2-(5-chloropentoxy)oxane

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A stirred solution of pentamethylene chlorohydrin (10.0 g, 0.0816 mol) in Et2O (165 ml) under nitrogen was treated with 3,4-dihydro-2H-pyran (10.3 g, 0.122 mol) and p-toluenesulfonic acid hydrate (0.5 g) and kept at ambient temperature for 4.5 hours. The mixture was washed with aqueous NaHCO3 and brine, dried (MgSO4) and concentrated. The residue was distilled to give 4.06 g, bp 79°-82° C. (0.1-0.07 mm Hg) and 10.54 g, bp 82°-84° C. (0.1-0.07 mm Hg) of 5-chloropentyl 2-tetrahydropyranyl ether. The mixture was washed with aqueous NaHCO3 and brine dried (MgSO4) concentrated The residue was distilled

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

実験手順: A solution of 2-(5-chloropentyloxy)tetrahydro-2H-pyrane (10) (20.67 g, 0.1 mol) in dry acetone (50 mL) was added in drops to a magnetically stirred solution of sodium iodide (16.49 g, 0.11 mol) in dry acetone (150 mL). The reaction mixture was refluxed in a nitrogen atmosphere over night. After cooling the precipitated sodium chloride was filtered out and acetone was distilled out on a rotary evaporator. The residue which still contained some sodium chloride was dissolved in dry pentane (200 mL). Sodium chloride was filtered out and pentane distilled out on a rotary evaporator, yielding 26.2 g (88%) of a yellowish brown oil. NMR indicated a pure product. The reaction mixture was refluxed in a nitrogen atmosphere over night was filtered out and acetone was distilled out on a rotary evaporator was dissolved in dry pentane (200 mL) Sodium chloride was filtered out and pentane distilled out on a rotary evaporator

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

実験手順: A solution of 2-(5-chloropentyloxy)tetrahydro-2H-pyrane (10) (20.67 g, 0.1 mol) in dry acetone (50 mL) was added in drops to a magnetically stirred solution of sodium iodide (16.49 g, 0.11 mol) in dry acetone (150 mL). The reaction mixture was refluxed in a nitrogen atmosphere over night. After cooling the precipitated sodium chloride was filtered out and acetone was distilled out on a rotary evaporator. The residue which still contained some sodium chloride was dissolved in dry pentane (200 mL). Sodium chloride was filtered out and pentane distilled out on a rotary evaporator, yielding 26.2 g (88%) of a yellowish brown oil. NMR indicated a pure product. The reaction mixture was refluxed in a nitrogen atmosphere over night was filtered out and acetone was distilled out on a rotary evaporator was dissolved in dry pentane (200 mL) Sodium chloride was filtered out and pentane distilled out on a rotary evaporator

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

実験手順: 5-chloro-1-pentanol (12.26 g, 0.1 mol) was dissolved in dry dichloromethane (400 mL). 3,4-Dihydro-2H-pyrane (12.62 g, 0.15 mol) and pyridine toluene-4-sulphonate (1.26 g, 5 mmol) was then added and the reaction mixture was stirred magnetically in a nitrogen atmosphere at room temperature over night. Sodium-hydrogen-carbonate, saturated solution (150 mL) was added and the phases were separated. The aqueous phase was then extracted with dichloromethane (4×25 mL). The combined dichloromethane phases were washed with water (2×20 mL) and then dried (MgSO4). Dichloromethane was then distilled out on a rotary evaporator and yielded 19.6 g (95%) of a pale yellow oil. NMR indicated a pure product. the phases were separated The aqueous phase was then extracted with dichloromethane (4×25 mL) The combined dichloromethane phases were washed with water (2×20 mL) dried (MgSO4) Dichloromethane was then distilled out on a rotary evaporator

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

実験手順: 5-chloro-1-pentanol (12.26 g, 0.1 mol) was dissolved in dry dichloromethane (400 mL). 3,4-Dihydro-2H-pyrane (12.62 g, 0.15 mol) and pyridine toluene-4-sulphonate (1.26 g, 5 mmol) was then added and the reaction mixture was stirred magnetically in a nitrogen atmosphere at room temperature over night. Sodium-hydrogen-carbonate, saturated solution (150 mL) was added and the phases were separated. The aqueous phase was then extracted with dichloromethane (4×25 mL). The combined dichloromethane phases were washed with water (2×20 mL) and then dried (MgSO4). Dichloromethane was then distilled out on a rotary evaporator and yielded 19.6 g (95%) of a pale yellow oil. NMR indicated a pure product. the phases were separated The aqueous phase was then extracted with dichloromethane (4×25 mL) The combined dichloromethane phases were washed with water (2×20 mL) dried (MgSO4) Dichloromethane was then distilled out on a rotary evaporator

