2-(12-bromododecoxy)oxane

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

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

Procedure: Into 250 ml of tetrahydrofuran (THF) is dissolved 57.8 g of 2-[(12-bromododecyl)oxy]tetrahydro-2H-pyran, to which a solution of 0.35 g of dilithium tetrachlorocuprate in 16 ml of THF is added dropwise at room temperature with stirring under nitrogen streams. To the resulting solution, a solution of 39.6 g of cyclohexylmagnesium bromide in 200 ml of THF is added dropwise while maintaining the reaction temperature at 10°-15° C. Thereafter, the reaction mixture is stirred for 7 hours at room temperature to complete the reaction. The reaction mixture is then acidified with 2N sulfuric acid under ice cooling. The undissolved substances are removed by filtration and the precipitates are washed with ethyl acetate. The THF layer and the ethyl acetate layer are combined and the resulting solution is washed with water, an aqueous sodium bicarbonate solution and then water and is dried. The solvent is removed by distillation under reduced pressure to leave crude [(12-cyclohexyldodecyl)oxy]-tetrahydro-2H-pyran which in turn is dissolved in 450 ml of methanol. Amberlyst® H-15 (4.5 g) is added to the methanol solution and the mixture is stirred at 45° C. for 2 hours. The resin is then filtered off and the filtrate is concentrated to leave a residue. Purification of the residue by silica gel column chromatography yields 20.6 g of the captioned compound as colorless solids. while maintaining the reaction temperature at 10°-15° C Thereafter, the reaction mixture is stirred for 7 hours at room temperature the reaction The undissolved substances are removed by filtration the precipitates are washed with ethyl acetate the resulting solution is washed with water an aqueous sodium bicarbonate solution and then water and is dried The solvent is removed by distillation under reduced pressure

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

Procedure: Diethyl acetamidomalonate (6.996 g) and 3.189 g of sodium ethoxide were dissolved in 130 ml of dry ethanol and a solution of 10.698 g of 1-bromo-12-tetrahydropyranyloxydodecane in 200 ml of dry ethanol was added thereto. The mixture was refluxed under heating for 8 hours. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 5.837 g of diethyl 2-acetamido-2-(12-tetrahydropyranyloxydodecyl)malonate. The mixture was refluxed under heating for 8 hours The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: Diethyl acetamidomalonate (6.996 g) and 3.189 g of sodium ethoxide were dissolved in 130 ml of dry ethanol and a solution of 10.698 g of 1-bromo-12-tetrahydropyranyloxydodecane in 200 ml of dry ethanol was added thereto. The mixture was refluxed under heating for 8 hours. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 5.837 g of diethyl 2-acetamido-2-(12-tetrahydropyranyloxydodecyl)malonate. The mixture was refluxed under heating for 8 hours The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The above-mentioned dodecanediol monotetrahydropyranyl ether (7.882 g) and 11.437 g of carbon tetrabromide were dissolved in 78 ml of dichloromethane. Triphenylphosphine (10.843 g) was added thereto under ice-cooling and the mixture was stirred at 0° C. for 5 minutes. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 4.029 g of 1-bromo-12-tetrahydropyranyloxydodecane. under ice-cooling The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: To a solution of 12-bromo-1-dodecanol (1 mole) in dichloromethane containing pyridinium p-toluenesulfonate (P-TSA) is added dihydropyran (2 moles). The reaction mixture is stirred for 24 hours and then washed twice with water and dried over anhydrous MgSO4. The dichloromethane is removed under reduced pressure. If necessary the resulting product is purified by chromatography on silica gel. washed twice with water dried over anhydrous MgSO4 The dichloromethane is removed under reduced pressure If necessary the resulting product is purified by chromatography on silica gel

