoro phosphonium bisulfate phosphonic acid; amorphous carbon- supported pyrrolium formate phosphonic acid;
  • amorphous carbon-supported triphenyl phosphonium formate phosphonic acid amorphous carbon-supported trimethyl phosphonium formate phosphonic acid; amorphous carbon-supported triethyl phosphonium formate phosphonic acid; amorphous carbon-supported tripropyl phosphonium formate phosphonic acid; amorphous carbon- supported tributyl phosphonium formate phosphonic acid; amorphous carbon- supported trifluoro phosphonium formate phosphonic acid; amorphous carbon- supported pyrrolium acetate phosphonic acid;
  • amorphous carbon-supported triphenyl phosphonium acetate phosphonic acid amorphous carbon-supported trimethyl phosphonium acetate phosphonic acid; amorphous carbon-supported triethyl phosphonium acetate phosphonic acid; amorphous carbon-supported tripropyl phosphonium acetate phosphonic acid; amorphous carbon-supported tributyl phosphonium acetate phosphonic acid; amorphous carbon- supported trifluoro phosphonium acetate phosphonic acid; amorphous carbon-supported ethanoyl-triphosphonium sulfonic acid;
  • the solid-supported catalyst is selected from: activated carbon- ⁇ supported
  • activated carbon-supported triphenyl phosphonium bisulfate sulfonic acid activated carbon-supported trimethyl phosphonium bisulfate sulfonic acid; activated carbon-supported triethyl phosphonium bisulfate sulfonic acid; activated carbon-supported tripropyl phosphonium bisulfate sulfonic acid; activated carbon- supported tributyl phosphonium bisulfate sulfonic acid; activated carbon- supported trifluoro phosphonium bisulfate sulfonic acid; activated carbon- supported pyrrolium formate sulfonic acid;
  • activated carbon-supported triphenyl phosphonium formate sulfonic acid activated carbon-supported trimethyl phosphonium formate sulfonic acid; activated carbon-supported triethyl phosphonium formate sulfonic acid; activated carbon-supported tripropyl phosphonium formate sulfonic acid; activated carbon- supported tributyl phosphonium formate sulfonic acid; activated carbon- supported trifluoro phosphonium formate sulfonic acid; activated carbon- supported pyrrolium acetate sulfonic acid;
  • activated carbon-supported triphenyl phosphonium acetate sulfonic acid activated carbon-supported trimethyl phosphonium acetate sulfonic acid; activated carbon-supported triethyl phosphonium acetate sulfonic acid; activated carbon-supported tripropyl phosphonium acetate sulfonic acid; activated carbon-supported tributyl phosphonium acetate sulfonic acid; activated carbon- supported trifluoro phosphonium acetate sulfonic acid; activated carbon- supported pyrrolium chloride phosphonic acid;;
  • activated carbon-supported pyridinium chloride phosphonic acid activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported
  • activated carbon- ⁇ supported triphenyl phosphonium bisulfate phosphonic acid activated carbon- ⁇ supported trimethyl phosphonium bisulfate phosphonic acid; activated carbon- ⁇ supported triethyl phosphonium bisulfate phosphonic acid; activated carbon- ⁇ supported tripropyl phosphonium bisulfate phosphonic acid; activated carbon- ⁇ supported tributyl phosphonium bisulfate phosphonic acid; activated carbon- ⁇ supported trifluoro phosphonium bisulfate phosphonic acid; activated carbon- ⁇ supported pyrrolium formate phosphonic acid;
  • activated carbon- ⁇ supported imidazolium formate phosphonic acid activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon-
  • the sugar alcohol and the catalyst are combined with one or more additional catalysts to produce the anhydrosugar alcohol.
  • the additional catalysts may include any suitable catalysts known in the art to convert, or facilitate the conversion of, the sugar alcohol into its correspondending anhydrosugar alcohol.
  • the monoanhydrosugar alcohol and the catalyst are combined with one or more additional catalysts to produce the dianhydrosugar alcohol.
  • the additional catalysts may include any suitable catalysts known in the art to convert, or facilitate the conversion of, the monoanhydrosugar alcohol into its correspondending dianhydrosugar alcohol.
  • Examples of other acid catalysts that may be used in combination with the polymeric or solid-supported catalysts described herein may be found in, for example, US 7439352, US 4408061, US 7982059, US 8445705, and US 7649099.
  • the sugar alcohol and the catalyst are combined in the further presence of a solvent, or a mixture of solvents, to produce the anhydrosugar alcohol.
  • the monoanhydrosugar alcohol and the catalyst are combined in the further presence of a solvent, or a mixture of solvents, to produce the dianhydrosugar alcohol.
  • the solvents used in the methods described herein may be obtained from any source, including any commercially available sources.
  • the sugar alcohol and the catalyst may be reacted at any temperature and pressure suitable to produce the anhydrosugar alcohol.
  • the sugar alcohol and catalyst are reacted at a temperature of about 25°C to about 200°C.
  • the combined sugar alcohol and catalyst are reacted in vaccum, or at a pressure between 0.05 Torr and 190,000 Torr.
  • the monoanhydrosugar alcohol and the catalyst may be reacted at any temperature and pressure suitable to produce the dianhydrosugar alcohol. In some embodiments, the monoanhydrosugar alcohol and catalyst are reacted at a temperature of about 25°C to about 200°C. In some embodiments, the combined monoanhydrosugar alcohol and catalyst are reacted in vacuum, or at a pressure between 0.05 Torr and 190,000 Torr.
  • the sugar alcohol and the catalyst are introduced into an interior chamber of a reactor, either concurrently or sequentially.
  • the reaction can be performed in a batch process or a continuous process.
  • method is performed in a batch process, where the contents of the reactor are continuously mixed or blended, and all or a substantial amount of the products of the reaction are removed.
  • the method is performed in a batch process, where the contents of the reactor are initially intermingled or mixed but no further physical mixing is performed.
  • the method is performed in a batch process, wherein once further mixing of the contents, or periodic mixing of the contents of the reactor, is performed (e.g. , at one or more times per hour), all or a substantial amount of the products of the reaction are removed after a certain period of time.
  • the method is repeated in a sequential batch process, wherein at least a portion of the catalyst is separated from at least a portion of the anhydrosugar alcohol produced (e.g., as described in more detail infra) and is recycled by further contacting additional sugar alcohol.
  • a method for producing an anhydrosugar alcohol by: a) combining a sugar alcohol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and b) producing an anhydrosugar alcohol from at least a portion of the reaction mixture; c) separating the anhydrosugar alcohol from the catalyst; d) combining additional sugar alcohol with the separated catalyst to form additional reaction mixture; and e) producing additional anhydrosugar alcohol from at least a portion of the additional reaction mixture.
  • the catalyst is recycled (e.g. , steps (c)-(e) above are repeated) at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or at least 10 times.
  • the catalyst retains at least 80% activity (e.g., at least 90%, 95%, 96%, 97%, 98%, or 99% activity) after being recycled 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times, when compared to the catalytic activity under identical conditions prior to being recycled.
  • the method is performed in a continuous process, where the contents flow through the reactor with an average continuous flow rate but with no explicit mixing.
  • the contents of the reactor are continuously or periodically mixed or blended, and after a period of time, less than all of the products of the reaction are removed.
  • method is performed in a continuous process, where the mixture containing the sugar alcohol and the catalyst is not actively mixed. Additionally, mixing of the sugar alcohol and the catalyst may occur as a result of the redistribution of catalysts settling by gravity, or the non-active mixing that occurs as the material flows through a continuous reactor.
  • the steps of combining the sugar alcohol with a catalyst and isolating the anhydrosugar alcohol produced are performed concurrently.
  • the reactors used for the methods described herein may be open or closed reactors suitable for use in containing the chemical reactions described herein.
  • Suitable reactors may include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor with ultrafiltration, a continuous plug-flow column reactor, an attrition reactor, or a reactor with intensive stirring induced by an electromagnetic field. See e.g. , Fernanda de Castilhos Corazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel, Optimal control in fed-batch reactor for the cellobiose hydrolysis, Acta Scientiarum. Technology, 25: 33-38 (2003); Gusakov, A.
  • reactor types may include, for example, fluidized bed, upflow blanket, immobilized, and extruder type reactors for hydrolysis and/or fermentation.
  • the reactor may include a continuous mixer, such as a screw mixer.
  • the reactors may be generally fabricated from materials that are capable of withstanding the physical and chemical forces exerted during the processes described herein. In some embodiments, such materials used for the reactor are capable of tolerating high concentrations of strong liquid acids; however, in other embodiments, such materials may not be resistant to strong acids.
  • additional sugar alcohol, monoanhydrosugar alcohol, and/or catalyst may be added to the reactor, either at the same time or one after the other.
  • the methods described herein further include isolating the anhydrosugar alcohol produced.
  • the anhydrosugar alcohol may be isolated using any method known in the art, including, for example, extraction, distillation (e.g. vacuum distillation), crystallization, recrystallization (e.g. , melt recrystallization, solvent recrystallization), or chromatography.
  • the anhydrosugar alcohol produced may be subjected to further processing steps (e.g. , as drying) or subsequent chemical treatment.
  • the catalysts containing acidic and ionic groups used in the methods of producing anhydrosugar alcohols from sugar alcohols as described herein may be recycled.
  • provided herein are methods of producing anhydrosugar alcohols from sugar alcohols using recyclable catalysts.
  • the catalysts containing acidic and ionic groups used in the methods of producing dianhydrosugar alcohols from monoanhydrosugar alcohols as described herein may also be recycled.
  • provided herein are methods of producing dianhydrosugar alcohols from monoanhydrosugar alcohols using recyclable catalysts.
  • the catalyst described herein is separated from the anhydrosugar alcohol produced, and the separated catalyst is combined with additional sugar alcohol to produce additional anhydrosugar alcohol.
  • process 200 depicts an exemplary scheme in which the catalyst is isolated in step 212 from the anhydrosugar alcohol produced, and the isolated catalyst is reused in step 204 to provide catalyst for an additional reaction with sugar alcohol to produce additional anhydrosugar alcohol.
  • Any method known in the art may be used to separate the catalyst for reuse, including, for example, centrifugation, filtration (e.g. , vacuum filtration), and gravity settling.
  • the methods described herein may be performed as batch or continuous processes. Recycling in a batch process may involve, for example, recovering the catalyst from the reaction mixture and reusing the recovered catalyst in one or more subsequent reaction cycles. Recycling in a continuous process may involve, for example, introducing additional sugar alcohol into the reactor, without additional of fresh catalyst.
  • the catalyst is recycled at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or at least 10 times.
  • the catalyst retains at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% activity after being recycled 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times, when compared to the catalytic activity under identical conditions prior to being recycled.
  • the number of moles of the reactant A is often measured at several points in time, ti, 3 ⁇ 4, tj, ... , t n during a single reaction cycle and used to calculate the conversions 3 ⁇ 4(t/X 3 ⁇ 4(3 ⁇ 4), ⁇ ⁇ ⁇ 3 ⁇ 4fe) at the corresponding times.
  • the first order rate constant k is then calculated by fitting the data for X A (t).
  • a reaction cycle refers to one period of use within a sequence of uses of the catalyst.
  • a reaction cycle corresponds to the discrete steps of charging a reactor system with reactants and catalyst, heating the reaction under suitable conditions to convert the reactants, maintaining the reaction conditions for a specified residence time, separating the reaction products from the catalyst, and recovering the catalyst for re-use.
  • a cycle refers a single reactor space time during the operation of the continuous process.
  • the continuous reactor space time is two hours
  • the first two hour period of continuous operation is the first reaction cycle
  • the next two hour period of continuous operation is the second reaction cycle, etc.
  • the "loss of activity" or “activity loss” of a catalyst is determined by the average fractional reduction in the catalyst activity between consecutive cycles. For example, if the catalyst activity in reaction cycle 1 is £(1) and the catalyst activity in reaction cycle 2 is k(2), then the loss in catalyst activity between cycle 1 and cycle 2 is calculated as [k(2) reaction cycles, the loss of activity is then determined as measured in units of fractional loss per cycle.
  • the rate constant for the conversion of additional reactant sugar alcohol is less than 20% lower than the rate constant for the conversion of the reactant sugar alcohol in the first reaction. In certain variations, the rate constant for conversion of the additional sugar alcohol is less than 15%, less than 12%, less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1% lower than the rate constant for the conversion of the reactant sugar alcohol in the first reaction. In some variations, the loss of activity is less than 20% per cycle, less than 15% per cycle, less than 10% per cycle, less than 8% per cycle, less than 4% per cycle, less than 2% per cycle, less than 1% per cycle, less than 0.5% per cycle, or less than 0.2% per cycle.
  • the reactant sugar alcohol is sorbitol
  • anhydrosugar alcohol is isosorbide
  • the rate constant of the catalyst described herein for the conversion of sorbitol in a second reaction is less than 2% lower than the rate constant for conversion of sorbitol in the first reaction.
  • the reactant sugar alcohol is sorbitol and the loss of activity is 0.5% per cycle.
  • catalyst lifetime refers to the average number of cycles that a catalyst particle can be re-used before it no longer effectively catalyzes the conversion of additional reactant sugar alcohol.
  • the catalyst lifetime is calculated as the reciprocal of the loss of activity. For example, if the loss of activity is 1% per cycle, then the catalyst lifetime is 100 cycles. In some variations, the catalyst lifetime is at least 1 cycle, at least 2 cycles, at least 10 cycles, at least 50 cycles, at least 100 cycles, at least 200 cycles, at least 500 cycles.
  • a portion of the total mass of the catalyst in a reaction may be removed and replaced with fresh catalyst between reaction cycles.
  • 0.1% of the mass of the catalyst may be replaced between reaction cycles, 1% of the mass of the catalyst may be replaced between reaction cycles, 2% of the mass of the catalyst may be replaced between reaction cycles, 5% of the mass of the catalyst may be replaced between reaction cycles, 10% of the mass of the catalyst may be replaced between reaction cycles, or 20% of the mass of the catalyst may be replaced between reaction cycles.
  • the "catalyst make-up rate" refers to the fraction of the catalyst mass that is replaced with fresh catalyst between reaction cycles.
  • the anhydrosugar alcohols produced by the methods described herein may be suitable as starting materials and intermediates to produce other useful compounds.
  • the anhydrosugar alcohols produced by the methods described herein may be used to produce plastics, polymers, food products, or cosmetics.
  • the anhydrosugar alcohols produced may be used to produce polyurethane, polycarbonate, polyester, or polyamide.
  • the sugar alcohol described herein is sorbitol
  • anhydrosugar alcohol produced is isosorbide.
  • provided is a method of producing isosorbide dimethyl ether or isosorbide dinitrate from the isosorbide produced by any of the methods described herein.
  • a method of producing an anhydrosugar alcohol from a sugar alcohol comprising: combining a sugar alcohol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing an anhydrosugar alcohol from at least a portion of the reaction mixture.
  • a method of producing isosorbide from sorbitol comprising: combining sorbitol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing isosorbide from at least a portion of the reaction mixture.
  • linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • each ionic monomer independently comprises at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof.
  • the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • polymeric backbone is selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, poly(acrylonitrile butadiene styrene), polyalkyleneammonium, polyalkylenediammonium, polyalkylenepyrrolium,
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyradizimium, polyalkylenethiazinium, polyalkylenemorpholinium, polyalkylenepiperidinium, polyalkylenepiperizinium, polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium
  • hydrophobic group at each occurrence is independently selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl.
  • the solid support comprises a material, wherein the material is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and any combinations thereof.
  • each Bronsted-Lowry acid is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
  • each Bronsted-Lowry acid is independently sulfonic acid or phosphonic acid.
  • each Bronsted-Lowry acid is sulfonic acid.
  • each Bronsted-Lowry acid is phosphonic acid.
  • each Bronsted-Lowry acid is acetic acid.
  • each Bronsted-Lowry acid is isophthalic acid.
  • each Bronsted-Lowry acid is boronic acid.
  • each Bronsted-Lowry acid is perfluorinated acid.
  • linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate
  • each acidic moiety independently has at least one Bronsted-Lowry acid, wherein the Bronsted-Lowry acid and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
  • each ionic moiety is selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
  • each ionic moiety independently has at least one nitrogen-containing cationic group
  • each nitrogen-containing cationic group is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • each ionic moiety independently has at least one phosphorous-containing cationic group, and wherein each phosphorous-containing cationic group is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
  • each ionic moiety independently has at least one nitrogen-containing cationic group, wherein the nitrogen-containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
  • each ionic moiety independently has at least one phosphorous-containing cationic group, wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
  • each hydrophobic moiety is selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
  • linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • carbon-supported triphenyl phosphonium bromide phosphonic acid carbon-supported trimethyl phosphonium bromide phosphonic acid; carbon-supported triethyl phosphonium bromide phosphonic acid; carbon-supported tripropyl phosphonium bromide phosphonic acid; carbon-supported tributyl phosphonium bromide phosphonic acid; carbon-supported trifluoro phosphonium bromide phosphonic acid; carbon- supported pyrrolium bisulfate phosphonic acid;
  • carbon-supported triphenyl phosphonium bisulfate phosphonic acid carbon-supported trimethyl phosphonium bisulfate phosphonic acid; carbon-supported triethyl phosphonium bisulfate phosphonic acid; carbon-supported tripropyl phosphonium bisulfate phosphonic acid; carbon- supported tributyl phosphonium bisulfate phosphonic acid; carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported carbon- ⁇ supported
  • a composition comprising: a sugar alcohol; and a catalyst, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support. producing an anhydrosugar alcohol from at least a portion of the reaction mixture.
  • composition of embodiment 78, wherein the sugar alcohol is a C6 sugar alcohol or a C5 sugar alcohol.
  • composition of embodiment 78, wherein the sugar alcohol is hexitol.
  • composition of embodiment 82, wherein the anhydrosugar alcohol produced is a dianhydrosugar alcohol.
  • composition of embodiment 83, wherein the dianhydrosugar alcohol is
  • a composition comprising: sorbitol; and a catalyst, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
  • composition of embodiment 85 further comprising isosorbide.
  • composition of embodiment 88, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
  • composition of embodiment 89 wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid and phosphonic acid.
  • the at least one Bronsted-Lowry acid at each occurrence in the catalyst is sulfonic acid.
  • composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is phosphonic acid.
  • composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is acetic acid.
  • composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is isophthalic acid.
  • composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is boronic acid.
  • composition of embodiment 98, wherein the linker at each occurrence is
  • unsubstituted or substituted alkylene unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • composition of embodiment 101, wherein the phosphorous -containing cationic group at each occurrence is independently selected from the group consisting of triphenyl
  • phosphonium trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • composition of embodiment 105, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • composition of embodiment 105 wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
  • composition of any one of embodiments 87 to 108, wherein the polymeric backbone is selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, poly(acrylonitrile butadiene styrene),
  • polyalkyleneammonium polyalkylenediammonium, polyalkylenepyrrolium,
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyradizimium, polyalkylenethiazinium, polyalkylenemorpholinium, polyalkylenepiperidinium, polyalkylenepiperizinium, polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium

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Abstract

Described herein are methods of producing anhydrosugar alcohols, such as isosorbide, from sugar alcohols, such as sorbitol, using catalysts that have both acidic and ionic group. Provided herein are methods of producing anhydrosugar alcohols using a catalyst that retains catalytic activity through multiple reaction cycles. The methods provided herein allow for commercially economical recovery and reuse of the catalysts over multiple reaction cycles.

