potassium;prop-2-enoate

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-bromo-6-hydroxymethyl-[8(4-methoxyphenyl)octyloxy]pyridine (5.00 g, 11.8 mmol) in DMF (22.8 ml) and water (1.2 ml) were added potassium acetate (2.91 g, 29.7 mmol), tetra-n-butylammonium iodide (4.37 g, 11.8 mmol), triphenylphosphine (0,245 g, 0.94 mmol), palladium chloride (83 mg, 0.47 mmol) and potassium acrylate (3.91 g, 35.4 mmol). The mixture was placed under nitrogen and stirred and heated at 120° C. for 3.3 h. Some potassium acrylate remained undissolved. The mixture was cooled, solids filtered and washed with ethyl acetate (2×60 ml). The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml). The organic layer was dried and evaporated. The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%). mp 112°114° C. The mixture was cooled solids filtered washed with ethyl acetate (2×60 ml) The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml) The organic layer was dried evaporated The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%) mp 112°114° C.

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-bromo-6-hydroxymethyl-[8(4-methoxyphenyl)octyloxy]pyridine (5.00 g, 11.8 mmol) in DMF (22.8 ml) and water (1.2 ml) were added potassium acetate (2.91 g, 29.7 mmol), tetra-n-butylammonium iodide (4.37 g, 11.8 mmol), triphenylphosphine (0,245 g, 0.94 mmol), palladium chloride (83 mg, 0.47 mmol) and potassium acrylate (3.91 g, 35.4 mmol). The mixture was placed under nitrogen and stirred and heated at 120° C. for 3.3 h. Some potassium acrylate remained undissolved. The mixture was cooled, solids filtered and washed with ethyl acetate (2×60 ml). The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml). The organic layer was dried and evaporated. The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%). mp 112°114° C. The mixture was cooled solids filtered washed with ethyl acetate (2×60 ml) The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml) The organic layer was dried evaporated The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%) mp 112°114° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Chloroethyl 4-acryloyloxybutyl carbonate (1.253 g, 5.00 mmol) prepared as described in Preparation 10 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.28 g (89%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.58 (3 H, d, J=5 Hz, CH3 --CH), 1.80 (4 H, m, CH2 --CH2), 4.24 (4 H, m, 2×CH2 --O), 5.7-6.7 (6 H, m, 2×CH=CH2), 6.87 (1 H, k, J=5 Hz, CH--CH3). as described in Preparation 10 After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Chloroethyl 4-acryloyloxybutyl carbonate (1.253 g, 5.00 mmol) prepared as described in Preparation 10 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.28 g (89%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.58 (3 H, d, J=5 Hz, CH3 --CH), 1.80 (4 H, m, CH2 --CH2), 4.24 (4 H, m, 2×CH2 --O), 5.7-6.7 (6 H, m, 2×CH=CH2), 6.87 (1 H, k, J=5 Hz, CH--CH3). as described in Preparation 10 After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Chloromethyl 4-acryloyloxybutyl carbonate (1.183 g, 5.00 mmol) prepared as described in Preparation 9 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.24 g (91%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.82 (4 H, m, CH2 --CH2), 4.23 (4 H, m, 2× CH2 --O), 5.88 (2 H, s, O--CH2 --O), 5.7-6.8 (6 H, 2×CH=CH2). as described in Preparation 9 After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Chloromethyl 4-acryloyloxybutyl carbonate (1.183 g, 5.00 mmol) prepared as described in Preparation 9 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.24 g (91%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.82 (4 H, m, CH2 --CH2), 4.23 (4 H, m, 2× CH2 --O), 5.88 (2 H, s, O--CH2 --O), 5.7-6.8 (6 H, 2×CH=CH2). as described in Preparation 9 After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Chloroethyl 4-acryloyloxybutyl carbonate (1.253 g, 5.00 mmol) prepared as described in Example 9 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.28 g (89%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.58 (3H, d, J=5 Hz, CH3 --CH), 1.80 (4H, m, CH2 --CH2), 4.24 (4H, m, 