* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
General procedure: Esterification of levulinic acid was carried out in a 50mL round bottom flask equipped with a reflux condenser. In a typical catalytic reaction the catalyst (40mg) was added to a mixture of levulinic acid and ethanol with the molar ratio of LA: alcohol=1:8 (ethanol acts as reagent cum solvent) and the mixture was magnetically stirred at 333K for 2h. A portion of the reaction mixture was separated after the scheduled reaction time through filtration and the filtrate was then analyzed through the gas chromatography (GC) equipped with a flame-ionized detector and a capillary column. All compounds were characterized on the basis of their spectroscopic data (1H NMR) and by comparison with those reported in the literature.
Reference：
[1] RSC Advances, 2016, vol. 6, # 3, p. 2106 - 2111
[2] Journal of the American Chemical Society, 1930, vol. 52, p. 4883
[3] Journal of the American Chemical Society, 1933, vol. 55, p. 3393
[4] Patent: US2029412, 1934, ,
[5] Journal fuer Praktische Chemie (Leipzig), 1955, vol. <4> 1, p. 153,154
[6] Patent: WO2010/102203, 2010, A2, . Location in patent: Page/Page column 26-27
[7] Green Chemistry, 2014, vol. 16, # 2, p. 785 - 791
[8] Journal of Molecular Catalysis A: Chemical, 2017, vol. 426, p. 30 - 38
[9] Applied Catalysis A: General, 2017, vol. 547, p. 237 - 247
[10] Catalysis Today, 2018, vol. 309, p. 253 - 262
Reference：
[1] Green Chemistry, 2014, vol. 16, # 2, p. 785 - 791
5
[ 71-23-8 ]
[ 57-50-1 ]
[ 1917-66-4 ]
[ 645-67-0 ]
Yield
Reaction Conditions
Operation in experiment
65 %Spectr.
at 180℃; for 40 h;
1.8 g of sucrose,0.361 g of SnCl4, 0. 058 g of BF3?, 20? Of n-propanol were added to 50 mLStainless steel-lined reactor with Teflon,Heated to 180 ° C,The reaction was carried out at that temperature for 40 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 89percent. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,Propoxyl methyl furfural and propyl propionate)The retention times in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was determined by 4 NMR,The product distribution results are:5-propoxymethylfurfural was 65percent,HMF was 0percent and propyl levulinate was 35percent.
1.8 g of sucrose,0.271 g of GeCl4, 0.091 g of BBr3, and 20 mL of n-propanol were added to 50 mL of a polyTetrafluoroethylene-lined stainless steel reactor,Heated to l00 ° C,The reaction was carried out at that temperature for 10 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 83percent. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,5-propoxymethylfurfural and propyl propionate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was confirmed by 1H NMR,The product distribution results are:5-propoxymethylfurfural was 72percent, HMF was 9percentPropyl propionate was 19percent
After mixing 50 grams of furfuryl alcohol, 375 grams of propanol, 10 grams of water, and 20 grams of SO42- / MxOy super strong acid, the reaction is carried out at a temperature of 80 C, and the stirring speed is controlled to 600 rpm, the condensation reflux temperature is 20 C, the reaction After 5 hours, after the temperature was lowered to room temperature, the catalyst was removed by filtration, and the propanol in the reaction mixture was distilled off under reduced pressure at 45 C to obtain light yellow propyl levulinate, which was analyzed by high performance liquid chromatography, the conversion rate of furfuryl alcohol and acetyl The yields of propyl propionate were 100% and 97.76%, respectively, and the yield was 97.76%.
