2-(chloromethoxy)ethyl acetate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 500 mL three-neck flask was charged with the crude chloromethylether 1 (317 g, 2.00 mol). Triisopropylphosphite (494 mL) was added dropwise through an additional funnel while heating in a 125° C. oil bath and stirring vigorously. Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g). Phosphite blanched reaction to yellow, continue heating another 2 h at 125° C. oil bath, then arrange for vacuum distillation using a vacuum pump. Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.), then changed to clean receiver. Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C. 258 g of the product 2 was given (47% yield from 1,3-dioxolane). Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g) reaction to yellow, continue heating another 2 h at 125° C. oil bath arrange for vacuum distillation Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.) Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 5 L three-neck flask was fitted with mechanical stirrer, thermometer, 500 mL additional funnel and argon purged. 1,3-Dioxalane (140 mL, 2.00 mol) in anhydrous Et2O (800 mL) and 1.0 M ZnCl2/Et2O (7.5 mL, 0.007 mol) were added. A solution of acetyl chloride (157 mL, 2.20 mol) in Et2O (200 mL) was added dropwise through an additional funnel over 20 min. A cold water bath was used to maintain temperature between 19-27° C. throughout. Continue stirring without external cooling for 4 h, reaction self heating at 20-25° C. for about 1 h. A clear, colorless solution retained under argon overnight. Stood for 3 days and formed an orange solution. Strip Et2O on rotavap (water aspirator) until no more distilled at 35° C. bath. A quantitative yield of product 318 g (theoretical yield 306 g) was obtained. A 5 L three-neck flask was fitted with mechanical stirrer thermometer, 500 mL additional funnel and argon purged A cold water bath was used without external cooling for 4 h reaction self heating at 20-25° C. for about 1 h Stood for 3 days formed an orange solution Strip Et2O on rotavap (water aspirator) until no more distilled at 35° C. bath

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

実験手順: A mixture of 1-acetoxy-2-(chloromethoxy)ethane (67.8 g, 444 mmol) and triethylphosphite (81.3 g, 490 mmol) was heated at 105°-110° C. for 12 hours. Vigorous gas evolution was noted initially. The reaction mixture was next cooled to room temperature and the crude material purified by distillation (0.9 mmHg, 130°-134° C.) to afford 76.9 g (68%) of 1-acetoxy-2-(diethylphosphonomethoxy)ethane as a colorless liquid. was heated at 105°-110° C. for 12 hours the crude material purified by distillation (0.9 mmHg, 130°-134° C.)

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

実験手順: A mixture of 1-acetoxy-2-(chloromethoxy)ethane (67.8 g, 444 mmol) and triethylphosphite (81.3 g, 490 mmol) was heated at 105°-110° C. for 12 hours. Vigorous gas evolution was noted initially. The reaction mixture was next cooled to room temperature and the crude material purified by distillation (0.9 mmHg, 130°-134° C.) to afford 76.9 g (68%) of 1-acetoxy-2-(diethylphosphonomethoxy)ethane as a colorless liquid. was heated at 105°-110° C. for 12 hours the crude material purified by distillation (0.9 mmHg, 130°-134° C.)

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

実験手順: A solution of acetyl chloride (43.2 g, 550 mmol) in 100 mL of dry ether was added dropwise over 1 hour to a solution of 1,3 dioxolane (37.1 g, 500 mmol) in 300 mL of ether containing a few crystals of zinc (II) chloride at room temperature under nitrogen. The reaction mixture was stirred at room temperature for an additional 2 hours and then concentrated in vacuo. The product was purified by distillation (0.6 mmHg, 56°-58° C.) to provide 67.9 g (89%) of 1-acetoxy-2-(chloromethoxy)ethane as a clear colorless oil. cf: Foye, W. O.; Kaufmann, J. M.; Kim, Y. H. J. Heterocyclic Chem. 1987, 19, 497. concentrated in vacuo The product was purified by distillation (0.6 mmHg, 56°-58° C.)

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

実験手順: A solution of acetyl chloride (43.2 g, 550 mmol) in 100 mL of dry ether was added dropwise over 1 hour to a solution of 1,3 dioxolane (37.1 g, 500 mmol) in 300 mL of ether containing a few crystals of zinc (II) chloride at room temperature under nitrogen. The reaction mixture was stirred at room temperature for an additional 2 hours and then concentrated in vacuo. The product was purified by distillation (0.6 mmHg, 56°-58° C.) to provide 67.9 g (89%) of 1-acetoxy-2-(chloromethoxy)ethane as a clear colorless oil. cf: Foye, W. O.; Kaufmann, J. M.; Kim, Y. H. J. Heterocyclic Chem. 1987, 19, 497. concentrated in vacuo The product was purified by distillation (0.6 mmHg, 56°-58° C.)

