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CAS No. : | 539-88-8 | MDL No. : | MFCD00009209 |
Formula : | C7H12O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GMEONFUTDYJSNV-UHFFFAOYSA-N |
M.W : | 144.17 | Pubchem ID : | 10883 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.71 |
Num. rotatable bonds : | 5 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 37.25 |
TPSA : | 43.37 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -7.13 cm/s |
Log Po/w (iLOGP) : | 1.29 |
Log Po/w (XLOGP3) : | 0.07 |
Log Po/w (WLOGP) : | 0.92 |
Log Po/w (MLOGP) : | 0.64 |
Log Po/w (SILICOS-IT) : | 1.13 |
Consensus Log Po/w : | 0.81 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.45 |
Solubility : | 51.4 mg/ml ; 0.356 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.53 |
Solubility : | 42.1 mg/ml ; 0.292 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -1.48 |
Solubility : | 4.74 mg/ml ; 0.0329 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.64 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H227-H302+H332-H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23.3 %Chromat. | at 110℃; for 1.5 h; Autoclave | General procedure: Catalytic experiments were performed in liquid phase in a stainless-steel stirred autoclave (500 mL) fitted with temperature control and a pressure gauge. Typically, 7.6 g of furfuryl alcohol were mixed with 3 g of catalyst and 300 mL of the corresponding alcohol used as reaction media (methanol, ethanol or 2-propanol).Catalytic tests were also carried out using α-angelica lactone, levulinic acid and iso-propyl levulinate as substrates. Decane was added as internal standard for analytical purposes in a concentration of 10 g L−1. After closing the reactor, stirring was fixed in 1000 rpm and a heating rate of 2.5C min−1 was established.Samples were taken periodically and the solution filtered into avial. Selected catalysts were tested in the temperature range of130–170C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With platinum doped titanium oxide; hydrogen In neat (no solvent) at 120℃; for 2h; chemoselective reaction; | |
With palladium on activated charcoal; ethanol at 60℃; Hydrogenation.Beim 6-taegigen Hydrieren; | ||
Multi-step reaction with 2 steps 1: / neat (no solvent) / Green chemistry 2: hydrogen; / neat (no solvent) / 12 h / 85 °C / 760.05 Torr / Green chemistry |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrazine hydrate; In ethanol; at 80℃; for 2h; | Ethyl levulinate (30g, 208mmol) was dissolved in ethanol (100mL), hydrazine hydrate (15.63g, 312mmol, 85%)was slowly added dropwise thereto and the mixture was refluxed at 80C for 2 hours. After the mixture was cooled toroom temperature, the target compound was precipitated from the reaction solution as 6-methyl-4,5-dihydropyridazin-3(2-hydro)-one (23g, yield 98%) which was used directly in the next step without purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 4-oxopentanoic acid ethyl ester In tetrahydrofuran at 0 - 20℃; for 14.5h; Inert atmosphere; | |
88% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 4-oxopentanoic acid ethyl ester In tetrahydrofuran at 0 - 20℃; for 14.5h; Inert atmosphere; | |
84% | With potassium hexamethylsilazane In toluene |
72% | Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 4-oxopentanoic acid ethyl ester In tetrahydrofuran at -78 - 20℃; Inert atmosphere; | 2 4-Methyl-4-pentenal (3) 20.6 mL of 2.5 M n-BuLi (51.5 mmol) was added dropwise to a solution of methyltrihenylphosphonium bromide (16.9 g, 357.2 mmol) in THF (125 mL) being coolen to 0 °C under argon. After stirring at 0 °C for 30 min, the mixture was cooled to -78 °C. A solution of ethyl levulinate (5.6 g, 39.0 mmol) in THF (35 mL) was added dropwise via syringe to the above mixture at -78 °C. Then the mixture was warmed to room temperature and stirred for 14 h. The reaction mixture was quenched with 20 ml saturated aqueous NH4Cl and extracted with pentane (25 mL * 4). The combined organic layer extracted was washed with water. The organic solution was dried and the solvent was removed under reduced pressure. Vacuum distillation of the residue gave 4.01 g (72%) of ethyl 4-methyl-4-pentenoate (2) as colorless liquid. 1H NMR (400 MHz, CDCl3) δ 4.74 (t, 1H, J = 0.8 Hz), 4.69 (t, 1H, J = 0.8 Hz), 4.13 (q, 2H, J = 7.2 Hz), 2.42-2.47 (td, 2H, J = 7.6 Hz, 1.6 Hz), 2.33 (t, 2H, J = 8.0 Hz), 1.74 (d, 3H, J = 0.4 Hz), 1.25 (t, 3H, 7.2 Hz); 13C NMR (100 MHz, CDCl3) δ 173.3, 144.1, 110.3, 60.3, 32.7, 32.6, 22.5, 14.1. |
58% | Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran for 1.5h; cooling; Stage #2: 4-oxopentanoic acid ethyl ester In tetrahydrofuran at -60 - 20℃; | |
Yield given. Multistep reaction; | ||
With n-butyllithium In tetrahydrofuran; hexane Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 3 (3S)-3,7a-Dimethyl-2,5-dioxohexahydro-1H-pyrrolo[1,2-a]imidazole L-Alaninamide hydrochloride (20.7 g, 0.166 mol) and ethyl 4-oxopentanoate (20 g, 0.13 mol) were reacted together according to the procedure of Example 2 to give the title compound, 4.5 g (19.1%), m.p. 228-230 (with decomposition), [alpha]D= + 50.7 (c=3, H2O). NMR (CDCl3): deltaH= 7.95 (bs, 1H, N H); 4.30 (q, J= 8 Hz, 1H, C H CH3); 3.00-2.10 (c.a., 4H, C H 2C H 2); 1.60 (s, 3H, C-C H 3; 1.45 (d, J= 8 Hz, 3H, C H 3CH). MS (E.I., 70 eV, 1.5 mA) m/z= 168 (M+), 153 (M-CH3)+, 125 (M-CHNO)+, 112 (M-C3H4O)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With iron(II) trifluoromethanesulfonate; formic acid; tris(2-diphenylphosphinoethyl)phosphine In 1,4-dioxane at 140℃; for 24h; | |
99% | With hydrogen In ethanol at 200℃; for 6h; Autoclave; | |
99% | With formic acid; triphenylphosphine In tetrahydrofuran at 160℃; for 8h; |
99% | With hydrogen In tetrahydrofuran at 130℃; for 6h; Autoclave; Green chemistry; | |
99% | With Pt/TiO2; sodium hydroxide In lithium hydroxide monohydrate; isopropanol at 25℃; for 12h; Inert atmosphere; | |
99.2% | With hydrogen In propan-2-one at 150℃; Autoclave; | 2.3. Catalytic experiments The evaluation of activity of catalyst was carried out in an autoclave reactor with a volume of 10 mL. Catalyst and 4 g of substrate-solvent mixture (EL = 0.2 g, solvent = 3.8 g) were added into the reactor at room temperature. After that, the reactor was sealed and purged with hydrogen for 3 times to remove the air inside. The reactor was then heated with hydrogen pressure of 4 MPa and a magnetic agitator stirringat 600 rpm. Once reaching target temperature, the reactor was hold forcertain time to ensure the completion of reaction. After that, the reactor cooled down to room temperature and the liquid products were recycled for further characterization. The separated catalysts were washed with ethanol and dried at 40 °C for further characterization or for the use incycling experiments. |
98% | Stage #1: 4-oxopentanoic acid ethyl ester With Triethoxysilane; Cs2CO3 In 2-methyltetrahydrofuran at 25℃; for 0.5h; Green chemistry; Stage #2: With ethanol In 2-methyltetrahydrofuran at 80℃; for 2h; Green chemistry; chemoselective reaction; | |
98.7% | With hydrogen In isopropanol at 200℃; for 6h; | 2 Example 2 Preparation of γ-valerolactone by hydrogenation of levulinic acid ester Experiment 16-19: 5g of ethyl levulinate, or 5g of levulinic acid ester and 45g of solvent, 0.5g of catalyst is added to the 50ml reaction kettle, after replacing the three gases with nitrogen, Then replace the hydrogen three times, and then charge the hydrogen to 6MPa. The temperature was raised to 200 ° C and stirred for 6 hours. After the reaction, drop to room temperature and filter the supernatant. Product detection was performed on an Agilent 7890B gas chromatograph. For valeric acid, ethyl valerate, γ-valerolactone in the product, yield calculation for levulinic acid, etc. The experimental results are shown in Table 1 (Experiments 16-19). |
97% | With hydrogen In ethanol at 200℃; for 8h; Autoclave; | 17 Example-17 In a 25 ml autoclave,Lmmol of ethyl levulinate was added,100 mg catalyst l% Pt / SAPO-ll and 12 ml of the reaction solvent ethanol,The autoclave was then sealed,Filled with hydrogen to 6MPa, the heating process from room temperature after 30min heating to200 ° C, for 8h,After the completion of the reaction, quantitative analysis of the starting materials and products was carried out using a Shimadzu gas chromatograph (Model GC2014, RTX-65 column). The conversion of ethyl levulinate was 98.5% and the yield of? -valerolactone was 97 |
97% | With hydrogen In hexane at 150℃; for 3h; Autoclave; | |
97.7% | With formic acid modulated zirconium alizarin red S In isopropanol at 159.84℃; for 8h; Autoclave; | 2.5. Catalytic reduction of ethyl levulinate to GVL In this step, EL was chosen as the reaction substrate to evaluate thereduction performance of the prepared catalysts and observe the influenceof each active site on the catalytic performance of FM-Zr-ARS. Allexperiments were performed in a 20 ml Teflon-lined stainless-steelautoclave equipped with a magnetic stir bar under oil-heating conditions.Typically, 1 mmol of selected intermediates (i.e., ethyl levulinate)was added to 5 ml of alcohol solution (i.e., isopropanol, IPA) withvarying amounts of catalysts (100 200 mg), and then the reactor was heated to and kept at the desired temperature for a certain time. Afterthe oil bath was heated to the target temperature, the reactor wasimmediately placed under magnetic stirring to initiate the reaction.After the reaction was completed, the reactor was quickly removed fromthe oil bath and cooled with cold water to terminate the reaction. Thequantification of reduction products was conducted on a GC-9790 (FuliAnalytical Instrument Co. Ltd., China) equipped with an FID detectorand SE-54 capillary column (30.0 m×0.32 mm × 0.25 μm). GC-MS(Bruker SCTONSQ-456-GC) was used for identification of products.Calibration curves were obtained from stock solutions, using decane asan internal standard. Catalyst performance was evaluated according tothe following equations: |
96.2% | With Zirconium trimetaphosphate In isopropanol at 160℃; for 8h; | |
