(乙氧基羰基甲基)二甲基溴化硫鎓

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of ethyl bromoacetate (98%, 287 g, 1.68 mol) and methyl sulfide (99%, 156 mL, 1.25 eq.) in acetone (500 mL) was kept at 15° C. A white precipitate started to appear immediately and became thicker upon stirring. After stirring for 18 h at 22° C., the solid was filtered, washed with acetone (3×100 mL), and dried under vacuum to afford 1 (477 g, 83.4%) as white crystals. 1H NMR (250 MHz, CDCl3) δ 5.20 (s, 2H); 4.29 (q, J=7.2, 2H); 3.46 (s, 6H); 1.32 (t, J=7.2, 3H). 13C NMR (62.5 MHz, CDCl3) δ 164.36; 63.38; 44.38; 25.22; 13.92. was kept at 15° C After stirring for 18 h at 22° C. the solid was filtered washed with acetone (3×100 mL) dried under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of ethyl bromoacetate (98%, 287 g, 1.68 mol) and methyl sulfide (99%, 156 mL, 1.25 eq.) in acetone (500 mL) was kept at 15° C. A white precipitate started to appear immediately and became thicker upon stirring. After stirring for 18 h at 22° C., the solid was filtered, washed with acetone (3×100 mL), and dried under vacuum to afford 1 (477 g, 83.4%) as white crystals. 1H NMR (250 MHz, CDCl3) δ 5.20 (s, 2H); 4.29 (q, J=7.2, 2H); 3.46 (s, 6H); 1.32 (t, J=7.2, 3H). 13C NMR (62.5 MHz, CDCl3) δ 164.36; 63.38; 44.38; 25.22; 13.92. was kept at 15° C After stirring for 18 h at 22° C. the solid was filtered washed with acetone (3×100 mL) dried under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer, dropping funnel, nitrogen inlet and a septum was placed sodium hydride (8.2 g, 0.17 moles, 50% dispersion). The dispersion was washed with petroleum either (2×100 ml) and dried under nitrogen. Trimethylsulfoxonium iodide (37.7 g, 0.17 moles) was added, followed by a dropwise addition of dry dimethylsulfoxide (45 ml) via a syringe over a 30-minute period. The suspension was stirred at room temperature for 1.5 hours, and then a solution of carbethoxymethyl dimethylsulfonium bromide (41.2 g, 0.18 moles) in dimethylsulfoxide (60 ml) was added over a 10-minute period, under continuous stirring. The milky white suspension was further stirred at room temperature for 1.5 hours. A suspension of 3,4,5-trimethoxy-3',4'-methylenedioxy chalcone XXIIa (55.9 g, 0.16 moles) [prepared according to the procedure described by S. Wattanasin and W. S. Murphy, Synthesis, 647 (1980)] in dimethylsulfoxide (185 ml) was added in a steady stream over a 5-minute period, and then the reaction mixture was stirred at room temperature for 17 hours. The reaction mixture was poured into cold 0.1N HCl (700 ml), and the resulting gummy material was separated from the aqueous solution. The aqueous solution was extracted from ether (2×500 ml). The combined extract together with an additional amount of ether (500 ml) was employed to dissolve the gummy precipitate. The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water, dried (Na2SO4 and MgSO4) and concentrated to yield the α-isomer of the title compound (68.0 g) as a light-yellow glass. The 1H NMR spectral data of this material was identical to the α-isomer reported by W. S. Murphy and S. Wattanasin, J.C.S. Perkin I, 271 (1982). In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer The dispersion was washed with petroleum either (2×100 ml) dried under nitrogen The milky white suspension was further stirred at room temperature for 1.5 hours prepared was added in a steady stream over a 5-minute period the reaction mixture was stirred at room temperature for 17 hours the resulting gummy material was separated from the aqueous solution The aqueous solution was extracted from ether (2×500 ml) The combined extract together with an additional amount of ether (500 ml) to dissolve the gummy precipitate The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water dried (Na2SO4 and MgSO4) concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer, dropping funnel, nitrogen inlet and a septum was placed sodium hydride (8.2 g, 0.17 moles, 50% dispersion). The dispersion was washed with petroleum ether (2×100 ml) and dried under nitrogen. Trimethylsulfoxonium iodide (37.7 g, 0.17 moles) was added, followed by a dropwise addition of dry dimethylsulfoxide (45 ml) via a syringe over a 30-minute period. The suspension was stirred at room temperature for 1.5 hours, and then a solution of carbethoxymethyl dimethylsulfonium bromide (41.2 g, 0.18 moles) in dimethylsulfoxide (60 ml) was added over a 10-minute period, under continuous stirring. The milky white suspension was further stirred at room temperature for 1.5 hours. A suspension of 3,4,5-trimethoxy-3',4'-methylenedioxy chalcone XXIIa (55.9 g, 0.16 moles) [prepared according to the procedure described by S. Wattanasin and W. S. Murphy, Synthesis, 647 (1980)] in dimethylsulfoxide (185 ml) was added