Description

METHODS OF PRODUCING ANHYDROSUGAR ALCOHOLS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Patent Application No.
62/108,460, filed January 27, 2015, the disclosure of which is hereby incorporated by reference in its entirety.
FIELD
[0002] The present disclosure relates generally to methods of producing anhydrosugar alcohols from sugar alcohols. More specifically, the present disclosure relates to the production of anhydrosugar alcohols, such as isosorbide, from sugar alcohols, such as sorbitol, using a catalyst with acidic and ionic groups.
BACKGROUND
[0003] Anhydrosugar alcohols and their derivatives are commercially used in various applications, such as the production of pharmaceutical compounds, cosmetics, food, and plastics. Isosorbide, also referred to as 1,4-3, 6-dianhydro-D- sorbitol, is an example of an anhydrosugar alcohol that is used as a monomer in the production of polymers and co-polymers, such as polyester polymers and co-polymers. In other examples, isosorbide is used to produce isosorbide dimethyl ether, which may be used as an industrial solvent; and isosorbide dinitrate, which may be used to treat heart-related chest pain.
[0004] Methods known in the art for producing anhydrosugar alcohols typically involve contacting a sugar alcohol with an acid catalyst at elevated temperatures. See e.g., U.S. Patent Nos. 4,408,061; 7,982,059; 7,439,352; 8,445,705; and 7,728,156. A significant decrease in the activity of the catalyst is often observed over each cycle of recovery and reuse in such known methods, unless costly further processing steps are used to maintain the activity of the catalyst. For example, the catalyst may be washed with an organic solvent between reaction cycles;
however, such additional processing can add significant cost to a commercial manufacturing process.
[0005] Thus, what is needed in the art are alternative methods of producing anhydrosugar alcohols using a recyclable catalyst that retains catalytic activity through multiple reaction cycles. BRIEF SUMMARY
[0006] Provided herein are methods of producing anhydrosugar alcohols using a catalyst that retains catalytic activity through multiple reaction cycles. The methods provided herein allow for commercially economical recovery and reuse of the catalysts over multiple reaction cycles.
[0007] In one aspect, provided is a method of producing a dianhydrosugar alcohol from a sugar alcohol, by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, provided is a method of producing a dianhydrosugar alcohol from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a dianhydrosugar alcohol.
[0008] In another aspect, provided is a method of producing a monoanhydrosugar alcohol from a sugar alcohol, by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a monoanhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, provided is a method of producing a monoanhydrosugar alcohol from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a monoanhydrosugar alcohol.
[0009] In yet another aspect, provided is a method of producing a dianhydrosugar alcohol from a monoanhydrosugar alcohol, by: combining a monoanhydrosugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, provided is a method of producing a dianhydrosugar alcohol from a monoanhydrosugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the monoanhydrosugar alcohol to produce a dianhydrosugar alcohol.
[0010] In some embodiments of the foregoing aspects, the catalyst is a polymeric catalyst. The polymeric catalyst has acidic monomers and ionic monomers connected to form a polymeric backbone. In other embodiments of the foregoing aspects, the catalyst is a solid-supported catalyst. The solid- supported catalyst has a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support. In some variations, the catalysts used in the methods described herein exhibit a loss of activity of less than 1% per cycle.
[0011] In some embodiments of the foregoing aspects, the dianhydrosugar alcohol produced is isosorbide, and the sugar alcohol is sorbitol. DESCRIPTION OF THE FIGURES
[0012] The present application can be understood by reference to the following description taken in conjunction with the accompanying figures.
[0013] FIG. 1 is an exemplary reaction scheme depicting the production of an anhydrosugar alcohol from a sugar alcohol in the presence of a catalyst.
[0014] FIG. 2A illustrates a portion of a catalyst with a polymeric backbone and side chains.
[0015] FIG. 2B illustrates a portion of an exemplary catalyst, in which a side chain with the acidic group is connected to the polymeric backbone by a linker and in which a side chain with the cationic group is connected directly to the polymeric backbone.
[0016] FIG. 3 depicts a reaction scheme to prepare a dual-functionalized catalyst from an activated carbon support, in which the catalyst has both acidic and ionic moieties.
[0017] FIG. 4 illustrates a portion of a polymeric catalyst, in which the monomers are arranged in blocks of monomers, and the block of acidic monomers alternates with the block of ionic monomers.
[0018] FIG. 5A illustrates a portion of a polymeric catalyst with cross-linking within a given polymeric chain.
[0019] FIG. 5B illustrates a portion of a polymeric catalyst with cross-linking within a given polymeric chain.
[0020] FIG. 6A illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
[0021] FIG. 6B illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
[0022] FIG. 6C illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
[0023] FIG. 6D illustrates a portion of a polymeric catalyst with cross-linking between two polymeric chains.
[0024] FIG. 7 illustrates a portion of a polymeric catalyst with a polyethylene backbone. [0025] FIG. 8 illustrates a portion of a polymeric catalyst with a polyvinylalcohol backbone.
[0026] FIG. 9 illustrates a portion of a polymeric catalyst, in which the monomers are randomly arranged in an alternating sequence.
[0027] FIG. 10 illustrates two side chains in a polymeric catalyst, in which there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
[0028] FIG. 11 illustrates two side chains in a polymeric catalyst, in which there are zero carbons between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
[0029] FIG. 12 illustrates a portion of a polymeric catalyst with an ionomeric backbone.
[0030] FIG. 13 is an exemplary process diagram depicting the steps of producing
anhydrosugar alcohol from sugar alcohol in the presence of a catalyst, in which the catalyst is recovered and reused for one or more reaction cycles.
[0031] FIG. 14 is a graph depicting the conversion of sorbitol to isosorbide over time using a catalyst loading of 0.1 kg catalyst per kg of sorbitol.
[0032] FIG. 15 is a high-performance liquid chromatography (HPLC) trace showing the reaction mixture contents after 1.5 hours during the conversion of sorbitol to isosorbide in the presence of a catalyst containing acidic and ionic groups.
[0033] FIG. 16 is an HPLC trace showing the reaction mixture contents after 5.5 hours during the conversion of sorbitol to isosorbide in the presence of a catalyst containing acidic and ionic groups.
[0034] FIG. 17 is a graph comparing the catalyst rate constant over four cycles of use of a catalyst during conversion of sorbitol to isosorbide.
DETAILED DESCRIPTION
[0035] The following description sets forth exemplary methods, parameters and the like. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments. [0036] Described herein are methods of producing anhydrosugar alcohols from sugar alcohols, using a catalyst that contains both acidic groups and ionic groups. Described herein are also methods of producing dianhydrosugar alcohols from monoanhydrosugar alcohols, using a catalyst that contains both acidic groups and ionic groups.
[0037] In one variation, the sugar alcohols can undergo a dehydration reaction in the presence of the catalysts described herein to produce dianhydrosugar alcohols. For example, in some aspects, sorbitol (an example of a sugar alcohol) may be dehydrated in the presence of the catalysts described herein to produce isosorbide (an example of a dianhydrosugar alcohol).
[0038] In another variation, the sugar alcohols can also undergo a dehydration reaction in the presence of the catalysts described herein to produce monanhydrosugar alcohols. For example, in some aspects, xylitol (an example of a sugar alcohol) may be dehydrated in the presence of the catalysts described herein to produce 1,4-anhydroxylitol (an example of a monoanhydrosugar alcohol).
[0039] In yet another variation, the monoanhydrosugar alcohols can undergo a dehydration reaction in the presence of the catalysts described herein to produce dianhydrosugar alcohols. For example, in some aspects, 2-(l,2-dihydroxyethyl)tetrahydrofuran-3,4-diol (an example of a monoanhydrosugar alcohol) may be dehydrated in the presence of the catalysts described herein to produce isosorbide (an example of a dianhydrosugar alcohol).
[0040] The catalysts used in the methods described herein may be recycled and reused. In some variations, the catalysts described herein are recycled over multiple reaction cycles, and the catalytic activity of a catalyst in the first reaction cycle may be the same or similar to the catalytic activity of the recycled catalyst used in subsequent reaction cycle(s). The ability of the catalysts described herein to retain catalytic activity over multiple reactions cycles of recovery and reuse presents several commercial advantages, including reducing the need to add fresh catalyst to achieve similar levels of catalytic activity, which can in turn reduce the cost of anhydrosugar alcohol production. Thus, in certain aspects, provided herein are methods of producing anhydrous sugar alcohols from sugar alcohols using recyclable catalysts, in which the catalytic activity of the recyclable catalysts in the first reaction is same or similar to the catalytic activity of the recyclable catalysts in one or more subsequent reaction cycles.
[0041] In one aspect, a dianhydrosugar alcohol is produced from a sugar alcohol by:
combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, a dianhydrosugar alcohol is produced from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a dianhydrosugar alcohol.
[0042] In another aspect, a dianhydrosugar alcohol is produced from a monoanhydrosugar alcohol by: combining a monoanhydrosugar alcohol with a catalyst to form a reaction mixture; and producing a dianhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, a dianhydrosugar alcohol is produced from a monoanhydrosugar alcohol, by: combining a monoanhydrosugar alcohol with a catalyst; and dehydrating the monoanhydrosugar alcohol to produce a dianhydrosugar alcohol.
[0043] In yet another aspect, a monoanhydrosugar alcohol is produced from a sugar alcohol by: combining a sugar alcohol with a catalyst to form a reaction mixture; and producing a monoanhydrosugar alcohol from at least a portion of the reaction mixture. In another aspect, a monoanhydrosugar alcohol is produced from a sugar alcohol, by: combining a sugar alcohol with a catalyst; and dehydrating the sugar alcohol to produce a monoanhydrosugar alcohol.
[0044] As used herein, "sugar alcohol" refers to acyclic compounds with the chemical formula (CHOH)n(CH20H)2, wherein n is greater than or equal to 1. Examples of sugar alcohols include glycerol, erythritol, threitol, arabinitol, xylitol, ribitol, sorbitol, mannitol, galactitol, fucitol, iditol, and inositol.
[0045] As used herein, "anhydrosugar alcohol" refers to both dianhydrosugar alcohols and monoanhydrosugar alcohols.
[0046] As used herein, "monoanhydrosugar alcohol" refers to a compound with the chemical formula C(CHOH)n_i(CH2OH)2, wherein n is greater than or equal to 1. Examples of
monoanhydrosugar alcohols include 2-(l,2-dihydroxyethyl)tetrahydrofuran-3,4-diol and 2- (hydroxymethyl)tetrahydrofuran-3,4-diol.
[0047] As used herein, "dianhydrosugar alcohol" refers to a compound with the chemical formula C2(CHOH)n_2(CH2OH)2, wherein n is greater than or equal to 2. Examples of
dianhydrosugar alcohols include isosorbide, isomannide, and isoidide.
[0048] With reference to FIG. 1, process 100 is an exemplary embodiment for producing dianhydrohexitol 110 from hexitol 102 in the presence of catalyst 104. In the methods described herein, the catalyst 104 contains both acidic and ionic groups. In some variations of process 100, catalyst 104 is a polymeric catalyst or a solid- supported catalyst. For example, in some variations, hexitol 102 is sorbitol, and isosorbide is dianhydrohexitol 110 produced. Thus, in one aspect, provided herein are methods of producing isosorbide from sorbitol using a catalyst containing both acidic and ionic groups. It should be generally understood that other sugar alcohols, as described herein, may be used to produce their corresponding anhydrosugar alcohols.
[0049] With reference again to FIG. 1, in some variations, one or more additional reagents may be used. For example, in one variation of process 100, hexitol 102 may be contacted with catalyst 104 and a solvent. In other variations, hexitol 102 may be contacted with catalyst 104 and an additional acid.
[0050] With reference again to FIG. 1, in other variations, process 100 may include one or more steps. For example, process 100 may further include isolating catalyst 104 from the reaction mixture to recover the catalyst. In some variations, the isolated catalyst may then be contacted with additional hexitol to produce additional dianhydrohexitol. Thus, catalyst 104 may be recycled for use in one or more subsequent reaction cycles.
[0051] With reference to FIG. 13, process 200 depicts an exemplary multi-step scheme for producing anhydrosugar alcohol from sugar alcohol in the presence of catalyst, in which the catalyst is recycled for use in one or more subsequent reaction cycles. In process 200, the sugar alcohol provided in step 202 and the catalyst provided in step 204 are combined in step 206 to produce anhydrosugar alcohol in step 210. In step 212, the catalyst is isolated from the anhydrosugar alcohol produced, and reused in step 204 to provide catalyst for another reaction cycle. Steps 212, 204, 206, and 210 may be repeated one or more cycles, after which the anhydrosugar alcohol produced is isolated in step 220.
[0052] It should be generally understood that one or more steps may be omitted or added to process 200. For example, in some variations, the sugar alcohol and catalyst are combined in step 206 in the further presence of a solvent. In other embodiments, the sugar alcohol and catalyst are combined in step 206 in the further presence of additional reactants.
[0053] With reference again to FIG. 13, in other variations, process 200 may include one or more steps, or one more steps in process 200 may be omitted. For example, in some variations, the anhydrosugar alcohol isolated in step 220 of process 200 may undergo further processing, for example, purification. In other variations, step 220 to isolate the anhydrosugar alcohol may be omitted and the reaction mixture containing anhydrosugar alcohol produced in step 210 may be used in a subsequent chemical transformation.
[0054] The sugar alcohol and monoanhydrosugar alcohol starting materials, catalysts, reaction conditions and anhydrosugar alcohol products are further described below.
Sugar Alcohol Starting Materials
[0055] The sugar alcohols used in the methods described herein may be obtained from any commercially available sources or produced according to any methods known in the art. For example, in some variations, the sugar alcohols used may be obtained from biomass.
[0056] Any suitable sugar alcohol that can be converted into an anhydrosugar alcohol may be used as a starting material in the methods described herein. Examples of suitable sugar alcohols include arabinitol, ribitol, sorbitol, mannitol, galactitol, iditol, mannitol, and xylitol. Any mixtures of the sugar alcohols described herein may also be used.
[0057] In some variations, the sugar alcohol is a C6 sugar alcohol. As used herein, a "C6 sugar alcohol" refers to a sugar alcohol with six carbon atoms. A C6 sugar alcohol may also be referred to as a "hexitol". In one variation, the sugar alcohol is sorbitol.
[0058] In other variations, the sugar alcohol is a C5 sugar alcohol. As used herein, a "C5 sugar alcohol" refers to a sugar alcohol with five carbon atoms. A C5 sugar alcohol may also be referred to as a "pentitol". In one variation, the sugar alcohol is xylitol.
Monoanhydrosugar Alcohol Starting Materials
[0059] The monoanhydrosugar alcohols used in the methods described herein may be obtained from any commercially available sources or produced according to any methods known in the art. For example, in some variations, the monoanhydrosugar alcohols used may be obtained from biomass.
[0060] Any suitable monoanhydrosugar alcohol that can be converted into a dianhydrosugar alcohol may be used as a starting material in the methods described herein. Examples of suitable sugar alcohols include 1,4-anhydroxylitol and 1,4-anhydrosorbitol. Any mixtures of the monoanhydrosugar alcohols described herein may also be used. Catalysts
[0061] The catalysts used in the methods described herein include polymeric catalysts and solid- supported catalysts.
[0062] In some embodiments, the catalyst is a polymer made up of acidic monomers and ionic monomers (which are also referred to herein as "ionomers") connected to form a polymeric backbone. Each acidic monomer includes at least one Bronsted-Lowry acid, and each ionic monomer includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or any combination thereof. In certain embodiments of the polymeric catalyst, at least some of the acidic and ionic monomers may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to a portion of the polymeric backbone. For the acidic monomers, the Bronsted-Lowry acid and the linker together form a side chain. Similarly, for the ionic monomers, the cationic group and the linker together form a side chain. With reference to the portion of the polymeric catalyst depicted in FIGS. 2A and 2B, the side chains are pendant from the polymeric backbone.
[0063] In another aspect, the catalyst is solid- supported, having acidic moieties and ionic moieties each attached to a solid support. Each acidic moiety independently includes at least one Bronsted-Lowry acid, and each ionic moiety includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or any combination thereof. In certain embodiments of the solid- supported catalyst, at least some of the acidic and ionic moieties may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to the solid support. With reference to FIG. 3, the produced catalyst is a solid- supported catalyst with acidic and ionic moieties.
Acidic Monomers and Moieties
[0064] The polymeric catalysts include a plurality of acidic monomers, where as the solid- supported catalysts include a plurality of acidic moieties attached to a solid support.
[0065] In some embodiments, a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic moieties (e.g., of a solid-supported catalyst) has at least one Bronsted- Lowry acid. In certain embodiments, a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic moieties (e.g., of a solid-supported catalyst) has one Bronsted- Lowry acid or two Bronsted-Lowry acids. In certain embodiments, a plurality of the acidic monomers (e.g. , of a polymeric catalyst) or a plurality of the acidic moieties (e.g. , of a solid- supported catalyst) has one Bronsted-Lowry acid, while others have two Bronsted-Lowry acids.
[0066] In some embodiments, each Bronsted-Lowry acids is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, each Bronsted-Lowry acids is independently sulfonic acid or phosphonic acid. In one embodiment, each Bronsted-Lowry acid is sulfonic acid. It should be understood that the Bronsted-Lowry acids in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid- supported catalyst) may be the same at each occurrence or different at one or more occurrences.
[0067] In some embodiments, one or more of the acidic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the acidic moieties of a solid- supported catalyst are directly connected to the solid support. In other embodiments, one or more of the acidic monomers (e.g. , of a polymeric catalyst) or one or more acidic moieties (e.g. , of a solid- supported catalyst) each independently further includes a linker connecting the Bronsted-Lowry acid to the polymeric backbone or the solid support (as the case may be). In certain embodiments, some of the Bronsted-Lowry acids are directly connected to the polymeric backbone or the solid support (as the case may be), while other the Bronsted-Lowry acids are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
[0068] In those embodiments where the Bronsted-Lowry acid is connected to the polymeric backbone or the solid support (as the case may be) by a linker, each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker. In certain
embodiments, the linker is unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.
[0069] In other embodiments, each linker in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid-supported catalyst) is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
[0070] Further, it should be understood that some or all of the acidic monomers (e.g. , of a polymeric catalyst) or one or more acidic moieties (e.g. , of a solid-supported catalyst) connected to the polymeric backbone by a linker may have the same linker, or independently have different linkers.
[0071] In some embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid- supported catalyst) may independently have the structure of Formulas IA-VIA:
Figure imgf000012_0001
IA IB IC ID IIA IIB
Figure imgf000013_0001
Figure imgf000013_0002
IIIC
Figure imgf000013_0003
IVA IVB
Figure imgf000013_0004
IVC IVD V
Figure imgf000013_0005
VIA
wherein: each Z is independently C(R2)(R3), N(R4), S, S(R5)(R6), S(0)(R5)(R6), S02, or O, wherein any two adjacent Z can (to the extent chemically feasible) be joined by a double bond, or taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl;
each m is independently selected from 0, 1, 2, and 3;
each n is independently selected from 0, 1, 2, and 3;
2 3 4
each R , R , and R is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; and
each R5 and R6 is independently alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl.
[0072] In some embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid- supported catalyst) may independently have the structure of Formulas IA, IB, IVA, or IVB. In other embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may
independently have the structure of Formulas IIA, IIB, IIC, IVA, IVB, or IVC. In other embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas IIIA, MB, or IIIC. In some embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formulas VA, VB, or VC. In some embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formula IA. In other embodiments, each acidic monomer (e.g. , of a polymeric catalyst) and each acidic moiety (e.g. , of a solid-supported catalyst) may independently have the structure of Formula IB.
[0073] In some embodiments, Z can be chosen from C(R2)(R3), N(R4), S02, and O. In some embodiments, any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl, and heteroaryl. In other embodiments, any two adjacent Z can be joined by a double bond. Any combination of these embodiments is also contemplated (as chemically feasible).
[0074] In some embodiments, m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some embodiments, R1 can be hydrogen, alkyl or heteroalkyl. In some embodiments, R1 can be
2 3 4
hydrogen, methyl, or ethyl. In some embodiments, each R , R and R can independently be
2 3 4 hydrogen, alkyl, heterocyclyl, aryl, or heteroaryl. In other embodiments, each R , R and R can independently be heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl. In some embodiments, each R5 and R6 can independently be alkyl, heterocyclyl, aryl, or heteroaryl. In another embodiment, any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
[0075] In some embodiments, the polymeric catalysts and solid- supported catalysts described herein contain monomers or moieties, respectively, that have at least one Bronsted- Lowry acid and at least one cationic group. The Bronsted-Lowry acid and the cationic group can be on different monomers/moieties or on the same monomer/moiety.
[0076] In certain embodiments, the acidic monomers of the polymeric catalyst may have a side chain with a Bronsted-Lowry acid that is connected to the polymeric backbone by a linker. In certain embodiments, the acidic moieties of the solid- supported catalyst may have a Bronsted- Lowry acid that is attached to the solid support by a linker. Side chains (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid- supported catalyst) with one or more Bronsted-Lowry acids connected by a linker can include, for example,
Figure imgf000015_0001
wherein:
L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; and r is an integer.
[0077] In certain embodiments, L is an alkyl linker. In other embodiments L is methyl, ethyl, propyl, or butyl. In yet other embodiments, the linker is ethanoyl, propanoyl, or benzoyl. In certain embodiments, r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
[0078] In some embodiments, at least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid- supported catalyst) may be:
Figure imgf000016_0001
wherein: s is 1 to 10; each r is independently 1 , 2, 3, 4, or 5 (as applicable or chemically feasible); and w is 0 to 10.
[0079] In certain embodiments, s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1. In certain embodiments, w is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
[0080] In certain embodiments, at least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid- supported catalyst) may be:
Figure imgf000016_0002
Figure imgf000017_0001
Figure imgf000018_0001
[0081] In other embodiments, the acidic monomers (e.g. , of a polymeric catalyst) can have a side chain with a Bronsted-Lowry acid that is directly connected to the polymeric backbone. In other embodiments, the acidic moieties (e.g. , of a solid- supported catalyst) may be directly attached to a solid support. Side chains directly connect to the polymeric backbone (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid-supported catalyst) directly attached to the solid support may can include, for example,
Figure imgf000018_0002
Ionic Monomers and Moieties
[0082] The polymeric catalysts include a plurality of ionic monomers, where as the solid- supported catalysts includes a plurality of ionic moieties attached to a solid support.
[0083] In some embodiments, a plurality of ionic monomers (e.g. , of a polymeric catalyst) or a plurality of ionic moieties (e.g. , of a solid-supported catalyst) has at least one nitrogen- containing cationic group, at least one phosphorous -containing cationic group, or any combination thereof. In certain embodiments, a plurality of ionic monomers (e.g. , of a polymeric catalyst) or a plurality of ionic moieties (e.g. , of a solid-supported catalyst) has one nitrogen-containing cationic group or one phosphorous -containing cationic group. In some embodiments, a plurality of ionic monomers (e.g. , of a polymeric catalyst) or a plurality of ionic moieties (e.g. , of a solid- supported catalyst) has two nitrogen-containing cationic groups, two phosphorous-containing cationic group, or one nitrogen-containing cationic group and one phosphorous-containing cationic group. In other embodiments, a plurality of ionic monomers (e.g. , of a polymeric catalyst) or a plurality of ionic moieties (e.g. , of a solid-supported catalyst) has one nitrogen-containing cationic group or phosphorous -containing cationic group, while others have two nitrogen-containing cationic groups or phosphorous-containing cationic groups.
[0084] In some embodiments, a plurality of ionic monomers (e.g. , of a polymeric catalyst) or a plurality of ionic moieties (e.g. , of a solid-supported catalyst) can have one cationic group, or two or more cationic groups, as is chemically feasible. When the ionic monomers (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid- supported catalyst) have two or more cationic groups, the cationic groups can be the same or different.
[0085] In some embodiments, each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is a nitrogen-containing cationic group. In other embodiments, each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid- supported catalyst) is a phosphorous-containing cationic group. In yet other embodiments, at least some of ionic monomers (e.g. , of a polymeric catalyst) or at least some of the ionic moieties (e.g. , of a solid- supported catalyst) are a nitrogen-containing cationic group, whereas the cationic groups in other ionic monomers (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid-supported catalyst) are a phosphorous-containing cationic group. In an exemplary embodiment, each cationic group in the polymeric catalyst or solid- supported catalyst is imidazolium. In another exemplary embodiment, the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid- supported catalyst) is imidazolium, while the cationic group in other monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid- supported catalyst) is pyridinium. In yet another exemplary embodiment, each cationic group in the polymeric catalyst or solid- supported catalyst is a substituted phosphonium. In yet another exemplary embodiment, the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid- supported catalyst) is triphenyl phosphonium, while the cationic group in other monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is imidazolium. [0086] In some embodiments, the nitrogen-containing cationic group at each occurrence can be independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium. In other embodiments, the nitrogen-containing cationic group at each occurrence can be independently selected from imidazolium, pyridinium, pyrimidinium, morpholinium, piperidinium, and piperizinium. In some embodiments, the nitrogen-containing cationic group can be imidazolium.
[0087] In some embodiments, the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium. In other embodiments, the phosphorous -containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, and triethyl phosphonium. In other embodiments, the phosphorous-containing cationic group can be triphenyl phosphonium.
[0088] In some embodiments, one or more of the ionic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the ionic moieties of a solid- supported catalyst are directly connected to the solid support. In other embodiments, one or more of the ionic monomers (e.g. , of a polymeric catalyst) or one or more ionic moieties (e.g. , of a solid-supported catalyst) each independently further includes a linker connecting the cationic group to the polymeric backbone or the solid support (as the case may be). In certain
embodiments, some of the cationic groups are directly connected to the polymeric backbone or the solid support (as the case may be), while other the cationic groups are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
[0089] In those embodiments where the cationic group is connected to the polymeric backbone or the solid support (as the case may be) by a linker, each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker. In certain
embodiments, the linker is unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker. [0090] In other embodiments, each linker in an ionic monomer (e.g. , of a polymeric catalyst) or an ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
[0091] Further, it should be understood that some or all of the ionic monomers (e.g. , of a polymeric catalyst) or one or more ionic moieties (e.g. , of a solid- supported catalyst) connected to the polymeric backbone by a linker may have the same linker, or independently have different linkers.
[0092] In some embodiments, each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is independently has the structure of Formulas VIIA-XIB:
Figure imgf000022_0001
VIIA VIIB VIIIA VIIIB
Figure imgf000022_0002
XB XIA XIB wherein: each Z is independently C(R2)(R3), N(R4), S, S(R5)(R6), S(0)(R5)(R6), S02, or O, wherein any two adjacent Z can (to the extent chemically feasible) be joined by a double bond, or taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl; each X is independently F, CI", Br", I", N02 ", N03 ", S04 2", R7S04 ", R7C02 ", P04 2", R7P03, or R 7 P02 - , where S042-" and P042-" are each independently associated with at least two cationic groups at any X position on any ionic monomer, and each m is independently 0, 1, 2, or 3; each n is independently 0, 1, 2, or 3; each R 1 , R2 , R 3 and R 4 is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; each R5 and R6 is independently alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; and n
each R is independently hydrogen, Ci_4alkyl, or Ci_4heteroalkyl.
2 3 4
[0093] In some embodiments, Z can be chosen from C(R")(RJ), N(R ), S02, and O. In some embodiments, any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl and heteroaryl. In other embodiments, any two adjacent Z can be joined
2- 7 - 7 - by a double bond. In some embodiments, each X can be CI", N03 ~, S04 , R'S04 ~, or R'C02 ~, where R can be hydrogen or Ci_4alkyl. In another embodiment, each X can be CI", B Γ, HS04 " , HC02 ", CH3C02 ", or N03 ". In other embodiments, X is acetate. In other embodiments, X is bisulfate. In other embodiments, X is chloride. In other embodiments, X is nitrate.
[0094] In some embodiments, m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some
2 3 4
embodiments, each R , R , and R can be independently hydrogen, alkyl, heterocyclyl, aryl, or
2 3 4
heteroaryl. In other embodiments, each R , R and R can be independently heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl. In some embodiments, each R5 and R6 can be independently alkyl, heterocyclyl, aryl, or heteroaryl. In another embodiment, any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
[0095] In certain embodiments, the ionic monomers of the polymeric catalyst may have a side chain with a cationic group that is connected to the polymeric backbone by a linker. In certain embodiments, the ionic moieties of the solid-supported catalyst may have a cationic group that is attached to the solid support by a linker. Side chains (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid- supported catalyst) with one or more cationic groups connected by a linker can include, for example, νΛΛΛ νΛΛΛΓ
Figure imgf000023_0001
wherein:
L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; each Rla, Rlb and Rlc are independently hydrogen or alkyl; or Rla and Rlb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heterocycloalkyl; or Rla and Rlb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and Rlc is absent; r is an integer; and
X is as described above for Formulas VIIA-XIB .
[0096] In other embodiments L is methyl, ethyl, propyl, butyl. In yet other embodiments, the linker is ethanoyl, propanoyl, benzoyl. In certain embodiments, r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
[0097] In other embodiments, each linker is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
[0098] In certain embodiments, each linker is an unsubstituted alkyl linker or an alkyl linker with an oxo substituent. In one embodiment, each linker is -(CH2XCH2)- or -(CH2)(C=0). In certain embodiments, r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible). [0099] In some embodiments, at least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
Figure imgf000025_0001
wherein: each Rla, Rlb and Rlc are independently hydrogen or alkyl; or Rla and Rlb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
heterocycloalkyl; or R a and R1D are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R c is absent; s is an integer; v is 0 to 10; and
X is as described above for Formulas VIIA-XIB .
[0100] In certain embodiments, s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1. In certain embodiments, v is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
[0101] In certain embodiments, at least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
Figure imgf000025_0002
Figure imgf000026_0001

Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003

Figure imgf000028_0001
Figure imgf000028_0002

Figure imgf000029_0001

Figure imgf000030_0001

Figure imgf000031_0001
Figure imgf000031_0002
30
Figure imgf000032_0001
31
Figure imgf000033_0001
Figure imgf000034_0001
[0102] In other embodiments, the ionic monomers (e.g. , of a polymeric catalyst) can have a side chain with a cationic group that is directly connected to the polymeric backbone. In other embodiments, the ionic moieties (e.g. , of a solid- supported catalyst) can have a cationic group that is directly attached to the solid support. Side chains (e.g. , of a polymeric catalyst) directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid- supported catalyst) directly attached to the solid support may can include, for example,
Figure imgf000034_0002
[0103] In some embodiments, the nitrogen-containing cationic group can be an N-oxide, where the negatively charged oxide (0-) is not readily dissociable from the nitrogen cation. Non- limiting examples of such groups include, for example,
Figure imgf000035_0001
[0104] In some embodiments, the phosphorous-containing side chain (e.g. , of a polymeric catalyst) or moiety (e.g. , of a solid- supported catalyst) is independently:
Figure imgf000035_0002
[0105] In other embodiments, the ionic monomers (e.g. , of a polymeric catalyst) can have a side chain with a cationic group that is directly connected to the polymeric backbone. In other embodiments, the ionic moieties (e.g. , of a solid- supported catalyst) can have a cationic group that is directly attached to the solid support. Side chains (e.g. , of a polymeric catalyst) directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid- supported catalyst) directly attached to the solid support may can include, for example,
Figure imgf000036_0001
[0106] The ionic monomers (e.g., of a polymeric catalyst) or ionic moieties (e.g., of a solid- supported catalyst) can either all have the same cationic group, or can have different cationic groups. In some embodiments, each cationic group in the polymeric catalyst or solid- supported catalyst is a nitrogen-containing cationic group. In other embodiments, each cationic group in the polymeric catalyst or solid- supported catalyst is a phosphorous-containing cationic group. In yet other embodiments, the cationic group in some monomers or moieties of the polymeric catalyst or solid- supported catalyst, respectively, is a nitrogen-containing cationic group, whereas the cationic group in other monomers or moieties of the polymeric catalyst or solid- supported catalyst, respectively, is a phosphorous -containing cationic group. In an exemplary embodiment, each cationic group in the polymeric catalyst or solid- supported catalyst is imidazolium. In another exemplary embodiment, the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is pyridinium. In yet another exemplary embodiment, each cationic group in the polymeric catalyst or solid- supported catalyst is a substituted phosphonium. In yet another exemplary embodiment, the cationic group in some monomers or moieties of the polymeric catalyst or solid- supported catalyst is triphenyl phosphonium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium.
Acidic-Ionic Monomers and Moieties
[0107] Some of the monomers in the polymeric catalyst contain both the Bronsted-Lowry acid and the cationic group in the same monomer. Such monomers are referred to as "acidic- ionic monomers". Similarly, some of the moieties in the solid-supported catalyst contain both the Bronsted-Lowry acid and the cationic group in the same moieties. Such moieties are referred to as "acidic-ionic moieties". For example, in exemplary embodiments, the acidic-ionic monomer (e.g., of a polymeric catalyst) or an acidic-ionic moiety (e.g., of a solid-supported catalyst) can contain imidazolium and acetic acid, or pyridinium and boronic acid. [0108] In some embodiments, the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) include both Bronsted-Lowry acid(s) and cationic group(s), where either the Bronsted-Lowry acid is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or solid support (e.g. , of a solid-supported catalyst) by a linker, and/or the cationic group is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or is attached to the solid support (e.g. , of a solid- supported catalyst) by a linker.
[0109] It should be understood that any of the Bronsted-Lowry acids, cationic groups and linkers (if present) suitable for the acidic monomers/moieties and/or ionic monomers/moieties may be used in the acidic-ionic monomers/moieties.
[0110] In certain embodiments, the Bronsted-Lowry acid at each occurrence in the acidic- ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently sulfonic acid or phosphonic acid. In one embodiment, the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is sulfonic acid.
[0111] In some embodiments, the nitrogen-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium. In one embodiment, the nitrogen- containing cationic group is imidazolium.
[0112] In some embodiments, the phosphorous-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium. In one embodiment, the phosphorous -containing cationic group is triphenyl phosphonium.
[0113] In some embodiments, the polymeric catalyst or solid- supported catalyst can include at least one acidic-ionic monomer or moiety, respectively, connected to the polymeric backbone or solid support, wherein at least one acidic-ionic monomer or moiety includes at least one Bronsted-Lowry acid and at least one cationic group, and wherein at least one of the acidic-ionic monomers or moieties includes a linker connecting the acidic-ionic monomer to the polymeric backbone or solid support. The cationic group can be a nitrogen-containing cationic group or a phosphorous-containing cationic group as described herein. The linker can also be as described herein for either the acidic or ionic moieties. For example, the linker can be selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
[0114] In other embodiments, the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support.
[0115] In certain embodiments, the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.
[0116] Monomers of a polymeric catalyst that have side chains containing both a Bronsted- Lowry acid and a cationic group can also be called "acidic ionomers". Acidic-ionic side chains (e.g. , of a polymeric catalyst) or acidic-ionic moieties (e.g. , of a solid-supported catalyst) that are connected by a linker can include, for example,
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
40 each X is independently selected from F, CI", Br", Γ, N02 ",N03 ", S04 2", R7S04 ", R7C02 ",
2 7 7 2 2
P04 ", R P03 ", and R'P02 ", where S04 " and P04 " are each independently associated with at least two Bronsted-Lowry acids at any X position on any side chain, and each R is independently selected from hydrogen, Ci_4alkyl, and Ci_4heteroalkyl.
[0117] In some embodiments, R1 can be selected from hydrogen, alkyl, and heteroalkyl. In some embodiments, R1 can be selected from hydrogen, methyl, or ethyl. In some embodiments,
- - 2- 7 - 7 - 7
each X can be selected from CI", N03 ", S04 ", R S04 ", and R C02 ", where R can be selected from hydrogen and Ci_4alkyl. In another embodiment, each X can be selected from CI", Br" , Γ, HS04 ", HC02 ", CH3C02 ", and N03 ". In other embodiments, X is acetate. In other embodiments, X is bisulfate. In other embodiments, X is chloride. In other embodiments, X is nitrate.
[0118] In some embodiments, the acidic-ionic side chain (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently:
Figure imgf000042_0001
[0119] In some embodiments, the acidic-ionic side chain (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid- supported catalyst) is independently:
Figure imgf000042_0002
[0120] In other embodiments, the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) can have both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support. Such side chains in acidic-ionic monomers (e.g., of a polymeric catalyst) or moieties (e.g., of a solid- supported catalyst) can include, for example,
Figure imgf000043_0001
Hydrophobic Monomers and Moieties
[0121] In some embodiments, the polymeric catalyst further includes hydrophobic monomers connected to form the polymeric backbone. Similarly, in some embodiments, the solid- supported catalyst further includes hydrophobic moieties attached to the solid support. In either instance, each hydrophobic monomer or moiety has at least one hydrophobic group. In certain embodiments of the polymeric catalyst or solid- supported catalyst, each hydrophobic monomer or moiety, respectively, has one hydrophobic group. In certain embodiments of the polymeric catalyst or solid-supported catalyst, each hydrophobic monomer or moiety has two hydrophobic groups. In other embodiments of the polymeric catalyst or solid-supported catalyst, some of the hydrophobic monomers or moieties have one hydrophobic group, while others have two hydrophobic groups.
[0122] In some embodiments of the polymeric catalyst or solid-supported catalyst, each hydrophobic group is independently selected from an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl. In certain embodiments of the polymeric catalyst or solid- supported catalyst, each hydrophobic group is an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl. In one embodiment, each hydrophobic group is phenyl. Further, it should be understood that the hydrophobic monomers may either all have the same hydrophobic group, or may have different hydrophobic groups.
[0123] In some embodiments of the polymeric catalyst, the hydrophobic group is directly connected to form the polymeric backbone. In some embodiments of the solid- supported catalyst, the hydrophobic group is directly attached to the solid support.
Other Characteristics of the Catalysts
[0124] In some embodiments, the acidic and ionic monomers make up a substantial portion of the polymeric catalyst. In some embodiments, the acidic and ionic moieties make up a substantial portion solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers or moieties of the catalyst, based on the ratio of the number of acidic and ionic monomers/moieties to the total number of monomers/moieties present in the catalyst.
[0125] In some embodiments, the polymeric catalyst or solid- supported catalyst has a total amount of Bronsted-Lowry acid of between about 0.1 and about 20 mmol, between about 0.1 and about 15 mmol, between about 0.01 and about 12 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 7 mmol, between about 3 and about 6 mmol, between about 1 and about 5, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid- supported catalyst.
[0126] In some embodiments of the polymeric catalyst or solid-supported catalyst, each ionic monomer further includes a counterion for each nitrogen-containing cationic group or phosphorous-containing cationic group. In certain embodiments of the polymeric catalyst or solid- supported catalyst, each counterion is independently selected from halide, nitrate, sulfate, formate, acetate, or organo sulfonate. In some embodiments of the polymeric catalyst or solid- supported catalyst, the counterion is fluoride, chloride, bromide, or iodide. In one embodiment of the polymeric catalyst or solid- supported catalyst, the counterion is chloride. In another embodiment of the polymeric catalyst or solid- supported catalyst, the counterion is sulfate. In yet another embodiment of the polymeric catalyst or solid-supported catalyst, the counterion is acetate.
[0127] In some embodiments, the polymeric catalyst or solid- supported catalyst has a total amount of nitrogen-containing cationic groups and counterions or a total amount of
phosphorous-containing cationic groups and counterions of between about 0.01 and about 10 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 6 mmol, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid- supported catalyst.
[0128] In some embodiments, the acidic and ionic monomers make up a substantial portion of the polymeric catalyst or solid- supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers of the polymeric catalyst or solid- supported catalyst, based on the ratio of the number of acidic and ionic monomers or moieties to the total number of monomers or moieties present in the polymeric catalyst or solid-supported catalyst.
[0129] The ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties can be varied to tune the strength of the catalyst. In some embodiments, the total number of acidic monomers or moieties exceeds the total number of ionic monomers or moieties in the polymer or solid support. In other embodiments, the total number of acidic monomers or moieties is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of ionic monomers or moieties in the polymeric catalyst or solid-supported catalyst. In certain embodiments, the ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1 or about 10: 1.
[0130] In some embodiments, the total number of ionic monomers or moieties exceeds the total number of acidic monomers or moieties in the catalyst. In other embodiments, the total number of ionic monomers or moieties is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of acidic monomers or moieties in the polymeric catalyst or solid- supported catalyst. In certain embodiments, the ratio of the total number of ionic monomers or moieties to the total number of acidic monomers or moieties is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 9: 1 or about 10: 1.
Arrangement of Monomers in Polymeric Catalysts
[0131] In some embodiments of the polymeric catalysts, the acidic monomers, the ionic monomers, the acidic-ionic monomers and the hydrophobic monomers, where present, can be arranged in alternating sequence or in a random order as blocks of monomers. In some embodiments, each block has not more than twenty, fifteen, ten, six, or three monomers.
[0132] In some embodiments of the polymeric catalysts, the monomers of the polymeric catalyst are randomly arranged in an alternating sequence. With reference to the portion of the polymeric catalyst depicted in FIG. 9, the monomers are randomly arranged in an alternating sequence.
[0133] In other embodiments of the polymeric catalysts, the monomers of the polymeric catalyst are randomly arranged as blocks of monomers. With reference to the portion of the polymeric catalyst depicted in FIG. 4, the monomers are arranged in blocks of monomers. In certain embodiments where the acidic monomers and the ionic monomers are arranged in blocks of monomers, each block has no more than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, or 3 monomers.
[0134] The polymeric catalysts described herein can also be cross-linked. Such cross-linked polymeric catalysts can be prepared by introducing cross-linking groups. In some embodiments, cross-linking can occur within a given polymeric chain, with reference to the portion of the polymeric catalysts depicted in FIGS. 5A and 5B. In other embodiments, cross-linking can occur between two or more polymeric chains, with reference to the portion of the polymeric catalysts in FIGS. 6A, 6B, 6C and 6D.
[0135] With reference to FIGS. 5A, 5B and 6A, it should be understood that R1, R2 and R3, respectively, are exemplary cross linking groups. Suitable cross-linking groups that can be used to form a cross-linked polymeric catalyst with the polymers described herein include, for example, substituted or unsubstituted divinyl alkanes, substituted or unsubstituted divinyl cycloalkanes, substituted or unsubstituted divinyl aryls, substituted or unsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, and dihaloalkynes, where the substituents are those as defined herein. For example, cross-linking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane, divinylpropane, dichloropropane, divinylbutane, dichlorobutane, ethylene glycol, and resorcinol. In one embodiment, the crosslinking group is divinyl benzene.
[0136] In some embodiments of the polymeric catalysts, the polymer is cross-linked. In certain embodiments, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% of the polymer is cross-linked.
[0137] In some embodiments of the polymeric catalysts, the polymers described herein are not substantially cross-linked, such as less than about 0.9% cross-linked, less than about 0.5% cross-linked, less than about 0.1% cross-linked, less than about 0.01% cross-linked, or less than 0.001% cross-linked.
Polymeric Backbones
[0138] In some embodiments, the polymeric backbone is formed from one or more substituted or unsubstituted monomers. Polymerization processes using a wide variety of monomers are well known in the art {see, e.g., International Union of Pure and Applied
Chemistry, et al., IUPAC Gold Book, Polymerization. (2000)). One such process involves monomer(s) with unsaturated substitution, such as vinyl, propenyl, butenyl, or other such substitutent(s). These types of monomers can undergo radical initiation and chain
polymerization.
[0139] In some embodiments, the polymeric backbone is formed from one or more substituted or unsubstituted monomers selected from ethylene, propylene, hydroxyethylene, acetaldehyde, styrene, divinyl benzene, isocyanates, vinyl chloride, vinyl phenols,
tetrafluoroethylene, butylene, terephthalic acid, caprolactam, acrylonitrile, butadiene, ammonias, diammonias, pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyrazine, pyradizimine, thiazine, morpholine, piperidine, piperizines, pyrollizine, triphenylphosphonate, trimethylphosphonate, triethylphosphonate, tripropylphosphonate, tributylphosphonate, trichlorophosphonate, trifluorophosphonate, and diazole.
[0140] The polymeric backbone of the polymeric catalysts described herein can include, for example, polyalkylenes, polyalkenyl alcohols, polycarbonates, polyarylenes,
polyaryletherketones, and polyamide-imides. In certain embodiments, the polymeric backbone can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly(acrylonitrile butadiene styrene). In certain embodiments of the polymeric catalyst, the polymeric backbone is polyethyelene or polypropylene. In one embodiment of the polymeric catalyst, the polymeric backbone is polyethylene. In another embodiment of the polymeric catalyst, the polymeric backbone is polyvinyl alcohol. In yet another embodiment of the polymeric catalyst, the polymeric backbone is polystyrene.
[0141] With reference to FIG. 7, in one embodiment, the polymeric backbone is
polyethylene. With reference to FIG. 8, in another embodiment, the polymeric backbone is polyvinyl alcohol.
[0142] The polymeric backbone described herein can also include an ionic group integrated as part of the polymeric backbone. Such polymeric backbones can also be called "ionomeric backbones". In certain embodiments, the polymeric backbone can be selected from:
polyalkyleneammonium, polyalkylenediammonium, polyalkylenepyrrolium,
polyalkyleneimidazolium, polyalkylenepyrazolium, polyalkyleneoxazolium,
polyalkylenethiazolium, polyalkylenepyridinium, polyalkylenepyrimidinium,
polyalkylenepyrazinium, polyalkylenepyridazinium, polyalkylenethiazinium,
polyalkylenemorpholinium, polyalkylenepiperidinium, polyalkylenepiperizinium,
polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,
poly alky lenetrimethylpho sphonium, poly alky lenetriethylpho sphonium,
polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium,
poly alky lenetrichloropho sphonium, poly alky lenetrifluoropho sphonium, and
polyalkylenediazolium, polyarylalkyleneammonium, polyarylalkylenediammonium,
polyarylalkylenepyrrolium, polyarylalkyleneimidazolium, polyarylalkylenepyrazolium, polyarylalkyleneoxazolium, polyarylalkylenethiazolium, polyarylalkylenepyridinium, polyarylalkylenepyrimidinium, polyarylalkylenepyrazinium, polyarylalkylenepyridazinium, polyarylalkylenethiazinium, polyarylalkylenemorpholinium, polyarylalkylenepiperidinium, polyarylalkylenepiperizinium, polyarylalkylenepyrollizinium,
poly arylalkylenetriphenylpho sphonium, poly arylalky lenetrimethylpho sphonium,
polyarylalkylenetriethylphosphonium, polyarylalkylenetripropylphosphonium,
poly arylalky lenetributylpho sphonium, poly arylalky lenetrichloropho sphonium,
polyarylalkylenetrifluorophosphonium, and polyarylalkylenediazolium. [0143] Cationic polymeric backbones can be associated with one or more anions, including for example F, CI", Br", Γ, N02 ",N03 ", S04 2", R7S04 ", R7C02 ", P04 2", R7P03 ", and R7P02 "' where R is selected from hydrogen, Ci_4alkyl, and Ci_4heteroalkyl. In one embodiment, each anion can be selected from CI", Br" , Γ, HS04 ", HC02 ", CH3C02 ", and N03 ". In other embodiments, each anion is acetate. In other embodiments, each anion is bisulfate. In other embodiments, each anion is chloride. In other embodiments, X is nitrate.
[0144] In other embodiments of the polymeric catalysts, the polymeric backbone is alkyleneimidazolium, which refers to an alkylene moiety, in which one or more of the methylene units of the alkylene moiety has been replaced with imidazolium. In one embodiment, the polymeric backbone is selected from polyethyleneimidazolium, polyprolyeneimidazolium, and polybutyleneimidazolium. It should further be understood that, in other embodiments of the polymeric backbone, when a nitrogen-containing cationic group or a phosphorous-containing cationic group follows the term "alkylene", one or more of the methylene units of the alkylene moiety is substituted with that nitrogen-containing cationic group or phosphorous -containing cationic group.
[0145] In other embodiments, monomers having heteroatoms can be combined with one or more difunctionalized compounds, such as dihaloalkanes, di(alkylsulfonyloxy)alkanes, and di(arylsulfonyloxy)alkanes to form polymers. The monomers have at least two heteroatoms to link with the difunctionalized alkane to create the polymeric chain. These difunctionalized compounds can be further substituted as described herein. In some embodiments, the difunctionalized compound(s) can be selected from 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2-dichlorobutane, l,3-dichlorobutane,l,4-dichlorobutane, 1,2- dichloropentane, l,3-dichloropentane,l,4-dichloropentane, 1,5-dichloropentane, 1,2- dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,2-dibromobutane, 1,3- dibromobutane, 1 ,4-dibromobutane, 1 ,2-dibromopentane, 1 ,3-dibromopentane, 1 ,4- dibromopentane, 1,5-dibromopentane, 1,2-diiodoethane, 1,2-diiodopropane, 1,3-diiodopropane,
1.2- diiodobutane, l,3-diiodobutane,l,4-diiodobutane, 1,2-diiodopentane, l,3-diiodopentane,l,4- diiodopentane, 1 ,5-diiodopentane, 1 ,2-dimethanesulfoxyethane, 1 ,2-dimethanesulfoxypropane,
1.3- dimethanesulfoxypropane, 1 ,2-dimethanesulfoxybutane, 1 ,3-dimethanesulfoxybutane, 1 ,4- dimethanesulfoxybutane, 1 ,2-dimethanesulfoxypentane, 1 ,3-dimethanesulfoxypentane, 1 ,4- dimethanesulfoxypentane, 1 ,5-dimethanesulfoxypentane, 1 ,2-diethanesulfoxyethane, 1 ,2- diethanesulfoxypropane, 1,3-diethanesulfoxypropane, 1,2-diethanesulfoxybutane, 1,3- diethanesulfoxybutane, 1 ,4-diethanesulfoxybutane, 1 ,2-diethanesulfoxypentane, 1,3- diethanesulfoxypentane, 1 ,4-diethanesulfoxypentane, 1 ,5-diethanesulfoxypentane, 1 ,2- dibenzenesulfoxyethane, 1,2-dibenzenesulfoxypropane, 1,3-dibenzenesulfoxypropane, 1,2- dibenzenesulfoxybutane, 1 ,3 -dibenzenesulfoxybutane, 1 ,4-dibenzenesulfoxybutane, 1 ,2- dibenzenesulfoxypentane, 1 ,3-dibenzenesulfoxypentane, 1 ,4-dibenzenesulfoxypentane, 1 ,5- dibenzenesulfoxypentane, 1,2-di-p-toluenesulfoxyethane, 1,2-di-p-toluenesulfoxypropane, 1,3- di-p-toluenesulfoxypropane, 1 ,2-di-p-toluenesulfoxybutane, 1 ,3-di-p-toluenesulfoxybutane, 1 ,4- di-p-toluenesulfoxybutane, 1 ,2-di-p-toluenesulfoxypentane, 1 ,3-di-p-toluene sulfoxypentane, 1 ,4- di-p-toluene sulfoxypentane, andl,5-di-p-toluene sulfoxypentane.
[0146] Further, the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone.
[0147] In some embodiments, the polymer can be a homopolymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer in the same manner. In other embodiments, the polymer can be a heteropolymer having at least two monomer units, and where at least one monomeric unit contained within the polymer that differs from the other monomeric units in the polymer. The different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers.
[0148] Other exemplary polymers include, for example, polyalkylene backbones that are substituted with one or more groups selected from hydroxyl, carboxylic acid, unsubstituted and substituted phenyl, halides, unsubstituted and substituted amines, unsubstituted and substituted ammonias, unsubstituted and substituted pyrroles, unsubstituted and substituted imidazoles, unsubstituted and substituted pyrazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted pyridines, unsubstituted and substituted pyrimidines, unsubstituted and substituted pyrazines, unsubstituted and substituted pyradizines, unsubstituted and substituted thiazines, unsubstituted and substituted morpholines, unsubstituted and substituted piperidines, unsubstituted and substituted piperizines, unsubstituted and substituted pyrollizines, unsubstituted and substituted triphenylphosphonates, unsubstituted and substituted trimethylphosphonates, unsubstituted and substituted triethylphosphonates, unsubstituted and substituted tripropylphosphonates, unsubstituted and substituted
tributylphosphonates, unsubstituted and substituted trichlorophosphonates, unsubstituted and substituted trifluorophosphonates, and unsubstituted and substituted diazoles. [0149] For the polymers as described herein, multiple naming conventions are well recognized in the art. For instance, a polyethylene backbone with a direct bond to an
unsubstituted phenyl group (-CH2-CH(phenyl)-CH2-CH(phenyl)-) is also known as polystyrene. Should that phenyl group be substituted with an ethenyl group, the polymer can be named a polydivinylbenzene (-CH2-CH(4-vinylphenyl)-CH2-CH(4-vinylphenyl)-). Further examples of heteropolymers may include those that are functionalized after polymerization.
[0150] One suitable example would be polystyrene-co-divinylbenzene: (-CH2-CH(phenyl)- CH2-CH(4-ethylenephenyl)-CH2-CH(phenyl)-CH2-CH(4-ethylenephenyl)-). Here, the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
[0151] With reference to FIG. 12, in yet another embodiment, the polymeric backbone is a polyalkyleneimidazolium.
[0152] Further, the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, or zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone. With reference to FIG. 10, in one embodiment, there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group. In another example, with reference to FIG. 11, there are zero atoms between the side chain with the acidic moiety and the side chain with the ionic moiety.
Solid Particles for Polymeric Catalysts
[0153] The polymeric catalysts described herein can form solid particles. One of skill in the art would recognize the various known techniques and methods to make solid particles from the polymers described herein. For example, a solid particle can be formed through the procedures of emulsion or dispersion polymerization, which are known to one of skill in the art. In other embodiments, the solid particles can be formed by grinding or breaking the polymer into particles, which are also techniques and methods that are known to one of skill in the art.
Methods known in the art to prepare solid particles include coating the polymers described herein on the surface of a solid core. Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material. Polymeric coated core particles can be made by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting. [0154] Other methods known in the art to prepare solid particles include coating the polymers described herein on the surface of a solid core. The solid core can be a non-catalytic support. Suitable materials for the solid core can include an inert material (e.g. , aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material. In one embodiment of the polymeric catalyst, the solid core is made up of iron.
Polymeric coated core particles can be made by techniques and methods that are known to one of skill in the art, for example, by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
[0155] The solid supported polymer catalyst particle can have a solid core where the polymer is coated on the surface of the solid core. In some embodiments, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50% of the catalytic activity of the solid particle can be present on or near the exterior surface of the solid particle. In some embodiments, the solid core can have an inert material or a magnetic material. In one embodiment, the solid core is made up of iron.
[0156] The solid particles coated with the polymer described herein have one or more catalytic properties. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80% or at least about 90% of the catalytic activity of the solid particle is present on or near the exterior surface of the solid particle.
[0157] In some embodiments, the solid particle is substantially free of pores, for example, having no more than about 50%, no more than about 40%, no more than about 30%, no more than about 20%, no more than about 15%, no more than about 10%, no more than about 5%, or no more than about 1% of pores. Porosity can be measured by methods well known in the art, such as determining the Brunauer-Emmett-Teller (BET) surface area using the absorption of nitrogen gas on the internal and external surfaces of a material (Brunauer, S. et al., J. Am.
Chem. Soc. 1938, 60:309). Other methods include measuring solvent retention by exposing the material to a suitable solvent (such as water), then removing it thermally to measure the volume of interior pores. Other solvents suitable for porosity measurement of the polymeric catalysts include, for example, polar solvents such as DMF, DMSO, acetone, and alcohols.
[0158] In other embodiments, the solid particles include a microporous gel resin. In yet other embodiments, the solid particles include a macroporous gel resin. Support of the Solid-Supported Catalysts
[0159] In certain embodiments of the solid- supported catalyst, the support may be selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g., mordenite), ceramics, and any combinations thereof. In one embodiment, the support is carbon. The support for carbon support can be biochar, amorphous carbon, or activated carbon. In one embodiment, the support is activated carbon.
[0160] The carbon support can have a surface area from 0.01 to 50 m /g of dry material. The carbon support can have a density from 0.5 to 2.5 kg/L. The support can be characterized using any suitable instrumental analysis methods or techniques known in the art, including for example scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy, and Fourier Transform infrared spectroscopy (FTIR). The carbon support can be prepared from carbonaceous materials, including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof. One of skill in the art would recognize suitable methods to prepare the carbon supports used herein. See e.g., M. Inagaki, L.R. Radovic, Carbon, vol. 40, p. 2263 (2002), or A.G. Pandolfo and A.F. Hollenkamp, "Review: Carbon Properties and their role in supercapacitors," Journal of Power Sources, vol. 157, pp. 11-27 (2006).
[0161] In other embodiments, the support is silica, silica gel, alumina, or silica-alumina. One of skill in the art would recognize suitable methods to prepare these silica- or alumina-based solid supports used herein. See e.g., Catalyst supports and supported catalysts, by A.B. Stiles, Butterworth Publishers, Stoneham MA, 1987.
[0162] In yet other embodiments, the support is a combination of a carbon support, with one or more other supports selected from silica, silica gel, alumina, magnesia, titania, zirconia, clays {e.g., kaolinite), magnesium silicate, silicon carbide, zeolites {e.g., mordenite), and ceramics.
Definitions
[0163] "Bronsted-Lowry acid" refers to a molecule, or substituent thereof, in neutral or ionic form that is capable of donating a proton (hydrogen cation, H+).
[0164] "Homopolymer" refers to a polymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer. One suitable example is polyethylene, where ethylene monomers are linked to form a uniform repeating chain (-CH2-CH2-CH2-). Another suitable example is polyvinyl chloride, having a structure (-CH2- CHC1-CH2-CHC1-) where the -CH2-CHC1- repeating unit is derived from the H2C=CHC1 monomer.
[0165] "Heteropolymer" refers to a polymer having at least two monomer units, and where at least one monomeric unit differs from the other monomeric units in the polymer. Heteropolymer also refers to polymers having difunctionalized or trifunctionalized monomer units that can be incorporated in the polymer in different ways. The different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers. One suitable example is polyethyleneimidazolium, where if in an alternating sequence, would be the polymer depicted in FIG. 12. Another suitable example is polystyrene - co-divinylbenzene, where if in an alternating sequence, could be (-CH2-CH(phenyl)-CH2-CH(4- ethylenephenyl)-CH2-CH(phenyl)-CH2-CH(4-ethylenephenyl)-). Here, the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
[0166] As used herein, . w \ denotes the attachment point of a moiety to the parent structure.
[0167] When a range of values is listed, it is intended to encompass each value and subrange within the range. For example, "Ci_6 alkyl" (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C l-6 alkyl) is intended to encompass, Ci, C2, C3, C4, C5, C6, Ci_6, Ci_5, Ci^, Q_ 3, C]_2, C2-6, C2-5, C2- , C2-3, C3_6, C3_5, C3^, C4_6, C4_5, and Cs_6 alkyl.
[0168] "Alkyl" includes saturated straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted. In some embodiments, alkyl as used herein may have 1 to 10 carbon atoms (e.g. , Ci_io alkyl), 1 to 6 carbon atoms (e.g. , Ci_6 alkyl), or 1 to 3 carbon atoms (e.g. , Ci_3 alkyl). Representative straight-chained alkyls include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Representative branched alkyls include, for example, isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylbutyl, 3- methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4- methylhexyl, 5-methylhexyl, and 2,3-dimethylbutyl. When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butyl" is meant to include n-butyl, sec- butyl, z'so-butyl, and tert-butyl; "propyl" includes n-propyl, and z'so-propyl. [0169] "Alkoxy" refers to the group -O-alkyl, which is attached to the parent structure through an oxygen atom. Examples of alkoxy may include methoxy, ethoxy, propoxy, and isopropoxy. In some embodiments, alkoxy as used herein has 1 to 6 carbon atoms (e.g. , 0-(Ci_6 alkyl)), or 1 to 4 carbon atoms (e.g. , 0-(Ci_4 alkyl)).
[0170] "Alkenyl" refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one double bond. In some embodiments, alkenyl has 2 to 10 carbon atoms (e.g. , C2-1o alkenyl), or 2 to 5 carbon atoms (e.g. , C2_5 alkenyl). When an alkenyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butenyl" is meant to include n-butenyl, sec-butenyl, and z'so-butenyl.
Examples of alkenyl may include -CH=CH2, -CH2-CH=CH2 and -CH2-CH=CH-CH=CH2. The one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl). Examples of C2_4 alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2- propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), and butadienyl (C4). Examples of C2_6 alkenyl groups include the aforementioned C2_4 alkenyl groups as well as pentenyl (C5), pentadienyl (C5), and hexenyl (C6). Additional examples of alkenyl include heptenyl (C7), octenyl (C8), and octatrienyl (C8).
[0171] "Alkynyl" refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one triple bond. In some
embodiments, alkynyl has 2 to 10 carbon atoms (e.g. , C2_io alkynyl), or 2 to 5 carbon atoms (e.g. , C2-5 alkynyl). When an alkynyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "pentynyl" is meant to include n-pentynyl, sec-pentynyl, z'so-pentynyl, and ieri-pentynyl. Examples of alkynyl may include -C≡CH or -C≡C-CH3.
[0172] In some embodiments, alkyl, alkoxy, alkenyl, and alkynyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents. In certain embodiments, substituted alkyl, substituted alkoxy, substituted alkenyl, and substituted alkynyl at each occurrence may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent. Examples of alkyl, alkoxy, alkenyl, and alkynyl substituents may include alkoxy, cycloalkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, oxo (=0), heteroalkyl (e.g. , ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, and thio. In certain embodiments, the one or more substituents of substituted alkyl, alkoxy, alkenyl, and alkynyl is independently selected from cycloalkyl, aryl, heteroalkyl (e.g. , ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo, -ORa, -N(Ra)2, -C(0)N(Ra)2, - N(Ra)C(0)Ra, -C(0)Ra, -N(Ra)S(0)tRa (where t is 1 or 2), -SRa, and -S(0)tN(Ra)2 (where t is 1 or 2). In certain embodiments, each Ra is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl (e.g. , bonded through a ring carbon), -C(0)R' and -S(0)tR' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl. In one embodiment, Ra is independently hydrogen, alkyl, haloalkyl, cycloalkyl, aryl, aralkyl (e.g. , alkyl substituted with aryl, bonded to parent structure through the alkyl group),
heterocycloalkyl, or heteroaryl.
[0173] "Heteroalkyl", "heteroalkenyl" and "hetero alkynyl" includes alkyl, alkenyl and alkynyl groups, respectively, wherein one or more skeletal chain atoms are selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus, or any combinations thereof. For example, heteroalkyl may be an ether where at least one of the carbon atoms in the alkyl group is replaced with an oxygen atom. A numerical range can be given, e.g., Ci_4 heteroalkyl which refers to the chain length in total, which in this example is 4 atoms long. For example, a - CH2OCH2CH3 group is referred to as a "C4" heteroalkyl, which includes the heteroatom center in the atom chain length description. Connection to the rest of the parent structure can be through, in one embodiment, a heteroatom, or, in another embodiment, a carbon atom in the heteroalkyl chain. Heteroalkyl groups may include, for example, ethers such as methoxyethanyl (- CH2CH2OCH3), ethoxymethanyl (-CH2OCH2CH3), (methoxymethoxy)ethanyl (- CH2CH2OCH2OCH3), (methoxymethoxy)methanyl (-CH2OCH2OCH3) and
(methoxyethoxy)methanyl (-CH2OCH2 CH2OCH3); amines such as -CH2CH2NHCH3, - CH2CH2N(CH3)2, -CH2NHCH2CH3, and -CH2N(CH2CH3)(CH3). In some embodiments, heteroalkyl, heteroalkenyl, or heteroalkynyl may be unsubstituted or substituted by one or more of substituents. In certain embodiments, a substituted heteroalkyl, heteroalkenyl, or