反応条件: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 500 mL three-neck flask was charged with the crude chloromethylether 1 (317 g, 2.00 mol). Triisopropylphosphite (494 mL) was added dropwise through an additional funnel while heating in a 125° C. oil bath and stirring vigorously. Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g). Phosphite blanched reaction to yellow, continue heating another 2 h at 125° C. oil bath, then arrange for vacuum distillation using a vacuum pump. Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.), then changed to clean receiver. Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C. 258 g of the product 2 was given (47% yield from 1,3-dioxolane). Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g) reaction to yellow, continue heating another 2 h at 125° C. oil bath arrange for vacuum distillation Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.) Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C

反応条件: temp:125.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 500 mL three-neck flask was charged with the crude chloromethylether 1 (317 g, 2.00 mol). Triisopropylphosphite (494 mL) was added dropwise through an additional funnel while heating in a 125° C. oil bath and stirring vigorously. Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g). Phosphite blanched reaction to yellow, continue heating another 2 h at 125° C. oil bath, then arrange for vacuum distillation using a vacuum pump. Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.), then changed to clean receiver. Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C. 258 g of the product 2 was given (47% yield from 1,3-dioxolane). Collect 2-chloropropane distillate via short-path head in a dry ice cooled receiver, argon blanket, collected 140 g distillate (theoretical 157 g) reaction to yellow, continue heating another 2 h at 125° C. oil bath arrange for vacuum distillation Distilled a yellow front cut (140 g, head to 135° C., bottom to 190° C.) Main fraction was collected at head temperature of 178-187° C. (mostly 185-187° C.) with vacuum unknown at bath temperature of 222-228° C

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 5 L three-neck flask was fitted with mechanical stirrer, thermometer, 500 mL additional funnel and argon purged. 1,3-Dioxalane (140 mL, 2.00 mol) in anhydrous Et2O (800 mL) and 1.0 M ZnCl2/Et2O (7.5 mL, 0.007 mol) were added. A solution of acetyl chloride (157 mL, 2.20 mol) in Et2O (200 mL) was added dropwise through an additional funnel over 20 min. A cold water bath was used to maintain temperature between 19-27° C. throughout. Continue stirring without external cooling for 4 h, reaction self heating at 20-25° C. for about 1 h. A clear, colorless solution retained under argon overnight. Stood for 3 days and formed an orange solution. Strip Et2O on rotavap (water aspirator) until no more distilled at 35° C. bath. A quantitative yield of product 318 g (theoretical yield 306 g) was obtained. A 5 L three-neck flask was fitted with mechanical stirrer thermometer, 500 mL additional funnel and argon purged A cold water bath was used without external cooling for 4 h reaction self heating at 20-25° C. for about 1 h Stood for 3 days formed an orange solution Strip Et2O on rotavap (water aspirator) until no more distilled at 35° C. bath

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

実験手順: A mixture of 1-acetoxy-2-(chloromethoxy)ethane (67.8 g, 444 mmol) and triethylphosphite (81.3 g, 490 mmol) was heated at 105°-110° C. for 12 hours. Vigorous gas evolution was noted initially. The reaction mixture was next cooled to room temperature and the crude material purified by distillation (0.9 mmHg, 130°-134° C.) to afford 76.9 g (68%) of 1-acetoxy-2-(diethylphosphonomethoxy)ethane as a colorless liquid. was heated at 105°-110° C. for 12 hours the crude material purified by distillation (0.9 mmHg, 130°-134° C.)

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

実験手順: A solution of acetyl chloride (43.2 g, 550 mmol) in 100 mL of dry ether was added dropwise over 1 hour to a solution of 1,3 dioxolane (37.1 g, 500 mmol) in 300 mL of ether containing a few crystals of zinc (II) chloride at room temperature under nitrogen. The reaction mixture was stirred at room temperature for an additional 2 hours and then concentrated in vacuo. The product was purified by distillation (0.6 mmHg, 56°-58° C.) to provide 67.9 g (89%) of 1-acetoxy-2-(chloromethoxy)ethane as a clear colorless oil. cf: Foye, W. O.; Kaufmann, J. M.; Kim, Y. H. J. Heterocyclic Chem. 1987, 19, 497. concentrated in vacuo The product was purified by distillation (0.6 mmHg, 56°-58° C.)