95% | With isopropanol In 2-sec-butylphenol at 150℃; for 16h; Inert atmosphere; | 8 Hydrogenation of levulinic acid to GVL is carried out by hydrogen transfer using alcohols as hydrogen donors and a metal oxide as ZrO2. The ZrO2 catalyst was prepared by precipitation of ZrO(NO3)2 with NH4OH (Aldrich), according to Serrano-Ruiz et al. (J. Catal., 241, (2006), 45-55). Solids were calcined in 60 cm3 (STP)/min flowing air at 723 K for 4 h prior to use in batch experiments. Quantification was performed using a gas chromatograph (Shimadzu GC-2010; Shimadzu Scientific Instruments, Columbia, Md.) equipped with a flame-ionization detector (FID). Identification of products in the liquid phase was performed using a gas chromatograph-mass spectrometer (Shimadzu Corp., GCMS-QP2010S) equipped with a Rxi-brand SHRXI-5MS capillary column (30 m×0.25 mm×0.25 μm) (Restek Corporation, Bellefonte, Pa.).The reactions were performed in a 50 mL batch reactor (Parr Instruments). For all experiments, the feed was 5 wt % levulinate ester or LA in a solvent (solvent composition is described in Table 8). ZrO2 was used as the catalyst. Reactor contents were pressurized under 300 psi He prior to heating to the reaction temperature (150° C.). In all cases, SBP was not converted during the reaction and behaved as an inert diluent. Besides GVL, the only other products observed were levulinate esters formed through transesterification or esterification reactions between the reactants and the hydrogen donors. As shown in Table 8, IPA, 2 BuOH, and 2HO are suitable hydrogen donors for these reactions. Also, the conversion of levulinate esters (Ethyl levulinate (EL) or butyl levulinate (BL) to GVL occurs at a higher rate than that for LA to GVL. |
95% | With dicarbonylhydro[2,5-di(trimethylsilyl)-3,4-butylene-1-hydroxy(η5-cyclopentadienyl)]iron; Sodium hydrogenocarbonate; isopropanol at 100℃; for 19h; Schlenk technique; Inert atmosphere; | |
95.5% | With isopropanol at 220℃; for 4h; Autoclave; | |
95% | With isopropanol at 150℃; for 8h; | |
94% | With hydrogen; cobalt at 130℃; for 3h; Autoclave; | |
94% | With methanol; sodium tetrahydridoborate at 0℃; | |
93.8% | With isopropanol at 170℃; for 8h; | |
93% | With scandium trifluoromethanesulphonate In isopropanol at 150℃; for 24h; Schlenk technique; | 12 Example 1 Preparation of γ-valerolactone General procedure: Take the schlenk tube, add 0.05mmol furfural, 5%mmol Sc(ONf)3, add 3mL isopropanol,Stir and react at 150 for 36h,The conversion rate of raw materials and the yield of products were determined, as shown in Table 1. |
92% | With ZrO2/SBA-15 In propylene glycol at 150℃; for 4h; Autoclave; Inert atmosphere; | 9 Example 8 It is as a result of reacting like the working example 1 except having replaced with levulinic acid methyl 2.0mmol, and having used levulinic acid ethyl 2.0mmol. 66% of an inversion rate and 60% (91% of selectivity) of gamma-valerolactone yield were obtained 1 hour afterward, and 97% of an inversion rate and 92% (94% of selectivity) of gamma-valerolactone yield were obtained 4 hours afterward |
91.9% | With isopropanol at 200℃; for 3h; Autoclave; Inert atmosphere; | |
90.7% | With naphthalene In isopropanol at 200℃; for 6h; Autoclave; | 3 Embodiment 2 Application of Microsphere Titanium-zirconium Oxide Catalyst in the Conversion of Ethyl Levulinate to Valerolactone. Weigh 0.072 g of titanium zirconium oxide catalyst (Ti:Zr=2:8) into a 25 ml autoclave.In the reaction vessel, 1 mmol (0.1442 g) of ethyl levulinate, 5 ml of isopropanol (as a hydrogen source and solvent) were added, and 0.02 g of naphthalene was added as an internal standard. The reaction vessel was reacted for 6 h at 180 oC. After the reaction was stopped, the reactor was placed in tap water and cooled to room temperature. After the cooled reaction solution was filtered, the yield of the product was analyzed by high performance gas chromatography. The conversion of ethyl levulinate was calculated to be 100% and the yield of valerolactone was 90.1% using an external standard method. |
90.12% | In isopropanol at 180℃; for 5h; Autoclave; | 2.3 CTH reaction and sample analysis General procedure: CTH reaction of ML was performed without stirring in a steel alloy autoclave (Fe-Cr-Ni alloy, GB1220-92) with an internal volume of 35 ML. Typically, carbonyl compounds (0.67 mmol), solvents (20 mL), and catalyst (0.1 g) were charged into the reactor, which was then sealed and heated to a designed temperature (140-220 °C) for an intended reaction time (1-24 h). After the reaction, the autoclave was taken out and cooled to ambient temperature. Identification of liquid products in the reaction mixture wasachieved by the TRACE ISQ GC-MS (Thermo Scientific Co,TR-WAX-MS column 30.0m×320 μm×0.25 μm). The temperatureprogram started at 60 °C for 1 min, then increased from 60 °C to 230 °Cat a rate of 15 °C /min and held for 2 min. Identification of liquid products in the reaction mixture wasachieved by the TRACE ISQ GC-MS (Thermo Scientific Co,TR-WAX-MS column 30.0m×320 μm×0.25 μm). The temperature program started at 60 °C for 1 min, then increased from 60 °C to 230 °C at a rate of 15 °C /min and held for 2 min. |
90.4% | With 27.5 wt% of cobalt loaded nitrogen doped carbon pyrolyzed at 900°C In isopropanol at 150℃; for 3h; | |
88.14% | With tris isopropylate aluminium; isopropanol at 40 - 160℃; for 0.666667h; Microwave irradiation; | 2 Example 2 To the glass reaction tube was added 0.5 g of ethyl levulinate,8 g isopropyl alcohol,0.25 g of aluminum isopropoxide,Stir evenly,Add stirrups,Installed and placed in the microwave synthesis reactor;Set the initial microwave power of 300W,Set the temperature 160 ,The reaction was carried out under constant stirring for 40 min,After the reaction is over,The system was rapidly cooled to 40 ° C by air cooling and the reaction mixture was removed.By gas chromatography analysis,The conversion of ethyl levulinate was 100%The yield of GVL was 88.14%. |
88% | With isopropanol at 190℃; for 11h; Autoclave; | 2.4. Experiment procedure 15 mL 0.2 M EL, 100 mg catalyst in 2-PrOH containing 10 mg/mL n-decane as an internal standard. The reaction was controlled at desired temperature and time in oil bath. After reaction, the autoclave was cooled to room temperature, the liquid samples were filtered and analyzed by gas chromatograph (GC). A similar procedure was performed in other optimization experiments. |
86% | With Na(1+)*C12H33AlNO4Si2(1-) In tetrahydrofuran; toluene at 0℃; for 1h; Inert atmosphere; chemoselective reaction; | Representative procedure for the chemoselective reduction of multifunctionalized compounds with new modified Red-Al General procedure: A dry and argon-flushed flask, equipped with a magnetic stirring bar and septum, was charged with 4-acetylbenzaldehyde (1.0 mmol) and THF (10 mL). After cooling to 0 C, the modified Red-Al (0.5 M, 2.2 mL in THF) was added dropwise and the mixture was stirred for 1 h at 0 C. The reaction was quenched with 1 N aqueous HCl (10 mL) and the product was extracted with diethylether (10 mL). The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure and the crude residue was purified by column chromatography (SiO2, ethyl acetate/hexane, 1:5 v/v) to affording the desired alcohol (123 mg, 83% yield). |
86% | With isopropanol at 150℃; for 9h; Autoclave; | |
85% | With [Zr6(μ3-O)4(μ3-OH)4(HCOO)6(benzene-1,3,5-tricarboxylate)2]; isopropanol at 130℃; for 3h; Further stages; | 4 Example 4: MOF-808 Evaluation of Zr-MOFs Possessing Different Physico-Chemical Properties for CTH Reaction of EL to GVL After confirming the active sites in UiO-66(Zr) for transfer hydrogenation of EL, the present inventors have checked the possibility whether other Zr-MOFs may be more suitable as candidates for the transfer hydrogenation reaction. To overcome the use of high reaction temperature was another object to solve in the present invention. To this end, two alternative Zr-MOFs (MOF-801 and MOF-808), which possess a metal center (Zr6O4(OH)4) in their framework as in UiO-66(Zr) were selected for the reaction. The porous properties of the selected Zr-MOFs along with linkers and molecular formulas are shown in Table 2 below. Representative structures of the two Zr-MOFs are shown in FIGS. 8A-8B. Since UiO-66(Zr) and MOF-801 have the coordination number (12) to the link in the metal center they have almost similar porous properties. However, MOF-808 with a central metal-to-linker coordination number of 6 possesses porous properties different from those of other two Zr-MOFs (Table 2 and FIGS. 9A-9B). Due to the large surface area and bigger pore size of MOF-808, the catalytic performance of the catalyst was examined at a moderate reaction temperature to represent the principle of green chemistry. |
82.8% | With isopropanol at 82℃; for 24h; Sealed tube; | |
82.8% | With isopropanol at 82℃; for 24h; | <Range of Substrate> General procedure: In addition to the hydrogenation reaction of FUR, the activity of the MOF catalyst according to the present disclosure was measured for hydrogenation reactions using various substrates. A hydrogenation reaction experiment was performed using representative aldehydes and ketones and other biomass-derived carbonyl compounds as the range of the substrate, and the results are shown in Table 5 below (reaction condition: 2.6 mmol of the substrate, 416 mmol of IPA, 0.1 g (10.6 mol %) of the catalyst, and a temperature of 82° C. (reflux)). |
81.5% | With ethanol; zirconium oxide at 249.84℃; for 3h; Green chemistry; | |
81.5% | With zirconium oxide In ethanol at 250℃; for 3h; Autoclave; | 9 2 g of ethyl levulinate and 38 g of ethanol (5% by weight) were added to a 100 mL autoclave, followed by addition of lgZr02 as a catalyst, sealed, homogenized (500 rpm), heated to 250 ° C and maintained for 0.5-4 h, To-room temperature and sampling, qualitative and quantitative detection using GC-MS (Shimadzu) and GC (Agilent), the detection results of different catalysts are listed in Table 1, No. 7 to 10. |
80% | With [Ph4(η4-2,3,4,5-tetraphenylcyclopentadienone)]Ru0(CO)3; hydrogen at 120℃; for 2h; | |
69% | With hydrogen In ethanol at 130℃; for 6h; | |
68% | With potassium diisobutyl-t-butoxy aluminum hydride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; chemoselective reaction; | 4.5 Chemoselective reduction of dicarbonyl compounds with PDBBA (Table3) General procedure: A dry and argon-flushed flask, equipped with a magnetic stirring bar and a septum, was charged with dicarbonyl compound (1.0 mmol) and 10 mL THF. After cooling to 0°C, PDBBA (1.3 mmol) was added dropwise and stirred for 1h at same temperature. The reaction was stopped by the aqueous 1N HCl (10mL) and extracted with diethyl ether (2×10mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. Purification of the residue by column chromatography on silica gel afforded the desired product. |
68% | With C25H37IrN6(2+)*2F6P(1-); barium(II) hydroxide In lithium hydroxide monohydrate; glycerol at 150℃; for 3h; Inert atmosphere; Autoclave; | |
63.2% | With Zr(IV)-metal-sodium lignosulfonate nanoparticle from industry waste paper In isopropanol at 150℃; for 6h; | |
62.4% | With isopropanol; zirconium oxide at 150℃; for 4h; Inert atmosphere; Sealed vessel; | |
58.6% | With graphene oxide-supported zirconia In isopropanol at 180℃; for 3h; Inert atmosphere; Sealed tube; Autoclave; | 2.4 General Procedure of the TransferHydrogenation of Ethyl Levulinate into GVL 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. |