heteroalkynyl may have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent. Examples for heteroalkyl, heteroalkenyl, or heteroalkynyl substituents may include the substituents described above for alkyl.
[0174] "Carbocyclyl" may include cycloalkyl, cycloalkenyl or cycloalkynyl. "Cycloalkyl" refers to a monocyclic or polycyclic alkyl group. "Cycloalkenyl" refers to a monocyclic or polycyclic alkenyl group (e.g. , containing at least one double bond). "Cycloalkynyl" refers to a monocyclic or polycyclic alkynyl group (e.g. , containing at least one triple bond). The cycloalkyl, cycloalkenyl, or cycloalkynyl can consist of one ring, such as cyclohexyl, or multiple rings, such as adamantyl. A cycloalkyl, cycloalkenyl, or cycloalkynyl with more than one ring can be fused, spiro or bridged, or combinations thereof. In some embodiments, cycloalkyl, cycloalkenyl, and cycloalkynyl has 3 to 10 ring atoms (i.e., C3-C10 cycloalkyl, C3-C10
cycloalkenyl, and C3-C10 cycloalkynyl), 3 to 8 ring atoms (e.g. , C3-C8 cycloalkyl, C3-C8 cycloalkenyl, and C3-C8 cycloalkynyl), or 3 to 5 ring atoms (i.e. , C3-C5 cycloalkyl, C3-C5 cycloalkenyl, and C3-C5 cycloalkynyl). In certain embodiments, cycloalkyl, cycloalkenyl, or cycloalkynyl includes bridged and spiro-fused cyclic structures containing no heteroatoms. In other embodiments, cycloalkyl, cycloalkenyl, or cycloalkynyl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups. C3_6 carbocyclyl groups may include, for example, cyclopropyl (C3), cyclobutyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C6), and cyclohexadienyl (C6). C3_8 carbocyclyl groups may include, for example, the aforementioned C3_6 carbocyclyl groups as well as cycloheptyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (C8), bicyclo[2.2.1]heptanyl, and bicyclo[2.2.2]octanyl. C3_io carbocyclyl groups may include, for example, the aforementioned C3_8 carbocyclyl groups as well as octahydro-lH-indenyl, decahydronaphthalenyl, and spiro [4.5] decanyl .
[0175] "Heterocyclyl" refers to carbocyclyl as described above, with one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorous, and sulfur.
Heterocyclyl may include, for example, heterocycloalkyl, heterocycloalkenyl, and
heterocycloalknyl. In some embodiments, heterocyclyl is a 3- to 18-membered non-aromatic monocyclic or polycyclic moiety that has at least one heteroatom selected from nitrogen, oxygen, phosphorous and sulfur. In certain embodiments, the heterocyclyl can be a monocyclic or polycyclic (e.g. , bicyclic, tricyclic or tetracyclic), wherein polycyclic ring systems can be a fused, bridged or spiro ring system. Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings.
[0176] An N-containing heterocyclyl moiety refers to an non-aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. The heteroatom(s) in the
heterocyclyl group is optionally oxidized. One or more nitrogen atoms, if present, are optionally quatemized. In certain embodiments, heterocyclyl may also include ring systems substituted with one or more oxide (-0-) substituents, such as piperidinyl N-oxides. The heterocyclyl is attached to the parent molecular structure through any atom of the ring(s). [0177] In some embodiments, heterocyclyl also includes ring systems with one or more fused carbocyclyl, aryl or heteroaryl groups, wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring. In some embodiments, heterocyclyl is a 5- 10 membered non- aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5- 10 membered heterocyclyl). In some embodiments, a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-8 membered heterocyclyl). In some embodiments, a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-6 membered heterocyclyl). In some embodiments, the 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen and sulfur. In some embodiments, the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen and sulfur. In some embodiments, the 5-6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen and sulfur.
[0178] "Aryl" refers to an aromatic group having a single ring (e.g. , phenyl), multiple rings (e.g. , biphenyl), or multiple fused rings (e.g. , naphthyl, fluorenyl, and anthryl). In some embodiments, aryl as used herein has 6 to 10 ring atoms (e.g., C6-Cio aromatic or C6-Cio aryl) which has at least one ring having a conjugated pi electron system. For example, bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals. In certain embodiments, aryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position. In certain embodiments, aryl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
[0179] "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, phosphorous, and sulfur. In some embodiments, 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. In certain embodiments, heteroaryl is a 5- to 18-membered monocyclic or polycyclic (e.g., bicyclic or tricyclic) aromatic ring system (e.g., having 6, 10 or 14 pi electrons shared in a cyclic array) having ring carbon atoms and 1 to 6 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous and sulfur (e.g. , 5-18 membered heteroaryl). In certain embodiments, heteroaryl may have a single ring (e.g. , pyridyl, pyridinyl, imidazolyl) or multiple condensed rings (e.g. , indolizinyl, benzothienyl) which condensed rings may or may not be aromatic. In other embodiments, heteroaryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position. In one embodiment, heteroaryl may have more than one ring where at least one ring is non-aromatic is connected to the parent structure at an aromatic ring position. Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings.
[0180] For example, in one embodiment, an N-containing "heteroaryl" refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. One or more heteroatom(s) in the heteroaryl group can be optionally oxidized. One or more nitrogen atoms, if present, are optionally quaternized. In other embodiments, heteroaryl may include ring systems substituted with one or more oxide (-0-) substituents, such as pyridinyl N-oxides. The heteroaryl may be attached to the parent molecular structure through any atom of the ring(s).
[0181] In other embodiments, heteroaryl may include ring systems with one or more fused aryl groups, wherein the point of attachment is either on the aryl or on the heteroaryl ring. In yet other embodiments, heteroaryl may include ring systems with one or more carbocycyl or heterocycyl groups wherein the point of attachment is on the heteroaryl ring. For polycyclic heteroaryl groups wherein one ring does not contain a heteroatom (e.g., indolyl, quinolinyl, and carbazolyl) the point of attachment can be on either ring, i.e., either the ring bearing a heteroatom (e.g., 2-indolyl) or the ring that does not contain a heteroatom (e.g., 5-indolyl). In some embodiments, a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5- 10 membered heteroaryl). In some embodiments, a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-8 membered heteroaryl). In some embodiments, a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-6 membered heteroaryl). In some embodiments, the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, phosphorous, and sulfur.
[0182] In some embodiments, carbocyclyl (including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl), aryl, heteroaryl, and heterocyclyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents. In certain embodiments, a substituted carbocyclyl (including, for example, substituted cycloalkyl, substituted cycloalkenyl or substituted cycloalkynyl), substituted aryl, substituted heteroaryl, substituted heterocyclyl at each occurrence may be independently may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent. Examples of carbocyclyl (including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl), aryl, heteroaryl, heterocyclyl substituents may include alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g. , ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo (=0), -ORa, -N(Ra)2, -C(0)N(Ra)2, - N(Ra)C(0)Ra, -C(0)Ra, -N(Ra)S(0)tRa (where t is 1 or 2), -SRa, and -S(0)tN(Ra)2 (where t is 1 or 2), wherein Ra is as described herein.
[0183] It should be understood that, as used herein, any moiety referred to as a "linker" refers to the moiety has having bivalency. Thus, for example, "alkyl linker" refers to the same residues as alkyl, but having bivalency. Examples of alkyl linkers
include -CH2-, -CH2CH2-, -CH2CH2CH2-, and -CH2CH2CH2CH2-. "Alkenyl linker" refers to the same residues as alkenyl, but having bivalency. Examples of alkenyl linkers include -CH=CH-, - CH2-CH=CH- and -CH2-CH=CH-CH2-. "Alkynyl linker" refers to the same residues as alkynyl, but having bivalency. Examples alkynyl linkers include -C≡C- or -C≡C-CH2-. Similarly, "carbocyclyl linker", "aryl linker", "heteroaryl linker", and "heterocyclyl linker" refer to the same residues as carbocyclyl, aryl, heteroaryl, and heterocyclyl, respectively, but having bivalency.
[0184] "Amino" or "amine" refers to -N(Ra)(Rb), where each Ra and Rb is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g. , bonded through a ring carbon), -C(0)R' and -S(0)tR' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl. It should be understood that, in one embodiment, amino includes amido (e.g. , -NRaC(0)Rb). It should be further understood that in certain embodiments, the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of Ra and Rb may be further substituted as described herein. Ra and Rb may be the same or different. For example, in one embodiment, amino is -NH2 (where Ra and Rb are each hydrogen). In other embodiments where Ra and Rb are other than hydrogen, Ra and Rb can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7- membered ring. Such examples may include 1-pyrrolidinyl and 4-morpholinyl.
[0185] "Ammonium" refers to -N(Ra)(Rb)(Rc)+, where each Ra, Rb and Rc is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g. , bonded through a ring carbon), -C(0)R' and -S(0)tR' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl; or any two of Ra, Rb and Rc may be taken together with the atom to which they are attached to form a cycloalkyl, heterocycloalkyl; or any three of Ra, Rb and Rc may be taken together with the atom to which they are attached to form aryl or heteroaryl. It should be further understood that in certain embodiments, the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of any one or more of Ra, Rb and Rc may be further substituted as described herein. Ra, Rb and Rc may be the same or different.
[0186] In certain embodiments, "amino" also refers to N-oxides of the groups -N+(H)(Ra)0", and -N+(Ra)(Rb)0-, where Ra and Rb are as described herein, where the N-oxide is bonded to the parent structure through the N atom. N-oxides can be prepared by treatment of the
corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid. The person skilled in the art is familiar with reaction conditions for carrying out the
N-oxidation.
[0187] "Amide" or "amido" refers to a chemical moiety with formula -C(O) N(Ra)(Rb) or - NRaC(0)Rb, where Ra and Rb at each occurrence are as described herein. In some embodiments, amido is a Ci_4 amido, which includes the amide carbonyl in the total number of carbons in the group. When a -C(O) N(Ra)(Rb) has Ra and Rb other than hydrogen, they can be combined with the nitrogen atom to form a 3-, 4-, 5-, 6-, or 7-membered ring.
[0188] "Carbonyl" refers to -C(0)Ra, where Ra is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, -N(R')2i -S(0)tR', where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl, and t is 1 or 2. In certain embodiments where each R' are other than hydrogen, the two R' moieties can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7-membered ring. It should be understood that, in one embodiment, carbonyl includes amido (e.g. , -C(O) N(Ra)(Rb))-
[0189] "Carbamate" refers to any of the following groups: -0-C(=0)-N(Ra)(Rb) and -N(Ra)- C(=0)-ORb, wherein Ra and Rb at each occurrence are as described herein.
[0190] "Cyano" refers to a -CN group.
[0191] "Halo", "halide", or, alternatively, "halogen" means fluoro, chloro, bromo or iodo. The terms "haloalkyl," "haloalkenyl," "haloalkynyl" and "haloalkoxy" include alkyl, alkenyl, alkynyl and alkoxy moieties as described above, wherein one or more hydrogen atoms are replaced by halo. For example, where a residue is substituted with more than one halo groups, it may be referred to by using a prefix corresponding to the number of halo groups attached. For example, dihaloaryl, dihaloalkyl, and trihaloaryl refer to aryl and alkyl substituted with two ("di") or three ("tri") halo groups, which may be, but are not necessarily, the same halogen; thus, for example, 3,5-difluorophenyl, 3-chloro-5-fluorophenyl, 4-chloro-3-fluorophenyl, and 3,5- difluoro-4-chlorophenyl is within the scope of dihaloaryl. Other examples of a haloalkyl group include difluoromethyl (-CHF2), trifluoromethyl (-CF3), 2,2,2-trifluoroethyl, and
l-fluoromethyl-2-fluoroethyl. Each of the alkyl, alkenyl, alkynyl and alkoxy groups of haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy, respectively, can be optionally substituted as defined herein. "Perhaloalkyl" refers to an alkyl or alkylene group in which all of the hydrogen atoms have been replaced with a halogen (e.g. , fluoro, chloro, bromo, or iodo). In some embodiments, all of the hydrogen atoms are each replaced with fluoro. In some embodiments, all of the hydrogen atoms are each replaced with chloro. Examples of perhaloalkyl groups include -CF3, - CF2CF3, -CF2CF2CF3, -CC13, -CFC12, and -CF2C1.
[0192] "Thio" refers to -SRa, wherein Ra is as described herein. "Thiol" refers to the group - RaSH, wherein Ra is as described herein.
[0193] "Sulfinyl" refers to -S(0)Ra. In some embodiments, sulfinyl is -S(0)N(Ra)(Rb). "Sulfonyl" refers to the -S(02)Ra. In some embodiments, sulfonyl is -S(02) N(Ra)(Rb) or - S(02)OH. For each of these moieties, it should be understood that Ra and Rb are as described herein. [0194] "Moiety" refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
[0195] As used herein, the term "unsubstituted" means that for carbon atoms, only hydrogen atoms are present besides those valencies linking the atom to the parent molecular group. One example is propyl (-CH2-CH2-CH3). For nitrogen atoms, valencies not linking the atom to the parent molecular group are either hydrogen or an electron pair. For sulfur atoms, valencies not linking the atom to the parent molecular group are either hydrogen, oxygen or electron pair(s).
[0196] As used herein, the term "substituted" or "substitution" means that at least one hydrogen present on a group (e.g. , a carbon or nitrogen atom) is replaced with a permissible substituent, e.g. , a substituent which upon substitution for the hydrogen results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction. Unless otherwise indicated, a
"substituted" group can have a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position. Substituents include one or more group(s) individually and independently selected from alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g. , ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo (=0), -ORa, -N(Ra)2, - C(0)N(Ra)2, -N(Ra)C(0)Ra, -C(0)Ra, -N(Ra)S(0)tRa (where t is 1 or 2), -SRa, and -S(0)tN(Ra)2 (where t is 1 or 2), wherein Ra is as described herein.
[0197] Where substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH20- is equivalent to -OCH2-.
[0198] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this specification pertains.
[0199] As used in the specification and claims, the singular form "a", "an" and "the" includes plural references unless the context clearly dictates otherwise.
[0200] Reference to "about" a value or parameter herein includes (and describes)
embodiments that are directed to that value or parameter per se. For example, description referring to "about x" includes description of "x" per se. In other instances, the term "about" when used in association with other measurements, or used to modify a value, a unit, a constant, or a range of values, refers to variations of between +0.1% and +15% of the stated number. For example, in one variation, "about 1" refers to a range between 0.85 and 1.15.
[0201] Reference to "between" two values or parameters herein includes (and describes) embodiments that include those two values or parameters per se. For example, description referring to "between x and y" includes description of "x" and "y" per se.
Representative Examples of Catalysts
[0202] It should be understood that the polymeric catalysts and the solid- supported catalysts can include any of the Bronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobic groups, cross-linking groups, and polymeric backbones or solid supports (as the case may be) described herein, as if each and every combination were listed separately. For example, in one embodiment, the catalyst can include benzenesulfonic acid (i.e., a sulfonic acid with a phenyl linker) connected to a polystyrene backbone or attached to the solid support, and an imidazolium chloride connected directly to the polystyrene backbone or attached directly to the solid support. In another embodiment, the polymeric catalyst can include boronyl-benzyl-pyridinium chloride (i.e., a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker) connected to a polystyrene backbone or attached to the solid support. In yet another
embodiment, the catalyst can include benzenesulfonic acid and imidazolium sulfate each individually connected to a polyvinyl alcohol backbone or individually attached to the solid support.
[0203] In some embodiments, the polymeric catalyst is selected from: poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-3H-imidazol-l-ium iodide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-3H-imidazol-l-ium bromide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-3H-imidazol-l-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium formate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium- acetate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium- nitrate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bromide- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-iodide-co-
3- methyl-l-(4-vinylbenzyl)-3H-imidazol- l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-acetate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-
4- ium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium formate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium acetate-co-divinylbenzene] ; poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-4-boronyl-l- (4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co- 1 -(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium nitrate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co- divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium chloride-co-divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium bisulfate-co-divinylbenzene] ; poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium acetate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-vinylbenzylmethylmorpholinium acetate -co -vinylbenzyltriphenyl phosphonium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenyl phosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium bisulfate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium nitrate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium bisulfate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene) ; poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(butyl-vinylimidazolium chloride-co-butylimidazolium bisulfate-co-4- vinylbenzenesulfonic acid);
poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium bisulfate-co^4- vinylbenzenesulfonic acid);
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl alcohol); and
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl alcohol) .
[0204] In some embodiments, the solid- supported catalyst is selected from: amorphous carbon- supported pyrrolium chloride sulfonic acid;
amorphous carbon- supported imidazolium chloride sulfonic acid;
amorphous carbon- supported pyrazolium chloride sulfonic acid; amorphous carbon-■ supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- supported piperidinium bromide sulfonic acid;
amorphous carbon- supported piperizinium bromide sulfonic acid;
amorphous carbon- supported pyrollizinium bromide sulfonic acid;
amorphous carbon- supported triphenyl phosphonium bromide sulfonic acid; amorphous carbon- supported trimethyl phosphonium bromide sulfonic acid; amorphous carbon- supported triethyl phosphonium bromide sulfonic acid; amorphous carbon- supported tripropyl phosphonium bromide sulfonic acid; amorphous carbon- supported tributyl phosphonium bromide sulfonic acid; amorphous carbon- supported trifluoro phosphonium bromide sulfonic acid; amorphous carbon- supported pyrrolium bisulfate sulfonic acid;
amorphous carbon- supported imidazolium bisulfate sulfonic acid;
amorphous carbon- supported pyrazolium bisulfate sulfonic acid;
amorphous carbon- supported oxazolium bisulfate sulfonic acid;
amorphous carbon- supported thiazolium bisulfate sulfonic acid;
amorphous carbon- supported pyridinium bisulfate sulfonic acid;
amorphous carbon- supported pyrimidinium bisulfate sulfonic acid;
amorphous carbon- supported pyrazinium bisulfate sulfonic acid;
amorphous carbon- supported pyridazinium bisulfate sulfonic acid;
amorphous carbon- supported thiazinium bisulfate sulfonic acid;
amorphous carbon- supported morpholinium bisulfate sulfonic acid;
amorphous carbon- supported piperidinium bisulfate sulfonic acid;
amorphous carbon- supported piperizinium bisulfate sulfonic acid;
amorphous carbon- supported pyrollizinium bisulfate sulfonic acid;
amorphous carbon- supported triphenyl phosphonium bisulfate sulfonic acid; amorphous carbon- supported trimethyl phosphonium bisulfate sulfonic acid; amorphous carbon- supported triethyl phosphonium bisulfate sulfonic acid; amorphous carbon- supported tripropyl phosphonium bisulfate sulfonic acid; amorphous carbon- supported tributyl phosphonium bisulfate sulfonic acid; amorphous carbon-■ supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- ■supported amorphous carbon- supported pyrazinium acetate sulfonic acid;
amorphous carbon- supported pyridazinium acetate sulfonic acid;
amorphous carbon- supported thiazinium acetate sulfonic acid;
amorphous carbon- supported morpholinium acetate sulfonic acid;
amorphous carbon- supported piperidinium acetate sulfonic acid;
amorphous carbon- supported piperizinium acetate sulfonic acid;
amorphous carbon- supported pyrollizinium acetate sulfonic acid;
amorphous carbon- supported triphenyl phosphonium acetate sulfonic acid; amorphous carbon- supported trimethyl phosphonium acetate sulfonic acid; amorphous carbon- supported triethyl phosphonium acetate sulfonic acid;
amorphous carbon- supported tripropyl phosphonium acetate sulfonic acid; amorphous carbon- supported tributyl phosphonium acetate sulfonic acid;
amorphous carbon- supported trifluoro phosphonium acetate sulfonic acid; amorphous carbon- supported pyrrolium chloride phosphonic acid;;
amorphous carbon- supported imidazolium chloride phosphonic acid;
amorphous carbon- supported pyrazolium chloride phosphonic acid;
amorphous carbon- supported oxazolium chloride phosphonic acid;
amorphous carbon- supported thiazolium chloride phosphonic acid;
amorphous carbon- supported pyridinium chloride phosphonic acid;
amorphous carbon- supported pyrimidinium chloride phosphonic acid;
amorphous carbon- supported pyrazinium chloride phosphonic acid;
amorphous carbon- supported pyridazinium chloride phosphonic acid;
amorphous carbon- supported thiazinium chloride phosphonic acid;
amorphous carbon- supported morpholinium chloride phosphonic acid;
amorphous carbon- supported piperidinium chloride phosphonic acid;
amorphous carbon- supported piperizinium chloride phosphonic acid;
amorphous carbon- supported pyrollizinium chloride phosphonic acid;
amorphous carbon- supported triphenyl phosphonium chloride phosphonic acid; amorphous carbon- supported trimethyl phosphonium chloride phosphonic acid; amorphous carbon- supported triethyl phosphonium chloride phosphonic acid; amorphous carbon- supported tripropyl phosphonium chloride phosphonic acid; amorphous carbon- supported tributyl phosphonium chloride phosphonic acid; amorphous carbon- supported trifluoro phosphonium chloride phosphonic acid; amorphous carbon- supported pyrrolium bromide phosphonic acid;
amorphous carbon- supported imidazolium bromide phosphonic acid;
amorphous carbon- supported pyrazolium bromide phosphonic acid;
amorphous carbon- supported oxazolium bromide phosphonic acid;
amorphous carbon- supported thiazolium bromide phosphonic acid;
amorphous carbon- supported pyridinium bromide phosphonic acid;
amorphous carbon- supported pyrimidinium bromide phosphonic acid;
amorphous carbon- supported pyrazinium bromide phosphonic acid;
amorphous carbon- supported pyridazinium bromide phosphonic acid;
amorphous carbon- supported thiazinium bromide phosphonic acid;
amorphous carbon- supported morpholinium bromide phosphonic acid;
amorphous carbon- supported piperidinium bromide phosphonic acid;
amorphous carbon- supported piperizinium bromide phosphonic acid;
amorphous carbon- supported pyrollizinium bromide phosphonic acid;
amorphous carbon- supported triphenyl phosphonium bromide phosphonic acid; amorphous carbon- supported trimethyl phosphonium bromide phosphonic acid; amorphous carbon- supported triethyl phosphonium bromide phosphonic acid; amorphous carbon- supported tripropyl phosphonium bromide phosphonic acid; amorphous carbon- supported tributyl phosphonium bromide phosphonic acid; amorphous carbon- supported trifluoro phosphonium bromide phosphonic acid; amorphous carbon- supported pyrrolium bisulfate phosphonic acid;
amorphous carbon- supported imidazolium bisulfate phosphonic acid;
amorphous carbon- supported pyrazolium bisulfate phosphonic acid; amorphous carbon- supported oxazolium bisulfate phosphonic acid;
amorphous carbon- supported thiazolium bisulfate phosphonic acid;
amorphous carbon- supported pyridinium bisulfate phosphonic acid;
amorphous carbon- supported pyrimidinium bisulfate phosphonic acid;
amorphous carbon- supported pyrazinium bisulfate phosphonic acid;
amorphous carbon- supported pyridazinium bisulfate phosphonic acid;
amorphous carbon- supported thiazinium bisulfate phosphonic acid;
amorphous carbon- supported morpholinium bisulfate phosphonic acid;
amorphous carbon- supported piperidinium bisulfate phosphonic acid;
amorphous carbon- supported piperizinium bisulfate phosphonic acid;
amorphous carbon- supported pyrollizinium bisulfate phosphonic acid;
amorphous carbon- supported triphenyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported trimethyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported triethyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported tripropyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported tributyl phosphonium bisulfate phosphonic acid; amorphous carbon- supported trifluoro phosphonium bisulfate phosphonic acid; amorphous carbon- supported pyrrolium formate phosphonic acid;
amorphous carbon- supported imidazolium formate phosphonic acid;
amorphous carbon- supported pyrazolium formate phosphonic acid;
amorphous carbon- supported oxazolium formate phosphonic acid;
amorphous carbon- supported thiazolium formate phosphonic acid;
amorphous carbon- supported pyridinium formate phosphonic acid;
amorphous carbon- supported pyrimidinium formate phosphonic acid;
amorphous carbon- supported pyrazinium formate phosphonic acid;
amorphous carbon- supported pyridazinium formate phosphonic acid;
amorphous carbon- supported thiazinium formate phosphonic acid;
amorphous carbon- supported morpholinium formate phosphonic acid; amorphous carbon- supported piperidinium formate phosphonic acid;
amorphous carbon- supported piperizinium formate phosphonic acid;
amorphous carbon- supported pyrollizinium formate phosphonic acid;
amorphous carbon- supported triphenyl phosphonium formate phosphonic acid; amorphous carbon- supported trimethyl phosphonium formate phosphonic acid; amorphous carbon- supported triethyl phosphonium formate phosphonic acid; amorphous carbon- supported tripropyl phosphonium formate phosphonic acid; amorphous carbon- supported tributyl phosphonium formate phosphonic acid; amorphous carbon- supported trifluoro phosphonium formate phosphonic acid; amorphous carbon- supported pyrrolium acetate phosphonic acid;
amorphous carbon- supported imidazolium acetate phosphonic acid;
amorphous carbon- supported pyrazolium acetate phosphonic acid;
amorphous carbon- supported oxazolium acetate phosphonic acid;
amorphous carbon- supported thiazolium acetate phosphonic acid;
amorphous carbon- supported pyridinium acetate phosphonic acid;
amorphous carbon- supported pyrimidinium acetate phosphonic acid;
amorphous carbon- supported pyrazinium acetate phosphonic acid;
amorphous carbon- supported pyridazinium acetate phosphonic acid;
amorphous carbon- supported thiazinium acetate phosphonic acid;
amorphous carbon- supported morpholinium acetate phosphonic acid;
amorphous carbon- supported piperidinium acetate phosphonic acid;
amorphous carbon- supported piperizinium acetate phosphonic acid;
amorphous carbon- supported pyrollizinium acetate phosphonic acid;
amorphous carbon- supported triphenyl phosphonium acetate phosphonic acid; amorphous carbon- supported trimethyl phosphonium acetate phosphonic acid; amorphous carbon- supported triethyl phosphonium acetate phosphonic acid; amorphous carbon- supported tripropyl phosphonium acetate phosphonic acid; amorphous carbon- supported tributyl phosphonium acetate phosphonic acid; amorphous carbon- supported trifluoro phosphonium acetate phosphonic acid; amorphous carbon- supported ethanoyl-triphosphonium sulfonic acid;
amorphous carbon- supported ethanoyl-methylmorpholinium sulfonic acid; and amorphous carbon- supported ethanoyl-imidazolium sulfonic acid.
In other embodiments, the solid- supported catalyst is selected from: activated carbon- ■ supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported
activated carbon- ■supported activated carbon-■ supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- supported morpholinium bisulfate sulfonic acid;
activated carbon- supported piperidinium bisulfate sulfonic acid;
activated carbon- supported piperizinium bisulfate sulfonic acid;
activated carbon- supported pyrollizinium bisulfate sulfonic acid;
activated carbon- supported triphenyl phosphonium bisulfate sulfonic acid; activated carbon- supported trimethyl phosphonium bisulfate sulfonic acid; activated carbon- supported triethyl phosphonium bisulfate sulfonic acid; activated carbon- supported tripropyl phosphonium bisulfate sulfonic acid; activated carbon- supported tributyl phosphonium bisulfate sulfonic acid; activated carbon- supported trifluoro phosphonium bisulfate sulfonic acid; activated carbon- supported pyrrolium formate sulfonic acid;
activated carbon- supported imidazolium formate sulfonic acid;
activated carbon- supported pyrazolium formate sulfonic acid;
activated carbon- supported oxazolium formate sulfonic acid;
activated carbon- supported thiazolium formate sulfonic acid;
activated carbon- supported pyridinium formate sulfonic acid;
activated carbon- supported pyrimidinium formate sulfonic acid;
activated carbon- supported pyrazinium formate sulfonic acid;
activated carbon- supported pyridazinium formate sulfonic acid;
activated carbon- supported thiazinium formate sulfonic acid;
activated carbon supported morpholinium formate sulfonic acid;
activated carbon- supported piperidinium formate sulfonic acid;
activated carbon- supported piperizinium formate sulfonic acid;
activated carbon- supported pyrollizinium formate sulfonic acid;
activated carbon- supported triphenyl phosphonium formate sulfonic acid; activated carbon- supported trimethyl phosphonium formate sulfonic acid; activated carbon- supported triethyl phosphonium formate sulfonic acid; activated carbon- supported tripropyl phosphonium formate sulfonic acid; activated carbon- supported tributyl phosphonium formate sulfonic acid; activated carbon- supported trifluoro phosphonium formate sulfonic acid; activated carbon- supported pyrrolium acetate sulfonic acid;
activated carbon- supported imidazolium acetate sulfonic acid;
activated carbon- supported pyrazolium acetate sulfonic acid;
activated carbon- supported oxazolium acetate sulfonic acid;
activated carbon- supported thiazolium acetate sulfonic acid;
activated carbon- supported pyridinium acetate sulfonic acid;
activated carbon- supported pyrimidinium acetate sulfonic acid;
activated carbon- supported pyrazinium acetate sulfonic acid;
activated carbon- supported pyridazinium acetate sulfonic acid;
activated carbon- supported thiazinium acetate sulfonic acid;
activated carbon- supported morpholinium acetate sulfonic acid;
activated carbon- supported piperidinium acetate sulfonic acid;
activated carbon- supported piperizinium acetate sulfonic acid;
activated carbon- supported pyrollizinium acetate sulfonic acid;
activated carbon- supported triphenyl phosphonium acetate sulfonic acid; activated carbon- supported trimethyl phosphonium acetate sulfonic acid; activated carbon- supported triethyl phosphonium acetate sulfonic acid; activated carbon- supported tripropyl phosphonium acetate sulfonic acid; activated carbon- supported tributyl phosphonium acetate sulfonic acid; activated carbon- supported trifluoro phosphonium acetate sulfonic acid; activated carbon- supported pyrrolium chloride phosphonic acid;;
activated carbon- supported imidazolium chloride phosphonic acid; activated carbon- supported pyrazolium chloride phosphonic acid;
activated carbon- supported oxazolium chloride phosphonic acid;
activated carbon- supported thiazolium chloride phosphonic acid;
activated carbon- supported pyridinium chloride phosphonic acid; activated carbon-■ supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon-■ supported triphenyl phosphonium bromide phosphonic acid; activated carbon- ■supported trimethyl phosphonium bromide phosphonic acid; activated carbon- ■supported triethyl phosphonium bromide phosphonic acid; activated carbon- ■supported tripropyl phosphonium bromide phosphonic acid; activated carbon- ■supported tributyl phosphonium bromide phosphonic acid; activated carbon- ■supported trifluoro phosphonium bromide phosphonic acid; activated carbon- ■supported pyrrolium bisulfate phosphonic acid;
activated carbon- ■supported imidazolium bisulfate phosphonic acid;
activated carbon- ■supported pyrazolium bisulfate phosphonic acid;
activated carbon- ■supported oxazolium bisulfate phosphonic acid;
activated carbon- ■supported thiazolium bisulfate phosphonic acid;
activated carbon- ■supported pyridinium bisulfate phosphonic acid;
activated carbon- ■supported pyrimidinium bisulfate phosphonic acid;
activated carbon- ■supported pyrazinium bisulfate phosphonic acid;
activated carbon- ■supported pyridazinium bisulfate phosphonic acid;
activated carbon- ■supported thiazinium bisulfate phosphonic acid;
activated carbon- ■supported morpholinium bisulfate phosphonic acid;
activated carbon- ■supported piperidinium bisulfate phosphonic acid;
activated carbon- ■supported piperizinium bisulfate phosphonic acid;
activated carbon- ■supported pyrollizinium bisulfate phosphonic acid;
activated carbon- ■supported triphenyl phosphonium bisulfate phosphonic acid; activated carbon- ■supported trimethyl phosphonium bisulfate phosphonic acid; activated carbon- ■supported triethyl phosphonium bisulfate phosphonic acid; activated carbon- ■supported tripropyl phosphonium bisulfate phosphonic acid; activated carbon- ■supported tributyl phosphonium bisulfate phosphonic acid; activated carbon- ■supported trifluoro phosphonium bisulfate phosphonic acid; activated carbon- ■supported pyrrolium formate phosphonic acid;
activated carbon- ■supported imidazolium formate phosphonic acid; activated carbon-■ supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- ■supported activated carbon- supported activated carbon- ■supported
activated carbon- ■supported activated carbon- ■supported
activated carbon- ■supported activated carbon- ■supported
activated carbon- ■supported activated carbon- ■supported
activated carbon- ■supported activated carbon- ■supported
activated carbon- ■supported activated carbon- ■supported
activated carbon- ■supported
[0206] Methods to prepare the polymeric and solid-supported catalysts described herein can be found in WO 2014/031956, which is hereby incorporated herein specifically with respect to paragraphs [0345]-[0380] and [0382]-[0472] .
Additional Catalysts
[0207] In some embodiments of the methods described herein, the sugar alcohol and the catalyst (e.g. , polymeric catalyst or solid-supported catalyst) are combined with one or more additional catalysts to produce the anhydrosugar alcohol. The additional catalysts may include any suitable catalysts known in the art to convert, or facilitate the conversion of, the sugar alcohol into its correspondending anhydrosugar alcohol.
[0208] In some embodiments of the methods described herein, the monoanhydrosugar alcohol and the catalyst (e.g. , polymeric catalyst or solid-supported catalyst) are combined with one or more additional catalysts to produce the dianhydrosugar alcohol. The additional catalysts may include any suitable catalysts known in the art to convert, or facilitate the conversion of, the monoanhydrosugar alcohol into its correspondending dianhydrosugar alcohol. [0209] Examples of other acid catalysts that may be used in combination with the polymeric or solid- supported catalysts described herein may be found in, for example, US 7439352, US 4408061, US 7982059, US 8445705, and US 7649099.
Solvents
[0210] In some embodiments of the methods described herein, the sugar alcohol and the catalyst (e.g., polymeric catalyst or solid-supported catalyst) are combined in the further presence of a solvent, or a mixture of solvents, to produce the anhydrosugar alcohol. In some embodiments of the methods described herein, the monoanhydrosugar alcohol and the catalyst (e.g., polymeric catalyst or solid-supported catalyst) are combined in the further presence of a solvent, or a mixture of solvents, to produce the dianhydrosugar alcohol. The solvents used in the methods described herein may be obtained from any source, including any commercially available sources.
Reaction Conditions
Reaction Temperature and Pressure