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

Procedure: Diethyl acetamidomalonate (6.996 g) and 3.189 g of sodium ethoxide were dissolved in 130 ml of dry ethanol and a solution of 10.698 g of 1-bromo-12-tetrahydropyranyloxydodecane in 200 ml of dry ethanol was added thereto. The mixture was refluxed under heating for 8 hours. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 5.837 g of diethyl 2-acetamido-2-(12-tetrahydropyranyloxydodecyl)malonate. The mixture was refluxed under heating for 8 hours The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The above-mentioned dodecanediol monotetrahydropyranyl ether (7.882 g) and 11.437 g of carbon tetrabromide were dissolved in 78 ml of dichloromethane. Triphenylphosphine (10.843 g) was added thereto under ice-cooling and the mixture was stirred at 0° C. for 5 minutes. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 4.029 g of 1-bromo-12-tetrahydropyranyloxydodecane. under ice-cooling The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The above-mentioned dodecanediol monotetrahydropyranyl ether (7.882 g) and 11.437 g of carbon tetrabromide were dissolved in 78 ml of dichloromethane. Triphenylphosphine (10.843 g) was added thereto under ice-cooling and the mixture was stirred at 0° C. for 5 minutes. The solvent was distilled away under reduced pressure and the residue was purified by silica gel column chromatography to give 4.029 g of 1-bromo-12-tetrahydropyranyloxydodecane. under ice-cooling The solvent was distilled away under reduced pressure the residue was purified by silica gel column chromatography

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

Procedure: 57.8 g (165 millimole) of 2-[(12-bromododecyl}oxy]tetrahydro-2H-pyran and 39.6 g (247 millimole) of cyclohexyl magnesium bromide were reacted by following a procedure similar to that of Working Example 16, to give crude 2-[(12-cyclohexyldodecyl)oxy]tetrahydro-2H-pyran. This crude product was dissolved in 450 ml of methanol, to which 4.5 g of Amberlist® H-15 was added, and the resulting mixture was stirred at 45° C. for 2 hours. The resin was filtrated off, and the filtrate was concentrated to dryness under reduced pressure. The residue wa subjected to column chromatography on silica gel (1 kg), and eluted with hexane-ethyl acetate (6:1), to give the above-captioned compound as colorless solid.

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

Procedure: 57.8 g (165 millimole) of 2-[(12-bromododecyl}oxy]tetrahydro-2H-pyran and 39.6 g (247 millimole) of cyclohexyl magnesium bromide were reacted by following a procedure similar to that of Working Example 16, to give crude 2-[(12-cyclohexyldodecyl)oxy]tetrahydro-2H-pyran. This crude product was dissolved in 450 ml of methanol, to which 4.5 g of Amberlist® H-15 was added, and the resulting mixture was stirred at 45° C. for 2 hours. The resin was filtrated off, and the filtrate was concentrated to dryness under reduced pressure. The residue wa subjected to column chromatography on silica gel (1 kg), and eluted with hexane-ethyl acetate (6:1), to give the above-captioned compound as colorless solid.

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

Procedure: Into 250 ml of tetrahydrofuran (THF) is dissolved 57.8 g of 2-[(12-bromododecyl)oxy]tetrahydro-2H-pyran, to which a solution of 0.35 g of dilithium tetrachlorocuprate in 16 ml of THF is added dropwise at room temperature with stirring under nitrogen streams. To the resulting solution, a solution of 39.6 g of cyclohexylmagnesium bromide in 200 ml of THF is added dropwise while maintaining the reaction temperature at 10°-15° C. Thereafter, the reaction mixture is stirred for 7 hours at room temperature to complete the reaction. The reaction mixture is then acidified with 2N sulfuric acid under ice cooling. The undissolved substances are removed by filtration and the precipitates are washed with ethyl acetate. The THF layer and the ethyl acetate layer are combined and the resulting solution is washed with water, an aqueous sodium bicarbonate solution and then water and is dried. The solvent is removed by distillation under reduced pressure to leave crude [(12-cyclohexyldodecyl)oxy]-tetrahydro-2H-pyran which in turn is dissolved in 450 ml of methanol. Amberlyst® H-15 (4.5 g) is added to the methanol solution and the mixture is stirred at 45° C. for 2 hours. The resin is then filtered off and the filtrate is concentrated to leave a residue. Purification of the residue by silica gel column chromatography yields 20.6 g of the captioned compound as colorless solids. while maintaining the reaction temperature at 10°-15° C Thereafter, the reaction mixture is stirred for 7 hours at room temperature the reaction The undissolved substances are removed by filtration the precipitates are washed with ethyl acetate the resulting solution is washed with water an aqueous sodium bicarbonate solution and then water and is dried The solvent is removed by distillation under reduced pressure