methyl 2,2,2-trichloroacetate

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of benzoic acid (1.53 g, 0.0125 mole), methyl trichloroacetate (2.22 g, 0.0125 mole), potassium carbonate (0.035 g) and 18-crown-6 cyclic polyether (0.066 g) was placed in a 25 ml round-bottom flask fitted with a stirrer, distillation head, dry ice receiver and trap. The mixture was heated with stirring to 150° C. Gas evolution was observed to begin at about 90° C. After about 3 hours, the heating was discontinued. The trap contained CHCl3 (approx. 1.5 g). Distillation of the remaining mixture gave methylbenzoate identified by gas-liquid chromatography and nuclear magnetic resonance spectroscopy. Purified yield was 85 percent. was placed in a 25 ml round-bottom flask fitted with a stirrer distillation head, dry ice receiver and trap The mixture was heated to begin at about 90° C Distillation of the remaining mixture

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of benzoic acid (1.53 g, 0.0125 mole), methyl trichloroacetate (2.22 g, 0.0125 mole), potassium carbonate (0.035 g) and 18-crown-6 cyclic polyether (0.066 g) was placed in a 25 ml round-bottom flask fitted with a stirrer, distillation head, dry ice receiver and trap. The mixture was heated with stirring to 150° C. Gas evolution was observed to begin at about 90° C. After about 3 hours, the heating was discontinued. The trap contained CHCl3 (approx. 1.5 g). Distillation of the remaining mixture gave methylbenzoate identified by gas-liquid chromatography and nuclear magnetic resonance spectroscopy. Purified yield was 85 percent. was placed in a 25 ml round-bottom flask fitted with a stirrer distillation head, dry ice receiver and trap The mixture was heated to begin at about 90° C Distillation of the remaining mixture

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

実験手順: To a suspension of 5.9 g (0.091 g-atom) of zinc powder (−325 mesh) in 40 mL of tetrahydrofuran was added 0.2 mL of 1,2-dibromoethane. The mixture was heated at gentle reflux for 30 minutes. The mixture was cooled to room temperature and 7.1 mL (0.06 mole) of methyl trichloroacetate was added dropwise, followed by 9.1 mL (0.097 mole) of trimethylsilyl chloride at rate such the internal temperature was below 50 degrees. The mixture was stirred at room temperature for 1 hour and then diluted with hexane. The resulting solid was removed by filtration, and the filtrate concentrated under reduced pressure. Solids were removed by filtration, washing with hexane. The filtrated was concentrated under reduced pressure and the residue was then distilled under vacuum to give 8.0 g of (2,2-dichloro-1-methoxy-vinyloxy)-trimethyl-silane as a colorless oil. Bp 45-48 degrees at 1 mm Hg. The mixture was heated at gentle reflux for 30 minutes was below 50 degrees The resulting solid was removed by filtration the filtrate concentrated under reduced pressure Solids were removed by filtration washing with hexane The filtrated was concentrated under reduced pressure the residue was then distilled under vacuum

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of benzoic acid (1.53 g, 0.0125 mole), methyl trichloroacetate (2.22 g, 0.0125 mole), potassium carbonate (0.035 g) and 18-crown-6 cyclic polyether (0.066 g) was placed in a 25 ml round-bottom flask fitted with a stirrer, distillation head, dry ice receiver and trap. The mixture was heated with stirring to 150° C. Gas evolution was observed to begin at about 90° C. After about 3 hours, the heating was discontinued. The trap contained CHCl3 (approx. 1.5 g). Distillation of the remaining mixture gave methylbenzoate identified by gas-liquid chromatography and nuclear magnetic resonance spectroscopy. Purified yield was 85 percent. was placed in a 25 ml round-bottom flask fitted with a stirrer distillation head, dry ice receiver and trap The mixture was heated to begin at about 90° C Distillation of the remaining mixture

反応条件: temp:-55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter three-necked flask equipped with a mechanical stirrer, thermometer, condenser, pressure equalizing addition funnel and an argon inlet was charged with zinc dust (78.0 g, 1.19 mol) followed by the addition of anhydrous tetrahydrofuran (400 ml). To this mixture was added 1,2-dibromoethane (2 ml) to activate the zinc. The resulting mixture was heated at a gentle reflux for 25 minutes. After cooling to −55° C., a solution of methyl trichloroacetate (100.3 g, 0.565 mol) and chlorotrimethylsilane (80 ml, 0.648 mol) was added at a rate to maintain the reaction temperature at −55 to −60° C. (1 hour required). After the addition was complete, the mixture was allowed to stir at room temperature for approximately 90 minutes. The resulting mixture was diluted with heptane (700 ml) and filtered under nitrogen through a Celite 545 pad. The filtercake was washed with additional heptane (1×300 ml, 3×200 ml). The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath) to give crude (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane as a dense oil (129.2 g). Quantitative proton NMR indicates this crude material contains 0.389 mol (68.8%) of (2,2-dichloro-1-methoxy-vinyloxy)-trimethylsilane. A 2-liter three-necked flask equipped with a mechanical stirrer thermometer, condenser, pressure equalizing addition funnel and an argon inlet The resulting mixture was heated at a gentle reflux for 25 minutes to maintain the reaction temperature at −55 to −60° C. (1 hour required) After the addition filtered under nitrogen through a Celite 545 pad The filtercake was washed with additional heptane (1×300 ml, 3×200 ml) The filtrate was then concentrated at reduced pressure on a rotary evaporator (approximately 10-15 mm Hg with a 22-27° C. water bath)