WO2014175989A1 - Catalytic synthesis of reduced furan derivatives - Google Patents
Catalytic synthesis of reduced furan derivatives Download PDFInfo
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- WO2014175989A1 WO2014175989A1 PCT/US2014/031933 US2014031933W WO2014175989A1 WO 2014175989 A1 WO2014175989 A1 WO 2014175989A1 US 2014031933 W US2014031933 W US 2014031933W WO 2014175989 A1 WO2014175989 A1 WO 2014175989A1
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- alkoxymethylfurfural
- furan
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Definitions
- the present invention relates to catalytic synthesis of furan derivatives. More particularly, the invention pertains to furan derivatives obtained by use of a multifunctional catalyst system in controlled hydrogenation of alkoxymethylfurfural ethers or
- Biomass contains carbohydrates (hexoses and pentoses) that can be converted into industrial chemicals from renewable hydrocarbon sources.
- carbohydrates hexoses and pentoses
- the production of furan derivatives from biomass sugars promotes achieving sustainable energy supply and chemicals production.
- Agricultural raw materials such as starch, cellulose, sucrose or inulin are inexpensive starting materials for the manufacture of hexoses, such as glucose and fructose.
- the dehydration of fructose produces 2-hydroxymethyl-5-furfuraldehyde, also known as hydroxymethylfurfural which is abbreviated, HMF.
- the structure of HMF is shown below:
- HMF represents one key intermediate substance readily derived from renewable carbohydrates.
- One of the concerns with HMF is that it has limited uses as a chemical per se, other than as a source for making derivatives.
- HMF is rather unstable and tends to polymerize and/or oxidize with prolonged storage.
- HMF esters and ethers can be converted to various furan derivatives by hydrogenation.
- the present invention provides multifunctional catalyst systems and methods to convert esters or ethers of alkoxymethylfurfural to various furan derivatives in a controlled manner.
- the method involves hydrogenating a starting material containing at least one of an alkoxymethylfurfural ether or ester with hydrogen in the presence of a catalytic system under mild conditions to produce a reduced furan derivative.
- mild conditions means an operational temperature of less than 150°C, or more typically less than 100°C, and/or at a pressure of less than 1250 psi (86 bar).
- the method further involves hydrolyzing at least one of an ether or an ester bond, respectively, from the alkoxymethylfurfural ether or
- Figure 1 represents a general schematic of a series of inter-related
- HMF ethers hydrogenation reaction pathways for converting alkoxymethylfurfural esters or ethers to produce a variety of furan derivatives therefrom.
- One desirable derivative of HMF ethers is a partially reduced furan derivative in which the aldehyde moiety of HMF is converted to an alcohol.
- Furan derivatives produced after hydrolyzing at least one of an ether or an ester bond could then be used as chemicals or fuels, depending on the remaining functionality.
- a feature of the present method is that it enables direct synthesis of reduced furan derivatives from alkoxymethylfurfural esters or ethers, using a multifunctional catalyst system.
- a multifunctional catalyst system comprises one or more catalysts having a plurality of functionalities and may include a promoter.
- a particular advantage of this invention is that the alcohol or acid produced can be recovered and recycled. Recycling the recovered alcohol or acid comprises using the alcohol in a second reaction operable to form an
- FIG. 1 is a general schematic process illustrating various hydrogenation pathways of acyloxymethylfurfural and alkoxymethylfurfural derivatives.
- FIG. 2 is a pathway of an acyloxymethylfurfural or alkoxymethylfurfural ether to 2,5-dimethyltetrahydrofuran with the generation of an alcohol or acid.
- FIG. 3 depicts the molar yield differences from hydrogenation of 5- butoxymethylfurfural at three different reaction times.
- FIG. 4 shows the effect of a catalyst system concentration on the molar yield of furan derivatives according to an embodiment of the present method.
- FIG. 5 depicts results of inventive examples using 5-butoxymethylfurfural, showing the effect of promoter on the percent (%) area of products obtained in ethyl acetate at 65°C, 1 hour and 60 bar.
- FIG. 6 depicts bar charts showing results of inventive examples of
- FIG. 7 depicts the product distribution differences resulting from
- alkoxymethylfurfural ether and “HMF ether” are used interchangeably herein and refer to molecules that are more technically designated R-5' alkoxy methyl furfural ethers having the general structure:
- HMF ester acyloxymethylfurfural ester
- alkoxymethylfurfural ester alkoxymethylfurfural ester
- hydroxymethylfurfural ester refers to molecules that are more technically designated R-5' acyl methyl furfural esters having the general structure:
- R is an alkyl group that may be at least one of straight chained, cyclic or branched, having from 1 to 24 carbon atoms, and may also contain oxygen, nitrogen or sulfur.
