| 98% |
at 70℃; for 24h; |
|
| 98% |
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 70℃; for 2h; |
3.2.1. General Procedure for the Esterification between Carboxylic Acids and Alcohols
General procedure: The mixture of carboxylic acid, alcohol, and 1,3-dibromo-5,5-dimethylhydantoin was stirredin a 25 mL reactor tube at 70 °C for 2-40 h. After reaction completion, the mixture was cooled toroom temperature and the alcohol was evaporated under reduced pressure. The isolation procedurewas as follows, except where noted dierently in the Supporting Information. The residue wasdissolved in 10 mL ethyl acetate and washed with a mixture of 1 mL saturated NaHCO3(aq), 1 mLsaturated Na2S2O3(aq), and 10 mL distilled water, and the water phase was extracted with ethyl acetate(2 10 mL). The organic layers were combined, dried over Na2SO4, and the solvent was evaporatedunder reduced pressure |
| 98% |
With 1-(4-Nitrophenyl)-1H-imidazole-3-ium trifluoromethanesulfonate at 80℃; for 4h; Sealed tube; Green chemistry; |
2.2. General procedure for the synthesis of biodiesel
General procedure: A magnetic stir bar placed in a sealed tube, Free Fatty Acids (FFAs), methanol, and ionic liquids were added. The esterification was then carried out for a length of time at a specific temperature with vigorous stirring. After the reaction was completed, the residue was cooled to room temperature and kept at the same temperature until phase separation. The reaction mixture was extracted with ether and water. The upper phase (volume) mainly containing the desired ester could be isolated simply by liquid/liquid phase separation, concentrated, and column chromatography; the bottom phase ionic liquid in water from the reaction could be reused after removal of water under reduced pressure. For several experiments separated organic phase was directly concentrated and the product was confirmed by NMR spectrometry/ mass spectrometry. |
| 97% |
With sulfonated poly-divinylbenzene-co-triallylamine at 24.84℃; for 10h; |
3 2.4. Esterification of long chain fatty acids
General procedure: For the synthesis of biodiesel compounds 1 mmol of each of the long chain fatty acids were taken in 5 mL of methanol. 10 mg PDVTA-SO3H was added to the reaction mixtures under stirring condition and the esterification was allowed to proceed at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was filtered off and the solvent was removed in a rotary evaporator to get the desired product. The solid compounds were characterized by 1H and 13C NMR spectroscopy. The separated catalyst was washed several times with methanol, dried in vacuum and reused further to check its recycling efficiency. |
| 96% |
With bromine for 4h; Ambient temperature; |
|
| 96% |
With Fe3O4 immobilized thiol functionalized mesoporous silica at 24.84℃; for 12h; |
|
| 92% |
With polysiloxane acidic ionic liquids containing pyridinium trifluoroacetate salts for 4h; Reflux; |
2.6 General procedure for biodiesel production using PMO-Py-IL materials
General procedure: In a typical reaction, fatty acids (10 mmol), methanol or ethanol (5 mL), and PMO-Py-IL (0.1 g) as nanocatalyst were mixed in a 50 mL single-necked round bottomed flask and stirred under reflux conditions for 4 h. Upon reaction completion, the mixture was cooled down at RT, PMO-Py-IL was recovered and washed with ethyl acetate for the next run. The combined filtrate and ethyl acetate washings were washed with water and the organic layer was separated and dried over sodium sulfate, filtered, and concentrated under vacuum to provide the desired methyl esters as pure products. |
| 90% |
With cerium(III) trislaurylsulfonate monohydrate In neat (no solvent) at 80℃; for 6h; |
General procedure for the synthesis of esters
General procedure: Carboxylic acid (1 mmol), alcohol (6 mmol) and 5 mol% catalyst were added to a 10 ml round-bottom flask with a reflux condenser.The reaction mixture was continuously stirred using a magnetic stirrer (800 rpm) at 80 °C in an oil-bath for an appropriate time, andthe progress of reaction was monitored by TLC. At the end of reac-tion, the mixture was cooled to room temperature and poured intowater. Afterwards, the filtered cake was purified by chromatography on silica gel using petroleum ether/ethyl acetate (20:1) aseluent to give the pure product. |