40% | With formic acid at 200 - 250℃; | 2.5; 2.6; 2.7 A feed stream comprising undiluted formic acid and undiluted ethyl levulinate was contacted with a commercially available Ni-comprising solid hydrogenating catalyst (the same catalyst as used in experiment 4 of EXAMPLE 1) at different formic acid/ethyl levulinate molar ratios, different weight hourly velocities and different temperatures at ambient pressure. Reactor tube, catalyst dilution, catalyst pre-reduction and reactant supply and withdrawal were as described for EXAMPLE 1. In Table 2 is shown the molar ratio of formic acid (FA) and ethyl levulinate (EL) in the feed stream, the operating temperature, weight hourly velocity of ethyl levulinate and gamma valerolactone (gVL) yield for the different experiments. TABLE 2 Experimental set-up and yield for EXAMPLE 2 (experiments 5 to 7) weight hourly velocity gVL yield FA/EL T (g EL/g (% of EL experiment (mole/mole) (° C.) cat · hr) feed) 5 1.0 200 5.0 40 1.7 68 6 1.0 250 4.5 73 0.9 84 7 3.0 250 1.1 81 0.7 80 |
38% | With formic acid at 200 - 300℃; | 1.4 Catalyst particles and silicon carbide particles (catalyst:SiC weight ratio of 0.2) were loaded in a 5 mL quartz reactor tube with a length/diameter ratio of 10. The catalyst was then reduced under 10 wt % hydrogen in nitrogen at 300° C. for 16 hours. The reactor tube was then maintained at 200° C. and a feed stream comprising undiluted formic acid and undiluted ethyl levulinate in a molar ratio of 1.0 was then continuously supplied to the catalyst at different weight hourly velocities. Reaction products were continuously withdrawn from the reactor tube and collected in an ice-cooled flask. The reactor was kept at ambient pressure. At these process conditions, reactants were in the gas phase when contacting the catalyst. Different catalysts were used in four different experiments. The condensed reaction product was analysed by off-line gas chromatography analysis. Experiment 1 A catalyst was used that was prepared by impregnating silica with a solution comprising nickel nitrate and Pt(NH3)4(NO3)2. The resultant catalyst particles comprised 10 wt % Ni and 0.05 wt % Pt. Experiment 2 A catalyst was used that was prepared by impregnating silica with a solution comprising HReO4 and Pt(NH3)4(NO3)2. The resultant catalyst comprised 10 wt % Re and 0.1 wt % Pt. Experiment 3 A commercially available catalyst (1808T, ex. Engelhard) comprising co-precipitated Cu and Cr was used. Experiment 4 A commercially available catalyst (UN-No2881; ex. Kataleuna) comprising Ni was used. In Table 1, the catalyst used, the weight hourly velocity, ethyl levulinate (EL) conversion and yield of gamma valerolactone (gVL) based on moles of ethyl 10 levulinate in the feed stream, for the different experiments are shown. TABLE 1 Experimental set-up and results for EXAMPLE 1 (experiments 1 to 4) weight hourly velocity EL (g EL/g conversion gVL yield experiment catalyst cat · hr) (% mole/mole) (% mole/mole) 1 Ni/Pt on 3.3 9.5 8.5 silica 0.8 32 31 2 Re/Pt on 3.3 6.0 5.7 silica 0.6 8.4 8.4 3 co- 7.0 8.3 7.2 precipitated 1.5 12 11 Cu/Cr 4 Ni 5.0 40 38 1.5 74 71 |
23% | With 1,1,4,4-tetramethyldisilylethylene; tris(pentafluorophenyl)borate In dichloromethane at 20℃; for 0.166667h; Inert atmosphere; | |
8.5% | With formic acid at 200 - 300℃; | 1.1 Catalyst particles and silicon carbide particles (catalyst:SiC weight ratio of 0.2) were loaded in a 5 mL quartz reactor tube with a length/diameter ratio of 10. The catalyst was then reduced under 10 wt % hydrogen in nitrogen at 300° C. for 16 hours. The reactor tube was then maintained at 200° C. and a feed stream comprising undiluted formic acid and undiluted ethyl levulinate in a molar ratio of 1.0 was then continuously supplied to the catalyst at different weight hourly velocities. Reaction products were continuously withdrawn from the reactor tube and collected in an ice-cooled flask. The reactor was kept at ambient pressure. At these process conditions, reactants were in the gas phase when contacting the catalyst. Different catalysts were used in four different experiments. The condensed reaction product was analysed by off-line gas chromatography analysis. Experiment 1 A catalyst was used that was prepared by impregnating silica with a solution comprising nickel nitrate and Pt(NH3)4(NO3)2. The resultant catalyst particles comprised 10 wt % Ni and 0.05 wt % Pt. Experiment 2 A catalyst was used that was prepared by impregnating silica with a solution comprising HReO4 and Pt(NH3)4(NO3)2. The resultant catalyst comprised 10 wt % Re and 0.1 wt % Pt. Experiment 3 A commercially available catalyst (1808T, ex. Engelhard) comprising co-precipitated Cu and Cr was used. Experiment 4 A commercially available catalyst (UN-No2881; ex. Kataleuna) comprising Ni was used. In Table 1, the catalyst used, the weight hourly velocity, ethyl levulinate (EL) conversion and yield of gamma valerolactone (gVL) based on moles of ethyl 10 levulinate in the feed stream, for the different experiments are shown. TABLE 1 Experimental set-up and results for EXAMPLE 1 (experiments 1 to 4) weight hourly velocity EL (g EL/g conversion gVL yield experiment catalyst cat · hr) (% mole/mole) (% mole/mole) 1 Ni/Pt on 3.3 9.5 8.5 silica 0.8 32 31 2 Re/Pt on 3.3 6.0 5.7 silica 0.6 8.4 8.4 3 co- 7.0 8.3 7.2 precipitated 1.5 12 11 Cu/Cr 4 Ni 5.0 40 38 1.5 74 71 |
7.2% | With formic acid at 200 - 300℃; | 1.3 Catalyst particles and silicon carbide particles (catalyst:SiC weight ratio of 0.2) were loaded in a 5 mL quartz reactor tube with a length/diameter ratio of 10. The catalyst was then reduced under 10 wt % hydrogen in nitrogen at 300° C. for 16 hours. The reactor tube was then maintained at 200° C. and a feed stream comprising undiluted formic acid and undiluted ethyl levulinate in a molar ratio of 1.0 was then continuously supplied to the catalyst at different weight hourly velocities. Reaction products were continuously withdrawn from the reactor tube and collected in an ice-cooled flask. The reactor was kept at ambient pressure. At these process conditions, reactants were in the gas phase when contacting the catalyst. Different catalysts were used in four different experiments. The condensed reaction product was analysed by off-line gas chromatography analysis. Experiment 1 A catalyst was used that was prepared by impregnating silica with a solution comprising nickel nitrate and Pt(NH3)4(NO3)2. The resultant catalyst particles comprised 10 wt % Ni and 0.05 wt % Pt. Experiment 2 A catalyst was used that was prepared by impregnating silica with a solution comprising HReO4 and Pt(NH3)4(NO3)2. The resultant catalyst comprised 10 wt % Re and 0.1 wt % Pt. Experiment 3 A commercially available catalyst (1808T, ex. Engelhard) comprising co-precipitated Cu and Cr was used. Experiment 4 A commercially available catalyst (UN-No2881; ex. Kataleuna) comprising Ni was used. In Table 1, the catalyst used, the weight hourly velocity, ethyl levulinate (EL) conversion and yield of gamma valerolactone (gVL) based on moles of ethyl 10 levulinate in the feed stream, for the different experiments are shown. TABLE 1 Experimental set-up and results for EXAMPLE 1 (experiments 1 to 4) weight hourly velocity EL (g EL/g conversion gVL yield experiment catalyst cat · hr) (% mole/mole) (% mole/mole) 1 Ni/Pt on 3.3 9.5 8.5 silica 0.8 32 31 2 Re/Pt on 3.3 6.0 5.7 silica 0.6 8.4 8.4 3 co- 7.0 8.3 7.2 precipitated 1.5 12 11 Cu/Cr 4 Ni 5.0 40 38 1.5 74 71 |
5.7% | With formic acid at 200 - 300℃; | 1.2 Catalyst particles and silicon carbide particles (catalyst:SiC weight ratio of 0.2) were loaded in a 5 mL quartz reactor tube with a length/diameter ratio of 10. The catalyst was then reduced under 10 wt % hydrogen in nitrogen at 300° C. for 16 hours. The reactor tube was then maintained at 200° C. and a feed stream comprising undiluted formic acid and undiluted ethyl levulinate in a molar ratio of 1.0 was then continuously supplied to the catalyst at different weight hourly velocities. Reaction products were continuously withdrawn from the reactor tube and collected in an ice-cooled flask. The reactor was kept at ambient pressure. At these process conditions, reactants were in the gas phase when contacting the catalyst. Different catalysts were used in four different experiments. The condensed reaction product was analysed by off-line gas chromatography analysis. Experiment 1 A catalyst was used that was prepared by impregnating silica with a solution comprising nickel nitrate and Pt(NH3)4(NO3)2. The resultant catalyst particles comprised 10 wt % Ni and 0.05 wt % Pt. Experiment 2 A catalyst was used that was prepared by impregnating silica with a solution comprising HReO4 and Pt(NH3)4(NO3)2. The resultant catalyst comprised 10 wt % Re and 0.1 wt % Pt. Experiment 3 A commercially available catalyst (1808T, ex. Engelhard) comprising co-precipitated Cu and Cr was used. Experiment 4 A commercially available catalyst (UN-No2881; ex. Kataleuna) comprising Ni was used. In Table 1, the catalyst used, the weight hourly velocity, ethyl levulinate (EL) conversion and yield of gamma valerolactone (gVL) based on moles of ethyl 10 levulinate in the feed stream, for the different experiments are shown. TABLE 1 Experimental set-up and results for EXAMPLE 1 (experiments 1 to 4) weight hourly velocity EL (g EL/g conversion gVL yield experiment catalyst cat · hr) (% mole/mole) (% mole/mole) 1 Ni/Pt on 3.3 9.5 8.5 silica 0.8 32 31 2 Re/Pt on 3.3 6.0 5.7 silica 0.6 8.4 8.4 3 co- 7.0 8.3 7.2 precipitated 1.5 12 11 Cu/Cr 4 Ni 5.0 40 38 1.5 74 71 |
With hydrogenchloride; sodium cyanotrihydridoborate 1.) tetrahydrofuran, room temp.; 2.) THF, room temp., 4 h, reflux, 18 h; Yield given. Multistep reaction; | ||
> 99 %Chromat. | With isopropanol at 20℃; for 9h; Inert atmosphere; | |
Multi-step reaction with 2 steps 1: hydrogen; 3Pd-10Nb-500AC / lithium hydroxide monohydrate / 5 h / 100 °C / 3750.38 Torr 2: hydrogen; 3Pd-10Nb-500AC / lithium hydroxide monohydrate / 5 h / 100 °C / 3750.38 Torr | ||
81 %Chromat. | With isopropanol at 150℃; for 2h; Autoclave; Inert atmosphere; | Catalytic Experiment General procedure: Typical procedure of catalytic reaction is as follows: to a stainless autoclave reactor equipped with a pressure gauge were charged levulinate ester (2 mmol), ZrO2 catalyst (40 mg as ZrO2), alcohol (10 mL), and a stirring bar. The reactor was purged and pressurized with 1.0 MPa of Ar. The reaction was performed at 150 °C for 2 h with magnetic stirring. After cooling to room temperature, the reaction mixture was filtered and analyzed by FID-GC. |
74.6 %Chromat. | With porous zirconium-phytic acid hybrid In isopropanol at 100℃; for 24h; | |