- Some preferred alkyl groups are the CI to C5 alkyl moieties such as methyl, ethyl, n- propyl, i-propyl, i-butyl, n-butyl, i-amyl and n-amyl.
- methyl substituted HMF ethers can be synthesized from methanol derived from biomass gasification.
- the CI to C5 alkyl groups can be obtained from ethanol and fusel oil alcohols.
- Fusel oil is a distillation by-product of fermentations to make ethanol whose main
- n-butanol may be derived from the fermentation to make acetone/ethanol or from the catalytic condensation of ethanol.
- acyloxymethylfurfural esters are obtained in the product mixture, together with carbohydrates, alkyl levulinates, humins, and other, poorly characterized products.
- This complicated product mixture containing acyloxymethylfurfural ester can be a furan starting material for the hydrogenation according to the methods herein.
- a multifunctional catalyst system which, in operation, is able to selectively yield furan derivatives from complicated product mixtures containing at least one of alkoxymethylfurfural ether or acyloxymethylfurfural ester.
- Suitable furan starting materials containing alkoxymethylfurfural ethers for the present disclosure may contain varying levels of alkoxymethylfurfural ethers.
- the desired furan derivatives are obtained even in the presence of carbohydrates, alkyl levulinates, humins, and other, poorly characterized products in the furan starting material.
- a furan starting material containing as little as 5% alkoxymethylfurfural ether on a dissolved solids basis in the form of butoxymethylfurfural can be converted to a reduced furan derivative in high yield.
- Suitable furan starting materials containing acyloxymethylfurfural esters for the present disclosure may contain varying levels of acyloxymethylfurfural esters.
- the desired furan derivatives are obtained even in the presence of carbohydrates, alkyl levulinates, humins, and other poorly characterized products in the furan starting material.
- acyloxymethylfurfural ester on a dissolved solids basis in the form of acetoxymethylfurfural can be converted to a reduced furan derivative in high yield.
- furan derivatives may refer to a partially or a fully reduced alkyl furan including but not limited to: 2,5-dimethyl-tetrahydrofuran (DMTHF), (5- (butoxymethyl)furan-2-yl)methanol, 5 -methyl-2-butoxymethylfuran, 5 -methyl-2- butoxymethyltetrahydrofuran, 2,5-dimethylfuran, (5-(butoxymethyl)tetrahydrofuran-2- yl)methanol,2-(butoxymethyl)-5-(ethoxymethyl)furan, 2-(butoxymethyl)-5- (ethoxymethyl)tetrahydro furan, (5 -methylfuran-2-yl)methanol, (5 -methyltetrahydrofuran-2- yl)methanol, 2-(butoxymethyl)furan, 2-(butoxymethyl)tetrahydrofuran, 2-methylfuran, 2- methyltetrahydrofuran, (5-formylfuran-2-yl)
- an acyloxymethylfurfural ester such as (5-formylfuran-2- yl)methyl acetate (A)
- the by-products are (5-methyltetrahydrofuran-2-yl)methyl acetate (D) and (tetrahydrofuran-2-yl)methyl acetate (E).
- a feature of the present method is that it enables direct synthesis of furan derivatives from HMF esters or ethers, using a multifunctional catalyst system.
- a "multifunctional catalyst system” is a combination of catalysts of different functionalities and may include a promoter.
- a multifunctional catalyst system may include the use of catalysts, promoters or a combination thereof having several functionalities including but not limited to those of acid, base, hydrogenation, dehydration, ring opening, and combinations thereof with a furan starting material and conditions applied to generate reduced furan derivatives.
- a multifunctional catalyst system comprising a bifunctional catalyst or a combination of single catalysts having an acidic or an alkaline and hydrogenation functionality to synthesize furan derivatives from HMF esters or ethers.
- a bi- or multifunctionalized catalyst as used herein refers to catalysts that have two or more different functionalities and therefore are able to accelerate two or more different reactions, preferably the hydrogenation and the subsequent hydrolysis of the intermediate. This process may include the use of a multifunctional catalyst system having several functionalities including but not limited to those combining acid, base, hydrogenation, dehydration, ring opening and may include a promoter or combinations thereof.