[0211] The sugar alcohol and the catalyst may be reacted at any temperature and pressure suitable to produce the anhydrosugar alcohol. In some embodiments, the sugar alcohol and catalyst are reacted at a temperature of about 25°C to about 200°C. In some embodiments, the combined sugar alcohol and catalyst are reacted in vaccum, or at a pressure between 0.05 Torr and 190,000 Torr.
[0212] The monoanhydrosugar alcohol and the catalyst may be reacted at any temperature and pressure suitable to produce the dianhydrosugar alcohol. In some embodiments, the monoanhydrosugar alcohol and catalyst are reacted at a temperature of about 25°C to about 200°C. In some embodiments, the combined monoanhydrosugar alcohol and catalyst are reacted in vacuum, or at a pressure between 0.05 Torr and 190,000 Torr.
Batch versus continuous processing
[0213] Generally, the sugar alcohol and the catalyst are introduced into an interior chamber of a reactor, either concurrently or sequentially. The reaction can be performed in a batch process or a continuous process. For example, in one embodiment, method is performed in a batch process, where the contents of the reactor are continuously mixed or blended, and all or a substantial amount of the products of the reaction are removed. In one variation, the method is performed in a batch process, where the contents of the reactor are initially intermingled or mixed but no further physical mixing is performed. In another variation, the method is performed in a batch process, wherein once further mixing of the contents, or periodic mixing of the contents of the reactor, is performed (e.g. , at one or more times per hour), all or a substantial amount of the products of the reaction are removed after a certain period of time.
[0214] In some embodiments, the method is repeated in a sequential batch process, wherein at least a portion of the catalyst is separated from at least a portion of the anhydrosugar alcohol produced (e.g., as described in more detail infra) and is recycled by further contacting additional sugar alcohol.
[0215] For example, in one aspect, provided is a method for producing an anhydrosugar alcohol, by: a) combining a sugar alcohol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and b) producing an anhydrosugar alcohol from at least a portion of the reaction mixture; c) separating the anhydrosugar alcohol from the catalyst; d) combining additional sugar alcohol with the separated catalyst to form additional reaction mixture; and e) producing additional anhydrosugar alcohol from at least a portion of the additional reaction mixture.
[0216] In some of embodiments wherein the method is performed in a batch process, the catalyst is recycled (e.g. , steps (c)-(e) above are repeated) at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or at least 10 times. In some of these embodiments, the catalyst retains at least 80% activity (e.g., at least 90%, 95%, 96%, 97%, 98%, or 99% activity) after being recycled 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times, when compared to the catalytic activity under identical conditions prior to being recycled. [0217] In other embodiments, the method is performed in a continuous process, where the contents flow through the reactor with an average continuous flow rate but with no explicit mixing. After introduction of the sugar alcohol and the catalyst into the reactor, the contents of the reactor are continuously or periodically mixed or blended, and after a period of time, less than all of the products of the reaction are removed. In one variation, method is performed in a continuous process, where the mixture containing the sugar alcohol and the catalyst is not actively mixed. Additionally, mixing of the sugar alcohol and the catalyst may occur as a result of the redistribution of catalysts settling by gravity, or the non-active mixing that occurs as the material flows through a continuous reactor. In some embodiments of the methods, the steps of combining the sugar alcohol with a catalyst and isolating the anhydrosugar alcohol produced are performed concurrently.
Reactors
[0218] The reactors used for the methods described herein may be open or closed reactors suitable for use in containing the chemical reactions described herein. Suitable reactors may include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor with ultrafiltration, a continuous plug-flow column reactor, an attrition reactor, or a reactor with intensive stirring induced by an electromagnetic field. See e.g. , Fernanda de Castilhos Corazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel, Optimal control in fed-batch reactor for the cellobiose hydrolysis, Acta Scientiarum. Technology, 25: 33-38 (2003); Gusakov, A. V., and Sinitsyn, A. P., Kinetics of the enzymatic hydrolysis of cellulose: 1. A mathematical model for a batch reactor process, Enz. Microb. Technol., 7: 346-352 (1985); Ryu, S. K., and Lee, J. M., Bioconversion of waste cellulose by using an attrition bioreactor, Biotechnol. Bioeng. 25: 53-65(1983); Gusakov, A. V., Sinitsyn, A. P., Davydkin, I. Y.,
Davydkin, V. Y., Protas, O. V., Enhancement of enzymatic cellulose hydrolysis using a novel type of bioreactor with intensive stirring induced by electromagnetic field, Appl. Biochem.
Biotechnol., 56: 141-153(1996). Other suitable reactor types may include, for example, fluidized bed, upflow blanket, immobilized, and extruder type reactors for hydrolysis and/or fermentation.
[0219] In certain embodiments where the method is performed as a continuous process, the reactor may include a continuous mixer, such as a screw mixer. The reactors may be generally fabricated from materials that are capable of withstanding the physical and chemical forces exerted during the processes described herein. In some embodiments, such materials used for the reactor are capable of tolerating high concentrations of strong liquid acids; however, in other embodiments, such materials may not be resistant to strong acids. [0220] It should also be understood that additional sugar alcohol, monoanhydrosugar alcohol, and/or catalyst may be added to the reactor, either at the same time or one after the other.
Other Processing Steps
[0221] In some embodiments, the methods described herein further include isolating the anhydrosugar alcohol produced. The anhydrosugar alcohol may be isolated using any method known in the art, including, for example, extraction, distillation (e.g. vacuum distillation), crystallization, recrystallization (e.g. , melt recrystallization, solvent recrystallization), or chromatography.
[0222] The anhydrosugar alcohol produced may be subjected to further processing steps (e.g. , as drying) or subsequent chemical treatment.
Recyclability of Catalysts
[0223] The catalysts containing acidic and ionic groups used in the methods of producing anhydrosugar alcohols from sugar alcohols as described herein may be recycled. Thus, in one aspect, provided herein are methods of producing anhydrosugar alcohols from sugar alcohols using recyclable catalysts.
[0224] The catalysts containing acidic and ionic groups used in the methods of producing dianhydrosugar alcohols from monoanhydrosugar alcohols as described herein may also be recycled. Thus, in another aspect, provided herein are methods of producing dianhydrosugar alcohols from monoanhydrosugar alcohols using recyclable catalysts.
[0225] In some variations, the catalyst described herein is separated from the anhydrosugar alcohol produced, and the separated catalyst is combined with additional sugar alcohol to produce additional anhydrosugar alcohol. With reference again to FIG. 13, process 200 depicts an exemplary scheme in which the catalyst is isolated in step 212 from the anhydrosugar alcohol produced, and the isolated catalyst is reused in step 204 to provide catalyst for an additional reaction with sugar alcohol to produce additional anhydrosugar alcohol.
[0226] Any method known in the art may be used to separate the catalyst for reuse, including, for example, centrifugation, filtration (e.g. , vacuum filtration), and gravity settling. [0227] The methods described herein may be performed as batch or continuous processes. Recycling in a batch process may involve, for example, recovering the catalyst from the reaction mixture and reusing the recovered catalyst in one or more subsequent reaction cycles. Recycling in a continuous process may involve, for example, introducing additional sugar alcohol into the reactor, without additional of fresh catalyst.
[0228] In some of embodiments wherein at least a portion of the catalyst is recycled, the catalyst is recycled at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or at least 10 times. In some of these embodiments, the catalyst retains at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% activity after being recycled 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times, when compared to the catalytic activity under identical conditions prior to being recycled.
[0229] As used herein, the "catalyst activity" refers to the effective first order kinetic rate constant for the molar conversion of reactants, k = - ln( 1 - X(t) ) 1 1. The molar conversion of the reactant A at time t is defined as ¾(t) = 1- mol(A,t) / mol(A,0), where mol(A,t) refers to the number of moles of species A present in the reaction mixture at time t and mol(A,0) refers to the number of moles of species A present at the start of the reaction, t = 0. In practice, the number of moles of the reactant A is often measured at several points in time, ti, ¾, tj, ... , tn during a single reaction cycle and used to calculate the conversions ¾(t/X ¾(¾), · · · ¾fe) at the corresponding times. The first order rate constant k is then calculated by fitting the data for XA(t).
[0230] As used herein, a reaction "cycle" refers to one period of use within a sequence of uses of the catalyst. For example, in a batch process, a reaction cycle corresponds to the discrete steps of charging a reactor system with reactants and catalyst, heating the reaction under suitable conditions to convert the reactants, maintaining the reaction conditions for a specified residence time, separating the reaction products from the catalyst, and recovering the catalyst for re-use. In a continuous process, a cycle refers a single reactor space time during the operation of the continuous process. For example, in a 1,000 liter reactor with a continuous volumetric flow of 200 liters per hour, the continuous reactor space time is two hours, and the first two hour period of continuous operation is the first reaction cycle, the next two hour period of continuous operation is the second reaction cycle, etc.
[0231] As used herein, the "loss of activity" or "activity loss" of a catalyst is determined by the average fractional reduction in the catalyst activity between consecutive cycles. For example, if the catalyst activity in reaction cycle 1 is £(1) and the catalyst activity in reaction cycle 2 is k(2), then the loss in catalyst activity between cycle 1 and cycle 2 is calculated as [k(2) reaction cycles, the loss of activity is then determined as
Figure imgf000091_0001
measured in units of fractional loss per cycle.
[0232] In some variations, the rate constant for the conversion of additional reactant sugar alcohol is less than 20% lower than the rate constant for the conversion of the reactant sugar alcohol in the first reaction. In certain variations, the rate constant for conversion of the additional sugar alcohol is less than 15%, less than 12%, less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1% lower than the rate constant for the conversion of the reactant sugar alcohol in the first reaction. In some variations, the loss of activity is less than 20% per cycle, less than 15% per cycle, less than 10% per cycle, less than 8% per cycle, less than 4% per cycle, less than 2% per cycle, less than 1% per cycle, less than 0.5% per cycle, or less than 0.2% per cycle.
[0233] For example, in some variations, the reactant sugar alcohol is sorbitol, the
anhydrosugar alcohol is isosorbide, and the rate constant of the catalyst described herein for the conversion of sorbitol in a second reaction is less than 2% lower than the rate constant for conversion of sorbitol in the first reaction. For example, in some variations, the reactant sugar alcohol is sorbitol and the loss of activity is 0.5% per cycle.
[0234] As used herein "catalyst lifetime" refers to the average number of cycles that a catalyst particle can be re-used before it no longer effectively catalyzes the conversion of additional reactant sugar alcohol. The catalyst lifetime is calculated as the reciprocal of the loss of activity. For example, if the loss of activity is 1% per cycle, then the catalyst lifetime is 100 cycles. In some variations, the catalyst lifetime is at least 1 cycle, at least 2 cycles, at least 10 cycles, at least 50 cycles, at least 100 cycles, at least 200 cycles, at least 500 cycles.
[0235] In certain embodiments, a portion of the total mass of the catalyst in a reaction may be removed and replaced with fresh catalyst between reaction cycles. For example, in some variations, 0.1% of the mass of the catalyst may be replaced between reaction cycles, 1% of the mass of the catalyst may be replaced between reaction cycles, 2% of the mass of the catalyst may be replaced between reaction cycles, 5% of the mass of the catalyst may be replaced between reaction cycles, 10% of the mass of the catalyst may be replaced between reaction cycles, or 20% of the mass of the catalyst may be replaced between reaction cycles. [0236] As used herein, the "catalyst make-up rate" refers to the fraction of the catalyst mass that is replaced with fresh catalyst between reaction cycles.
Use of Anhydrosugar Alcohols
[0237] The anhydrosugar alcohols produced by the methods described herein may be suitable as starting materials and intermediates to produce other useful compounds. For example, the anhydrosugar alcohols produced by the methods described herein may be used to produce plastics, polymers, food products, or cosmetics. In some variations, the anhydrosugar alcohols produced may be used to produce polyurethane, polycarbonate, polyester, or polyamide.
[0238] In certain variations, the sugar alcohol described herein is sorbitol, and the
anhydrosugar alcohol produced is isosorbide. In some aspects, provided is a method of producing isosorbide dimethyl ether or isosorbide dinitrate from the isosorbide produced by any of the methods described herein.
ENUMERATED EMBODIMENTS
[0239] The following enumerated embodiments are representative of some aspects of the invention.
1. A method of producing an anhydrosugar alcohol from a sugar alcohol, comprising: combining a sugar alcohol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing an anhydrosugar alcohol from at least a portion of the reaction mixture.
2. The method of embodiment 1, further comprising: separating at least a portion of the catalyst from the anhydrosugar alcohol produced.
3. The method of embodiment 2, further comprising: combining the separated catalyst with additional sugar alcohol to form additional reaction mixture; and producing additional anhydrosugar alcohol from at least a portion of the additional reaction mixture.
4. The method of embodiment 2, further comprising: combining the separated catalyst with additional sugar alcohol; and dehydrating the additional sugar alcohol to produce additional anhydrosugar alcohol.
5. The method of any one of embodiments 1 to 4, wherein the sugar alcohol is a C6 sugar alcohol or a C5 sugar alcohol.
6. The method of any one of embodiments 1 to 5, wherein the sugar alcohol is an acyclic sugar alcohol or a monoanhydrosugar alcohol.
7. The method of any one of embodiments 1 to 6, wherein the sugar alcohol is hexitol.
8. The method of any one of embodiments 1 to 7, wherein the anhydrosugar alcohol produced is a dianhydrosugar alcohol.
9. The method of embodiment 8, wherein the dianhydrosugar alcohol is dianhydrohexitol.
10. A method of producing isosorbide from sorbitol, comprising: combining sorbitol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing isosorbide from at least a portion of the reaction mixture.
11. The method of any one of embodiments 1 to 10, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone. 12. The method of embodiment 11, wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid.
13. The method of embodiment 12, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
14. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid and phosphonic acid.
15. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is sulfonic acid.
16. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is phosphonic acid.
17. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is acetic acid.
18. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is isophthalic acid.
19. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is boronic acid.
20. The method of embodiment 13, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is perfluorinated acid.
21. The method of any one of embodiments 12 to 20, wherein one or more of the acidic monomers are directly connected to the polymeric backbone.
22. The method of any one of embodiments 12 to 20, wherein one or more of the acidic monomers each further comprise a linker connecting the Bronsted-Lowry acid to the polymeric backbone.
23. The method of embodiment 22, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
24. The method of embodiment 22, wherein the Bronsted-Lowry acid and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000095_0001
25. The method of any one of embodiments 11 to 24, wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof.
26. The method of embodiment 25, wherein the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
27. The method of embodiment 25, wherein the phosphorous -containing cationic group at each occurrence is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
28. The method of any one of embodiments 11 to 27, wherein one or more of the ionic monomers are directly connected to the polymeric backbone.
29. The method of any one of embodiments 11 to 27, wherein one or more of the ionic monomers each further comprise a linker connecting the nitrogen-containing cationic group or the phosphorous -containing cationic group to the polymeric backbone.
30. The method of embodiment 29, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
31. The method of embodiment 29, wherein the nitrogen-containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000096_0001
Figure imgf000097_0001
96
Figure imgf000098_0001
Figure imgf000099_0001
98
Figure imgf000100_0001
32. The method of embodiment 29, wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000100_0002
33. The method of any one of embodiments 11 to 32, wherein the polymeric backbone is selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, poly(acrylonitrile butadiene styrene), polyalkyleneammonium, polyalkylenediammonium, polyalkylenepyrrolium,
polyalkyleneimidazolium, polyalkylenepyrazolium, polyalkyleneoxazolium,
polyalkylenethiazolium, polyalkylenepyridinium, polyalkylenepyrimidinium,
polyalkylenepyrazinium, polyalkylenepyradizimium, polyalkylenethiazinium, polyalkylenemorpholinium, polyalkylenepiperidinium, polyalkylenepiperizinium, polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,
poly alky lenetrimethylpho sphonium, poly alky lenetriethylpho sphonium,
polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium,
poly alky lenetrichloropho sphonium, poly alky lenetrifluoropho sphonium, and
polyalkylenediazolium.
34. The method of any one of embodiments 11 to 33, further comprising hydrophobic monomers connected to the polymeric backbone, wherein each hydrophobic monomer comprises a hydrophobic group.
35. The method of embodiment 34, wherein the hydrophobic group at each occurrence is independently selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl.
36. The method of embodiment 34 or 35, wherein the hydrophobic group is directly connected to the polymeric backbone.
37. The method of any one of embodiments 11 to 36, further comprising acidic-ionic monomers connected to the polymeric backbone, wherein each acidic-ionic monomer comprises a Bronsted-Lowry acid and a cationic group.
38. The method of embodiment 37, wherein the cationic group is a nitrogen-containing cationic group or a phosphorous -containing cationic group.
39. The method of embodiment 37 or 38, wherein one or more of the acidic-ionic monomers each further comprise a linker connecting the Bronsted-Lowry acid or the cationic group to the polymeric backbone.
40. The method of embodiment 39, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate. 41. The method of embodiment 39, wherein the Bronsted-Lowry acid, the cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000102_0001
42. The method of any one of embodiments 1 to 10, wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
43. The method of embodiment 42, wherein the solid support comprises a material, wherein the material is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and any combinations thereof.
44. The method of embodiment 43, wherein the material is selected from the group consisting of carbon, magnesia, titania, zirconia, clays, zeolites, ceramics, and any combinations thereof.
45. The method of any one of embodiments 42 to 44, wherein each acidic moiety
independently has at least one Bronsted-Lowry acid.
46. The method of embodiment 45, wherein each Bronsted-Lowry acid is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
47. The method of embodiment 46, wherein each Bronsted-Lowry acid is independently sulfonic acid or phosphonic acid.
48. The method of embodiment 46, wherein each Bronsted-Lowry acid is sulfonic acid.
49. The method of embodiment 46, wherein each Bronsted-Lowry acid is phosphonic acid.
50. The method of embodiment 46, wherein each Bronsted-Lowry acid is acetic acid.
51. The method of embodiment 46, wherein each Bronsted-Lowry acid is isophthalic acid.
52. The method of embodiment 46, wherein each Bronsted-Lowry acid is boronic acid.
53. The method of embodiment 46, wherein each Bronsted-Lowry acid is perfluorinated acid.
54. The method of any one of embodiments 42 to 53, wherein one or more of the acidic moieties are directly attached to the solid support.
55. The method of any one of embodiments 42 to 53, wherein one or more of the acidic moieties are attached to the solid support by a linker. 56. The method of embodiment 55, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate
57. The method of embodiment 55, wherein each acidic moiety independently has at least one Bronsted-Lowry acid, wherein the Bronsted-Lowry acid and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000104_0001
Figure imgf000105_0001
58. The method of any one of embodiments 42 to 57, wherein each ionic moiety
independently has at least one nitrogen-containing cationic group or at least one phosphorous- containing cationic group, or a combination thereof.
59. The method of any one of embodiments 42 to 57, wherein each ionic moiety is selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
60. The method of embodiment 58, wherein each ionic moiety independently has at least one nitrogen-containing cationic group, and wherein each nitrogen-containing cationic group is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
61. The method of embodiment 58, wherein each ionic moiety independently has at least one phosphorous-containing cationic group, and wherein each phosphorous-containing cationic group is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
62. The method of any one of embodiments 42 to 61, wherein one or more of the ionic moieties are directed attached to the solid support. 63. The method of any one of embodiments 42 to 61, wherein one or more of the ionic moieties are attached to the solid support by a linker.
64. The method of embodiment 63, wherein each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
65. The method of embodiment 63, wherein each ionic moiety independently has at least one nitrogen-containing cationic group, wherein the nitrogen-containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000106_0001
Figure imgf000107_0001
106
Figure imgf000108_0001
107
Figure imgf000109_0001
66. The method of embodiment 63, wherein each ionic moiety independently has at least one phosphorous-containing cationic group, wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000109_0002
Figure imgf000110_0001
67. The method of any one of embodiments, wherein 42 to 66, further comprising hydrophobic moieties attached to the solid support.
68. The method of embodiment 67, wherein each hydrophobic moiety is selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
69. The method of any one of embodiments 42 to 68, further comprising acidic-ionic moieties attached to the solid support, wherein each acidic-ionic moiety comprises a Bronsted- Lowry acid and a cationic group.
70. The method of embodiment 69, wherein the cationic group is a nitrogen-containing cationic group or a phosphorous -containing cationic group.
71. The method of embodiment 69 or 70, wherein one or more of the acidic-ionic monomers each further comprise a linker connecting the Bronsted-Lowry acid or the cationic group to the polymeric backbone.
72. The method of embodiment 71, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
73. The method of embodiment 71, wherein the Bronsted-Lowry acid, the cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000111_0001
74. The method of any one of embodiments 42 to 73, wherein the material is carbon, and wherein the carbon is selected from the group consisting of biochar, amorphous carbon, and activated carbon. 75. The method of any one of embodiments 1 to 10, wherein the catalyst is selected from the group consisting of:
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium iodide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bromide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium acetate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium formate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium-acetate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium-nitrate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bromide- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-iodide-co-
3- methyl-l-(4-vinylbenzyl)-3H-imidazol- l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-acetate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-
4- ium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium formate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium acetate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium acetate-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co-4-boronyl-l- (4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium acetate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium nitrate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ; poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co- divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium chloride-co-divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium acetate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ; poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-vinylbenzylmethylmorpholinium acetate -co -vinylbenzyltriphenyl phosphonium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenyl phosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium bisulfate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium nitrate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium bisulfate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ; poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ; poly(butyl-vinylimidazolium chloride-co-butylimidazolium bisulfate-co-4- vinylbenzenesulfonic acid);
poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium bisulfate-co^4- vinylbenzenesulfonic acid);
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl alcohol); and
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl alcohol) .
76. The method of any one of embodiments 1 to 10, wherein the catalyst is selected from the group consisting of: carbon- supported pyrrolium chloride sulfonic acid;
carbon- supported imidazolium chloride sulfonic acid;
carbon- supported pyrazolium chloride sulfonic acid;
carbon- supported oxazolium chloride sulfonic acid;
carbon- supported thiazolium chloride sulfonic acid;
carbon- supported pyridinium chloride sulfonic acid;
carbon- supported pyrimidinium chloride sulfonic acid;
carbon- supported pyrazinium chloride sulfonic acid;
carbon- supported pyridazinium chloride sulfonic acid;
carbon- supported thiazinium chloride sulfonic acid;
carbon- supported morpholinium chloride sulfonic acid;
carbon- supported piperidinium chloride sulfonic acid;
carbon- supported piperizinium chloride sulfonic acid;
carbon- supported pyrollizinium chloride sulfonic acid;
carbon- supported triphenyl phosphonium chloride sulfonic acid;
carbon- supported trimethyl phosphonium chloride sulfonic acid;
carbon- supported triethyl phosphonium chloride sulfonic acid;
carbon- supported tripropyl phosphonium chloride sulfonic acid;
carbon- supported tributyl phosphonium chloride sulfonic acid; carbon- supported trifluoro phosphonium chloride sulfonic acid; carbon- supported pyrrolium bromide sulfonic acid;
carbon- supported imidazolium bromide sulfonic acid;
carbon- supported pyrazolium bromide sulfonic acid;
carbon- supported oxazolium bromide sulfonic acid;
carbon- supported thiazolium bromide sulfonic acid;
carbon- supported pyridinium bromide sulfonic acid;
carbon- supported pyrimidinium bromide sulfonic acid;
carbon- supported pyrazinium bromide sulfonic acid;
carbon- supported pyridazinium bromide sulfonic acid;
carbon- supported thiazinium bromide sulfonic acid;
carbon- supported morpholinium bromide sulfonic acid;
carbon- supported piperidinium bromide sulfonic acid;
carbon- supported piperizinium bromide sulfonic acid;
carbon- supported pyrollizinium bromide sulfonic acid;
carbon- supported triphenyl phosphonium bromide sulfonic acid; carbon- supported trimethyl phosphonium bromide sulfonic acid; carbon- supported triethyl phosphonium bromide sulfonic acid; carbon- supported tripropyl phosphonium bromide sulfonic acid; carbon- supported tributyl phosphonium bromide sulfonic acid; carbon- supported trifluoro phosphonium bromide sulfonic acid; carbon- supported pyrrolium bisulfate sulfonic acid;
carbon- supported imidazolium bisulfate sulfonic acid;
carbon- supported pyrazolium bisulfate sulfonic acid;
carbon- supported oxazolium bisulfate sulfonic acid;
carbon- supported thiazolium bisulfate sulfonic acid;
carbon- supported pyridinium bisulfate sulfonic acid;
carbon- supported pyrimidinium bisulfate sulfonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported trimethyl phosphonium formate sulfonic acid; carbon- supported triethyl phosphonium formate sulfonic acid; carbon- supported tripropyl phosphonium formate sulfonic acid; carbon- supported tributyl phosphonium formate sulfonic acid; carbon- supported trifluoro phosphonium formate sulfonic acid; carbon- supported pyrrolium acetate sulfonic acid;
carbon- supported imidazolium acetate sulfonic acid;
carbon- supported pyrazolium acetate sulfonic acid;
carbon- supported oxazolium acetate sulfonic acid;
carbon- supported thiazolium acetate sulfonic acid;
carbon- supported pyridinium acetate sulfonic acid;
carbon- supported pyrimidinium acetate sulfonic acid;
carbon- supported pyrazinium acetate sulfonic acid;
carbon- supported pyridazinium acetate sulfonic acid;
carbon- supported thiazinium acetate sulfonic acid;
carbon- supported morpholinium acetate sulfonic acid;
carbon- supported piperidinium acetate sulfonic acid;
carbon- supported piperizinium acetate sulfonic acid;
carbon- supported pyrollizinium acetate sulfonic acid;
carbon- supported triphenyl phosphonium acetate sulfonic acid; carbon- supported trimethyl phosphonium acetate sulfonic acid; carbon- supported triethyl phosphonium acetate sulfonic acid; carbon- supported tripropyl phosphonium acetate sulfonic acid; carbon- supported tributyl phosphonium acetate sulfonic acid; carbon- supported trifluoro phosphonium acetate sulfonic acid; carbon- supported pyrrolium chloride phosphonic acid;;
carbon- supported imidazolium chloride phosphonic acid;
carbon- supported pyrazolium chloride phosphonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported piperidinium bromide phosphonic acid;
carbon- supported piperizinium bromide phosphonic acid;
carbon- supported pyrollizinium bromide phosphonic acid;
carbon- supported triphenyl phosphonium bromide phosphonic acid; carbon- supported trimethyl phosphonium bromide phosphonic acid; carbon- supported triethyl phosphonium bromide phosphonic acid; carbon- supported tripropyl phosphonium bromide phosphonic acid; carbon- supported tributyl phosphonium bromide phosphonic acid; carbon- supported trifluoro phosphonium bromide phosphonic acid; carbon- supported pyrrolium bisulfate phosphonic acid;
carbon- supported imidazolium bisulfate phosphonic acid;
carbon- supported pyrazolium bisulfate phosphonic acid;
carbon- supported oxazolium bisulfate phosphonic acid;
carbon- supported thiazolium bisulfate phosphonic acid;
carbon- supported pyridinium bisulfate phosphonic acid;
carbon- supported pyrimidinium bisulfate phosphonic acid;
carbon- supported pyrazinium bisulfate phosphonic acid;
carbon- supported pyridazinium bisulfate phosphonic acid;
carbon- supported thiazinium bisulfate phosphonic acid;
carbon- supported morpholinium bisulfate phosphonic acid;
carbon- supported piperidinium bisulfate phosphonic acid;
carbon- supported piperizinium bisulfate phosphonic acid;
carbon- supported pyrollizinium bisulfate phosphonic acid;
carbon- supported triphenyl phosphonium bisulfate phosphonic acid; carbon- supported trimethyl phosphonium bisulfate phosphonic acid; carbon- supported triethyl phosphonium bisulfate phosphonic acid; carbon- supported tripropyl phosphonium bisulfate phosphonic acid; carbon- supported tributyl phosphonium bisulfate phosphonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported pyrazinium acetate phosphonic acid;
carbon- supported pyridazinium acetate phosphonic acid;
carbon- supported thiazinium acetate phosphonic acid;
carbon- supported morpholinium acetate phosphonic acid;
carbon- supported piperidinium acetate phosphonic acid;
carbon- supported piperizinium acetate phosphonic acid;
carbon- supported pyrollizinium acetate phosphonic acid;
carbon- supported triphenyl phosphonium acetate phosphonic acid;
carbon- supported trimethyl phosphonium acetate phosphonic acid;
carbon- supported triethyl phosphonium acetate phosphonic acid;
carbon- supported tripropyl phosphonium acetate phosphonic acid;
carbon- supported tributyl phosphonium acetate phosphonic acid;
carbon- supported trifluoro phosphonium acetate phosphonic acid;
carbon- supported ethanoyl-triphosphonium sulfonic acid;
carbon- supported ethanoyl-methylmorpholinium sulfonic acid; and
carbon- supported ethanoyl-imidazolium sulfonic acid.
77. The method of any one of embodiments 1 to 76, wherein the catalyst has a catalyst activity loss of less than 1% per cycle.
78. A composition comprising: a sugar alcohol; and a catalyst, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support. producing an anhydrosugar alcohol from at least a portion of the reaction mixture.
79. The composition of embodiment 78, wherein the sugar alcohol is a C6 sugar alcohol or a C5 sugar alcohol. 80. The composition of embodiment 78, wherein the sugar alcohol is an acyclic sugar alcohol or a monoanhydrosugar alcohol.
81. The composition of embodiment 78, wherein the sugar alcohol is hexitol.
82. The composition of any one of embodiments 78 to 81, further comprising: an anhydrosugar alcohol.
83. The composition of embodiment 82, wherein the anhydrosugar alcohol produced is a dianhydrosugar alcohol.
84. The composition of embodiment 83, wherein the dianhydrosugar alcohol is
dianhydrohexitol .
85. A composition comprising: sorbitol; and a catalyst, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
86. The composition of embodiment 85, further comprising isosorbide.
87. The composition of any one of embodiments 78 to 86, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone.
88. The composition of embodiment 87, wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid.
89. The composition of embodiment 88, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
90. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is independently selected from the group consisting of sulfonic acid and phosphonic acid. 91. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is sulfonic acid.
92. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is phosphonic acid.
93. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is acetic acid.
94. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is isophthalic acid.
95. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is boronic acid.
96. The composition of embodiment 89, wherein the at least one Bronsted-Lowry acid at each occurrence in the catalyst is perfluorinated acid.
97. The composition of any one of embodiments 87 to 96, wherein one or more of the acidic monomers are directly connected to the polymeric backbone.
98. The composition of any one of embodiments 87 to 96, wherein one or more of the acidic monomers each further comprise a linker connecting the Bronsted-Lowry acid to the polymeric backbone.
99. The composition of embodiment 98, wherein the linker at each occurrence is
independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
100. The composition of embodiment 98, wherein the Bronsted-Lowry acid and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000128_0001
101. The composition of any one of embodiments 87 to 100, wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof. 102. The composition of embodiment 101, wherein the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
103. The composition of embodiment 101, wherein the phosphorous -containing cationic group at each occurrence is independently selected from the group consisting of triphenyl
phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
104. The composition of any one of embodiments 87 to 103, wherein one or more of the ionic monomers are directly connected to the polymeric backbone.
105. The composition of any one of embodiments 87 to 103, wherein one or more of the ionic monomers each further comprise a linker connecting the nitrogen-containing cationic group or the phosphorous -containing cationic group to the polymeric backbone.
106. The composition of embodiment 105, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
107. The composition of embodiment 105, wherein the nitrogen-containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000129_0001
Figure imgf000130_0001

