| 86% |
With thionyl chloride; at 0℃; for 0.666667h;Reflux; |
Dimethyl Furan-2,5-dicarboxylates (17)To a solution of the compound 2,5-furandicarboxylic acid (204.4 mg, 1.309 mmol) in MeOH (13 mL) was added thionyl chloride (0.955 mL, 13.09 mmol) at 0C. The reaction mixture was refluxed for 40 min, then quenched with saturated aqueous NaHCO3and extracted with ethyl acetate for three times. The combined organic layer was dried over Na2SO4and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel eluted with nhexane-EtOAc (3 : 1) to give 17(231.9 mg, 0.130 mmol, 86%). Recrystallized from ethyl acetate-hexane to give colorless cr ystal; mp 110.0 -111.5C; 1H-NMR (400 MHz, CDCl3) delta: 7.22 (s, 2H), 3.94 (s, 6H); 13C-NMR (100 MHz, CDCl3) delta: 158.39 (C), 146.64 (C), 118.45 (CH), 52.37 (CH3); IR (KBr) 1728, 1281 cm-1; HR-MS (EI) Calcd for C8H8O5184.0372. Found 184.0376. |
| 82% |
With chloro-trimethyl-silane; In methanol; for 2h;Inert atmosphere; Reflux; |
A reaction flask was charged with furan-2,5-dicarboxylic acid (1, 250 mg, 1.55 mmol, 97%, purchased from Aldrich), equipped with condenser and flushed with argon. Methanol (0.8 mL) was added, followed by trimethylsilyl chloride (0.4 mL, 3.10 mmol). The reaction mixture was stirred for 2 hours under reflux. After removal of the solvent in vacuo, product was isolated by flash column chromatography on silica gel (CH2Cl2). Colourless crystals, yield 82%, 234 mg, mp 111-112 C; 1H NMR (300 MHz, CDCl3): deltaH 3.94 (6H, s, COOCH3), 7.23 (2H, s, H-3, H-4). |
| 75% |
With hydrogenchloride; In water; for 18h;Reflux; |
Dimethyl 2,5-furandicarboxylate (FDCA-Me2) was synthetized following the method reported by Gubbels et al. [30] based on the Fischer esterification of FDCA with MeOH. A round bottom flask was charged with 25.6 mmol (4 g) of FDCA, 1.38 mol (55.3 g) of MeOH, and 1 mL of 12 M HCl. The mixture left to react for 18 h under reflux and the reaction was then stopped by adding 0.5 M methanol solution of KOH. The solution was then evaporated to dryness and the residue extracted with CHCl3. The extract was then washed with water (200 mL), dried on MgSO4 and evaporated to render a solid that was crystallized from CHCl3 upon adding hexane and cooling. Yield: 75%. m.p.: 112C; 1H NMR (delta ppm, CDCl3, 300 MHz): 3.94 (s, 6H), 7.23 (s, 2H). 13C NMR (delta ppm, CDCl3, 300 MHz): 52.4, 118.5, 146.9, 158.4. |
| 75% |
With sulfuric acid; for 5h;Reflux; |
2,5-Furandicarboxylicacid (15.6 g), anhydrous methanol (200 mL) and concentrated sulfuric acid(2mL) were placed in a round bottom flask (500 mL) and the mixture was refluxedfor 5 h. The excessofthe methanol was distilled off, and thesolution was filtered through a disposable Teflon membranefilter.During filtration, dimethylfurandicarboxylate (DMFD) was precipitated as whitepowder and,aftercooling, distilled water (100 mL) was added. The dispersion was partiallyneutralized by addingNa2CO3 5% w/v during stirring, while pH was measured continuously. Thewhite powder was filteredandthe solid was washed several times with distilled water and dried. The isolatedwhite dimethylesterwas recrystallized with a mixture of 50/50v/v methanol/water.After cooling, 2,5-DMFD wasprecipitated in theform of white needles. The reaction yield was calculated at 75%. |
|
at 180℃; for 3h;Autoclave; |
Example 3: Synthesis of DMFD 100.0 g of crude FDCA, obtained from a different batch than Example 1 but made by the procedure and using the feeds of Example 1 b, was used as the feedstock. This batch of FDCA contained some FFCA. 410 g of MeOH and the FDCA were mixed in a clean and dry 1 L autoclave at a molar ratio of methanol to FDCA of 20:1 and no esterification catalyst was added. The autoclave mixture was heated to 180 C in a closed system to let the pressure develop. After 3 h at 180 C the reaction mixture was cooled to room temperature. The volatiles were removed to obtain 1 14 g of crude product. GC analysis of the crude product showed the following composition: 95.64 wt% of DMFD based on the weight of reaction product, 0.50 wt% of 5- (methoxycarbonyl)furan-2-carboxylic acid (MCFC) based on the weight of product, 1 .78 wt% of _methyl 5-formylfuran-2-carboxylate (MFFC) based on the weight of product, and 0.74 wt% of water. |