in a steady stream over a 5-minute period, and then the reaction mixture was stirred at room temperature for 17 hours. The reaction mixture was poured into cold 0.1N HCl (700 ml), and the resulting gummy material was separated from the aqueous solution. The aqueous solution was extracted with ether (2×500 ml). The combined extract together with an additional amount of ether (500 ml) was employed to dissolve the gummy precipitate. The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water, dried (Na2SO4 and MgSO4) and concentrated to yield the α-isomer of the title compound (68.0 g) as a light-yellow glass. The 1H NMR spectral data of this material was identical to the α-isomer reported by W. S. Murphy and S. Wattanasin, J.C.S. Perkin I, 271 (1982). In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer The dispersion was washed with petroleum ether (2×100 ml) dried under nitrogen The milky white suspension was further stirred at room temperature for 1.5 hours prepared was added in a steady stream over a 5-minute period the reaction mixture was stirred at room temperature for 17 hours the resulting gummy material was separated from the aqueous solution The aqueous solution was extracted with ether (2×500 ml) The combined extract together with an additional amount of ether (500 ml) to dissolve the gummy precipitate The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water dried (Na2SO4 and MgSO4) concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer, dropping funnel, nitrogen inlet and a septum was placed sodium hydride (8.2 g, 0.17 moles, 50% dispersion). The dispersion was washed with petroleum ether (2×100 ml) and dried under nitrogen. Trimethylsulfoxonium iodide (37.7 g, 0.17 moles) was added, followed by a dropwise addition of dry dimethylsulfoxide (45 ml) via a syringe over a 30-minute period. The suspension was stirred at room temperature for 1.5 hours, and then a solution of carbethoxymethyl dimethylsulfonium bromide (41.2 g, 0.18 moles) in dimethylsulfoxide (60 ml) was added over a 10-minute period, under continuous stirring. The milky white suspension was further stirred at room temperature for 1.5 hours. A suspension of 3,4,5-trimethoxy-3',4'-methylenedioxy chalcone XXIIa (55.9 g, 0.16 moles) [prepared according to the procedure described by S. Wattanasin and W. S. Murphy, Synthesis, 647 (1980)] in dimethylsulfoxide (185 ml) was added in a steady stream over a 5-minute period, and then the reaction mixture was stirred at room temperature for 17 hours. The reaction mixture was poured into cold 0.1N HCl (700 ml), and the resulting gummy material was separated from the aqueous solution. The aqueous solution was extracted with ether (2×500 ml). The combined extract together with an additional amount of ether (500 ml) was employed to dissolve the gummy precipitate. The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water, dried (Na2SO4 and MgSO4) and concentrated to yield the α-isomer of the title compound (68.0 g) as a light-yellow glass. The 1H NMR spectral data of this material was identical to the α-isomer reported by W. S. Murphy and S. Wattanasin, J. C. S. Perkin I, 271 (1982). In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer The dispersion was washed with petroleum ether (2×100 ml) dried under nitrogen The milky white suspension was further stirred at room temperature for 1.5 hours prepared was added in a steady stream over a 5-minute period the reaction mixture was stirred at room temperature for 17 hours the resulting gummy material was separated from the aqueous solution The aqueous solution was extracted with ether (2×500 ml) The combined extract together with an additional amount of ether (500 ml) to dissolve the gummy precipitate The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water dried (Na2SO4 and MgSO4) concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer, dropping funnel, nitrogen inlet and a septum was placed sodium hydride (8.2 g, 0.17 moles, 50% dispersion). The dispersion was washed with petroleum ether (2×100 ml) and dried under nitrogen. Trimethylsulfoxonium iodide (37.7 g, 0.17 moles) was added, followed by a dropwise addition of dry dimethylsulfoxide (45 ml) via a syringe over a 30-minute period. The suspension was stirred at room temperature for 1.5 hours, and then a solution of carbethoxymethyl dimethylsulfonium bromide (41.2 g, 0.18 moles) in dimethylsulfoxide (60 ml) was added over a 10-minute period, under continuous stirring. The milky white suspension was further stirred at room temperature for 1.5 hours. A suspension of 3,4,5-trimethoxy-3',4'-methylenedioxy chalcone XXIIa (55.9 g, 0.16 moles) [prepared according to the procedure described by S. Wattanasin and W. S. Murphy, Synthesis, 647 (1980)] in dimethylsulfoxide (185 