2×CH2 --O), 5.7-6.7 (6H, m, 2×CH=CH2), 6.87 (1H, k, J=5 Hz, CH--CH3). After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Chloroethyl 4-acryloyloxybutyl carbonate (1.253 g, 5.00 mmol) prepared as described in Example 9 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.28 g (89%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.58 (3H, d, J=5 Hz, CH3 --CH), 1.80 (4H, m, CH2 --CH2), 4.24 (4H, m, 2×CH2 --O), 5.7-6.7 (6H, m, 2×CH=CH2), 6.87 (1H, k, J=5 Hz, CH--CH3). After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Chloromethyl 4-acryloyloxybutyl carbonate (1.183 g, 5.00 mmol) prepared as described in Example 8 is added to a suspension of freeze dried potassium acrylate (0.606 g, 5.50 mmol) and 18-crown-6 (0.066 g, 0.25 mmol) in dimethylformamide (50 ml) under a dry N2 atmosphere. After 5 days at 20° C. the solvent is removed under reduced pressure and the residue dissolved by adding dichloromethane (60 ml) and water (30 ml). After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) and the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml). The organic phase is dried (MgSO4) and the solvent removed under reduced pressure to give 1.24 g (91%) of the title product. 1H NMR (60 MHz, CDCl3): δ 1.82 (4H, m, CH2 --CH2), 4.23 (4H, m, 2×CH2 --O), 5.88 (2H, s, O--CH2 --O), 5.7-6.8 (6H, 2×CH=CH2). After 5 days at 20° C. the solvent is removed under reduced pressure the residue dissolved by adding dichloromethane (60 ml) and water (30 ml) After separating the phases the aqueous layer is extracted with dichloromethane (3×30 ml) the combined organic phase washed with saturated aqueous sodium hydrogen carbonate (50 ml) The organic phase is dried (MgSO4) the solvent removed under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1 mole triphenylchloromethane was stirred with 1.5 moles potassium acrylate in 998 g dimethyl formamide in the presence of 0.14 g hydroquinone under the conditions described in Example 1. The precipitated potassium chloride was filtered off and the triphenyl methyl acrylate solution was concentrated by rotary evaporation at 65° to 100° C. and reduced to produce liquid triphenylmethyl acrylate. This was dissolved at 70 percent in xylene and filtered. The precipitated potassium chloride was filtered off the triphenyl methyl acrylate solution was concentrated by rotary evaporation at 65° to 100° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1 mole triphenylchloromethane was stirred with 1.5 moles potassium acrylate in 998 g dimethyl formamide in the presence of 0.14 g hydroquinone under the conditions described in Example 1. The precipitated potassium chloride was filtered off and the triphenyl methyl acrylate solution was concentrated by rotary evaporation at 65° to 100° C. and reduced to produce liquid triphenylmethyl acrylate. This was dissolved at 70 percent in xylene and filtered. The precipitated potassium chloride was filtered off the triphenyl methyl acrylate solution was concentrated by rotary evaporation at 65° to 100° C.

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-bromo-6-hydroxymethyl-[8(4-methoxyphenyl)octyloxy]pyridine (5.00 g, 11.8 mmol) in DMF (22.8 ml) and water (1.2 ml) were added potassium acetate (2.91 g, 29.7 mmol), tetra-n-butylammonium iodide (4.37 g, 11.8 mmol), triphenylphosphine (0,245 g, 0.94 mmol), palladium chloride (83 mg, 0.47 mmol) and potassium acrylate (3.91 g, 35.4 mmol). The mixture was placed under nitrogen and stirred and heated at 120° C. for 3.3 h. Some potassium acrylate remained undissolved. The mixture was cooled, solids filtered and washed with ethyl acetate (2×60 ml). The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml). The organic layer was dried and evaporated. The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%). mp 112°114° C. The mixture was cooled solids filtered washed with ethyl acetate (2×60 ml) The filtrate was washed with water (250 ml) and with 5% sodium chloride solution (2×125 ml) The organic layer was dried evaporated The pure product was obtained by flash column chromatography (silica, 2,0% ether in dichloromethane) (3.52 g, 72%) mp 112°114° C.