| 89% |
With Fe(SO4)3 * xH2O In benzene for 1.5h; Heating; |
|
| 82% |
With sulfuric acid Reflux; |
|
| 80% |
Stage #1: n-tetradecanoic acid With 7,7-dichlorocyclohepta-1,3,5-triene; triethylamine In dichloromethane at 20℃; for 0.416667h; Inert atmosphere;
Stage #2: methanol In dichloromethane at 20℃; Inert atmosphere; |
|
| 77% |
With sulfuric acid at 25℃; for 0.25h; ultrasonic irradiation; |
|
| 76% |
With sulfuric acid Heating; |
|
|
With sulfuric acid |
|
|
With sulfuric acid |
|
| 98 %Chromat. |
With scandium tris(trifluoromethanesulfonate) at 150℃; for 0.0166667h; Microwave irradiation; |
|
| 227 mg |
With HZnPS-1, porous sulfonated zinc phosphonate material at 24.84℃; for 24h; |
|
|
With sulfuric acid |
|
| 89.8 %Spectr. |
With mesoporous 1-butyl-3-methylimidazolium supported sulfated zirconia nanocrystal at 59.84℃; for 8h; Inert atmosphere; Green chemistry; |
2.4. Esterifiaction of long chain fatty acids and transesterificationreactions
General procedure: 2.4. Esterifiaction of long chain fatty acids and transesterificationreactionsFor each of the catalytic reaction 1 mmol of the reactant fattyacid was dissolved in 0.96 g methanol taken in a 50 ml round bottomflask. Then 80 mg of M-IL-SZO-1C catalyst was added into the RBflask. The reaction mixture was refluxed at 333 K for 8 h under thenitrogen atmosphere. To study the progress of the reaction, thereaction mixtures were collected at different time intervals and theprogress of the reactions were monitored by TLC. |
|
With sulfuric acid Heating; |
|
|
With boron trifluoride diethyl etherate In benzene at 100℃; for 1h; |
|
|
With sulfonic acid-functionalized pyrazinium phosphotungstate at 25℃; for 20h; Green chemistry; |
2.4. Catalysis tests
General procedure: Catalytic activity of different IL-POM hybrids in the esterificationof oleic acid with methanol was evaluated. Taking the majorcatalyst PzS-PW as an example, in a typical batch experiment,25 mg of PzS-PW was added into a mixture of oleic acid (1 mmol,0.28 g) and anhydrous methanol (10 mmol, 0.32 g) in a 25 mLround-bottom flask equipped with a magnetic stirrer and a watercondenser system. At the end of the reaction, the catalyst wasseparated by filtration. |
|
With acetyl chloride Reflux; Inert atmosphere; |
General Synthesis Procedure of Alkanolamide Reference Standards
General procedure: General Synthesis Procedure of Alkanolamide Reference Standards (0090) The substrate (free fatty acid) was placed in a three-necked flask and dissolved in methanol (12 mL/g). Acetyl chloride (1.2 equiv.) catalyst was added and the mixture was heated to reflux under nitrogen atmosphere for several hours. After completion of methyl ester formation, a part of the solvent (methanol) was removed under reduced pressure, the reaction mixture was extracted with diethylether, and the diethyether layer was washed three times with 5% NaHCO3 and dried over anhydrous MgSO4. Dried diethylether layer was filtered and crude methyl ester was recovered by removing diethylether under reduced pressure. The methyl ester was carried to the next step without further purification. The crude material was treated with alkanolamine (6 equiv.) for several hours at ambient temperature and was recrystallized from methanol (except for C22 FAAA synthesis where purification was achieved by column chromatography using 3:7 acetone:hexane mixture as the eluent) to obtain the pure alkanolamides. The identity and purity of the isolated products were confirmed by 1H-NMR, mass spectrometry, and GC (for ethanolamides). NMR spectra are shown in FIGS. 12A-12B, 13A-13B, 14A-14B, 15A-15B, 19A-19B, 20A-20B, 21A-21B, 22A-22B, 23, and 24. (0091) N-(2-hydroxyethyl)tetradecanamide (0092) Yield 40.1%, white crystals, 1H-NMR (600 MHz, CDCl-3) δ (ppm); 5.97 (s, 1H, -NH-), 3.71-3.73 (m, 2H, -CH2OH), 3.41-3.43 (m, 2H, -CH2NH-), 2.20 (t, J=7.5 Hz, 2H, -CH2CO-), 1.60-1.65 (m, 2H, -CH-2-), 1.25-1.30 (m, 20H, -(CH2)10-), 0.87 (t, J=6.96 Hz, -CH3). 13C NMR (600 MHz, CDCl3) δ (ppm): 174.8, 62.8, 42.6, 36.8, 32.1, 29.8, 29.6, 29.5, 29.4, 25.9, 22.8, 14.3. NMR spectral data matched that of the literature. |