Figure imgf000131_0001
Figure imgf000132_0001
131
Figure imgf000133_0001
108. The composition of embodiment 105, wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000133_0002
109. The composition of any one of embodiments 87 to 108, wherein the polymeric backbone is selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, poly(acrylonitrile butadiene styrene),
polyalkyleneammonium, polyalkylenediammonium, polyalkylenepyrrolium,
polyalkyleneimidazolium, polyalkylenepyrazolium, polyalkyleneoxazolium,
polyalkylenethiazolium, polyalkylenepyridinium, polyalkylenepyrimidinium,
polyalkylenepyrazinium, polyalkylenepyradizimium, polyalkylenethiazinium, polyalkylenemorpholinium, polyalkylenepiperidinium, polyalkylenepiperizinium, polyalkylenepyrollizinium, polyalkylenetriphenylphosphonium,
poly alky lenetrimethylpho sphonium, poly alky lenetriethylpho sphonium,
polyalkylenetripropylphosphonium, polyalkylenetributylphosphonium,
poly alky lenetrichloropho sphonium, poly alky lenetrifluoropho sphonium, and
polyalkylenediazolium.
110. The composition of any one of embodiments 87 to 109, further comprising hydrophobic monomers connected to the polymeric backbone, wherein each hydrophobic monomer comprises a hydrophobic group.
111. The composition of embodiment 110, wherein the hydrophobic group at each occurrence is independently selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl.
112. The composition of embodiment 110 or 111, wherein the hydrophobic group is directly connected to the polymeric backbone.
113. The composition of any one of embodiments 98 to 112, further comprising acidic-ionic monomers connected to the polymeric backbone, wherein each acidic-ionic monomer comprises a Bronsted-Lowry acid and a cationic group.
114. The composition of embodiment 113, wherein the cationic group is a nitrogen-containing cationic group or a phosphorous -containing cationic group.
115. The composition of embodiment 113 or 114, wherein one or more of the acidic-ionic monomers each further comprise a linker connecting the Bronsted-Lowry acid or the cationic group to the polymeric backbone.
116. The composition of embodiment 115, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate. 117. The composition of embodiment 115, wherein the Bronsted-Lowry acid, the cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000135_0001
118. The composition of any one of embodiments 78 to 86, wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
119. The composition of embodiment 118, wherein the solid support comprises a material, wherein the material is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and any combinations thereof.
120. The composition of embodiment 119, wherein the material is selected from the group consisting of carbon, magnesia, titania, zirconia, clays, zeolites, ceramics, and any combinations thereof.
121. The composition of any one of embodiments 118 to 120, wherein each acidic moiety independently has at least one Bronsted-Lowry acid.
122. The composition of embodiment 121, wherein each Bronsted-Lowry acid is
independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
123. The composition of embodiment 122, wherein each Bronsted-Lowry acid is
independently sulfonic acid or phosphonic acid.
124. The composition of embodiment 122, wherein each Bronsted-Lowry acid is sulfonic acid.
125. The composition of embodiment 122, wherein each Bronsted-Lowry acid is phosphonic acid.
126. The composition of embodiment 122, wherein each Bronsted-Lowry acid is acetic acid.
127. The composition of embodiment 122, wherein each Bronsted-Lowry acid is isophthalic acid.
128. The composition of embodiment 122, wherein each Bronsted-Lowry acid is boronic acid.
129. The composition of embodiment 122, wherein each Bronsted-Lowry acid is
perfluorinated acid. 130. The composition of any one of embodiments 118 to 129, wherein one or more of the acidic moieties are directly attached to the solid support.
131. The composition of any one of embodiments 118 to 129, wherein one or more of the acidic moieties are attached to the solid support by a linker.
132. The composition of embodiment 131, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
133. The composition of embodiment 131, wherein each acidic moiety independently has at least one Bronsted-Lowry acid, wherein the Bronsted-Lowry acid and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000137_0001
Figure imgf000138_0001
134. The composition of any one of embodiments 118 to 133, wherein each ionic moiety independently has at least one nitrogen-containing cationic group or at least one phosphorous- containing cationic group, or a combination thereof.
135. The composition of any one of embodiments 118 to 133, wherein each ionic moiety is selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
136. The composition of embodiment 134, wherein each ionic moiety independently has at least one nitrogen-containing cationic group, and wherein each nitrogen-containing cationic group is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyridazinium , thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
137. The composition of embodiment 134, wherein each ionic moiety independently has at least one phosphorous-containing cationic group, and wherein each phosphorous -containing cationic group is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
138. The composition of any one of embodiments 118 to 137, wherein one or more of the ionic moieties are directed attached to the solid support. 139. The composition of any one of embodiments 118 to 137, wherein one or more of the ionic moieties are attached to the solid support by a linker.
140. The composition of embodiment 139, wherein each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
141. The composition of embodiment 139, wherein each ionic moiety independently has at least one nitrogen-containing cationic group, wherein the nitrogen-containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000139_0001
Figure imgf000140_0001