ml) was added in a steady stream over a 5-minute period, and then the reaction mixture was stirred at room temperature for 17 hours. The reaction mixture was poured into cold 0.1N HCl (700 ml), and the resulting gummy material was separated from the aqueous solution. The aqueous solution was extracted with ether (2×500 ml). The combined extract together with an additional amount of ether (500 ml) was employed to dissolve the gummy precipitate. The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water, dried (Na2SO4 and MgSO4) and concentrated to yield the α-isomer of the title compound (68.0 g) as a light-yellow glass. The 1H NMR spectral data of this material was identical to the α-isomer reported by W. S. Murphy and S. Wattanasin, J. C. S. Perkin I, 271 (1982). In a three-neck one-liter round-bottom flask, equipped with a magnetic stirrer The dispersion was washed with petroleum ether (2×100 ml) dried under nitrogen The milky white suspension was further stirred at room temperature for 1.5 hours prepared was added in a steady stream over a 5-minute period the reaction mixture was stirred at room temperature for 17 hours the resulting gummy material was separated from the aqueous solution The aqueous solution was extracted with ether (2×500 ml) The combined extract together with an additional amount of ether (500 ml) to dissolve the gummy precipitate The etheral solution was sequentially washed with aqueous NaHCO3 solution (500 ml, 5%) and water dried (Na2SO4 and MgSO4) concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of carboethoxymethyl dimethylsulfonium bromide (45.5 g, 198.6 mmol) in toluene (350 mL) was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (30.2 g, 198.4 mmol). The resulting mixture was stirred at room temperature. After one hour, the reaction mixture was treated with 2-cyclopenten-1-one (19.57 g, 238.4 mmol). After an additional 18 hours, the reaction mixture was added to a 1N hydrochloric acid/sodium chloride solution. The resulting mixture was extracted with diethyl ether. The combined ether extracts were dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was purified using silica-gel chromatography, eluting with a linear gradient of 10% ethyl acetate/hexanes to 50% ethyl acetate/hexanes, to give 22.81 g (68%) of the title compound. Melting point: 36-38° C. After an additional 18 hours The resulting mixture was extracted with diethyl ether The combined ether extracts were dried over magnesium sulfate filtered concentrated in vacuo The residue was purified eluting with a linear gradient of 10% ethyl acetate/hexanes to 50% ethyl acetate/hexanes

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl bromoacetate (265 g) and dimethyl sulfide (114 g) in acetone (500 mL) was stirred at room temperature. After three days, the title compound was isolated by filtration of the reaction mixture. Melting point 88-90° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl bromoacetate (265 g) and dimethyl sulfide (114 g) in acetone (500 mL) was stirred at room temperature. After three days, the title compound was isolated by filtration of the reaction mixture. Melting point 88-90° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of carboethoxymethyl dimethylsulfonium bromide (45.5 g) in toluene (350 mL) was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (30.2 g). The resulting mixture was stirred at room temperature. After one hour, the reaction mixture was treated with 2-cyclopenten-1-one (19.57 g). After an additional 18 hours, the reaction mixture was added to a 1N hydrochloric acid/sodium chloride solution. The resulting mixture was extracted with diethyl ether. The combined ether extracts were dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was purified using silica-gel chromatography, eluting with a linear gradient of 10% ethyl acetate/hexanes to 50% ethyl acetate/hexanes, to give 22.81 g of the title compound. Melting point: 36-38° C. After an additional 18 hours The resulting mixture was extracted with diethyl ether The combined ether extracts were dried over magnesium sulfate filtered concentrated in vacuo The residue was purified eluting with a linear gradient of 10% ethyl acetate/hexanes to 50% ethyl acetate/hexanes

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl bromoacetate (265 g) and dimethyl sulfide (114 g) in acetone (500 mL) was stirred at room temperature. After three days, the title compound was isolated by filtration of the reaction mixture. Melting point 88-90° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of ethyl bromoacetate (265 g) and dimethyl sulfide (114 g) in acetone (500 mL) was stirred at room temperature. After three days, the title compound was isolated by filtration of the reaction mixture. Melting point 88-90° C.