- the multifunctional catalyst system includes at least one of the following: a bifunctional catalyst; a combination of single catalysts having an alkaline and hydrogenation functionality; a catalyst having several functionalities, including acid, base, hydrogenation, dehydration, ring opening, and may include a promoter or combinations thereof.
- the multifunctional catalyst system may include at least a heterogeneous catalyst or a
- the multifunctional catalyst system exhibits degrees of selectivities for desired furan derivatives, such as: a) 2,5 -dimethyl-tetrahydro furan of at least about 30%; b) (5-(butoxymethyl)tetrahydrofuran-2-yl) methanol of at least about 80%; c) (5- (butoxymethyl)furan-2-yl) methanol of at least about 30%; d) 2-(butoxymethyl)-5- methyltetrahydrofuran of at least about 30%; e) (5-(hydroxymethyl)tetrahydrofuran-2- yl)methyl acetate of at least about 85%; f) 5-methyltetrahydrofuran of at least about 25%.
- desired furan derivatives such as: a) 2,5 -dimethyl-tetrahydro furan of at least about 30%; b) (5-(butoxymethyl)tetrahydrofuran-2-yl) methanol of at least about 80%; c) (5- (but
- a catalyst for direct synthesis of reduced furan derivatives from HMF esters or ethers as used herein may include a transition metal of group VIII to XI.
- multifunctional catalyst systems that may be employed in the present process may include, for examples, Pd, Pt, Ru, or Ni, Cu-Cr, or different combinations of such metals.
- Platinum, palladium, rhodium, and ruthenium form highly active catalysts, which operate at lower temperatures and lower pressures of H2.
- Non-precious metal catalysts especially those based on nickel (such as Raney nickel and Urushibara nickel) have also been developed as economical alternatives, but they are often slower or require higher temperatures.
- One exemplary catalyst comprises a palladium on carbon support (Pd/C) catalyst with about 0.5- 10% palladium loading.
- the multifunctional catalyst system includes an alkaline promoter including but not limited to triethylamine, or an ion exchange resin of a polymer of unmodified 4-vinylpyridine residues and divinylbenzene residues.
- a promoter as used herein refers to a substance which enhances the
- the promoter can be a heterogeneous acid catalyst, which is a substrate comprising a solid material having an acidic group bound thereto.
- the solid material can be comprised of materials selected from acid clays, silicas, sulfated zirconia, molecular sieves, zeolites, ion exchange resins,
- heteropolyacids carbon, tin oxide, niobia, titania and combinations thereof.
- the substrate is a polymeric resin material such as polystyrene.
- the ion exchange resin may also be a sulfonated divinylbenzene/styrene copolymer resin.
- Some of these resin based catalysts are ordinarily used for cation exchange chromatography. Perhaps the most common acid group for cation exchange resins and other heterogeneous acid catalyst is a sulfonic group. Suitable heterogeneous acid catalysts containing a sulfonic group are AmberlystTM and AmberliteTM, DianionTM, and LewatitTM. Examples include
- AmberlystTM 35, AmberlystTM 15, AmberlystTM 36, AmberlystTM 70, XN1010, IRC76, and XE586 (Rohm & Haas), RCP21H (Mitsubishi Chemical Corp.), DowexTM 50WX4 (Dow Chemical Co.), AG50W-X12 (Bio-Rad), and LewatitTM S2328, LewatitTM K2431, LewatitTM S2568, LewatitTM K2629 (Bayer Corporation), HPK25 (Mitsubishi), Nafion-50 (DuPont).
- Other acid groups bound to substrates may also be used as the promoter. Suitable examples of other promoters include CRP-200 phosphonic/polystyrene (Rohm & Haas).
- the multifunctional catalyst system includes an acidic promoter that is at least one of a homogeneous acid, heterogeneous acid, a mineral acid, and/or an organic acid.
- the acidic promoter may comprise a homogeneous catalyst, such as a mineral acid. Suitable mineral acid catalysts include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like.
- the acidic promoter may also comprise an organic acid including but not limited to p-toluenesulfonic acid, trifluoroacetic acid, levulinic acid, and p- methanesulfonic acid.
- the catalyst may contain a metal that is Pt, Pd, or Ni;
- the metal may be added to the reaction mixture for producing furan derivatives as a heterogeneous particulate powder.
- the metal is bound to a substrate forming a heterogeneous metal catalyst substrate.
- Typical substrates include, but are not limited to kieselguhr, diatomaceous earth, silica and polymeric resin materials.