sulfuric acid; In n-propyl levulinate; water; at 120℃; for 2.95h;
Example 7; A 2 L two-neck flask equipped with a magnetic stir bar, a Dean-Stark trap, and a thermocouple was charged with 232.52g (2.002mol) levulinic acid (obtained from the Langfang Triple Well Chemicals Company, Ltd. of Langfang City, HeBei, China), 241.52g (4.019 mol) n-propanol (>;99.8%, obtained from the Sigma-Aldrich Company of St. Louis, MO), 600 mL toluene, and 2 mL cone, sulfuric acid. The reaction was heated on a heating mantle to reflux. After refluxing overnight, total amount of 42.7 mL of water was collected and removed from the Dean-Stark trap. The reaction flask was allowed to cool to room temperature. Then 100 g basic alumina (obtained from the Sigma-Aldrich Company of St. Louis, MO) was added to the reaction solution and stirred for about 80 minutes. The solids were then filtered off, and the filtrate was concentrated on a rotary evaporator with the filtrate in a flask immersed in an oil bath set to 750C and 15 Torr vacuum to remove toluene and n- propanol. The residue was distilled on the rotary evaporator in a flask immersed in an oil bath set to 110-120C and 15 Torr vacuum to yield 284.48 g colorless liquid in the catch flask. The product was determined by GC-MS to be 99.51% n-propyl levulinate.The procedure of Example 1 was used to generate a profile of boiling points using n-propanol and n-propyl levulinate. The measured boiling points are shown in Table 3.Table 3. Boiling points of n-propanol/n-propyl levulinate mixtures. A 500 niL four-neck flask was equipped with a magnetic stir bar, a dropping funnel, a condenser, and a thermocouple. The flask was charged with 100.02g (0.632mol) n-propyl levulinate (synthesized from levulinic acid as described above), 16.48g (0.274mol) n-propanol, 1.463 mL deionized water, and 0.575 mL cone, sulfuric acid. The mixture was heated with a heating mantle to a temperature at 1200C. A mixture of 49.07g (0.495mol) furfuryl alcohol (99%, obtained from Acros Organics of Geel, Belgium) and 43.06g (0.716 mol) n-propanol was added to the reaction mixture dropwise over about 117 minutes. The reaction was refluxed for additional 1 hour after addition was complete. Then the reaction flask was allowed to cool to room temperature. The crude reaction mixture appeared to be homogeneous, with no insoluble or phase-separated material observed. About 50.1O g of the reaction mixture was transferred to a 250 mL flask and distilled using a Kugelrohr apparatus at about 4-8 Torr and an air bath temperature of up to about 1790C.After distillation, total amount of undistillable solid left in the flask was 1.16 g, which contained 0.25 g sulfuric acid and 0.91 g of a tarry residue. Ratio of the amount of tarry residue formed in the reaction to the amount of furfuryl alcohol added was 7.8%. GC-MS analysis of the crude reaction product was carried out as for Example 2 and showed that n-propyl levulinate was present at 99.1%.
With silica-alumina; at 180℃;
General procedure: The catalytic activity experiments were conducted in a fixed bed quartz reactor (14 mm id and 280 mm length)at atmospheric pressure. In each catalytic experiment, 250 mg of catalyst is diluted with equal amount of quartz particles and placed at the centre of the reactor. Priorto the reaction, the catalyst was flushed in a N2 flow of1800 mL h-1 at 180 C for 1 h. The liquid feed withrequired molar ratio of FAL to alcohol was continuouslyfed at a liquid hour space velocity (LHSV) of 1 h-1 usinga feed pump (M/s. B. Braun Co., Germany). Unless otherwisespecified the reaction conditions are same. The liquidproduct mixture was collected in an ice cold trap andanalyzed at regular intervals. This product mixture wasanalyzed by a flame ionization detector (FID) equippedgas chromatograph, GC-17A (M/s. Shimadzu Instruments,Japan) with EB-5 capillary column (30 m × 0.53 mm ×5.0 μm) and the product components were confirmed byusing GC-MS, QP-2010 (M/s. Shimadzu Instruments, Japan) with EB-5 MS capillary column (30 m × 0.25 mm× 0.25 μm).
With zeolite HZSM-5 (SAR95) catalyst; for 6h;Reflux;
In a typical procedure, the alcoholysis of furfuryl alcohol was performedin a liquid phase batch reaction under magnetic stirring at thedesired temperature. The required molar composition of furfuryl alcoholand butanol, and the catalyst (with respect to the total reactants) weretaken in a 25 mL round bottom flask connected to a condenser. Thereaction of furfuryl alcohol was also conducted with other alcohols witha similar procedure under reflux conditions. The samples of the reactionmixture were periodically collected and quantitatively analyzed by gaschromatography (GC) (Agilent Technologies 7820A) equipped with HP-5 capillary column (0.25 mm I.D., 30 m length) coupled with the flameionization detector. The identity of the products was confirmed by Gaschromatography mass spectrometry (GCMS). The furfuryl alcohol conversionand butyl levulinate selectivity were determined using theexternal standard method in the GC.