Figure imgf000141_0001
Figure imgf000142_0001
142. The composition of embodiment 139, wherein each ionic moiety independently has at least one phosphorous-containing cationic group, wherein the phosphorous -containing cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000142_0002
Figure imgf000143_0001
143. The composition of any one of embodiments, wherein 118 to 142, further comprising hydrophobic moieties attached to the solid support.
144. The composition of embodiment 143, wherein each hydrophobic moiety is selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
145. The composition of any one of embodiments 118 to 144, further comprising acidic-ionic moieties attached to the solid support, wherein each acidic-ionic moiety comprises a Bronsted- Lowry acid and a cationic group.
146. The composition of embodiment 145, wherein the cationic group is a nitrogen-containing cationic group or a phosphorous -containing cationic group.
147. The composition of embodiment 145 or 146, wherein one or more of the acidic-ionic monomers each further comprise a linker connecting the Bronsted-Lowry acid or the cationic group to the polymeric backbone.
148. The composition of embodiment 147, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
149. The composition of embodiment 147, wherein the Bronsted-Lowry acid, the cationic group and the linker form a side chain, wherein each side chain is independently selected from the group consisting of:
Figure imgf000144_0001
150. The composition of any one of embodiments 118 to 149, wherein the material is carbon, and wherein the carbon is selected from the group consisting of biochar, amorphous carbon, and activated carbon. 151. The composition of any one of embodiments 78 to 86, wherein the catalyst is selected from the group consisting of:
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4-vinylbenzyl)-3H-imidazol- 1-ium nitrate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium iodide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bromide-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium acetate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co-3 -methyl- l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium formate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium-acetate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- l-(4-vinylbenzyl)-pyridinium-nitrate- co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bromide- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-iodide-co-
3- methyl-l-(4-vinylbenzyl)-3H-imidazol- l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-bisulfate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-acetate- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-
4- ium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin- 4-ium formate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium acetate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium chloride-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylbenzenesulfonic acid-co- 1 -methyl- 1 -(4-vinylbenzyl)-piperdin- 1 - ium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium acetate-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co-4-boronyl-l- (4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium acetate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium nitrate-co-l-(4- vinylphenyl)methylphosphonic acid-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium chloride-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium bisulfate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylchloride-co-l-methyl-2- vinyl-pyridinium acetate-co-divinylbenzene] ;
poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ; poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium chloride-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co- divinylbenzene] ;
poly[styrene-co-3-carboxymethyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium acetate-co- divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium chloride-co-divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-l-(4-vinylbenzyl)- 3H-imidazol- 1 -ium acetate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-co-divinylbenzene] ;
poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium acetate-co-divinylbenzene] ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenyl phosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene) ; poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-vinylbenzylmethylmorpholinium acetate -co -vinylbenzyltriphenyl phosphonium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenyl phosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene)
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium bisulfate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium nitrate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium chloride-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium bisulfate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium acetate-co- divinylbenzene);
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ; poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate- co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulf ate-co-divinylbenzene) ;
poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene) ; poly(butyl-vinylimidazolium chloride-co-butylimidazolium bisulfate-co-4- vinylbenzenesulfonic acid);
poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium bisulfate-co^4- vinylbenzenesulfonic acid);
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl alcohol); and
poly(benzyl alcohol-co-4-vinylbenzylalcohol sulfonic acid-co- vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl alcohol) .
152. The composition of any one of embodiments 78 to 86, wherein the catalyst is selected from the group consisting of: carbon- supported pyrrolium chloride sulfonic acid;
carbon- supported imidazolium chloride sulfonic acid;
carbon- supported pyrazolium chloride sulfonic acid;
carbon- supported oxazolium chloride sulfonic acid;
carbon- supported thiazolium chloride sulfonic acid;
carbon- supported pyridinium chloride sulfonic acid;
carbon- supported pyrimidinium chloride sulfonic acid;
carbon- supported pyrazinium chloride sulfonic acid;
carbon- supported pyridazinium chloride sulfonic acid;
carbon- supported thiazinium chloride sulfonic acid;
carbon- supported morpholinium chloride sulfonic acid;
carbon- supported piperidinium chloride sulfonic acid;
carbon- supported piperizinium chloride sulfonic acid;
carbon- supported pyrollizinium chloride sulfonic acid;
carbon- supported triphenyl phosphonium chloride sulfonic acid;
carbon- supported trimethyl phosphonium chloride sulfonic acid;
carbon- supported triethyl phosphonium chloride sulfonic acid;
carbon- supported tripropyl phosphonium chloride sulfonic acid;
carbon- supported tributyl phosphonium chloride sulfonic acid; carbon- supported trifluoro phosphonium chloride sulfonic acid; carbon- supported pyrrolium bromide sulfonic acid;
carbon- supported imidazolium bromide sulfonic acid;
carbon- supported pyrazolium bromide sulfonic acid;
carbon- supported oxazolium bromide sulfonic acid;
carbon- supported thiazolium bromide sulfonic acid;
carbon- supported pyridinium bromide sulfonic acid;
carbon- supported pyrimidinium bromide sulfonic acid;
carbon- supported pyrazinium bromide sulfonic acid;
carbon- supported pyridazinium bromide sulfonic acid;
carbon- supported thiazinium bromide sulfonic acid;
carbon- supported morpholinium bromide sulfonic acid;
carbon- supported piperidinium bromide sulfonic acid;
carbon- supported piperizinium bromide sulfonic acid;
carbon- supported pyrollizinium bromide sulfonic acid;
carbon- supported triphenyl phosphonium bromide sulfonic acid; carbon- supported trimethyl phosphonium bromide sulfonic acid; carbon- supported triethyl phosphonium bromide sulfonic acid; carbon- supported tripropyl phosphonium bromide sulfonic acid; carbon- supported tributyl phosphonium bromide sulfonic acid; carbon- supported trifluoro phosphonium bromide sulfonic acid; carbon- supported pyrrolium bisulfate sulfonic acid;
carbon- supported imidazolium bisulfate sulfonic acid;
carbon- supported pyrazolium bisulfate sulfonic acid;
carbon- supported oxazolium bisulfate sulfonic acid;
carbon- supported thiazolium bisulfate sulfonic acid;
carbon- supported pyridinium bisulfate sulfonic acid;
carbon- supported pyrimidinium bisulfate sulfonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported trimethyl phosphonium formate sulfonic acid; carbon- supported triethyl phosphonium formate sulfonic acid; carbon- supported tripropyl phosphonium formate sulfonic acid; carbon- supported tributyl phosphonium formate sulfonic acid; carbon- supported trifluoro phosphonium formate sulfonic acid; carbon- supported pyrrolium acetate sulfonic acid;
carbon- supported imidazolium acetate sulfonic acid;
carbon- supported pyrazolium acetate sulfonic acid;
carbon- supported oxazolium acetate sulfonic acid;
carbon- supported thiazolium acetate sulfonic acid;
carbon- supported pyridinium acetate sulfonic acid;
carbon- supported pyrimidinium acetate sulfonic acid;
carbon- supported pyrazinium acetate sulfonic acid;
carbon- supported pyridazinium acetate sulfonic acid;
carbon- supported thiazinium acetate sulfonic acid;
carbon- supported morpholinium acetate sulfonic acid;
carbon- supported piperidinium acetate sulfonic acid;
carbon- supported piperizinium acetate sulfonic acid;
carbon- supported pyrollizinium acetate sulfonic acid;
carbon- supported triphenyl phosphonium acetate sulfonic acid; carbon- supported trimethyl phosphonium acetate sulfonic acid; carbon- supported triethyl phosphonium acetate sulfonic acid; carbon- supported tripropyl phosphonium acetate sulfonic acid; carbon- supported tributyl phosphonium acetate sulfonic acid; carbon- supported trifluoro phosphonium acetate sulfonic acid; carbon- supported pyrrolium chloride phosphonic acid;;
carbon- supported imidazolium chloride phosphonic acid;
carbon- supported pyrazolium chloride phosphonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported piperidinium bromide phosphonic acid;
carbon- supported piperizinium bromide phosphonic acid;
carbon- supported pyrollizinium bromide phosphonic acid;
carbon- supported triphenyl phosphonium bromide phosphonic acid; carbon- supported trimethyl phosphonium bromide phosphonic acid; carbon- supported triethyl phosphonium bromide phosphonic acid; carbon- supported tripropyl phosphonium bromide phosphonic acid; carbon- supported tributyl phosphonium bromide phosphonic acid; carbon- supported trifluoro phosphonium bromide phosphonic acid; carbon- supported pyrrolium bisulfate phosphonic acid;
carbon- supported imidazolium bisulfate phosphonic acid;
carbon- supported pyrazolium bisulfate phosphonic acid;
carbon- supported oxazolium bisulfate phosphonic acid;
carbon- supported thiazolium bisulfate phosphonic acid;
carbon- supported pyridinium bisulfate phosphonic acid;
carbon- supported pyrimidinium bisulfate phosphonic acid;
carbon- supported pyrazinium bisulfate phosphonic acid;
carbon- supported pyridazinium bisulfate phosphonic acid;
carbon- supported thiazinium bisulfate phosphonic acid;
carbon- supported morpholinium bisulfate phosphonic acid;
carbon- supported piperidinium bisulfate phosphonic acid;
carbon- supported piperizinium bisulfate phosphonic acid;
carbon- supported pyrollizinium bisulfate phosphonic acid;
carbon- supported triphenyl phosphonium bisulfate phosphonic acid; carbon- supported trimethyl phosphonium bisulfate phosphonic acid; carbon- supported triethyl phosphonium bisulfate phosphonic acid; carbon- supported tripropyl phosphonium bisulfate phosphonic acid; carbon- supported tributyl phosphonium bisulfate phosphonic acid; carbon-■ supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- ■supported carbon- supported pyrazinium acetate phosphonic acid;
carbon- supported pyridazinium acetate phosphonic acid;
carbon- supported thiazinium acetate phosphonic acid;
carbon- supported morpholinium acetate phosphonic acid;
carbon- supported piperidinium acetate phosphonic acid;
carbon- supported piperizinium acetate phosphonic acid;
carbon- supported pyrollizinium acetate phosphonic acid;
carbon- supported triphenyl phosphonium acetate phosphonic acid;
carbon- supported trimethyl phosphonium acetate phosphonic acid;
carbon- supported triethyl phosphonium acetate phosphonic acid;
carbon- supported tripropyl phosphonium acetate phosphonic acid;
carbon- supported tributyl phosphonium acetate phosphonic acid;
carbon- supported trifluoro phosphonium acetate phosphonic acid;
carbon- supported ethanoyl-triphosphonium sulfonic acid;
carbon- supported ethanoyl-methylmorpholinium sulfonic acid; and
carbon- supported ethanoyl-imidazolium sulfonic acid.
EXAMPLES
[0240] The following Examples are merely illustrative and are not meant to limit any aspects of the present disclosure in any way. Except where otherwise indicated, commercial reagents were purified prior to use following the guidelines of Perrin and Armarego (Perrin, D. D. & Armarego, W. L. F., Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press, Oxford (1988)). Nitrogen gas for use in chemical reactions was of ultra-pure grade and was dried over phosphorous pentoxide or calcium chloride as required. Unless indicated otherwise, at bench- scale, all non-aqueous reagents were transferred under an inert atmosphere via syringe or Schlenk flask. Where necessary, chromatographic purification of reactants or products was performed using forced-flow chromatography on 60 mesh silica gel according to the method described in Still et al., J. Org. Chem., 43: 2923 (1978). Thin-layer chromatography (TLC) was performed using silica-coated glass plates. Visualization of the developed chromatographic plate was performed using either cerium molybdate (i.e., Hanessian) stain or KMn04 stain, with gentle heating as required. Fourier- Transform Infrared (FTIR) spectroscopic analysis of solid samples was performed on a Perkin-Elmer 1600 instrument using a horizontal attenuated total reflectance (ATR) configuration with a zinc selenide crystal.
[0241] The moisture content of reagents was determined using a Mettler- Toledo MJ-33 moisture-analyzing balance with a sample size of 0.5 - 1.0 g and a heating cut-off temperature of 115°C. All moisture contents were determined as the average percent weight (%wt) loss on drying obtained from triplicate measurements.
[0242] The sugar, sugar alcohol, organic acid, furanic aldehyde and oligosaccharide content of reaction mixtures was determined by a combination of high performance liquid
chromatography (HPLC) and spectrophotometric methods. HPLC determination of soluble sugars and sugar alcohols was performed on a Hewlett-Packard 1100 Series instrument equipped with a refractive index (RI) detector at 40°C using a 30 cm x 7.8 mm BioRad Aminex HPX-87P column at 80°C with water at 0.6 mL/min as the mobile phase. The sugar column was protected by both a lead-exchanged sulfonated-polystyrene guard column and a tri- alkylammoniumhydroxide anionic-exchange guard column. All HPLC samples were
microfiltered using a 0.2 μιη syringe filter prior to injection. Sample concentrations were determined by reference to calibrations generated from a standard solution containing glucose, xylose, arabinose, galactose, sorbitol, and xylitol, in known concentrations.
[0243] The concentrations of sugar dehydration products, including anhydrosugars, anhydrosugar alcohols, organic acids, and furanic aldehydes, was determined by high
performance liquid chromatography (HPLC) on a Hewlett-Packard 1100 Series instrument equipped with a refractive index (RI) detector at 30°C using a 30 cm x 7.8 mm BioRad Aminex HPX-87H column at 50°C with 50 mM sulfuric acid at 0.65 mL/min as the mobile phase. The analytical column was protected by a sulfonated-polystyrene guard column and all HPLC samples were microfiltered using a 0.2 μιη syringe filter prior to injection. Sample
concentrations were determined by reference to calibrations generated from a standard solution containing formic acid, acetic acid, levulinic acid, 5-hydroxymethylfurfural, and 2-furaldehyde or a standard solution containing sorbitol, 1,4-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide (1,4:3 ,6-Dianhydro-D- sorbitol) .
[0244] The conversion X(t) of monoanhydrosugar alcohols or sugar alcohols at time t was determined according to A"(f.) = 1— m^E g1'^, where mol(DPl,t) denotes the total moles of monoanhydrosugar alcohols or sugar alcohols present in the reaction at time t and mol(DPl,0) denotes the total moles of monoanhydrosugar alcohols or sugar alcohols initially charged to the reaction. Similarly, the yield to a given sugar dehydration species B was determined according to g t) = p ^ 0%> where mol(fi,i) denotes the total moles of species B at reaction time t.
Finally, the molar selectivity to a given product B was determined as the ratio of yield to conversion, namely S(f.) = YB(t)/X(t).
[0245] The catalytic activity at a given reaction temperature and catalyst loading was determined as the effective first order rate constant for the conversion of reactants,
=— hi(l— X{t))/t. The rate constant was calculated from reaction time-course data, typically by averaging the rate constant determined at multiple reaction times. The loss of catalyst activity upon re-use was determined as the fractional decrease in k\ between consecutive cycles. The average loss of activity was determined as the arithmetic average of the catalyst activity loss computed for each consecutive reaction cycle.
[0246] The production of bi-products, such as polyfuranics, solid humins, and other poly- condensation products, was determined by inference from the reaction molar balance.
Specifically, the molar yield to bi-products was determined as the arithmetic difference of the conversion and the sum of the yields to all quantifiable species.
[0247] The viscosity of solutions was determined using a Brookfield viscosometer mounted above a temperature-controlled oil bath used to control the temperature of the solution being measured from room temperature up to approximately 140 degrees Celsius.
[0248] The acid content of catalyst samples and aqueous solutions was determined using a Hana Instruments 902-C autotitrator with sodium hydroxide as the titrant, calibrated against a standard solution of potassium hydrogen phthalate (KHP). A known dry mass of solid catalyst was suspended in 40mL of 10% sodium chloride solution at 60°C for 120 minutes prior to titration. The catalyst acidity was determined by dividing the total proton equivalents determined by titration by the dry mass of the dispensed catalyst and was reported in units of mmol H+ / g dry catalyst.
[0249] The ionic content of catalyst samples was determined by titration against standardized silver nitrate solution. Solid catalyst for analysis was washed repeatedly on a fritted glass funnel with 100 mL volumes of 10% hydrochloric acid solution, followed by washing repeatedly with distilled water until the effluent eluted neutral. A sample of the acid-washed catalyst with known dry mass was then suspended in 40 mL of a 50% v/v solution of dimethylformamide (DMF) in water at 60°C for 120 minutes prior to titration to a potassium chromate endpoint. The catalyst ionic content was determined by dividing the total chloride ion equivalents determined by titration by the dry mass of the dispensed catalyst and was reported in units of mmol ionic groups / g dry catalyst.
[0250] Concentration of liquid samples was performed using a Buchi rl24 series rotary evaporator unit.
Example 1
Preparation of Catalyst
[0251] This Example demonstrates the preparation and characterization of poly-(styrene sulfonic acid-co-vinylbenzylimidazolium sulfate-co-divinylbenzene) .
[0252] To a 30 L jacketed glass reactor, housed within a walk-in fume hood and equipped with a 2 inch bottom drain port and a multi-element mixer attached to an overhead air-driven stirrer, was charged 14 L of N,N-dimethylformamide (DMF, ACS Reagent Grade, Sigma- Aldrich, St. Louis, MO, USA) and 2.1 kg of lH-imidazole (ACS Reagent Grade, Sigma- Aldrich, St. Louis, MO, USA) at room temperature. The DMF was stirred to dissolve the imidazole. To the reactor was then added 7.0 kg of cross-linked poly-(styrene-co-divinylbenzene-co- vinylbenzyl chloride) to form a stirred suspension. The reaction mixture was heated to 90 degrees Celsius by pumping heated bath fluid through the reactor jacket, and the reaction mixture was allowed to react for 24 hours, after which it was gradually cooled.
[0253] Then, the DMF and residual unreacted lH-imidazole was drained from the resin, after which the retained resin was washed repeatedly with acetone to remove residual heavy solvent or unreacted reagents. The reaction yielded cross-linked poly-(styrene-co-divinylbenzene-co-lH- imidazolium chloride) as off-white spherical resin beads. The resin beads were removed from the reactor and heated at 70 degrees Celsius in air to dry.
[0254] The cleaned 30 L reactor system was charged with 2.5 L of 95% sulfuric acid (ACS Reagent Grade) and then approximately 13 L of oleum (20% free S03 content by weight, Puritan Products, Inc., Philadelphia, PA, USA). To the stirred acid solution was gradually added 5.1 kg of the cross -linked poly-(styrene-co-divinylbenzene-co-lH-imidazolium chloride). After the addition, the reactor was flushed with dry nitrogen gas, the stirred suspension was heated to 90 degrees Celsius by pumping heated bath fluid through the reactor jacket, and the suspension was maintained at 90 degrees Celsius for approximately four hours. After completion of the reaction, the mixture was allowed to cool to approximately 60 degrees Celsius and the residual sulfuric acid mixture was drained from the reactor. The resin was washed with 80 wt% sulfuric acid solution, followed by 60 wt% sulfuric acid solution. Then the resin was washed repeatedly with distilled water until the pH of the wash water was above 5.0, as determined by pH paper, to yield the solid catalyst. The acid functional density of catalyst was determined to be at least 2.0 mmol H+ / g dry resin by ion-exchange acid-base titration.
Example 2
Production of Isosorbide from Sorbitol
[0255] This Example demonstrates the production of isosorbide from sorbitol using a catalyst with both acidic and ionic groups. The catalyst was prepared according to the procedure set forth in Example 1 above.
[0256] Sorbitol (30.0 g wet, 29.7 g dry, 163 mmol) at a moisture content of 1% and the catalyst from Example 1 (5.5 g wet, 2.7 g dry solids) were added to a 250 mL round bottom flask equipped with a magnetic stir bar and a vacuum distillation apparatus comprising a riser, a jacketed condenser, a descending elbow with a vacuum fitting, and a 500 mL round bottom flask collection vessel. The mixture was gradually heated to 130°C under vacuum (P = 10 Torr) with gentle mixing, resulting in a suspension of catalyst in a syrup with viscosity of 1,000-2,000 cP at 50 RPM. The walls of the 250 mL round bottom flask were maintained at 130 + 2 degrees Celsius using a temperature-controlled oil bath, and the condenser jacket was maintained at approximately 2 degrees Celsius using a circulator-chiller with bath fluid made from 50% ethylene glycol in distilled water.
[0257] At 30 minutes intervals, an approximately 250 mg sample of the reaction mixture was removed, dissolved in 15 mL of distilled water, and analyzed by HPLC to determine the conversion of sorbitol to sorbitans and isosorbide. FIG. 14 summarizes the % mole fraction of sorbitol, isosorbide, sorbitan, and 2,5-dianhydrosorbitol present in the reaction mixture over time. FIG. 15 depicts the HPLC trace of the reaction sampled at 1.5 h. FIG. 16 is the HPLC trace of the reaction sampled at 5.5 h. Yield data as a function of the reaction time are provided in Table 1. The results show sorbitol was converted to isosorbide with a yield of over 80% after 6 hours of reaction in the presence of the catalyst. The average catalyst activity was determined from the sorbitol conversion data to be k\ = 0.67 / hr, with a selectivity to isosorbide of 89% mol/mol. The viscosity of the product mixture was determined to be 550 - 650 cP at 50 RPM.
Table 1. Conversion of sorbitol and yield of conversion products as a function of time
0.0 hr 1.5 hr 4.0 hr 5.5 hr
Conversion of sorbitol 0% 66% 95% 96%
Yield to sorbitan 0% 36% 4% 1%
Yield to 2,5-dianhydrosorbitol 0% 12% 11% 9%
Yield to isosorbide 0% 18% 78% 80%
Example 3
Recovery of Catalyst Following Sorbitol Conversion
[0258] This example demonstrates quantification of catalyst recovery following the conversion of sorbitol to isosorbide described in Example 2.
[0259] Following the completion of the reaction as described in Example 2, approximately 30 mL of distilled water was added to the mixture to dilute the products. The solid catalyst was recovered from the resulting solution by vacuum filtration using a 5 fritted-glass funnel with a coarse frit. The catalyst was then washed twice with 30 mL of distilled water to recover additional soluble products from the solid catalyst. Filtration yielded approximately 2.7 g dry catalyst, indicating a quantitative mass recovery of the catalyst, to within experimental error.
Example 4
Recovery and Reuse of the Catalyst in Multiple Rounds of Converting Sorbitol to
Isosorbide
[0260] This Example demonstrates the retention of catalyst activity upon recovery and reuse in multiple reactions of converting sorbitol to isosorbide. The catalyst used in this Example was prepared according to the procedure set forth in Example 1 above. The reactions converting sorbitol to isosorbide were performed according to the procedure set forth in Example 2 above. Following each reaction, the catalyst was recovered according to the procedure set forth in Example 3 above. [0261] The same sample of catalyst was used in four reactions converting sorbitol to isosorbide. The first conversion was performed using a fresh sample of the catalyst, while in all subsequent reactions, the catalyst used was that which was recovered from the previous reaction cycle. In each reaction cycle, a fresh charge of reagent sorbitol was used. The catalyst activity as a function of re-use was determined as reported in Table 2. FIG. 17 is a graph comparing the catalyst rate constant over the four cycles of use. From these data, the loss of catalyst activity upon re-use was determined to be approximately 0.5% / cycle.
Table 2. Catalyst activity in multiple cycles of re-use
Reaction Initial Initial T Activity ki
Sorbitol Catalyst (°C) (1/hr)
(dry g) (dry g)
Cycle 1 29.7 2.7 130 0.669
Cycle 2 29.7 2.7 130 0.665
Cycle 3 29.7 2.7 130 0.664
Cycle 4 29.7 2.7 130 0.659