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

実験手順: A stirred solution of pentamethylene chlorohydrin (10.0 g, 0.0816 mol) in Et2O (165 ml) under nitrogen was treated with 3,4-dihydro-2H-pyran (10.3 g, 0.122 mol) and p-toluenesulfonic acid hydrate (0.5 g) and kept at ambient temperature for 4.5 hours. The mixture was washed with aqueous NaHCO3 and brine, dried (MgSO4) and concentrated. The residue was distilled to give 4.06 g, bp 79°-82° C. (0.1-0.07 mm Hg) and 10.54 g, bp 82°-84° C. (0.1-0.07 mm Hg) of 5-chloropentyl 2-tetrahydropyranyl ether. The mixture was washed with aqueous NaHCO3 and brine dried (MgSO4) concentrated The residue was distilled

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

実験手順: A solution of 2-(5-chloropentyloxy)tetrahydro-2H-pyrane (10) (20.67 g, 0.1 mol) in dry acetone (50 mL) was added in drops to a magnetically stirred solution of sodium iodide (16.49 g, 0.11 mol) in dry acetone (150 mL). The reaction mixture was refluxed in a nitrogen atmosphere over night. After cooling the precipitated sodium chloride was filtered out and acetone was distilled out on a rotary evaporator. The residue which still contained some sodium chloride was dissolved in dry pentane (200 mL). Sodium chloride was filtered out and pentane distilled out on a rotary evaporator, yielding 26.2 g (88%) of a yellowish brown oil. NMR indicated a pure product. The reaction mixture was refluxed in a nitrogen atmosphere over night was filtered out and acetone was distilled out on a rotary evaporator was dissolved in dry pentane (200 mL) Sodium chloride was filtered out and pentane distilled out on a rotary evaporator

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

実験手順: 5-chloro-1-pentanol (12.26 g, 0.1 mol) was dissolved in dry dichloromethane (400 mL). 3,4-Dihydro-2H-pyrane (12.62 g, 0.15 mol) and pyridine toluene-4-sulphonate (1.26 g, 5 mmol) was then added and the reaction mixture was stirred magnetically in a nitrogen atmosphere at room temperature over night. Sodium-hydrogen-carbonate, saturated solution (150 mL) was added and the phases were separated. The aqueous phase was then extracted with dichloromethane (4×25 mL). The combined dichloromethane phases were washed with water (2×20 mL) and then dried (MgSO4). Dichloromethane was then distilled out on a rotary evaporator and yielded 19.6 g (95%) of a pale yellow oil. NMR indicated a pure product. the phases were separated The aqueous phase was then extracted with dichloromethane (4×25 mL) The combined dichloromethane phases were washed with water (2×20 mL) dried (MgSO4) Dichloromethane was then distilled out on a rotary evaporator

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A small portion of a solution of the product from Step I (21.1 g, 0.102 mol) in THF (105 ml) was added, under nitrogen, to magnesium turnings (5.0 g, 0.204 g-atom). The mixture was warmed in an oil bath at 75°-80° and the reaction was started by the addition of 1.5 ml of a 1M solution of 1,2-dibromoethane in THF. The remaining chloroalkane solution was then added during 20 minutes. The resulting mixture was refluxed for 45 minutes, cooled in an ice bath and treated during 15 minutes with a solution of acetone (9.0 ml, 0.123 ml) in THF (95 ml). It was kept at ambient temperature for 16 hours, cooled in an ice bath and treated during 15 minutes with saturated aqueous NH4Cl (115 ml). The resulting mixture was extracted with EtO. The extract was washed with water and brine, dried (MgSO4) and concentrated to give 30.5 g of crude product. Distillation gave 16.77 g of 6-hydroxy-6-methylheptyl 2-tetrahydropyranyl ether, bp 107°-115° (0.07-0.1 mm Hg). The CI mass spectrum had m/z 231 (M+H)+. The mixture was warmed in an oil bath at 75°-80° The resulting mixture was refluxed for 45 minutes cooled in an ice bath cooled in an ice bath The resulting mixture was extracted with EtO The extract was washed with water and brine dried (MgSO4) concentrated to give 30.5 g of crude product Distillation

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

実験手順: A stirred solution of pentamethylene chlorohydrin (10.0 g, 0.0816 mol) in Et2O (165 ml) under nitrogen was treated with 3,4-dihydro-2H-pyran (10.3 g, 0.122 mol) and p-toluenesulfonic acid hydrate (0.5 g) and kept at ambient temperature for 4.5 hours. The mixture was washed with aqueous NaHCO3 and brine, dried (MgSO4) and concentrated. The residue was distilled to give 4.06 g, bp 79°-82° C. (0.1-0.07 mm Hg) and 10.54 g, bp 82°-84° C. (0.1-0.07 mm Hg) of 5-chloropentyl 2-tetrahydropyranyl ether. The mixture was washed with aqueous NaHCO3 and brine dried (MgSO4) concentrated The residue was distilled