With hydrogen In methanol at 210℃; Green chemistry; | ||
98.2 %Chromat. | With isopropanol at 200℃; for 1h; | |
With hydrogen In ethanol at 180℃; Flow reactor; | ||
91 %Chromat. | With isopropanol at 150℃; for 3h; Autoclave; Inert atmosphere; | 2.4. Procedures for catalytic reactions General procedure: In a typical reaction, a reaction mixture containing catalyst(40 mg as ZrO2), substrate (2 mmol), and alcohol (10 mL) wascharged into a 60 mL cylindrical stainless steel high-pressure reac-tor (EYELA, Inc.) equipped with a bourdon pressure gauge, whichwas then sealed, purged and pressurized with 1.0 MPa of Arand then heated to 150C. During the reaction, magnetic stir-ring at 600 rpm was continued. After the predetermined reactiontime, the reactor was cooled to room temperature and the liq-uid products recovered from the reaction mixture were analyzedby a gas chromatograph (Shimadzu GC-14B) with a frame ioniza-tion detector equipped with a capillary column (ULBON HR-20 M;0.53 mm × 30 m; Shinwa Chemical Ind., Ltd.). Conversion of sub-strate and yields of products were quantified using biphenyl as aninternal standard. To assess the catalyst reusability, the spent cat-alyst was retrieved from the reaction mixture by filtration, washedwith acetone, dried at 100C and then subjected to multiple cat-alytic runs (for detailed procedures for catalyst reusability test, seethe Supplementary Information). |
With benzylic alcohol at 150℃; for 10h; Inert atmosphere; Autoclave; Green chemistry; | ||
With ruthenium (III) chloride; hydrogen In lithium hydroxide monohydrate at 110℃; for 4h; Autoclave; Green chemistry; | ||
> 99 %Spectr. | With C12H14N4*Ir(1+)*2CO*BF4(1-)*C3H7NO; hydrogen; potassium hydroxide In isopropanol at 100℃; for 4h; Autoclave; | |
98 %Chromat. | With isopropanol-d<SUB>8</SUB> at 160℃; for 6h; | |
With γ-Fe2O3(at)HAP at 180℃; for 12h; Autoclave; Inert atmosphere; Sealed tube; | 38 Examples 37-41 General procedure: 40 mg of catalyst γ-Fe2O3 HAP was added to the inside of a clean autoclave, and 1 mmol of differentReaction substrate and 15 mL isopropanol, sealed stainless steel high-pressure reactor after N2 ventilation three times, and then filled at room temperature10barN2, 180 under the reaction of different time, after the end of the reaction by liquid chromatography to detect product composition, the specific experimental resultsSee Table 8: | |
85 %Chromat. | With zirconium(IV) oxychloride octahydrate; isopropanol; humic acid at 150℃; for 15h; Autoclave; | |
With isopropanol at 200℃; for 0.166667h; Autoclave; Sealed tube; Inert atmosphere; | ||
88 %Chromat. | With isopropanol at 90℃; for 24h; Irradiation; | |
With hydrogen In 1,4-dioxane at 160℃; for 12h; | ||
Multi-step reaction with 2 steps 1: hydrogen / lithium hydroxide monohydrate / 6 h / 80 °C / 22502.3 Torr / Autoclave 2: hydrogen / lithium hydroxide monohydrate / 2 h / 80 °C / 22502.3 Torr / Autoclave | ||
Multi-step reaction with 3 steps 1: hydrogen / lithium hydroxide monohydrate / 6 h / 80 °C / 22502.3 Torr / Autoclave 2: Acidic conditions 3: hydrogen / lithium hydroxide monohydrate / 6 h / 80 °C / 22502.3 Torr / Autoclave | ||
94 %Chromat. | With isopropanol at 120℃; for 8h; | |
92 %Chromat. | With isopropanol at 160℃; for 10h; | |
Multi-step reaction with 2 steps 1: sodium tetrahydridoborate; methanol / tetrahydrofuran / 2 h / 0 - 5 °C 2: toluene-4-sulfonic acid / methanol / 24 h / 20 °C | ||
92 %Chromat. | With isopropanol at 160℃; for 12h; Sealed tube; | |
With Ni-Fe(3/1)LDH In isopropanol at 150℃; for 12h; | 32 Example 29-32 General procedure: Weigh 0.2g of Ni-Fe(3/1)LDH into the lining of a clean high pressure reactor.Add 1 mmol of substrate (acetophenone, 5-hydroxymethylfurfural, 5-methylfurfural, ethyl levulinate),5mL of isopropanol and appropriately sized magnetonsAfter packaging the stainless steel high pressure reactor,150 ° C reaction under magnetic stirring,After the reaction is completed, the supernatant is taken for detection and analysis. The specific experimental results are shown in Table 8.It can be seen that the Ni-Fe(3/1)LDH catalyst can catalyze the hydrogenation of a compound containing a carbonyl functional group.especially,Suitable for aromatic compounds containing carbonyl groups,Its selectivity can reach more than 90%. | |
With isopropanol at 150℃; for 14h; Sealed tube; Green chemistry; | ||
98 %Chromat. | With [RuCl(6-(4-methoxyphenyl)-2-aminomethylpyridine)(1,1′-bis(diphenylphosphino)ferrocene)]; potassium carbonate; isopropanol at 82℃; for 0.25h; Inert atmosphere; Schlenk technique; | |
88.8 %Chromat. | With isopropanol at 150℃; for 9h; Autoclave; | |
79.8 %Chromat. | With hydrogen In isopropanol at 250℃; for 2h; | 2.4. Ethyl levulinate hydrogenation The catalytic conversion of EL was performed in a 50 mL batch reactor(Parr 4597). For each reaction, 0.2883 g (2 mmol) of EL and0.4258 g (2.5 mmol) of dodecane (internal standard) were dissolved in20 mL of isopropanol, together with 0.1 g of catalyst. Thenceforth, the reaction was carried out at a certain temperature, H2 pressure and reactiontime with the mechanical stirring speed of 1000 rpm. After thereaction, the liquid products were analyzed by GC-MS (Agilent 6890A-5975C) and GC (SP-7890). The conversion of EL and the yield of GVLwere calculated according to the following equations: |
97 %Chromat. | With biomass-derived chitosan-supported Zr catalyst In isopropanol at 160℃; for 8h; | |
96.8 %Chromat. | With iso-butanol at 150℃; for 8h; Autoclave; | |
95 %Spectr. | With borane-ammonia complex; lithium hydroxide monohydrate at 20℃; for 4h; Inert atmosphere; Schlenk technique; Glovebox; Green chemistry; | |
Multi-step reaction with 2 steps 1: borane-ammonia complex; methanol / 4 h / 20 °C / Inert atmosphere; Schlenk technique; Glovebox; Green chemistry 2: borane-ammonia complex; lithium hydroxide monohydrate / 4 h / 20 °C / Inert atmosphere; Schlenk technique; Glovebox; Green chemistry | ||
With isopropanol at 180℃; for 3h; Inert atmosphere; Green chemistry; | ||
98.7 %Chromat. | With C6H4B2O4(4-)*Zr(4+); isopropanol at 130℃; for 6h; Sealed tube; | |
97 %Chromat. | With isopropanol at 180℃; for 12h; Autoclave; Green chemistry; | |
94.23 %Chromat. | With isopropanol at 160℃; for 8h; Autoclave; Green chemistry; | 2.4 CTH of EL to GVL The CTH reaction from EL to GVL was carried out in a25mL Teflon-lined stainless-steel reactor equipped with amagnetic stirrer. In a typical procedure, EL (1mmol), isopropanol(5mL), and the catalyst (0.2g) were added intothe reactor. The reactor was sealed and placed into a preheatedoil-bath at a desired temperature for a known time.At the end of the reaction, the reactor was cooled to roomtemperature and the liquid samples were collected and analyzedby gas chromatography (GC 9790) using naphthaleneas the internal standard, and identification of the liquidproducts was identified by GC-MS (ULTRA QP2010). The conversion of EL and yield of GVL were calculated by theformula following: Yield of GVL = Moles of GVL formed/Moles of EL used× 100% (1) Conversion of EL = Moles of EL converted/Moles of EL used× 100% (2) |
91 %Spectr. | With hydrogen; potassium hydroxide In isopropanol at 100℃; for 24h; Schlenk technique; Green chemistry; | |
With hydrogen; isopropanol at 230℃; for 1.5h; Autoclave; | ||
With hydrogen In neat liquid at 220℃; for 10h; | ||
With nickel phosphide; hydrogen In ethanol at 250℃; for 6h; Molecular sieve; | 2.2. Catalytic activity measurements General procedure: The HDO activity of nickel phosphide was evaluated using 7 wt% ethyl levulinate (99%, Sigma-Aldrich) in 3 ml of ethanol (>99%, Reakhim) absolutized by 3 Å molecular sieves (Sigma-Aldrich, pellets, 3.2 mm). The resulting solution and the catalyst (substrate/metal = 25) was put into a stainless-steel batch-reactor with magnetic stirring. The reactor was sealed and was filled by 5 MPa of H2 (≥98%, Air Liquide). The reaction was carried out at 200-350 C during 15, 30, 45 min, 1, 3 and 6 h. After the reaction the reactor was cooled. The reaction products were separated from the catalyst by centrifugation (5000 rpm) and then were analyzed. Also, a series of experiments of γ-valerolactone (99%, Sigma-Aldrich, 7 wt% in ethanol) hydrogenation was carried out at 300 C during 15, 30, 45 and 60 min by the same technique described above. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid In water at 0 - 20℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
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7%; 30% | With formic acid;UN-No2881 ex. Kataleuna; at 275℃; | A feed stream comprising undiluted formic acid and undiluted levulinic acid at a molar ratio of 1.0 was contacted with a commercially available Ni-comprising solid hydrogenating catalyst (the same catalyst as used in experiment 4 of EXAMPLE 1 and in all experiments of EXAMPLE 2) at a weight hourly velocity of 3 g/g.hr (grams levulinic acid per gram catalyst per hour), at a temperature of 275 C. and at ambient pressure. Reactor tube, catalyst dilution, catalyst pre-reduction and reactant supply and withdrawal were as described for EXAMPLE 1. A yield of 30 mole % gamma valerolactone and 7 mole % alpha-angelica lactone, based on the moles of levulinic acid in the feed stream, was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With platinum doped titanium oxide; hydrogen In neat (no solvent) at 120℃; for 6h; chemoselective reaction; | |
With hydrogen In 1,4-dioxane at 150℃; for 8h; | 13 Examples 13-15; Preparation of 5-Methyl-N-(2-lsopropyl Phenyl)-2-Pyrrolidone (2-IPPhMP) by Batch Reduction of Ethyl Levulinate (EL) Using 2-Isopropyl Aniline as the Aryl Amine [0075] To a 5 ml pressure vessel was added 50 gm of catalyst, and 1 gm of a solution containing 30 wt % ethyl levulinate, 25% aryl or alkyl amine and 45% dioxane. The vessel was sealed, charged with 5.52 MPa hydrogen and heated to 150° C. for 4 hours. The pressure was maintained at 5.52 MPa during the course of the reaction. At the end of the reaction, the vessel was rapidly cooled in ice, vented and an internal GC standard of methoxyethylether was added. The solution was separated by pipette from the catalyst and analyzed by GC-MS using an HP 6890 (Agilent; Palo Alto, Calif.) equipped with a FFAP 7717 (30 meter) column. The results set forth in the tables below are based on area %.[0080] The temperature and pressure of the reactions were 150° C. and 6.90 MPa, respectively. The feedstock used was ethyl levulinate (EL) and 2-isopropyl aniline (2-IPA) at a ratio (wt. %) of 52/48. The results are set forth in the following table. | |