- One exemplary metal catalyst is represented by G-69BTM, available from Sud-Chemie, (Louisville, KY) which is a powdered catalyst having an average particle size of 10-14 microns containing nominally 62% Nickel on kieselguhr, with a Zr promoter.
- Other suitable catalysts containing Ni include, but are not limited to, sponge nickel and G-96BTM also available from Sud-Chemie Corp.
- G-96BTM is a nickel on silica/alumina, 66% nickel by weight, particle size 6-8 microns.
- Another preferred nickel catalyst is G-49BTM available from Sud-Chemie Corp. Particle size is 7-11 microns and 55% nickel by weight.
- Another preferred catalyst is palladium on carbon, exemplified by the catalyst Pd/C.
- G22/2TM also available from Sud-Chemie Corp.
- G22/2TM is barium promoted copper chromite catalyst, 39% Cu and 24% Cr.
- Other suitable catalysts containing Cu include, but are not limited to, sponge copper available from Johnson Matthey.
- the catalyst can be a platinum catalyst, exemplified by the catalyst Pt/C.
- Carbon-supported, zirconia-supported or zeolite-supported metal catalysts are also envisioned as workable multifunctional catalyst systems with the present method.
- the promoter and the hydrogenation catalyst are provided on the same substrate, forming a heterogeneous bifunctional catalyst.
- exemplary catalysts of this nature include AmberlystTM CH10 and CH28, each available from Rohm and Haas Company (Midland, MI).
- AmberlystTM CH10 is a macroreticular palladium metal hydrogenation resin containing sulfonic acid as the acid promoter component.
- AmberlystTM CH28 is a macroreticular styrene DVB copolymer palladium doped hydrogenation resin also containing sulfonic acid as the acid promoter component.
- LewatitTM K7333 catalyst available from Lanxess (Germany) is a palladium-doped polymer based resin containing trialkyl ammonium groups in OH-form.
- the present invention utilizes these exemplary resins as multifunctional catalyst systems for an efficient one pot conversion of furan starting materials under mild conditions to produce a plurality of furan derivatives.
- the hydrogenation reactions of the present method can be performed under relatively mild conditions over a wide range of temperatures and pressures.
- "mild conditions” refers to certain operational parameters within a reactor in which operational temperatures do not exceed about 150°C and/or pressures do not exceed about 1,230 psi (-85 bar). In a preferred practice, the temperature is usually 150°C and the pressure is less than 1230 psi. The only upper limitation on pressure is what the reactor can bear so higher pressures can be used if desired.
- the reaction can be conducted at an operational temperature within a range from, for instance, ambient room temperature of about 18°C to 20°C, up to about 130°C, and at a minimal pressure of about 85 psi (-5.8 bar) up to about 1,015 psi (-70 bar), or any combination of temperatures and pressures therein between.
- the reactions have an operational temperature of less than or equal to 100°C, at a pressure of less than or equal to 950 psi (-65.5 bar).
- the operational temperature of the reaction is within a range from 25°C - 95°C and the operational pressure is from about 90 psi - 950 psi (e.g., about 88°C, and about 940 psi (-65 bar)).
- the operational pressure is from about 90 psi - 950 psi (e.g., about 88°C, and about 940 psi (-65 bar)).
- alkoxymethylfurfural ether or ester at a temperature in a range from about 60°C to about 98°C, and at a pressure in a range from about 290 psi (-20 bar) to about 895 psi (-62 bar) to obtain a furan derivative.
- the hydrogenation reactions can be executed at an operational temperature in a range from about 20°C to 88°C or any combination therein. Particular examples may operate at temperatures in a range from about 40°C to about 85°C (e.g., about 50°C or 55°C to about 75°C or 80°C).
- the operational pressure within the reactor is within a range from about 100 psi to about 940 psi.
- Particular examples may operate in between about 20 bar and about 895 psi (-62 bar), typically in a range from about 300 psi (-20.7 bar) or 320 psi (-22.1 bar) to about 875 psi (-60.3 bar) or about 880 psi (-60.7 bar).
- Some embodiments may operate at pressures between about 500 psi (-34.5 bar) or 725 psi (-50 bar) and about 885 psi (-61 bar).
- Other temperatures may be within a range, for example, from about 35°C to
- 92°C, and other operational pressures may be within a range, for example, from about 130 psi to 900 psi.
- the time can be suitably determined by taking into account the reaction conditions, the scale of the reaction, the multifunctional catalyst system, and the like.
- the hydrogenation reactions can be run for a predetermined time period, such as about 1 hour, up to about 5 or 6 hours or longer.