Claims

CLAIMS What is claimed is:
1. A method of producing an anhydrosugar alcohol from a sugar alcohol, comprising: combining a sugar alcohol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing an anhydrosugar alcohol from at least a portion of the reaction mixture.
2. The method of claim 1, further comprising: separating at least a portion of the catalyst from the anhydrosugar alcohol produced.
3. The method of claim 2, further comprising: combining the separated catalyst with additional sugar alcohol to form additional reaction mixture; and producing additional anhydrosugar alcohol from at least a portion of the additional reaction mixture.
4. The method of claim 2, further comprising: combining the separated catalyst with additional sugar alcohol; and dehydrating the additional sugar alcohol to produce additional anhydrosugar alcohol.
5. The method of any one of claims 1 to 4, wherein the sugar alcohol is a C6 sugar alcohol or a C5 sugar alcohol.
6. The method of any one of claims 1 to 5, wherein the sugar alcohol is an acyclic sugar alcohol or a monoanhydrosugar alcohol.
7. The method of any one of claims 1 to 6, wherein the sugar alcohol is hexitol.
8. The method of any one of claims 1 to 7, wherein the anhydrosugar alcohol produced is a dianhydrosugar alcohol.
9. The method of claim 8, wherein the dianhydrosugar alcohol is dianhydrohexitol.
10. A method of producing isosorbide from sorbitol, comprising: combining sorbitol with a catalyst to form a reaction mixture, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, or wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support; and producing isosorbide from at least a portion of the reaction mixture.
11. The method of any one of claims 1 to 10, wherein the catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone.
12. The method of claim 11, wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid.
13. The method of claim 10 or 11, wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group, at least one phosphorous -containing cationic group, or a combination thereof.
14. The method of any one of claims 1 to 13, wherein the catalyst comprises a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support.
15. The method of claim 14, wherein the solid support comprises a material, wherein the material is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and any combinations thereof.
16. The method of claim 14 or 15, wherein each acidic moiety independently has at least one Bronsted-Lowry acid.
17. The method of any one of claims 14 to 16, wherein each ionic moiety independently has at least one nitrogen-containing cationic group or at least one phosphorous-containing cationic group, or a combination thereof.
18. The method of any one of claims 1 to 17, wherein the catalyst has a catalyst activity loss of less than 1% per cycle.
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CN107722030A (en) * 2016-08-10 2018-02-23 中国科学院大连化学物理研究所 A kind of method for preparing dissident's sugar alcohol

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US20070173652A1 (en) * 2006-01-26 2007-07-26 Holladay Johnathan E Method of forming a dianhydrosugar alcohol
WO2014159558A1 (en) * 2013-03-14 2014-10-02 Midori Renewables, Inc. Polymeric ionic salt catalysts and methods of producing thereof
US20150005516A1 (en) * 2012-03-12 2015-01-01 Archer Daniels Midland Company Processes for making sugar and/or sugar alcohol dehydration products

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US20150005516A1 (en) * 2012-03-12 2015-01-01 Archer Daniels Midland Company Processes for making sugar and/or sugar alcohol dehydration products
WO2014159558A1 (en) * 2013-03-14 2014-10-02 Midori Renewables, Inc. Polymeric ionic salt catalysts and methods of producing thereof

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