General procedure: In a typical procedure, levulinic acid (14.7mmol, 1.0 eq.), ionic liquid(0.01-1.0 eq.) and alcohol (1.0-3.0 eq.) were placed in a round bottomed flask, equipped with a magnetic stirring bar. The mixture was stirred vigorously under pre-set reaction conditions (750 rpm,5-120 h, at 0, 25, 50 or 100 C). The progress of the reaction was monitoredby GC and TLC analyses. In most cases, a biphasic system wasformed, and the upper organic phase, containing excess of alcohol andester, was decanted. In a few cases of incomplete separation of the organicphase, the esters were isolated by extractionwith hexane or chloroform.The excess alcohol (and solvent, if used) was evaporated underreduced pressure. The procedure for cetyl levulinate synthesis, required dissolution of the solid cetyl alcohol in diisopropyl ether before reaction.
With sulfuric acid; In toluene;Reflux;
Example 7; A 2 L two-neck flask equipped with a magnetic stir bar, a Dean-Stark trap, and a thermocouple was charged with 232.52g (2.002mol) levulinic acid (obtained from the Langfang Triple Well Chemicals Company, Ltd. of Langfang City, HeBei, China), 241.52g (4.019 mol) n-propanol (>;99.8%, obtained from the Sigma-Aldrich Company of St. Louis, MO), 600 mL toluene, and 2 mL cone, sulfuric acid. The reaction was heated on a heating mantle to reflux. After refluxing overnight, total amount of 42.7 mL of water was collected and removed from the Dean-Stark trap. The reaction flask was allowed to cool to room temperature. Then 100 g basic alumina (obtained from the Sigma-Aldrich Company of St. Louis, MO) was added to the reaction solution and stirred for about 80 minutes. The solids were then filtered off, and the filtrate was concentrated on a rotary evaporator with the filtrate in a flask immersed in an oil bath set to 750C and 15 Torr vacuum to remove toluene and n- propanol. The residue was distilled on the rotary evaporator in a flask immersed in an oil bath set to 110-120C and 15 Torr vacuum to yield 284.48 g colorless liquid in the catch flask. The product was determined by GC-MS to be 99.51% n-propyl levulinate.The procedure of Example 1 was used to generate a profile of boiling points using n-propanol and n-propyl levulinate. The measured boiling points are shown in Table 3.Table 3. Boiling points of n-propanol/n-propyl levulinate mixtures. A 500 niL four-neck flask was equipped with a magnetic stir bar, a dropping funnel, a condenser, and a thermocouple. The flask was charged with 100.02g (0.632mol) n-propyl levulinate (synthesized from levulinic acid as described above), 16.48g (0.274mol) n-propanol, 1.463 mL deionized water, and 0.575 mL cone, sulfuric acid. The mixture was heated with a heating mantle to a temperature at 1200C. A mixture of 49.07g (0.495mol) furfuryl alcohol (99%, obtained from Acros Organics of Geel, Belgium) and 43.06g (0.716 mol) n-propanol was added to the reaction mixture dropwise over about 117 minutes. The reaction was refluxed for additional 1 hour after addition was complete. Then the reaction flask was allowed to cool to room temperature. The crude reaction mixture appeared to be homogeneous, with no insoluble or phase-separated material observed. About 50.1O g of the reaction mixture was transferred to a 250 mL flask and distilled using a Kugelrohr apparatus at about 4-8 Torr and an air bath temperature of up to about 1790C.After distillation, total amount of undistillable solid left in the flask was 1.16 g, which contained 0.25 g sulfuric acid and 0.91 g of a tarry residue. Ratio of the amount of tarry residue formed in the reaction to the amount of furfuryl alcohol added was 7.8%. GC-MS analysis of the crude reaction product was carried out as for Example 2 and showed that n-propyl levulinate was present at 99.1%.