|
With thionyl chloride; at 65 - 70℃; for 3h; |
In to a 2L four neck round bottom flask connected to a mechanical stirrer equippedwith reflux condenser, addition funnel, thermometer socket, guard tube are charged2,5-furan dicarboxylic acid (50.Og, 0.32 moE) and methanol (1.0 Lt). To the stirred suspension, thionyl chloride (190.4g, 1.6 mol) was added dropwise at room temperature. After addition, the reaction mixture was heated to 65-70C and maintained for 3 hours. The reaction mixture was then cooled to 20-25C and filteredafforded 52.4g (88.0%) of dimethyl 2,5-furandicarboxylate as white crystalline solid. The product is recrystallized from methanol to get very pure dimethyl 2,5- furandicarboxylate as white crystals suitable for polymerization reactions.HPLC purity: >99.9% |
| 60%Spectr. |
With sulfuric acid; at 70℃; for 20h;Large scale; |
Example 1.1Production of dimethyl 2,5-furandicarboxylate (=Step a)3.30 kg of methanol were used as initial charge together with 0.10 kg of concentrated sulfuric acid in a 10 L glass reactor equipped with heating jacket, reflux condenser, and mechanical stirrer. 1.6 kg of 2,5-furandicarboxylic acid (2,5-FDCA) were slowly added to this mixture, with vigorous stirring. The dense white suspension that forms was then heated to 70 C. (reflux). The course of the reaction was monitored by means of HPLC analysis, whereupon after about 20 h a clear solution was obtained, with complete conversion of the 2,5-FDCA. The reaction mixture was then cooled to 65 C., and neutralized with saturated NaHCO3 solution and solid NaHCO3 (pH 7). During the neutralization, a dense white suspension again formed, and was cooled to 10 C., stirred for a further 0.5 h, and then filtered by way of a P2 sintered glass frit. The filtercake was washed three times with 1 L of cold water, whereupon about 2 kg of wet solid was obtained. For purification and recrystallization, the wet solid was added to 6.00 kg of 2-butanone in a 10 L glass reactor equipped with heating jacket, reflux condenser, and mechanical stirrer. The suspension was heated to 70 C., whereupon a clear solution was obtained. 1.00 kg of water was then added, and this led to formation of a brownish orange aqueous phase. It was sometimes necessary to add 900 mL of saturated sodium chloride solution in order to achieve phase separation. The aqueous phase was removed, and the organic phase was cooled to 20 C., without stirring, whereupon the crystallization of the product began (usually at about 35 C.). The crystalline suspension was then cooled to 0 C. and stirred overnight. The suspension was then filtered by way of a P2 sintered glass frit, and the filtercake was washed with 1 L of cold methanol. The solid residue was dried at room temperature in vacuo. The desired dimethyl 2,5-furandicarboxylate was obtained in a yield of from 50 to 60% and in a purity of >99%. The identity and purity of the final product was determined by means of NMR and HPLC (HPLC column: Varian Polaris 3mu C18-A, 150×4.6 mm). |
|
With sulfuric acid; at 70℃; for 20h;Large scale; |