- the reaction is performed at conditions that will allow one a degree of control in the reduction of the molecule, without having to heat the starting materials to high temperatures (i.e., > 150°C).
- high temperatures i.e., > 150°C.
- hydrogenation reactions have been carried out under stringent conditions at high temperatures and pressures resulting in the formation of a plethora of products.
- an efficient, practicable process for selective hydrogenation, using a catalyst with sufficient activity and selectivity would be a substantial contribution to the art.
- controlled manner means the adjustment of reaction conditions, such as temperature, pressure, time, and/or multifunctional catalyst system to achieve high selectivity of a reduced furan derivative from a furan starting material containing at least one of the alkoxymethylfurfural ether and acyloxymethylfurfural ester and simultaneously to suppress inter-related hydrogenation reaction pathways.
- the furan starting material comprises at least butoxymethylfurfural, and a portion of the starting material is converted to a reduced furan derivative.
- the difference in conditions for obtaining at least one of the fully reduced furan derivative (7) and the reduced furan derivative 6 is the multifunctional catalyst system. Under an exemplary reaction at 25-60°C, 6 to 10 bar H2, with at least one of the
- the dominant product will be the fully reduced furan derivative 7 in 30 min to 2 hours of reaction time.
- the choice of metal loading for each hydrogenation catalyst, with or without a promoter, may also control selectivity of reduced furan derivatives.
- the metals may be present in various forms (e.g., elemental, metal oxide, metal hydroxides, metal ions etc.).
- the metal(s) at a surface of a support may constitute from about 0.25% to about 10% of the catalyst weight.
- DMTHF (6) of at least
- alkoxymethylfurfural ether or acyloxymethylfurfural ester is contacted with H2, and a multifunctional catalyst system comprising a homogeneous acidic promoter and a hydrogenation catalyst.
- a multifunctional catalyst system comprising a bifunctional catalyst and/or a combination of an heterogeneous acid catalyst promoter with a hydrogenation catalyst at a temperature of between 25 and 100°C and a pressure of between about 6 to 60 bar for a time of between 1 to 2 hours produces DMTHF at least about 70% selectivity.
- the temperature is 60°C
- the pressure is 60 bar
- the time is 1 hour.
- the selectivity of the reaction can be controlled by loading of the
- the method enables one to selectively reduce HMF ethers to produce furan derivatives including but not limited to substituted furan, substituted tetrahydro furan or tetrahydrofuran compounds. Ring- opened products including hexanediols may also be formed.
- the ability to simplify in one step the reduction and collection of the product can increase synthesis efficiency and save recovery costs.
- Another advantage of the present process is that a catalyst system can be separated from the reaction mixture in a simple manner and recycled to be optionally used again.
- a palladium catalyst fixed on an ion-exchange resin is hardly deactivated because palladium metal is fixed on a matrix of the ion-exchange resin, and handling in recovery and reuse of such catalysts is extremely easy because the relative particle size of catalyst is very large.
- an ability to convert an HMF ether or ester containing starting material to furan derivatives can be adopted to be processed by methods such as a continuous flow system, semi-batch reactions, or batch reactions according to embodiments of the present invention.
- this reaction can be carried out batch wise or continuously in a fluidized bed, tubular reactor, column, or pipe.
- the process may involve the selective synthesis of a number of derivatives disclosed by simply changing the scale of the reaction, the reaction conditions, the catalyst system employed, and the like.
- Several reactors may be in line and the selectivity of product may be controlled by the switch of a valve or change in temperature, time or pressure.
- the method described herein is not limited to batch reactions, but can be performed as a continuous process.
- Table 1 provides a list of reference numbers, as used herein, for the various furan starting materials and furan derivatives in generic terms as shown in Figure 1.
- a fully reduced furan derivative (7) species is formed with greater than 90% selectivity when the hydrogenation is conducted with a multifunctional catalyst system comprising palladium catalyst on carbon support (e.g., ⁇ 5% Pd/C) in the presence of a alkaline resin (e.g.,
- Reaction mixtures were prepared as described below and introduced into at least one of a 100 mL MC Series Stirred Reactor (Pressure Products Industries, Warminster, PA) or a Multi-reactor system (Parr Industries, Moline, IL) with solvent and multifunctional catalyst system added.
- the vessel was purged with hydrogen (4X500 psi) with stirring (625 rpm).
- the vessel was then pressurized and heated to the desired temperature with continual stirring. After a set time, the reaction was allowed to cool to room temperature, the remaining hydrogen gas was removed, the vessel was returned to ambient pressure, the vessel was opened, the contents removed and the catalyst collected by vacuum filtration.