With tungsten oxide doped mesoporous silica-16 catalyst; at 250℃;Inert atmosphere; Flow reactor;
General procedure: The catalytic activity tests were conducted in fixed bed down flow reactor (14 mm id and 300 mm length) at atmospheric conditions. In a typical experiment about 0.5 g of the catalyst was mixed with same amount of quartz particles and sandwiched between two plugs at the centre of the reactor. Before the catalytic run, the catalyst was preheated in N2 flow (30 mL min-1)at 250C for 1 h. The liquid feed with required molar ratio of levulinic acid and alcohol was fed at a flow rate of 1 mL/h using syringe feed pump (M/s. B. Braun, Germany). The product mixture collected from an ice cooled trap was analyzed by FID equipped GC-17A (M/s. Shimadzu Instruments, Japan) with EB-5 capillary column (30 m × 0.53 mm × 5.0 m) and confirmed by GC-MS, QP-2010 (M/s. Shimadzu Instruments, Japan) with EB-5 MS capillary column (30 m × 0.25 mm × 0.25 m).
With heteropoly acid on silicalite 1 possesing intracrystalline nanovoids; at 100℃; for 5h;Catalytic behavior;
The esterification reaction was carried out in a double-necked RBflask fitted with a reflux condenser and CaCl2 tube. 50 mmol of LA and250 mmol of alcohol were taken in the RB flask and then heated todesired temperature using a silicone oil bath fitted with digital temperaturecontroller and stirrer. After achieving the desired temperature,the weighed quantity of catalyst was added into the mixture. Beforeaddition, the catalyst was pre-activated at 200 C for 2 h under nitrogenflow and then cooled down to room temperature in a desiccator.Quantification of levulinic acid present in reaction mixture was done byusing a gas chromatograph (Shimadzu GC 2010 plus, RTX-1 capillarycolumn, length 30 m, 0.32 mm ID, film thickness 0.5 μm) by internalstandard method. n-Nonane was used as an internal standard and it wasadded into the reaction mixtures after completion of the reaction. Theproducts were confirmed by gas chromatograph coupled with massspectrometer (Perkin Elmer, Clarus 680 Clarus 600 (Electron ionization).The propanol ester of LA, propyl levulinate was isolated by thefollowing procedure: The reaction mixture after filtration of the catalyst was added into 15 ml dichloromethane followed by washing with 50 mlwater. The washing was repeated for three times. After washing, thecontents were dried using MgSO4 and then propyl levulinate was separatedby evaporating the solvent using a rotary evaporator. Thestructure of the product, propyl levulinate was confirmed by 1H and 13CNMR spectra (Bruker FT-NMR 400 MHz) and GC-MS analysis. Turnoverfrequency (TOF) was calculated using the following formula under theconditions which give less than 50% conversion of LA as mentionedbelow:TOF =Number of moles of acid sites/(moles of LA converted × reactiontime in hours)Conditions for measuring TOF values: Catalyst = HPA/Sil-1,temperature = 100 C, 1-propanol/LA mole ratio= 5, catalystweight = 50 mg, reaction time = 5 h, conversion =46%;Catalyst = HPA/Sil-1, temperature = 100 C, 1-propanol/LA moleratio = 5, catalyst weight =100 mg, reaction time = 5 h, conversion= 31%.
88%Chromat.
With caesium carbonate; In toluene; for 2h;
General procedure: Esterification of levulinic acid was carried out in a 50mL round bottom flask equipped with a reflux condenser. In a typical catalytic reaction the catalyst (40mg) was added to a mixture of levulinic acid and ethanol with the molar ratio of LA: alcohol=1:8 (ethanol acts as reagent cum solvent) and the mixture was magnetically stirred at 333K for 2h. A portion of the reaction mixture was separated after the scheduled reaction time through filtration and the filtrate was then analyzed through the gas chromatography (GC) equipped with a flame-ionized detector and a capillary column. All compounds were characterized on the basis of their spectroscopic data (1H NMR) and by comparison with those reported in the literature.
87.9%Chromat.