|
With [(n-C4H9)4N]6[α-PW11Al(OH)O39Zr(η5-C5H5)2]2 at 80℃; for 6h; Schlenk technique; |
Esterification of FFAs with methanol
A sample catalyst was placed in a 60 mL Schlenk tube in air. FFAs (linoleic acid, oleic acid, palmitic acid, myristic acid and lauric acid) and methanol (49.3 mmol) were added using a micropipette. The reaction mixture was heated in an oil bath at 60 ± 2 and 80 ± 2 °C. The reaction solution was analyzed by liquid chromatography (Shim-pack VP-ODS column, 4.6 mm× 150 mm). Values of the products were assigned by comparing the obtained results with the analysis results obtained from analyzing authentic samples under thes ame conditions. The conversion (%) and turnover number (TON) was calculated as [mol of substrate]0- [mol of substrate]t}/[mol ofsubstrate]0 × 100 and [mol of corresponding product]t/[mol of catalyst], respectively. |
|
With polystyrene supported superacidic fluoroalkyl sulfonic acid catalyst at 65℃; |
|
|
With O40PW12(3-)*2H(1+)*2H3N*Ag(1+) |
|
|
at 90℃; for 24h; Acidic conditions; |
|
| 97 %Spectr. |
With sulfonated pyrene knitted porous polymer at 70℃; for 5h; Green chemistry; |
|
|
With sulfuric acid at 20℃; for 12h; |
4.3. Preparation of Methyl and Ethyl Esters
General procedure: Prior to Gas Chromatography-Mass Spectrometry (GC-MS) analysis, active fractions andcommercial decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, and tetradecanoic acid(purity > 98%; Sigma-Aldrich, St. Louis, MI, USA) were methylated and ethylated. Samples (30 mg)were diluted with 10 mL acidified methanol or ethanol (1% sulfuric acid) and stirred for 12 h at roomtemperature. The product of the reaction was suspended in an aqueous solution of 20% Na2CO3(20 mL) and extracted with CHCl3 (3, 20 mL, each one) and the solvent was eliminated under vacuumuntil dry. These derivatives were stored at 4 C until use in assays [60]. |
|
With poly(1,3-diethynylbenzene)-SO3H Reflux; |
|
|
With sulfonic acid functionalized microporous ionic polymers for 7.5h; Reflux; |
2.3. Catalytic activity and transesterification of prepared PIP-C8 catalyst
General procedure: Oleic acid (99.9% purified-Mackline) esterification reactions wereperformed in a 150 ml three-necked flask equipped with a magneticstirrer and a digital thermometer in an oil bath. Reactions were performedusing oleic acid (C18:1), which is the most commonly used FFAto evaluate the catalytic performance [20], and 95 mg of catalystloading at ethanol reflux temperature with different alcohol to acidmolar ratios. The acid value of the ethyl oleate phase was determined bytitration after the removal of excess ethanol with a standard potassiumhydroxide (0.01 mol L-1) potassium hydroxide (KOH, energy chemical,99.0%) solution [21]. |
|
With sulfuric acid at 80℃; for 1.5h; |
Preparation of Fatty Acid Methyl Esters
General procedure: A solution of methanolic sodium hydroxide (9:1, 5 mL) was added to an oil sample(30 mg) and the mixture was heated under reflux for 90 min. After cooling, deionized water(10 mL) was added and the mixture was shaken for a few seconds. Unsaponified fatty acidswere discarded by extraction with hexane (3 5 mL). The layer below was collected andadjusted to pH 3 (by 6 N HCl), followed by extraction with hexane (3 5 mL). The organiclayer was removed under reduced pressure. The obtained fatty acid was further mixedwith a solution of 2% H2SO4 in methanol, and the mixture was heated under reflux at 80 Cfor 90 min. After cooling to ambient temperature, water (0.5 mL) was added, followed byextraction with hexane (3 5 mL). The methyl ester was evaporated to dryness, weighedand solubilized in hexane (1 mL) before injection into the gas chromatograph. |
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