With hydrogen In 1,4-dioxane at 150℃; for 8h; | 15 Examples 13-15; Preparation of 5-Methyl-N-(2-lsopropyl Phenyl)-2-Pyrrolidone (2-IPPhMP) by Batch Reduction of Ethyl Levulinate (EL) Using 2-Isopropyl Aniline as the Aryl Amine [0075] To a 5 ml pressure vessel was added 50 gm of catalyst, and 1 gm of a solution containing 30 wt % ethyl levulinate, 25% aryl or alkyl amine and 45% dioxane. The vessel was sealed, charged with 5.52 MPa hydrogen and heated to 150° C. for 4 hours. The pressure was maintained at 5.52 MPa during the course of the reaction. At the end of the reaction, the vessel was rapidly cooled in ice, vented and an internal GC standard of methoxyethylether was added. The solution was separated by pipette from the catalyst and analyzed by GC-MS using an HP 6890 (Agilent; Palo Alto, Calif.) equipped with a FFAP 7717 (30 meter) column. The results set forth in the tables below are based on area %.[0080] The temperature and pressure of the reactions were 150° C. and 6.90 MPa, respectively. The feedstock used was ethyl levulinate (EL) and 2-isopropyl aniline (2-IPA) at a ratio (wt. %) of 52/48. The results are set forth in the following table. |
With hydrogen In 1,4-dioxane at 150℃; for 12h; | 14 Examples 13-15; Preparation of 5-Methyl-N-(2-lsopropyl Phenyl)-2-Pyrrolidone (2-IPPhMP) by Batch Reduction of Ethyl Levulinate (EL) Using 2-Isopropyl Aniline as the Aryl Amine [0075] To a 5 ml pressure vessel was added 50 gm of catalyst, and 1 gm of a solution containing 30 wt % ethyl levulinate, 25% aryl or alkyl amine and 45% dioxane. The vessel was sealed, charged with 5.52 MPa hydrogen and heated to 150° C. for 4 hours. The pressure was maintained at 5.52 MPa during the course of the reaction. At the end of the reaction, the vessel was rapidly cooled in ice, vented and an internal GC standard of methoxyethylether was added. The solution was separated by pipette from the catalyst and analyzed by GC-MS using an HP 6890 (Agilent; Palo Alto, Calif.) equipped with a FFAP 7717 (30 meter) column. The results set forth in the tables below are based on area %.[0080] The temperature and pressure of the reactions were 150° C. and 6.90 MPa, respectively. The feedstock used was ethyl levulinate (EL) and 2-isopropyl aniline (2-IPA) at a ratio (wt. %) of 52/48. The results are set forth in the following table. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate; In N,N,N,N,N,N-hexamethylphosphoric triamide; | EXAMPLE 40 (3RS,5SR)-3-[N-(N-Benzyloxycarbonylaminoacetyl)aminoacetyl]oxymethyl-4-oxa-1-azabicyclo[3.2.0]heptan-7-one (40A) and (3RS,5SR)-3-[N-(Aminoacetyl)aminoacetyl]oxymethyl-4-oxa-1-azabicyclo[3.2.0]heptan-7-one hydrochloride(40B) A mixture of (3RS,5SR)-3-Bromomethyl-4-oxa-1-azabicyclo[3.2.0]heptan-7-one (2.0 g,9.71 mmol), N-(benzyloxycarbonylaminoacetyl)aminoacetic acid (2.6 g,11.6 mmol) and Cesium carbonate (3.8 g, 11.6 mmol) in Hexamethylphosphoric triamide (15 ml) was stirred at 65-70 C. for 2 hrs. Resulting mixture was poured onto ice-water and extracted with Ethyl acetate. The extract was washed with water, brine and dried over Magnesium sulfate. Solvent was removed in vacuo and the residue was purified on a silica gel column chromatography using ethyl acetate-acetone (9:1) as the eluent gave an off-white solid (40A). Yield:3.0 g (79%). 1 H NMR (DMSO-d6,delta):2.70-2.85(2H,m),3.30(1H,dd,J=16.1,2.4),3.62-4.20 (7H,m),4.48-4.62(1H,m),5.11(2H,s),5.32(1H,d,J=2.5),7.35(5H,s),7.55 (1H,t,J=5.7),8.35(1H,t,J=5.7). IR(Nujol,cm-1):3461,3405,1781,1750,1722,1636. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.1 g (78%) | With hydrogenchloride; In 1,4-dioxane; ethanol; hexane; acetic acid; | Step 1 Ethyl 2-(5-bromo-2-methyl-1H-indol-3-yl)acetate A mixture of 4-bromophenylhydrazine hydrochloride (2.23 g, 10 mmol) and ethyl levulinate (1.58 g, 11 mmol) in 10 mL HOAc was heated to reflux for 20 h. The HOAc was removed under vaccum. The residue was dissolved in 10 mL EtOH. A solution of HCl in dioxane (12 mmol, 4M solution) was added. The mixture was heated to reflux for 4 h. The mixture was concentrated under vacuum and the residue was purified by flash chromatography on silica gel, eluding with 20% EtOAc in hexane to afford 2.1 g (78%) of the title compound. 1 H NMR (CD3 COCD3) 1.20 (3H, t, J=7.1 Hz), 2.41 (3H, s), 3.66 (2H, s), 4.08 (2H, q, J=7.1 Hz), 7.14 (1H, d, J=1.9 Hz), 7.24 (1H, d, J=1.8 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With phosphoric acid; methylmagnesium bromide; In diethyl ether; ethyl acetate; benzene; | EXAMPLE 1 5,5-Dimethyl-dihydrofuran-2-one (IV) A solution of ethyl levulinate (50.0 g, 0.345 mole) in anhydrous ethyl ether (200 mL) and anhydrous benzene (200 mL) was treated with methylmagnesium bromide (3.0M solution in diethyl ether, 121.0 mL, 0.365 mole) dropwise at 0° C. over 30 minutes. At this time the ether was removed by slow distillation and the resulting benzene solution was heated at reflux for 2 hours. An ice cold solution of 20percent phosphoric acid (500 mL) and ethyl acetate (500 mL) were then added at 0° C. The organic phase was then separated, washed with brine (1*300 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The resulting crude oil was purified by distillation (b.p., 43° C., 0.35 mm Hg) yielding 26.0 g of the title furan-2-one (Y: 66percent); 1 H-NMR (CDCl3): delta2.62 (t, J=8.5 Hz, 2H), 2.05 (t, J=8.5 Hz, 2H), 1.42 (s, 6H). |
66% | With phosphoric acid; methylmagnesium bromide; In diethyl ether; ethyl acetate; benzene; | EXAMPLE 1 5,5-Dimethyl-dihydrofuran-2-one (IV) A solution of ethyl levulinate (50.0 g, 0.345 mole) in anhydrous ethyl ether (200 mL) and anhydrous benzene (200 mL) was treated with methylmagnesium bromide (3.0M solution in diethyl ether, 121.0 mL, 0.365 mole) dropwise at 0° C. over 30 minutes. At this time the ether was removed by slow distillation and the resulting benzene solution was heated at reflux for 2 hours. An ice cold solution of 20percent phosphoric acid (500 mL) and ethyl acetate (500 mL) were then added at 0° C. The organic phase was then separated, washed with brine (1*300 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The resulting crude oil was purified by distillation (b.p., 43° C., 0.35 mm Hg) yielding 26.0 g of the title furan-2-one (Y: 66percent); 1 H-NMR (CDCl3): delta 2.62 (t, J=8.5 Hz, 2H), 2.05 (t, J=8.5 Hz, 2H), 1.42 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.34% | With hydrogen at 25 - 150℃; for 1h; | 21 EXAMPLES 1-22 Preparation of 5-Methyl-N-Alkyl-2-Pyrrolidone; Ethyllevulinate (EtLA) and the indicated alkyl amine (R-NH2) were mixed in approximately equal molar equivalents at room temperature (25° C.) to prepare a solution. To this solution was added the unsupported (Platinum black) or supported metal catalyst. The reactor was pressurized with hydrogen at the indicated pressure and heated for the indicated time. At the end of the reaction, the reactor was cooled, vented and the product analyzed by GC-MS using an HP 6890 (Agilent; Palo Alto, Calif.) equipped with a WCOT fused silica column, 25 m×0.25 MM ID, coating CP-wax 58 (FFAP)-CB DF=0.2 (Varian, Palo Alto, Calif.). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 4 (3 R,S)-3,7a-Dimethyl-2,5-dioxohexahydro-1H-pyrrolo[1,2-a]-imidazole DL-Alaninamide hydrochloride (6.9 g), 0.055 mol) and ethyl 4-oxopentanoate (6.7 g, 0.043 mol) were reacted together according to the procedure of Example 2 to give the title compound, 1.65 g (22.8%), m.p. 184-192. NMR (DMSO-d6: deltaH =8.80 (bs, 1H, NH); 3.90 (q, J=7.5 Hz, 1H, CHCH3) 3.00-2.00 (c.a., 4H, CH2 CH2); 1.42 (s, 3H, C--CH3); 1.22 (d, J=7.5 Hz, 1H, CHCH3). | ||
EXAMPLE 4 (3R,S)-3,7a-Dimethyl-2,5-dioxohexahydro-1H-pyrrolo[1,2-a]imidazole DL-Alaninamide hydrochloride (6.9 g), 0.055 mol) and ethyl 4-oxopentanoate (6.7 g, 0.043 mol) were reacted together according to the procedure of Example 2 to give the title compound, 1.65 g (22.8%), m.p. 184-192. NMR (DMSO-d6: deltaH= 8.80 (bs, 1H, N H); 3.90 (q, J = 7.5 Hz, 1H, C H CH3) 3.00-2.00 (c.a., 4H, C H 2C H 2); 1.42 (s, 3H, C-C H 3); 1.22 (d, J = 7.5 Hz, 1H, CHC H 3) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With sulfuric acid; In methyl magnesium iodide; water; | EXAMPLE 38 STR47 4,5-Dihydro-5,5-dimethyl-2(3H)-furanone A solution of ethyl levulinate (130.2 g, 0.9 mole) in 400 ml ether and 500 ml benzene was cooled in an ice bath and treated with the slow addition of methylmagnesium iodide (1 mole in 500 ml ether). The ether was removed by distillation, and the remaining solution was refluxed for 3 hours. After cooling the reaction mixture was quenched with 1N sulfuric acid. The aqueous phase was washed with diethyl ether, and then the combined organic solutions were treated with aqueous potassium hydroxide (40 g in 200 ml water) and stirred for 1 hour. The aqueous layer was acidified with 50percent sulfuric acid and extracted with ether. The ether layer was dried over sodium sulfate, filtered and evaporated to a brown syrup, which was distilled to give the title compound (50 g, 49percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In diethyl ether; benzene; at 0℃; for 5h;Heating / reflux; | Ethyl Levulinate (5Og) was dissolved in 500 ml of diethylether/benzene (1/1 v/v), cooled to O0C and a MeMgBr solution (127ml, 3M in diethylether) was added drop wise over 2 h. The ether was evaporated and the resulting benzene solution heated to a gentle reflux for 3 h. Removed benzene and redissolved in EtOAc, washed with IN H2SO4, H2O and cone. NaHCO3. Dried over MgSO4, filtered and concentrated to give 5,5-Dimethyl- dihydro-furan-2-one. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100%Chromat. | sulfuric acid; at 80℃; under 40 Torr; for 3h;Product distribution / selectivity; | A 500 ml 3-neck round bottom flask was charged with 36.64g (0.3 mol) erythritol (obtained from the Cargill Company of Wayzata, MN) and 346.01g (2.4 mol) ethyl levulinate (obtained from the Sigma Aldrich Company of St. Louis, MO). The flask was equipped with a Dean Stark trap, mechanical stirrer, and thermocouple. The contents of the flask were heated to 80C, at which point15.99mul of concentrated sulfuric acid (obtained from the Sigma Aldrich Company) was added to the reaction flask via a metered microliter pipette. A vacuum was applied to the reaction flask, slowly bringing the pressure down to 40 torr. This pressure was maintained with stirring while liquid was observed to collect in the Dean Stark trap. About 1 hour, 45 minutes after addition of sulfuric acid, the vacuum was released and a small sample was removed from the reaction flask. The vacuum was then reestablished. After an additional 1 hour, 15 minutes reaction time, liquid had stopped collecting in the Dean Stark trap. The vacuum was released, and the contents of the flask were allowed to cool to ambient temperature. A second sample was removed from the reaction flask.Both samples removed were analyzed by GC-MS. The GC portions of the analyses are shown in FIGS. 2 A and 2B. FIG. 2 A shows the GC of the sample removed after the initial 1 hour, 45 minutes of reaction time. FIG 2B shows the GC of the sample removed after a total of 3 hours reaction time, or an additional 1 hour, 15 minutes after the first sample was taken. The percentages of products were calculated by disregarding the presence of ethyl levulinate, because of the excess molar equivalents of ethyl levulinate used in the reaction. Thus, the percentages of erythritol, the monoketal of erythritol with one molar equivalent of ethyl levulinate, and the bisketal of erythritol with two molar equivalents of ethyl levulinate were calculated by determination of their relative GC peak areas. The sample removed at 1 hour, 45 minutes was found to contain 93.03% of the bisketal, 6.97% of the monoketal, and 0% erythritol by GC peak area. The sample removed after the additional 1 hour, 15 minutes reaction time was found to contain 100% of the bisketal.; Examplesl2-15An 896g sample of the polyketal made according to Example 3 was added to the addition flask of a short path wiped film evaporator equipped with carbon blades. A vacuum was applied to the apparatus until the pressure in the apparatus reached 100 millitorr. While under vacuum the entire apparatus was heated to 150C. The wiped film column blades were rotated at 70% at the maximum rate available on the apparatus. The cold finger of the wiped film apparatus was adjusted to O0C using a refrigerated chiller. Upon reaching the target temperature the contents of the reaction flask were dripped into the wiped film column at a rate of 160 drops/minute. After 3 hours, 15 minutes the contents of the addition flask had been emptied into the column. The non-distilled residue that was captured was analyzed by GPC, GC-MS, and 1H NMR.Using the same procedure, the compounds according to Examples 1, 5, and 6 were purified and analyzed. The results of subsequent analyses are shown in Table 2. |
100%Chromat. | aminosulfonic acid; at 90℃; under 30 Torr; for 8h;Product distribution / selectivity; | Using the procedure of Example 1, various polyketal compounds were synthesized. Table 1 shows reagents, temperature, and time of reaction as well as the percent yield of products obtained at the end of the reaction, as determined by GC-MS (GC peak area) employing the calculation described in Example 1. Unless noted, the pressure of the reaction vessel was 30 torr during the reaction.Butyl levulinate was obtained from the Sigma Aldrich Company of St. Louis, MO. Ethyl acetoacetate was obtained from Acros Organics of Geel, Belgium. Sorbitol was obtained from Acros Organics. Mannitol was obtained from the Sigma Aldrich Company. Pentaerythritol was obtained from the Sigma Aldrich Company. Diglycerol was obtained from Tokyo Kasei Kogyo of Tokyo, Japan. Sulfamic acid was obtained from the Sigma Aldrich Company. Amberlyst-15 was obtained from the Rohm and Haas Company of Philadelphia, PA. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.46 - 6.97%Chromat.; 93.03 - 97.54%Chromat. | sulfuric acid; at 80 - 90℃; under 30 - 40 Torr; for 1.75 - 4h;Product distribution / selectivity; | A 500 ml 3-neck round bottom flask was charged with 36.64g (0.3 mol) erythritol (obtained from the Cargill Company of Wayzata, MN) and 346.01g (2.4 mol) ethyl levulinate (obtained from the Sigma Aldrich Company of St. Louis, MO). The flask was equipped with a Dean Stark trap, mechanical stirrer, and thermocouple. The contents of the flask were heated to 80C, at which point15.99mul of concentrated sulfuric acid (obtained from the Sigma Aldrich Company) was added to the reaction flask via a metered microliter pipette. A vacuum was applied to the reaction flask, slowly bringing the pressure down to 40 torr. This pressure was maintained with stirring while liquid was observed to collect in the Dean Stark trap. About 1 hour, 45 minutes after addition of sulfuric acid, the vacuum was released and a small sample was removed from the reaction flask. The vacuum was then reestablished. After an additional 1 hour, 15 minutes reaction time, liquid had stopped collecting in the Dean Stark trap. The vacuum was released, and the contents of the flask were allowed to cool to ambient temperature. A second sample was removed from the reaction flask.Both samples removed were analyzed by GC-MS. The GC portions of the analyses are shown in FIGS. 2 A and 2B. FIG. 2 A shows the GC of the sample removed after the initial 1 hour, 45 minutes of reaction time. FIG 2B shows the GC of the sample removed after a total of 3 hours reaction time, or an additional 1 hour, 15 minutes after the first sample was taken. The percentages of products were calculated by disregarding the presence of ethyl levulinate, because of the excess molar equivalents of ethyl levulinate used in the reaction. Thus, the percentages of erythritol, the monoketal of erythritol with one molar equivalent of ethyl levulinate, and the bisketal of erythritol with two molar equivalents of ethyl levulinate were calculated by determination of their relative GC peak areas. The sample removed at 1 hour, 45 minutes was found to contain 93.03% of the bisketal, 6.97% of the monoketal, and 0% erythritol by GC peak area. The sample removed after the additional 1 hour, 15 minutes reaction time was found to contain 100% of the bisketal.; Examples 2-11Using the procedure of Example 1, various polyketal compounds were synthesized. Table 1 shows reagents, temperature, and time of reaction as well as the percent yield of products obtained at the end of the reaction, as determined by GC-MS (GC peak area) employing the calculation described in Example 1. Unless noted, the pressure of the reaction vessel was 30 torr during the reaction.Butyl levulinate was obtained from the Sigma Aldrich Company of St. Louis, MO. Ethyl acetoacetate was obtained from Acros Organics of Geel, Belgium. Sorbitol was obtained from Acros Organics. Mannitol was obtained from the Sigma Aldrich Company. Pentaerythritol was obtained from the Sigma Aldrich Company. Diglycerol was obtained from Tokyo Kasei Kogyo of Tokyo, Japan. Sulfamic acid was obtained from the Sigma Aldrich Company. Amberlyst-15 was obtained from the Rohm and Haas Company of Philadelphia, PA. |
1.00%Chromat.; 99.00%Chromat. | Amberlyst-15; at 90℃; under 30 Torr; for 8h;Product distribution / selectivity; | Using the procedure of Example 1, various polyketal compounds were synthesized. Table 1 shows reagents, temperature, and time of reaction as well as the percent yield of products obtained at the end of the reaction, as determined by GC-MS (GC peak area) employing the calculation described in Example 1. Unless noted, the pressure of the reaction vessel was 30 torr during the reaction.Butyl levulinate was obtained from the Sigma Aldrich Company of St. Louis, MO. Ethyl acetoacetate was obtained from Acros Organics of Geel, Belgium. Sorbitol was obtained from Acros Organics. Mannitol was obtained from the Sigma Aldrich Company. Pentaerythritol was obtained from the Sigma Aldrich Company. Diglycerol was obtained from Tokyo Kasei Kogyo of Tokyo, Japan. Sulfamic acid was obtained from the Sigma Aldrich Company. Amberlyst-15 was obtained from the Rohm and Haas Company of Philadelphia, PA. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 49.4% 2: 12.3% 3: 3% | at 20 - 170℃; for 0.616667h; Microwave irradiation; Sealed tube; | 8.1 In a first experiment, a mixture of crystalline dextrose (4 g) in ethanol (40 mL) and dry Amberlyst 35 resin (4 g) was placed in a sealed Teflon-lined reaction vessel inside a high-density rotor for treatment via microwaves in a MicroSYNTH Microwave Labstation. The sample was heated from room temperature to 170°C in 7 min. and maintained at this temperature for 30 min. using an irradiation power of 1000 Watts. The vessel was then cooled. Analysis indicated a 49.4% molar yield of ethyl levulinate 12.3% molar yield of HMF and 3% molar yield of ethoxymethylfurfural from dextrose. These same conditions, when performed using conventional heating methods, provided 24% molar yield of ethyl levulinate, 9% dextrose, and 2% yield of HMF. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1-n-propylimidazole hydrochloride at 90℃; for 15h; | 2 Exemplary Embodiment 2Direct Conversion into Alternative Fuel from Agar that is Carbohydrate Derived from Red Macroalgae with a Solid Brønsted Acid Catalyst and a Solid Catalyst5 g of ethylmethylimidazolium chloride [EMIM]Cl (prepared by Sigma-Aldrich Co. Ltd.) and 500 mg of CrCl2 (5 wt % of the substrate) were put into a 500 mL round bottom flask, and heated up to 90° C. The above mixture was cooled at room temperature for 10 minutes. 50 ml of ethanol (prepared by Sigma-Aldrich Co. Ltd.) and 5 g (dry weight) of activated Dowex resin were added into the mixture, and then 50 ml ethanol and 10 g of agar as the substrate were added again and underwent magnetic stirring. The reaction was carried out at 90° C. for 15 hours. After the reaction is completed, ethanol was evaporated under a decompression condition (about 15 Torr). Residues were dissolved in DCM, and 3 times cleaned with salt water. An organic layer was separated and dried into MgSO4, and DCM was evaporated to get a brownish liquid (3.9 g). The crude was analyzed by GC-MS (see FIG. 2) and 1H FT-NMR (see FIG. 3), and it was thus ascertained that 5-ethoxymethyl-2-furfural (EMF) and levulinic acid butyl ester (LAEE) were produced at a ratio of 5:2 (EMF:LAFE=5:2).Then, this is separated by chromatography (silica, CH2Cl2:Et2O=2:1) and refined, and therefore a yellow mixture solution of EMF and LAEE was produced at a yield of 30% wt/wt (3 g). EMF: 1H NMR (400 MHz, CDCl3) δ9.61 (s, 1H), 7.21 (d, 1H, J=3.4 Hz), 6.52 (d, 1H, J=3.2 Hz), 4.53 (s, 2H), 3.59 (q, 2H, J=7.0 Hz), 1.23 (t, 3H, J=6.9 Hz) 13C NMR (100 MHz, CDCl3) δ 178.1, 159.1, 152.9, 122.3, 111.3, 67.0, 65.0, 15.4. LAEE: 1H NMR (400 MHz, CDCl3) δ 4.12 (q, 2H, J=7.2 Hz), 2.74 (t, 2H, J=6.8 Hz), 2.59 (t, 2H, J=6.8 Hz), 2.19 (s, 3H), 1.24 (t, 3H, J=7.1 Hz) 13C NMR (100 MHz, CDCl3) δ 207.1, 173.1, 61.0, 38.2, 30.2, 28.3, 14.5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 68% 2: 10% 3: 13% | With mesoporous silica Al-MCM-41 (50) catalyst at 140℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dual acidic Glu-TsOH-Ti catalyst at 90℃; for 6h; | |
1: 76% 2: 23% | With mesoporous silica Z-SBA-15 catalyst at 140℃; for 5h; | |
1: 22% 2: 71% | With partially reduced graphene oxide (S-RGO) at 140℃; for 24h; |
With [N,N-dimethylacetamide]+[CH3SO3]- at 120℃; for 15h; Overall yield = 92 %; Overall yield = 0.56 g; | ||
1: 81 %Chromat. 2: 6 %Chromat. | With aluminosilicate type Al-TUD-1(4)-at with Si/Al ratio 4 at 140℃; for 24h; | |