With divinylbenzene-triallylamine-based porous organic polymer functionalized with sulfonic acid; at 115℃; for 2.33333h;
General procedure: Catalytic experiments were performed in 10ml round-bottomflask, which was coupled with a reflux condenser usingthe following general procedure. Typically, the PDVTASO3Hcatalyst was added into the mixture of levulinic acid(LA, 10mmol) and n-butanol (100mmol). Then the reactionstarted at the desired reaction temperature for a certaintime. After reaction, the reaction mixture was cooled downto room temperature. The products were analyzed quantitativelyby Shimadzu GC-2014 gas chromatograph (GC).The gas chromatograph was equipped with a HP-5 capillarycolumn (30m length, 0.32mm internal diameter, 0.50mfilm thickness) and a fame ionization detector (FID). Thetemperatures of the injection port, the oven and the detectorwere set to 250C, 180C, and 250C, respectively. Themixture in the reaction solution was detected by GC-MS, a Shimadzu GC system equipped with a capillary (30mlength, 0.32mm internal diameter, 0.25m film thickness).
With O40PW12(3-)*6H2O*1.5Sn(2+); at 59.84℃; for 6h;
General procedure: The catalytic reactions were carried in a glass reactor (50 mL) fittedwith a refllux condenser and sampling septum. The solutions weremagnetically stirred and heated in an oil bath. Typically, the solid acidcatalyst (ca. 0.6 mol %) was added to the solution of the alkyl alcohol(ca. 144 mmol) and heated at the reaction temperature. Afterward, theLA (ca. 8 mmol) was added, and the reaction was started, being monitoredby GC analyses of the samples collected at regular time intervals(Shimadzu 2014 plus GC, FID, CP-WAX capillary chromatographic column(25 m ×0.32 mm x0.30 μm).Dodecane was internal standard (ca. 0.1 mL). The plotting of GC peakareas of the substrate and main products in their calibrating curvesallowed calculating the conversion and the checking the reaction massbalance.
With phosphotungstic acid encapsulated within hyper-cross linked hollow microporous polylactide-b-polystyrene polymer nanospheres; In N,N-dimethyl-formamide; at 120℃; for 4.5h;
General procedure: All catalysts were dried in a 110 C oven for 2 h before use and allcatalytic reactions were carried out in a 10 mL two-neck flask connectedto a reflow device with a water separator. Briefly, 0.9 mol% HPWcatalyst, 1 mmol acetic acid, 1.5 mmoL n-butanol and 1.5 mL toluenewere added to the reaction bottle, and reflux stirred at 110 C for 4 h.The yield was calculated by GC analysis. The catalyst was washed threetimes with ethanol and placed in a 100 C oven overnight for the nextcycle. In addition, the other specific esterification reaction conditionsare as shown in the Table 1.
With HY-6; at 150 - 160℃; under 15001.5 Torr; for 20h;Autoclave; Inert atmosphere;
General procedure: A 50 ml autoclave (Microclave reactor from Autoclave Engineers) was charged with 250 mg glucose, 150 mg of one of the catalysts: HY 2.6, HY 6, HY 30, Hbeta 12.5, Hbeta 19, Hbeta 150, and HZSM-5 (purchased from Zeolyst International, USA) and 10 mL solvent (methanol, ethanol, propanol or butanol) and then pressurized with argon (20 bar). The autoclave was heated to 160 C and the stirring was started at 300 rpm once the temperature reached 150 C. After 20 hours of stirring, the autoclave was quenched withcold water and 50 mg naphthalene (internal standard) added to the reaction mixture and the content thereafter analyzed. Aliquots of the reaction mixtures were subjected to GC-FID analysis (Agilent 6890N instrument, HP-S capillary column 30.0 m x 320 pm x 0.25 pm). The reaction mixtures were also analyzed by HPLC with RI detection (Agilent 1200 series, 30 cm Aminex HPX-87H column, 0.005 M aqueous sulfuric acid solution as eluent at a flowrate of 0.6 mI/mm). An Agilent 6850 GC system coupled with an Agilent 5975C mass detector was used for qualitative analysis. Sugar conversions to levulinic acid esters were determined by HPLC. The amounts of unreacted monosaccharides were calculated from their individual HPLC standards. Sucrose inverts to fructose and glucose on the acidic HPLCcolumn used, and the conversions were calculated from the monosaccharides fructose,glucose and mannose on a carbon-basis. The yield of levulinate esters were calculated from GC results on series of individual levulinate ester standards with naphthalene as internal standard. The results are shown in Tables 3 and 7.