- compositional analysis shows that 1 ,4-dioxane provided higher selectivity of the fully reduced furan derivative (7a) as compared to the EtOAc solvent (Table 2, entry 4).
- BMF was converted with 20% selectivity to the partially reduced BMF (2a) and 78% selectivity to 7a (Table 2, entry 5).
- Table 2 Effect of alkaline promoters on BMF conversion.
- Entry 4 is performed in 1 ,4-dioxane.
- multifunctional catalyst system comprising 10% Pd/C catalyst loading of 0.5 g per g BMF in the presence of H2S04 promoter (0.08 g per g BMF).
- the selectivity for the furan derivative DMTHF (6) rose from 33% to 41% and the selectivity for MTHF alcohol butyl ether (4a) rose from 29% to 45%.
- a longer reaction time of 120 min in EtOAc solvent provided an even higher 55% product selectivity for the furan derivative DMTHF.
- the furan derivative MTHF alcohol butyl ether (4) was generated at 43% selectivity.
- Furan derivatives were synthesized from a representative
- acyloxymethylfurfural ester 5-acetoxymethylfurfural (AcMF, lb)
- AcMF was a commercial product obtained from Sigma-Aldrich.
- Examples 37 - 40 The multi-reactor system was used with a series of reactions using multifunctional catalyst systems comprising either 5% Pd/C or 10% Pd/C (0.1 g per g AcMF) in either EtOAc of 1 ,4-dioxane and AcMF with PuroliteTM D-5149 (0.3 g per g of AcMF), 7 bar hydrogen pressure and temperatures varied.
- the product selectivities were significantly affected by varying multifunctional catalyst systems, reaction times, and temperatures (Table 5).
- the highest selectivity of the fully reduced derivative of AcMF (7b) was 94% using 5% Pd/C with heating to 60°C for 1 hour.
- Promoter is Purolite D-5149 resin (0.3 g per g of AcMF) at 7 bar, Pd/C catalyst (0.1 g per g AcMF). Experiments were performed in EtOAc except entry 39. [0067] Although the examples presented herein describe a multifunctional catalyst system that employs Pd catalysts, various other catalyst systems, such as nickel, platinum, ruthenium, or copper can also be used and may include an alkaline or acidic promoter.
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BR112015026740A BR112015026740A2 (en) | 2013-04-25 | 2014-03-27 | method for synthesizing furan derivatives, and method for preparing furan derivatives |
EP14787760.9A EP2989094A4 (en) | 2013-04-25 | 2014-03-27 | Catalytic synthesis of reduced furan derivatives |
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WO2017065980A1 (en) * | 2015-10-13 | 2017-04-20 | Archer Daniels Midland Company | Preparation of a sugar-derived ester, glycol and polymers therefrom |
CN114573527A (en) * | 2022-03-11 | 2022-06-03 | 湖南师范大学 | Method for preparing 2, 5-dihydroxymethyl furan by transfer hydrogenation of 5-hydroxymethylfurfural |
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- 2014-03-27 JP JP2016510677A patent/JP2016522184A/en active Pending
- 2014-03-27 WO PCT/US2014/031933 patent/WO2014175989A1/en active Application Filing
- 2014-03-27 MX MX2015014835A patent/MX2015014835A/en unknown
- 2014-03-27 US US14/781,524 patent/US20160052902A1/en not_active Abandoned
- 2014-03-27 BR BR112015026740A patent/BR112015026740A2/en not_active IP Right Cessation
- 2014-03-27 EP EP14787760.9A patent/EP2989094A4/en not_active Withdrawn
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Cited By (2)
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WO2017065980A1 (en) * | 2015-10-13 | 2017-04-20 | Archer Daniels Midland Company | Preparation of a sugar-derived ester, glycol and polymers therefrom |
CN114573527A (en) * | 2022-03-11 | 2022-06-03 | 湖南师范大学 | Method for preparing 2, 5-dihydroxymethyl furan by transfer hydrogenation of 5-hydroxymethylfurfural |
Also Published As
Publication number | Publication date |
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EP2989094A1 (en) | 2016-03-02 |
BR112015026740A2 (en) | 2017-07-25 |
JP2016522184A (en) | 2016-07-28 |
MX2015014835A (en) | 2016-03-11 |
CN105143211A (en) | 2015-12-09 |
EP2989094A4 (en) | 2016-11-02 |
US20160052902A1 (en) | 2016-02-25 |
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