4-ethenoxybutan-1-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 3 L flask equipped with a mechanical stirrer and N2 purge was added 1000 g of tetrahydrofuran and 220.7 g (2.3 mol) of sodium t-butoxide. Hydroxybutyvinyl ether (236 g, 2.03 mol) was added dropwise at a rate to maintain the temperature at ≤40° C. This reaction mass was cooled to -40° C. A solution of benzenesulfonyl chloride (353 g, 2 mol) in 300 g of tetrahydrofuran was added dropwise at a rate to maintain the reaction temperature at ≤-20° C. After the addition was complete, the reaction mixture was allowed to warm to room temperature to obtain the butylvinyl ether benzenesulfonate, ##STR8## Into a 3 L flask equipped with a mechanical stirrer N2 purge to maintain the temperature at ≤40° C to maintain the reaction temperature at ≤-20° C After the addition to warm to room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 liter three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether (133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 milliliters) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 milliliters), dissolved in methylene chloride (1 liter), washed with water (1×750 milliliters), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 grams of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae reflux condenser to reflux about 5 hours to quench any residual isocyanate the solution was stirred for 0.5 hour the residual oil was triturated with hexane (3×500 milliliters) dissolved in methylene chloride (1 liter) washed with water (1×750 milliliters) dried over anhydrous magnesium sulfate filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 liter three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether (133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 milliliters) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 milliliters), dissolved in methylene chloride (1 liter), washed with water (1×750 milliliters), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 grams of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae reflux condenser to reflux about 5 hours to quench any residual isocyanate the solution was stirred for 0.5 hour the residual oil was triturated with hexane (3×500 milliliters) dissolved in methylene chloride (1 liter) washed with water (1×750 milliliters) dried over anhydrous magnesium sulfate filtered concentrated in vacuo

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1,000 g (8.61 mol) of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical) and 448 g (11.2 mol) of sodium hydroxide were charged in a 3 L cylindrical flask equipped with a stirrer, a thermometer and a dropping funnel. The temperature was raised to 40° C. under stirring, 1,243 g (13.4 mol) of epichlorohydrin was then gradually added, and a reaction was conducted under controlling to 40° C. to 60° C. At after 8 hours of the reaction, the sodium chloride generated by the reaction was removed by filtration, 1,000 g of hexane was put therein, and the mixture was washed with 400 g of a 3% aqueous solution of sodium hydrogen sulfate and further washed with 800 g of 17% brine. The organic layer was concentrated by using a rotary evaporator to thereby distill the hexane off, and filtration was conducted to give the objective vinyloxybutyl glycidyl ether with a purity of 94% and a yield of 94%. At this time, the 4-hydroxybutyl vinyl ether contained in the obtained substance was 0.5%. equipped with a stirrer under controlling to 40° C. to 60° C At after 8 hours of the reaction was removed by filtration, 1,000 g of hexane the mixture was washed with 400 g of a 3% aqueous solution of sodium hydrogen sulfate further washed with 800 g of 17% brine The organic layer was concentrated a rotary evaporator to thereby distill the hexane off, and filtration

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1,000 g (8.61 mol) of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical) and 448 g (11.2 mol) of sodium hydroxide were charged in a 3 L cylindrical flask equipped with a stirrer, a thermometer and a dropping funnel. The temperature was raised to 40° C. under stirring, 1,243 g (13.4 mol) of epichlorohydrin was then gradually added, and a reaction was conducted under controlling to 40° C. to 60° C. At after 8 hours of the reaction, the sodium chloride generated by the reaction was removed by filtration, 1,000 g of hexane was put therein, and the mixture was washed with 400 g of a 3% aqueous solution of sodium hydrogen sulfate and further washed with 800 g of 17% brine. The organic layer was concentrated by using a rotary evaporator to thereby distill the hexane off, and filtration was conducted to give the objective vinyloxybutyl glycidyl ether with a purity of 94% and a yield of 94%. At this time, the 4-hydroxybutyl vinyl ether contained in the obtained substance was 0.5%. equipped with a stirrer under controlling to 40° C. to 60° C At after 8 hours of the reaction was removed by filtration, 1,000 g of hexane the mixture was washed with 400 g of a 3% aqueous solution of sodium hydrogen sulfate further washed with 800 g of 17% brine The organic layer was concentrated a rotary evaporator to thereby distill the hexane off, and filtration

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The 2-[(4-chlorophenyl)sulfonylmethyl]-1,4-difluorobenzene (0.94 g, 3.1 mmol) obtained in Example 5 was dissolved in toluene (30 ml). After addition of 4-vinyloxy-1-butanol (0.51 ml, 4.2 mmol) and cyanomethylenetri-n-butylphosphorane (1.0 g, 4.1 mmol), the resulting mixture was heated under reflux for 3 days under an argon atmosphere. The reaction mixture was allowed to cool down and then concentrated under reduced pressure. The residue thus obtained was purified by silica gel chromatography (hexane:ethyl acetate=10:1) to yield a white solid. The resulting white solid was washed with hexane, whereby the title compound (0.97 g, 78%) was obtained as a white powder. the resulting mixture was heated under reflux for 3 days under an argon atmosphere to cool down concentrated under reduced pressure The residue thus obtained was purified by silica gel chromatography (hexane:ethyl acetate=10:1) to yield a white solid The resulting white solid was washed with hexane, whereby the title compound (0.97 g, 78%) was obtained as a white powder