39%Chromat.
With HY-6; at 150 - 160℃; under 15001.5 Torr; for 20h;Autoclave; Inert atmosphere;
General procedure: A 50 ml autoclave (Microclave reactor from Autoclave Engineers) was charged with 225 mginulin, 150 mg of a catalyst (HY 6, H beta 19), and 10 ml solvent (methanol, ethanol) andthen pressurized with argon (20 bar). The autoclave was heated to 160 C and the stirring was started once the temperature reached 150 C (300 rpm). After 20 hours of stirring, the autoclave was quenched with cold water, 50 mg naphthalene (internal standard) added and the reaction mixture analyzed as described in examples 1. The results are shown in Table 5and 6.
Manganese sulfate, manganese nitrate, manganese carbonate, manganese acetate, manganese acetate, manganese chloride, manganese sulfide, manganese dioxide, manganese trioxide, manganese tetroxide, Manganese oxalate, manganese acetylacetonate (?), Manganese acetylacetonate (m), manganese citrate and the like. Reaction conditions: 0.39 g of <strong>[645-67-0]n-<strong>[645-67-0]propyl levulinate</strong></strong>, 5 mol% of catalyst (relative to <strong>[645-67-0]n-<strong>[645-67-0]propyl levulinate</strong></strong>), mL of acetic acid, 100 C, 10 h, 0.6 MPa of oxygen. After completion of the reaction, esterification reaction, Propanol and 0.15 g of concentrated sulfuric acid at reflux for 6 h. The product was analyzed according to the procedure of Example 1 to give the conversion of <strong>[645-67-0]n-<strong>[645-67-0]propyl levulinate</strong></strong> and the selectivity of di-n-propyl succinate as shown in Table II.
With boron trifluoride-tetrahydrofuran complex; tin(IV) chloride; at 180℃; for 40h;
1.8 g of sucrose,0.361 g of SnCl4, 0. 058 g of BF3?, 20? Of n-propanol were added to 50 mLStainless steel-lined reactor with Teflon,Heated to 180 C,The reaction was carried out at that temperature for 40 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 89%. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,Propoxyl methyl furfural and propyl propionate)The retention times in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was determined by 4 NMR,The product distribution results are:5-propoxymethylfurfural was 65%,HMF was 0% and propyl levulinate was 35%.
With boron tribromide; germaniumtetrachloride; at 100℃; for 10h;
1.8 g of sucrose,0.271 g of GeCl4, 0.091 g of BBr3, and 20 mL of n-propanol were added to 50 mL of a polyTetrafluoroethylene-lined stainless steel reactor,Heated to l00 C,The reaction was carried out at that temperature for 10 h. Filtration,To remove unreacted sucrose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL H20 was added and the organic phase was extracted with methyl isobutyl ketone,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 83%. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,5-propoxymethylfurfural and propyl propionate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was confirmed by 1H NMR,The product distribution results are:5-propoxymethylfurfural was 72%, HMF was 9%Propyl propionate was 19%
With SBA-15-SO3H; tin-containing molecular sieve; In water; at 170℃; for 7h;High pressure;
A mixture of 1 part of α-glucose, 20 parts of n-propanol, 0.1 part of SBA-15-SO3H and 0.1 g of Sn-Beta was mixed and placed in a hydrothermal reactor and heated at 170C for 7 hours. After cooling, The yield of propyl levulinate was 35 mol%.
With copper(II) acetate hydrate; C43H39FeNP2; In toluene;Inert atmosphere;
Under nitrogen protection,Taniaphos ligand L3 (R4=R5=Ph) (5.3 mg) was added to the dry reaction flask.Cu(OAc)2·H2O (3.0 mg), toluene (1.0 mL),Polymethylhydrogensiloxane (100muL),Stir thoroughly. To the above mixture, <strong>[2177-70-0]phenyl methacrylate</strong> (200 muL) was added dropwise with stirring.A solution of propyl 3- levulinate (128 mg) in toluene (4.0 mL),After the addition was complete, the reaction was stirred overnight. Saturated aqueous NH4F solution (2 mL) was added to the reaction mixture.After stirring for 30 min, the phases were separated and the aqueous phase was extracted with dichloromethane (3 x 5 mL).The combined organic phases are washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated.After column chromatography, gamma-methyl-gamma-(1-methyl-1-phenoxycarbonylethyl)-gamma-cyclobutyrolactone (203 mg, yield 77%, ee value) was obtained as a colorless oily liquid. 16%).
