2-chlorocyclododecan-1-one

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with 100 g (0.46 mol) of 2-chlorocyclododecanone and 122 g of tetrahydrofuran, and at −10 to 0° C., a THF solution of vinylmagnesium chloride (0.82 mol) was added dropwise. The mixture was allowed to stand for reaction for 30 minutes, and 420 g (3.27 mol) of N,N′-dimethylpropyleneurea (DMPU) was added. The mixture was heated to 50° C. and allowed to stand for reaction for 1 hour, and saturated ammonium chloride aqueous solution was added dropwise for inactivation. The reaction mixture was subjected to extraction with hexane, and the solvent was recovered. The residue was distilled to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (80 g, 0.38 mol, chemical purity 98%, cis form:trans form=88:12). The yield was 82%. A four-neck flask equipped with a thermometer, stirrer and condenser tube to stand for reaction for 30 minutes to stand for reaction for 1 hour The reaction mixture was subjected to extraction with hexane the solvent was recovered The residue was distilled

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with 100 g (0.46 mol) of 2-chlorocyclododecanone and 122 g of tetrahydrofuran, and at −10 to 0° C., a THF solution of vinylmagnesium chloride (0.82 mol) was added dropwise. The mixture was allowed to stand for reaction for 30 minutes, and 420 g (3.27 mol) of N,N′-dimethylpropyleneurea (DMPU) was added. The mixture was heated to 50° C. and allowed to stand for reaction for 1 hour, and saturated ammonium chloride aqueous solution was added dropwise for inactivation. The reaction mixture was subjected to extraction with hexane, and the solvent was recovered. The residue was distilled to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (80 g, 0.38 mol, chemical purity 98%, cis form:trans form=88:12). The yield was 82%. A four-neck flask equipped with a thermometer, stirrer and condenser tube to stand for reaction for 30 minutes to stand for reaction for 1 hour The reaction mixture was subjected to extraction with hexane the solvent was recovered The residue was distilled

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.94 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.42 g, 11.5 mmol, chemical purity 99%, cis form:trans form=86:14). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and toluene (16 ml) was added to the solution. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.93 g, 13.5 mmol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.44 g, 11.5 mmol, chemical purity 98%, cis form:trans form=59:41). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added to the solution was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.93 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.44g, 11.5 mmol, chemical purity 98%, cis form:trans form=58:42). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.93 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.44g, 11.5 mmol, chemical purity 98%, cis form:trans form=58:42). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (1.31 mol), and toluene (600 ml) was added to the solution. At 0° C., a toluene solution of 2-chlorocyclododecanone (159 g, 0.735 mol) was added dropwise to the solution, for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (120 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (320 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (370 g, 2.78 mol) and benzyltriethylammonium chloride (1.86 g 0.00816 mol), and the mixture was stirred for reaction at 95° C. for 6 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with a saline solution. The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 133 g of a distillate. It was analyzed by means of capillary gas chromatography and found to be a mixture containing 61% of cis-1-vinyl-13-oxabicyclo[10.1.0]tridecane and 37% of trans-1-vinyl-13-oxabicyclo[10.1.0]tridecane (yield was 85%). The distillate was partially separated by means of silica gel chromatography for isolation into trans-1-vinyl-13-oxabicyclo[10.1.0]tridecane and cis-1-vinyl-13-oxabicyclo[10.1.0]tridecane. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added to the solution was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (320 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with a saline solution The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure to obtain 133 g of a distillate

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with 100 g (0.46 mol) of 2-chlorocyclododecanone and 122 g of tetrahydrofuran, and at −10 to 0° C., a THF solution of vinylmagnesium chloride (0.82 mol) was added dropwise. The mixture was allowed to stand for reaction for 30 minutes, and 420 g (3.27 mol) of N,N′-dimethylpropyleneurea (DMPU) was added. The mixture was heated to 50° C. and allowed to stand for reaction for 1 hour, and saturated ammonium chloride aqueous solution was added dropwise for inactivation. The reaction mixture was subjected to extraction with hexane, and the solvent was recovered. The residue was distilled to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (80 g, 0.38 mol, chemical purity 98%, cis form:trans form=88:12). The yield was 82%. A four-neck flask equipped with a thermometer, stirrer and condenser tube to stand for reaction for 30 minutes to stand for reaction for 1 hour The reaction mixture was subjected to extraction with hexane the solvent was recovered The residue was distilled

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.94 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.42 g, 11.5 mmol, chemical purity 99%, cis form:trans form=86:14). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and toluene (16 ml) was added to the solution. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.93 g, 13.5 mmol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.44 g, 11.5 mmol, chemical purity 98%, cis form:trans form=59:41). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added to the solution was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (24 mmol), and to the solution, toluene (16 ml) was added. At 0° C., a toluene solution of 2-chlorocyclododecanone (2.93 g, 13.5 mol) was added dropwise for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (5 g) was for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (6.8 g, 51.0 mmol) and tetrabutylammonium chloride (0.0417 g, 0.150 mmol), and the mixture was stirred for reaction at 95° C. for 2 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) and a saline solution (10 ml). The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 1-vinyl-13-oxabicyclo[10.1.0]tridecane (2.44g, 11.5 mmol, chemical purity 98%, cis form:trans form=58:42). The yield was 85%. A four-neck flask equipped with a thermometer, stirrer and condenser tube was for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (10 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with 10% sulfuric acid (5 ml), saturated sodium hydrogencarbonate aqueous solution (10 ml) The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure

Conditions: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A four-neck flask equipped with a thermometer, stirrer and condenser tube was charged with a tetrahydrofuran solution of vinylmagnesium (1.31 mol), and toluene (600 ml) was added to the solution. At 0° C., a toluene solution of 2-chlorocyclododecanone (159 g, 0.735 mol) was added dropwise to the solution, for reaction for 1 hour. After completion of reaction, 16% hydrochloric acid (120 g) was added for hydrolysis, and the solution was separated to take out the organic layer. The organic layer was washed with 2% sodium hydroxide aqueous solution (320 ml). To the obtained toluene solution, added were 30% sodium hydroxide aqueous solution (370 g, 2.78 mol) and benzyltriethylammonium chloride (1.86 g 0.00816 mol), and the mixture was stirred for reaction at 95° C. for 6 hours. After completion of reaction, the solution was separated to take out the organic layer, and the organic layer was washed with a saline solution. The solvent was distilled away under reduced pressure, and the residue was distilled for purification under reduced pressure, to obtain 133 g of a distillate. It was analyzed by means of capillary gas chromatography and found to be a mixture containing 61% of cis-1-vinyl-13-oxabicyclo[10.1.0]tridecane and 37% of trans-1-vinyl-13-oxabicyclo[10.1.0]tridecane (yield was 85%). The distillate was partially separated by means of silica gel chromatography for isolation into trans-1-vinyl-13-oxabicyclo[10.1.0]tridecane and cis-1-vinyl-13-oxabicyclo[10.1.0]tridecane. A four-neck flask equipped with a thermometer, stirrer and condenser tube was added to the solution was added for hydrolysis the solution was separated The organic layer was washed with 2% sodium hydroxide aqueous solution (320 ml) To the obtained toluene solution, added After completion of reaction the solution was separated the organic layer was washed with a saline solution The solvent was distilled away under reduced pressure the residue was distilled for purification under reduced pressure to obtain 133 g of a distillate