1: Ca. 80 %Chromat. 2: Ca. 18 %Chromat. | With HSO3-functionalised carbon (40 wt%)/MCF (cellular foam) composite at 110℃; for 6h; Green chemistry; | |
1: 43 %Chromat. 2: Ca. 40 %Chromat. | With HSO3-functionalised carbon (63 wt%)/MCF (cellular foam) composite at 110℃; for 24h; Green chemistry; | |
With DeAl-H-beta (12.5)-700 zeolite; Amberlyst-15 at 125℃; for 10h; Sealed tube; | ||
87.5 %Chromat. | With sulfonic acid functionalized organic porous polymer at 110℃; for 0.5h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With 5-isopropyl-2-methylbenzenesulfonic acid In Isopropylbenzene at 50℃; for 20h; | |
75% | With Amberlyst-15 at 77℃; for 23h; | 3.2.3.2. Ethyl levulinate Levulinic acid (5.81g, 50 mmol), anhydrous ethyl alcohol (4.61 g, 500 mmol), and the catalyst(500 mg) were added to a flask equipped with a thermometer and a reflux condenser. The reactionmixture was heated to 77 °C and then stirred at the same temperature for 23 h. After cooling down toroom temperature, the solution was filtered through a Celite layer. The Celite layer was washed withethyl alcohol (15 mL × 2) and the combined alcohol solution was evaporated to give an oil. The oilwas diluted with diethyl ether (40 mL) and the solution was washed with deionized water(30 mL × 2). The ether layer was separated and dried with magnesium sulfate. After removing themagnesium sulfate by filtration, the ether layer was evaporated to give the ethyl levulinate. When thesulfonated carbons, and Amberlyst-15 were used as a catalyst in the reaction, the yields of the ester ineach case were 75% (Amberlyst-15), 67% (SC-I), and 51% (SC-I recovered after 1st use), respectively. |
With H-ZSM-5 |
65.8 %Chromat. | With amberlyst36 at 75℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 70% 2: 18% | With sulfuric acid at 100℃; for 24h; Sealed tube; | |
With [N,N-dimethylacetamide]+[CH3SO3]- at 120℃; for 16h; Overall yield = 64 %; Overall yield = 1.09 g; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [N,N-dimethylacetamide]+[CH3SO3]- at 120℃; for 20h; Overall yield = 22 %; Overall yield = 0.21 g; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 81% 2: 16% | With sulfuric acid at 75℃; for 24h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 71% 2: 10% 3: 16% | With Amberlyst-15 resin at 110℃; Sealed tube; | |
1: 30% 2: 58% 3: 12% | With partially reduced graphene oxide (S-RGO) at 140℃; for 24h; | |
1: 52% 2: 27% 3: 8% | With Amberlyst-15 resin at 75℃; for 24h; Sealed tube; |
1: 43% 2: 42% 3: 9% | With partially reduced graphene oxide (S-RGO) at 140℃; for 24h; | |
1: 67 %Chromat. 2: 11 %Chromat. 3: 10 %Chromat. | With aluminosilicate type Al-TUD-1(21) with Si/Al ratio 21 at 110℃; for 24h; | |
1: 72 %Chromat. 2: 8 %Chromat. 3: 7 %Chromat. | With aluminosilicate type Al-TUD-1(21) with Si/Al ratio 21 at 110℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Amberlyst-15 resin at 110℃; for 30h; Sealed tube; | ||
With tungstosilicic acid supported on high surface area graphite at 140℃; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 21% 2: 64% 3: 13% | With dual acidic Glu-TsOH-Ti catalyst at 120℃; for 24h; | |
1: 60% 2: 29% 3: 6% | With dual acidic Glu-TsOH-Ti catalyst at 120℃; for 6h; | |
1: 43% 2: 21% 3: 8% | In hexane at 100℃; for 0.666667h; Ionic liquid; Sealed tube; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 74% 2: 6% | With calcium carbonate for 1h; Reflux; | 5 Method b 4.5 5-Ethoxymethylfurfural (4) Compound 2 (500 mg, 2.65 mmol) and CaCO3 (265 mg, 2.65 mmol) were stirred in ethanol (10 mL) until dissolution of 2. Then reaction mixture was placed on the oil bath and refluxed for 1 h. After this reaction mixture was cooled down, evaporated to the small volume and partitioned between Et2O (30 mL) and water (30 mL). Water fraction was additionally extracted with Et2O (3 * 30 mL). Organic fractions were combined and dried with Na2SO4, then volatiles were removed to give crude 4 (387 mg, 95%) as yellowish oil. Analysis showed that crude product contained also 9% of 6. |
In water at 70℃; for 0.5h; Overall yield = 98 %; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 18% 2: 58% | With titanium(IV) oxide at 150℃; for 1h; Inert atmosphere; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With hydrogen In toluene at 170℃; Flow reactor; | 2.4. General procedure for reductive amination of EL General procedure: The catalytic experiments were carried out using fixed-bed continuous flow reactor (inner diameter 9mm and total length 265mm). The catalyst precursor (750mg) was diluted with silicon carbide (fraction of 0.2-0.3mm) in a ratio of 1:3 and placed in the reactor between two layers of SiC. Before the experiments, the precursor was reduced in situ in H2 flow (100mL min-1) at the ambient pressure. The samples were heated to 600°C (for Ni2P/SiO2) or to 400°C (for Ni/SiO2) at a heating rate of 1°C min-1 and kept at the reduction temperature for 1h or 2h, respectively [32-34]. (0010) After pre-reduction of the catalyst, the reactor was cooled to the reaction temperature and solvent was supplied into the reactor by a high-pressure pump (Gilson 305). The solvent was then changed to the reaction mixture containing ethyl levulinate (0.04M) and primary amine (0.041M). This point in time was chosen as the starting point of the experiment. The reaction was usually performed at temperature of 170°C, total pressure of 10-20bar, liquid flow rate (V) of 20-30mL h-1 and hydrogen flow rate (VH2) of 30mL min-1 using n-decane as an internal standard. The first sample of liquid products was collected 2h after feeding of the substrate; the following samples were taken every 30min for 2h. The performance of the catalysts was evaluated by averaging three samples taken in the interval 3-4h after the start of the experiment. (0011) The composition of the reaction products was determined by gas chromatography (Agilent 6890N instrument with a HP 1-MS capillary column 30m×0.32mm×1.00μm). The conversion, selectivity and yield were calculated based on ethyl levulinate. The identification of the products was performed by GC-MS (Agilent 7000B Triple Quad System). Evaluation of the response factors for the reaction products (Supplementary Material) made it possible to conclude that the material balance between the inlet and outlet streams exceeds 97% during all tests using toluene as a solvent. |
62% | With platinum doped titanium oxide; hydrogen In neat (no solvent) at 120℃; for 2h; chemoselective reaction; | |
Multi-step reaction with 2 steps 1: / neat (no solvent) / Green chemistry 2: hydrogen; / neat (no solvent) / 12 h / 85 °C / 760.05 Torr / Green chemistry |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With platinum doped titanium oxide; hydrogen In neat (no solvent) at 120℃; for 2h; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With SBA-15-supported sulfated ZrO2 In ethanol at 140℃; for 5h; Autoclave; | 2.3. Catalytic experiments General procedure: HMF etherification with ethanol was carried out in a Parr autoclave reactor (Teflon-lined) equipped with a Parr 4848 controller. Reaction tests were carried out at 140 °C for 5 h under autogenous pressure. The absence of interphase and intraphase gradients was checked by varying the stirring speed and the particle size until there was no effect on the reactant conversion [39]. As a general procedure, 2.5 mmol HMF was dissolved in 3.4 ml ethanol and put into the reactor containing the catalyst. The mixture was stirred at ca. 1500 rpm, and the progress of the reaction was followed by taking samples at regular periods and analyzed by Finnigan GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 17% 2: 4% | With dual acidic Glu-TsOH-Ti catalyst at 120℃; for 24h; | |
With H-USY (6); Amberlyst-15 at 125℃; for 6h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With H-USY (6) zeolite; Amberlyst-15 In ethanol at 96℃; for 6h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With methanesulfonic acid; In glycerol; at 140 - 170℃; for 4.0h; | 69 gram of <strong>[3198-49-0]ethyl glucoside</strong> was mixed with 231 gram ethanol and 60 gram of glycerol. This mixture was transferred to a stirred tank reactor; 2.4 gram of commercially available methylsulfonic acid [MSA] was added as an acid catalyst to the reaction mass in the reactor. The reactor was closed and then heated under stirred condition at 170 C. for one hour. Then reactor was maintained at 140 C. for three hours. After four hours the reactor was cooled and the reaction mass was analyzed for ethyl levulinate formation by gas chromatography. Molar yield of ethyl levulinate was found to be 29%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen; In ethanol; at 139.84℃; under 45004.5 Torr; for 0.5h;Autoclave; | General procedure: The FFA hydrogenolysis reactions were carried out in astainless steel autoclave reactor (100 mL) at a stirring speed of800 r/min. Prior to each reaction, the calcined catalyst samplewas reduced at 623 K in 20% H2-80% N2 at a flow of 40mL/min for 3 h. In a typical trial, 40 g of 10 wt% FFA dissolvedin ethanol was added into reactor together with a quantity ofthe reduced catalyst. After flushing with H2, the reactor waspressurized with H2 to 6.0 MPa, and then heated to 413 K overthe course of 0.5 h. The concentrations of the reactant and liquidproducts were analyzed by gas chromatography (Agilent7890A GC) with a PONA capillary column (50 m × 0.20 mm ×0.50 mum). Products were also identified using an Agilent7890A/5975C gas chromatograph-mass spectrometer (GC-MS)with an HP-5MS column. The liquid products identified in thismanner consisted of 1,2-PeD, 1,5-PeD, 1,4-pentanediol,2-methyl furan (2-MF), 2-methyl tetrahydrofuran (2-MTHF),1-pentanol, 2-pentanol, n-pentane and tetrahydrofurfuryl alcohol(THFA). FFA conversions and product selectivities werecalculated on the basis of the following equations.Conversion (%) = (moles of FFA charged - moles ofFFA left)/moles of FFA charged 100%Selectivity (%) = moles of a product generated/(moles of FFA charged - moles of FFA left) 100% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With well ordered hexagonal sulfonated mesoporous silica carbon nanocomposite In ethanol at 140℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 76 %Spectr. 2: 6 %Spectr. 3: 18 %Spectr. | With aluminium(III) triflate; iron(III) chloride hexahydrate at 30℃; for 18h; Overall yield = 51 %; | 5 1.8 g of sucrose, (λ 120 g of FeCl3 · 6H20,(X060gAluminum trifluoromethanesulfonate,20 mL of ethanol was charged into a 50 mL stainless steel reaction vessel equipped with a Teflon-Heated to 30 ° C,The reaction was carried out at that temperature for 18 h. Filtration, removal of 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 ethyl acetate,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 51%. The qualitative analysis of the reaction products was carried out by gas chromatography-mass spectrometry (GC-MS)And with the standard material (HMF,5-ethoxymethylfurfural and ethyl levulinate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the yield distribution of different furan derivatives was determined by 1 NMR,The product distribution results are:5-ethoxymethylfurfural was 76%, HMF was 18%,Acetylpropanoic vinegar for support6% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 85 %Spectr. 2: 9 %Spectr. 3: 6 %Spectr. | With boron trifluoride diethyl etherate; zinc(II) chloride at 100℃; for 4h; Overall yield = 90 %; | 1 1.8 g of fructose,0.038 g of ZnCl2, 0.014 gBF3Et20, 20 mL of ethanol was added to 50 mLStainless steel-lined reactor with Teflon,Heated to l00 ° C,The reaction was carried out at that temperature for 4 h.Filtration,To remove unreacted fructose and other insoluble impurities,The solvent was removed by rotary evaporation,2 mL of H20,The organic phase was extracted with ethyl acetate,The resulting organic phase was rotary evaporated to a high purity furan derivative,The isolated yield was 90%. Using gas chromatography-mass spectrometry(GC-MS)The qualitative analysis of the reaction product,And with the standard material (HMF,5-ethoxymethylfurfural and ethyl levulinate) in gas chromatography (GC) were compared and confirmed. Quantitative analysis of the product distribution of different furan derivatives was confirmed by 1H NMR,The product distribution results are:5-ethoxymethylfurfural was 85%,HMF 6%,Ethyl propionate was 9% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