With hydrogen; acetic acid; In tetrahydrofuran; at 119.84℃; under 67506.8 Torr; for 20h;Autoclave;
General procedure: The hydrogenation of the various esters of levulinic acidwas carried out using an in situ modification method, i.e.,modifier and auxiliary modifier were added to the reactionmedia [36, 37]. A 0.94 g sample of nickel oxide (WakoPure Chemical Industries, Ltd.) was treated at 623 K for1 h under a H2stream (30 mL min-1) to obtain the reducednickel catalyst. Sodium bromide in 50 μL H2Oand (R,R)-tartaric acid (TA) (the amounts are stated in the text) wereadded to a mixture of levulinate (2.9 × 10-2 mol), acetic acid(0.065 g), and the solvent (7 mL). This substrate solution andthe reduced nickel catalyst were placed in a magneticallystirredautoclave [OM Lab-Tech Co., Ltd. (Tochigi, Japan)].Hydrogenation was carried out under the initial hydrogenpressure of 9 MPa for 20 h. The stirring rate of the autoclavewas 1130 rpm.
With graphene oxide-supported zirconia; at 180℃; under 7500.75 Torr; for 3h;Inert atmosphere; Sealed tube; Autoclave;
General procedure: The transfer hydrogenation of ethyl levulinate into GVLwas performed in a stainless steel 40 mL Parr batch reactor.A representative procedure was as follows: ethyl levulinate(1 mmol), ZrO2/GO (40 mg) catalyst and iso-propanol(10 mL) were charged in the reactor. The air in the reactorwas exchanged with nitrogen for five times and sealed underN2pressure (1.0 MPa). Then the autoclave was heated fromroom temperature to 180 C within 10 min and then the reactionwas performed at 180 C for 3 h. After cooling the reactorto room temperature, the reaction mixture was filtrated,and the clear solution was analyzed by gas chromatography.
Mix 50 grams of furfuryl alcohol with 300 ml of propanol and pour into a 500 ml round bottom flask,Add 20 grams of Nafion-H and stir in an oil bath at 80 C with a stirring speed of 500 rpm.Condensation reflux temperature is 20 , after 5 hours of reaction, the temperature will drop to room temperature,Filter to remove the catalyst,The propanol in the reaction mixture was distilled off under reduced pressure at 45 C,The light yellow propyl levulinate was obtained and analyzed by high performance liquid chromatography,The conversion rate of furfuryl alcohol and the yield of propyl levulinate were 100% and 97.52%,The yield was 97.52%.
With ruthenium supported on montmorillonite K10; at 120℃; under 30003 Torr;Autoclave;
General procedure: 160ml, Parr). Autoclave was flled with an appropriateamount of catalyst (10wt% in case of Ru catalysts, 20wt%in case of Ni catalysts, based on levulinic acid), levulinicacid (10g, Merck, 98%), internal standard-mesitylene(0.8g, Acros Organics, 99%) and 100ml of solvent-toluene,1,4-dioxane, heptane, cyclohexane, methanol, propan-2-ol, propan-1-ol, butan-1-ol, ethyl acetate (all Penta, p.a.),ethanol (Penta, 96.5%) or butan-2-ol (Lachema, 99%). Samplestaken during the reaction were centrifuged and analyzedusing gas chromatograph coupled with mass detector(Shimadzu 2010 Plus, GCMS-QP2010 Ultra) equipped withnonpolar column DB-5. Injector temperature was 250C,the programmed temperature program ranged from 80C to250C using rate 10Cmin-1, detector voltage was 0.8kVand ion source had temperature 220C. Experiments wererepeated two times and the error between these two measurementswas not higher than 8%. Reuse experiment: reactionmixture was centrifuged, catalyst was separated and washed3 times with toluene (10ml). Wet catalyst was mixed withfresh reactants and the reaction was performed as usual.
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