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The 2-[(4-chlorophenyl)sulfonylmethyl]-1,4-difluorobenzene (0.94 g, 3.1 mmol) obtained in Example 5 was dissolved in toluene (30 ml). After addition of 4-vinyloxy-1-butanol (0.51 ml, 4.2 mmol) and cyanomethylenetri-n-butylphosphorane (1.0 g, 4.1 mmol), the resulting mixture was heated under reflux for 3 days under an argon atmosphere. The reaction mixture was allowed to cool down and then concentrated under reduced pressure. The residue thus obtained was purified by silica gel chromatography (hexane:ethyl acetate=10:1) to yield a white solid. The resulting white solid was washed with hexane, whereby the title compound (0.97 g, 78%) was obtained as a white powder. the resulting mixture was heated under reflux for 3 days under an argon atmosphere to cool down concentrated under reduced pressure The residue thus obtained was purified by silica gel chromatography (hexane:ethyl acetate=10:1) to yield a white solid The resulting white solid was washed with hexane, whereby the title compound (0.97 g, 78%) was obtained as a white powder

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 L three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 g, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 g, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 L). 1,4-Butanediol vinyl ether (133.2 g, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 mL) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 mL), dissolved in methylene chloride (1 L), washed with water (1×750 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 g of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae reflux condenser to reflux about 5 hours to quench any residual isocyanate the solution was stirred for 0.5 hour the residual oil was triturated with hexane (3×500 mL) dissolved in methylene chloride (1 L) washed with water (1×750 mL) dried over anhydrous magnesium sulfate filtered concentrated in vacuo

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 3 L flask equipped with a mechanical stirrer and N2 purge was added 1000 g of tetrahydrofuran and 220.7 g (2.3 mol) of sodium t-butoxide. Hydroxybutyvinyl ether (236 g, 2.03 mol) was added dropwise at a rate to maintain the temperature at ≤40° C. This reaction mass was cooled to -40° C. A solution of benzenesulfonyl chloride (353 g, 2 mol) in 300 g of tetrahydrofuran was added dropwise at a rate to maintain the reaction temperature at ≤-20° C. After the addition was complete, the reaction mixture was allowed to warm to room temperature to obtain the butylvinyl ether benzenesulfonate, ##STR8## Into a 3 L flask equipped with a mechanical stirrer N2 purge to maintain the temperature at ≤40° C to maintain the reaction temperature at ≤-20° C After the addition to warm to room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 liter three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether (133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 milliliters) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 milliliters), dissolved in methylene chloride (1 liter), washed with water (1×750 milliliters), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 grams of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae reflux condenser to reflux about 5 hours to quench any residual isocyanate the solution was stirred for 0.5 hour the residual oil was triturated with hexane (3×500 milliliters) dissolved in methylene chloride (1 liter) washed with water (1×750 milliliters) dried over anhydrous magnesium sulfate filtered concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2 liter three neck flask equipped with a stopper, dropping funnel, stir bar, and reflux condenser was added trimethyl-1,6-diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers, 118.7 grams, 0.57 mol, obtained from Sigma-Aldrich, Milwaukee, Wis.), dibutyltin dilaurate (3.56 grams, 5.6 mmol, obtained from Sigma-Aldrich) and anhydrous tetrahydrofuran (1 liter). 1,4-Butanediol vinyl ether (133.2 grams, 1.2 mol, obtained from Sigma-Aldrich) was added slowly dropwise to the stirring solution via the addition funnel. The reaction mixture was brought to reflux and was kept at this temperature until deemed complete by infrared spectroscopy (about 5 hours, confirmed by the disappearance of the isocyanate peak at 2200 cm−1). When the reaction was complete, methanol (500 milliliters) was added to quench any residual isocyanate and the solution was stirred for 0.5 hour. The solvent was stripped in vacuo and the residual oil was triturated with hexane (3×500 milliliters), dissolved in methylene chloride (1 liter), washed with water (1×750 milliliters), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to afford 221 grams of a pale yellow oil (89 percent yield). The product was believed to be a mixture of compounds of the formulae reflux condenser to reflux about 5 hours to quench any residual isocyanate the solution was stirred for 0.5 hour the residual oil was triturated with hexane (3×500 milliliters) dissolved in methylene chloride (1 liter) washed with water (1×750 milliliters) dried over anhydrous magnesium sulfate filtered concentrated in vacuo