14.4%Chromat.; 23.3%Chromat. | With zeolite H-beta; at 110℃; for 1.5h;Autoclave; | General procedure: Catalytic experiments were performed in liquid phase in a stainless-steel stirred autoclave (500 mL) fitted with temperature control and a pressure gauge. Typically, 7.6 g of furfuryl alcohol were mixed with 3 g of catalyst and 300 mL of the corresponding alcohol used as reaction media (methanol, ethanol or 2-propanol).Catalytic tests were also carried out using alpha-angelica lactone, levulinic acid and iso-propyl levulinate as substrates. Decane was added as internal standard for analytical purposes in a concentration of 10 g L-1. After closing the reactor, stirring was fixed in 1000 rpm and a heating rate of 2.5C min-1 was established.Samples were taken periodically and the solution filtered into avial. Selected catalysts were tested in the temperature range of130-170C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 30percent Tantalum tungstophosphoric acid dispersed on tin oxide In ethanol at 120℃; for 0.75h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 53.4% 2: 11.8% | With lignosulfonate acidic carbonaceous catalyst at 110℃; for 15h; Sealed tube; | |
42% | With SO3H-CD carbon In tetrahydrofuran at 160℃; for 6h; Sonication; | |
1: 11 %Spectr. 2: 22 %Spectr. | With sodium perrhenate at 160℃; for 16h; Schlenk technique; | 2.2.1. General procedure for the conversion of carbohydrates into EL General procedure: To a Schlenk flask equipped with a J. Young tap containing a solutionof carbohydrate (0.180 g, 1.0 mmol of hexose) in ethanol (5 mL)was added HReO4 (0.025 g, 10 mol%). The reaction mixture was stirredin a closed Schlenk at 160 °C during 16 h. The yields of the productswere determined by spectroscopy 1H NMR using mesitylene as internalstandard. |
1: 50 %Spectr. 2: 12 %Spectr. | With [ReOCl3(PPh3)2] at 160℃; for 16h; Schlenk technique; | 2.2.1. General procedure for the conversion of carbohydrates into EL General procedure: To a Schlenk flask equipped with a J. Young tap containing a solutionof carbohydrate (0.180 g, 1.0 mmol of hexose) in ethanol (5 mL)was added HReO4 (0.025 g, 10 mol%). The reaction mixture was stirredin a closed Schlenk at 160 °C during 16 h. The yields of the productswere determined by spectroscopy 1H NMR using mesitylene as internalstandard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With SO3H-CD carbon In tetrahydrofuran at 120℃; for 6h; Sonication; | |
1: 55.9% 2: 8.1% 3: 7.4% | With alkaline lignin acidic carbonaceous catalyst at 110℃; for 15h; Sealed tube; | |
1: 49.8% 2: 8.4% 3: 7.3% | With sulfuric acid at 110℃; for 15h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydrogen In hexane at 180℃; for 4h; Autoclave; | 1-32 Example 1 120 mg 10Cu-5Ni/Al2O3 (Cu content 10% wt, Ni content 5% wt),1 mmol of ethyl levulinate and 12 mL of n-hexane were placed in a 25 mL autoclave.Charged at 4 MPa H2, reacted at 800 rmp for 4 h at 180 °C.The reaction product was 2-methyltetrahydrofuran, and the yield was close to 98% by gas chromatography. |
Multi-step reaction with 2 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 5 h / 190 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 2 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 5 h / 190 °C / 30003 Torr / Autoclave |
Multi-step reaction with 2 steps 1: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 3 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 2 h / 230 °C / 30003 Torr / Autoclave 3: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 3 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 2 h / 230 °C / 30003 Torr / Autoclave 3: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 3 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 2 h / 230 °C / 30003 Torr / Autoclave 3: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 4 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 5 h / 190 °C / 30003 Torr / Autoclave 3: hydrogen / 1,4-dioxane / 2 h / 230 °C / 30003 Torr / Autoclave 4: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave | ||
Multi-step reaction with 4 steps 1: hydrogen / 1,4-dioxane / 2 h / 190 °C / 30003 Torr / Autoclave 2: hydrogen / 1,4-dioxane / 5 h / 190 °C / 30003 Torr / Autoclave 3: hydrogen / 1,4-dioxane / 2 h / 230 °C / 30003 Torr / Autoclave 4: hydrogen / 1,4-dioxane / 8 h / 230 °C / 30003 Torr / Autoclave |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16.8% | 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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 57% 2: 6% | With tin(IV) oxide at 160℃; | 1 Example 1: General example for preparation of ethyl levulinate Glucose concentration in ethanol from 33.33 g/L with physical mixture of H-USY and SnO2catalyst loading of 70 wt% with respect to glucose was subjected to thermal treatment at temperature range of 160°C for different time span of 7 h. All the reactions were carried out at 800 RPM to overcome external mass transfer limitations during the reaction. The reaction mixture was cooled in cold water bath to reach 30degree followed by separation from the catalyst by centrifugation. Supernatant reaction mixture was diluted with ethanol and injected into Gas Chromatography (GC) system (chemito-1000) equipped with TR capillary column (30 mmx0.32 mmx0.25mm) and Flame Ionization Detector with carrier gas N2 with flow rate (0078) 1.0 mL min-1. Injection port temperature, oven temperature and detector temperature were programmed at 230°C, 50 to 280°C with heating rate 20°C min-1 and 260°C for feed and product analysis. Yields of EL, EMF and ELA are calculated by following equations: (0079) % Yield of EL= (Moles of EL/Moles of Glucose)* 100 (0080) % Yield of EMF= (Moles of EMF/Moles of Glucose)* 100 (0081) % Yield of ELA= (Moles of ELA/Moles of Glucose)* 100 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silica-supported nickel phosphide at 150℃; for 3h; Inert atmosphere; Autoclave; | General procedure: For catalytic experiments, a stainless-steel batch reactor of 100mL (Parr Instrument) was charged with a catalyst (100mg), furanyl substrate, and solvent (19mL) in which the substrate concentration was set at 0.21M. The reactor was then purged with inert N2 at 25°C for 1h and heated to a desired temperature (usually, 150°C). The reaction started with stirring at 600rpm and was performed for 3h. After the reaction was complete, the heating and stirring were stopped and cooled to 25°C. From the collected etherification product mixture, a sample (1.5mL) was taken and then mixed with 0.08g of toluene (99.5 %) that is an external standard for GC analysis using an Agilent 7890A GC with a flame ionization detector (FID) and a INNOWAX capillary column (30m × 0.25mm × 0.25μm). While the injector and detector were set at 250 and 300°C, respectively, the oven temperature was programmed as follows: 40°C for 2min, ramping to 160°C at 20°Cmin-1, holding at 160°C for 2min, followed by ramping to 250°C at 10°Cmin-1, and finally holding at 250°C for 5min. The product was confirmed by GC-MS analysis (Agilent INNOWAX column). For quantitative measurement, the experiments were repeated at least three times and the average product compositions were reported in this context. Finally, the conversion of furanyl alcohol and the selectivity and yield of each product were calculated as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With pyrrolidine In ethanol at 45℃; for 24h; Molecular sieve; Inert atmosphere; | 1.3.a [0203] (a) Synthesis of benzopyran-4-one: 2,5-dihydroxyacetophenone (0.5 g, 3.28 mmol), ethyl levulinate (0.46 mL, 3.28 mmol) and pyrrolidine (0.87 mL, 9.86 mmol), were dissolved in absolute EtOH (10 mL) with a 3-Å (100 mg) molecular sieve.6 The mixture was shaken at 45°C for 24 h under a N2 atmosphere. Then the reaction mixture was filtered and the filtrate was diluted with CH2Cl2 (100 mL) and washed with HCI 1N (3 x 50 mL), H2O (3 x 50 mL) and brine (3 x 50 mL), dried on anhydrous Na2SO4 and evaporated in the rotary evaporator. The residue was purified by silica gel column chromatography (hexane-AcOEt, 70:30) to obtain the benzopyran-4-one (729 mg, 2.62 mmol, 80%) as a yellowish oil. NMR 1H (400 MHz, CDCl3) 7.34 (d, J= 3.0 Hz, H-5), 7.07 (dd, J= 8.9, 3.0 Hz, H-7), 6.80 (d, J= 8.9 Hz, H-8), 4.14 (q, J= 7.1Hz, 2H, COOCH2CH3), 2.78 (d, J= 16.7 Hz, 1H, CH2a-3), 2.63 (d, J= 16.7 Hz, 1H, CH2b-3), 2.53-2.46 (m, 2H, CH2-2'), 2.1 (m, 2H, CH2-1'), 1.38 (s, 3H, CH3-4'), 1.25 (t, J= 7.1Hz, 3H, COOCH2CH3); 13C NMR (100 MHz, CDCl3) 193.0 (C-4), 173.3 (COOCH2CH3-3'), 153.7 (C-8a), 150.2 (C-6), 125.2 (CH-7), 120.1 (C-4a), 119.5 (CH-8), 110.6 (CH-5), 79.8 (C-2), 60.8 (COOCH2CH3), 47.2 (CH2-3), 34.1 (CH2-1'), 28.7 (CH2-2'), 23.3 (CH3-4'), 14.1 (COOCH2CH3); EIMS m/z 278 [M: C15H18O5]+ (35), 233 (25), 177 (100), 137 (75); HREIMS (%) m/z 278.11408 [M]+ (278.11542 calc for C15H18O5). |
80% | With pyrrolidine In ethanol at 60℃; for 24h; Molecular sieve; |
Tags: 539-88-8 synthesis path| 539-88-8 SDS| 539-88-8 COA| 539-88-8 purity| 539-88-8 application| 539-88-8 NMR| 539-88-8 COA| 539-88-8 structure
[ 58012-34-3 ]
Ethyl 2-(4-oxocyclohexyl)acetate
Similarity: 0.89
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