3.30 kg of methanol were used as initial charge together with 0.10 kg of concentrated sulfuric acid in a 10 L glass reactor equipped with heating jacket, reflux condenser, and mechanical stirrer. 1.6 kg of 2,5-furandicarboxylic acid (2,5-FDCA) were slowly added to this mixture, with vigorous stirring. The dense white suspension that forms was then heated to 70 C. (reflux). The course of the reaction was monitored by means of HPLC analysis, whereupon after about 20 h a clear solution was obtained, with complete conversion of the 2,5-FDCA. The reaction mixture was then cooled to 65 C., and neutralized with saturated NaHCO3 solution and solid NaHCO3 (pH 7). During the neutralization, a dense white suspension again formed, and was cooled to 10 C., stirred for a further 0.5 h, and then filtered by way of a P2 sintered glass frit. The filtercake was washed three times with 1 L of cold water, whereupon about 2 kg of wet solid was obtained. For purification and recrystallization, the wet solid was added to 6.00 kg of 2-butanone in a 10 L glass reactor equipped with heating jacket, reflux condenser, and mechanical stirrer. The suspension was heated to 70 C., whereupon a clear solution was obtained. 1.00 kg of water was then added, and this led to formation of a brownish orange aqueous phase. It was sometimes necessary to add 900 mL of saturated sodium chloride solution in order to achieve phase separation. The aqueous phase was removed, and the organic phase was cooled to 20 C., without stirring, whereupon the crystallization of the product began (usually at about 35 C.). The crystalline suspension was then cooled to 0 C. and stirred overnight. The suspension was then filtered by way of a P2 sintered glass frit, and the filtercake was washed with 1 L of cold methanol. The solid residue was dried at room temperature in vacuo. The desired dimethyl 2,5-furandicarboxylate was obtained in a yield of from 50 to 60% and in a purity of >99%. The identity and purity of the final product was determined by means of NMR and HPLC (HPLC column: Varian Polaris 3mu C18-A, 150×4.6 mm). |
|
With sulfuric acid; at 70℃;Large scale; |
using methanol as an initial charge of 3.30 kg equipped with a heating jacket, a reflux condenser and a mechanical stirrer 10 liters glass reactor together with 0.10 kg of concentrated sulfuric acid. With vigorous stirring 1.6 kg of 2,5-furan-dicarboxylic acid (2,5-rocA) was slowly added to this mixture. Then dense white suspension formed was heated to 70 C (reflux). The reaction was monitored by HPLC analysis of the process, about 20 hours, the clear solution was obtained, 2,5-FDCA complete conversion. Then the reaction mixture was cooled to 65 C, and washed with saturated NaHC03 solution and solid NaHC03 neutralization (pH 7). And in the process, once again formed a dense white suspension and cooled to l C, stirred for an additional 0.5 hours and then filtered through a sintered glass frit P2. The filter cake was washed three times with 1 liter of cold water, this time to obtain about 2 kg of wet solids.For purification and recrystallization, equipped with heating jacket, reflux condenser and mechanical stirrer 10 l glass reactor was added to the wet solid 6.00 kg of 2-butanone. The suspension was heated to 70 , at this time a clear solution. Then was added 1.00 kg of water, which results in the formation of brown-orange aqueous phase. It may be added to 900 ml of saturated sodium chloride solution to effect phase separation. The aqueous phase was removed, and the organic phase was cooled to 20 deg.] C without filtration, the product began to crystallize at this time (typically at about 35 ). Then the crystalline suspension was cooled to 0 and stirred overnight. The suspension was then dried over P2 sintered glass frit and the filter cake was washed with 1 liter of methanol cold. The solid residue was dried under vacuum at room temperature. In 50-60% yield and> 99% purity of the desired 2,5-furan dicarboxylate. By means of NMR and HPLC (HPLC column: VarianPolaris3muC18-A, 150 × 4.6mm) the identity of the final product was measured (Identity) and purity. |
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