戊酸甲酯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of dimethyl methylphosphonate (3.25 mL, 30 mmol) in anhydrous THF (30 mL), cooled at −78° C. was added n-BuLi (1.6 M in hexane, 20.6 mL, 33 mmol). The mixture was stirred for 30 minutes at this temperature under nitrogen. Methyl valerate (2.0 mL, 15 mmol) was added dropwise for 10 minutes. The mixture was stirred for 2 hours at −78° C., gradually was warm to room temperature. The mixture was quenched with addition of 1N HCl to pH 4-5. The organic layer was separated, washed with brine and dried over MgSO4. The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98) to give the product (3.0 g) with colorless oil in 96% yield. 1H NMR (CDCl3) δ 0.848 (t, J=7.3 Hz, 3H), 1.28 (m, 2H), 1.52 (m, 2H), 2.57 (t, J=2.4 Hz, 2H) 3.074 (d, J=21 Hz, 2H), 3.760 (s, 3H), 3.762 (s, 3H). The mixture was stirred for 2 hours at −78° C. The mixture was quenched with addition of 1N HCl to pH 4-5 The organic layer was separated washed with brine dried over MgSO4 The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98)

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of lithium diisopropyl amide, which was prepared from diisopropylamine (6.6 g) in dry tetrahydrofuran (50 ml) and 15% butyl lithium in hexane solution (38 ml) at -65° to -60° C. in a nitrogen atmosphere, were added dropwise a solution of methyl pentanoate (7 g) in dry tetrahydrofuran (65 ml) followed by a solution of 5-bromo-1-pentene (9 g) in dry tetrahydrofuran (30 ml) at the same temperature. The mixture was stirred for 4 hours at -65° to 0° C. All the operations described above were carried out in a nitrogen atmosphere. Diluted hydrochloric acid (25 ml) and toluene (200 ml) were added at 0° C. to the mixture, which was further stirred. The organic layer was separated, washed with water, dried and concentrated. The resulting oily residue (9 g) was purified by silica gel column chromatography to give colorless oil of methyl 2-propyl-6-heptenoate (4.8 g). The organic layer was separated washed with water dried concentrated The resulting oily residue (9 g) was purified by silica gel column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of lithium diisopropyl amide, which was prepared from diisopropylamine (6.6 g) in dry tetrahydrofuran (50 ml) and 15% butyl lithium in hexane solution (38 ml) at -65° to -60° C. in a nitrogen atmosphere, were added dropwise a solution of methyl pentanoate (7 g) in dry tetrahydrofuran (65 ml) followed by a solution of 5-bromo-1-pentene (9 g) in dry tetrahydrofuran (30 ml) at the same temperature. The mixture was stirred for 4 hours at -65° to 0° C. All the operations described above were carried out in a nitrogen atmosphere. Diluted hydrochloric acid (25 ml) and toluene (200 ml) were added at 0° C. to the mixture, which was further stirred. The organic layer was separated, washed with water, dried and concentrated. The resulting oily residue (9 g) was purified by silica gel column chromatography to give colorless oil of methyl 2-propyl-6-heptenoate (4.8 g). The organic layer was separated washed with water dried concentrated The resulting oily residue (9 g) was purified by silica gel column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of lithium diisopropyl amide, which was prepared from diisopropylamine (6.6 g) in dry tetrahydrofuran (50 ml) and 15% butyl lithium in hexane solution (38 ml) at -65° to -60° C. in a nitrogen atmosphere, were added dropwise a solution of methyl pentanoate (7 g) in dry tetrahydrofuran (65 ml) followed by a solution of 5-bromo-1-pentene (9 g) in dry tetrahydrofuran (30 ml) at the same temperature. The mixture was stirred for 4 hours at -65° to 0° C. All the operations described above were carried out in a nitrogen atmosphere. Diluted hydrochloric acid (25 ml) and toluene (200 ml) were added at 0° C. to the mixture, which was further stirred. The organic layer was separated, washed with water, dried and concentrated. The resulting oily residue (9 g) was purified by silica gel column chromatography to give colorless oil of methyl 2-propyl-6-heptenoate (4.8 g). The organic layer was separated washed with water dried concentrated The resulting oily residue (9 g) was purified by silica gel column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of dimethyl methylphosphonate (3.25 mL, 30 mmol) in anhydrous THF (30 mL), cooled at −78° C. was added n-BuLi (1.6 M in hexane, 20.6 mL, 33 mmol). The mixture was stirred for 30 minutes at this temperature under nitrogen. Methyl valerate (2.0 mL, 15 mmol) was added dropwise for 10 minutes. The mixture was stirred for 2 hours at −78° C., gradually was warm to room temperature. The mixture was quenched with addition of 1N HCl to pH 4-5. The organic layer was separated, washed with brine and dried over MgSO4. The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98) to give the product (3.0 g) with colorless oil in 96% yield. 1H NMR (CDCl3) δ 0.848 (t, J=7.3 Hz, 3H), 1.28 (m, 2H), 1.52 (m, 2H), 2.57 (t, J=2.4 Hz, 2H) 3.074 (d, J=21 Hz, 2H), 3.760 (s, 3H), 3.762 (s, 3H). The mixture was stirred for 2 hours at −78° C. The mixture was quenched with addition of 1N HCl to pH 4-5 The organic layer was separated washed with brine dried over MgSO4 The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of dimethyl methylphosphonate (3.25 mL, 30 mmol) in anhydrous THF (30 mL), cooled at −78° C. was added n-BuLi (1.6 M in hexane, 20.6 mL, 33 mmol). The mixture was stirred for 30 minutes at this temperature under nitrogen. Methyl valerate (2.0 mL, 15 mmol) was added dropwise for 10 minutes. The mixture was stirred for 2 hours at −78° C., gradually was warm to room temperature. The mixture was quenched with addition of 1N HCl to pH 4-5. The organic layer was separated, washed with brine and dried over MgSO4. The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98) to give the product (3.0 g) with colorless oil in 96% yield. 1H NMR (CDCl3) δ 0.848 (t, J=7.3 Hz, 3H), 1.28 (m, 2H), 1.52 (m, 2H), 2.57 (t, J=2.4 Hz, 2H) 3.074 (d, J=21 Hz, 2H), 3.760 (s, 3H), 3.762 (s, 3H). The mixture was stirred for 2 hours at −78° C. The mixture was quenched with addition of 1N HCl to pH 4-5 The organic layer was separated washed with brine dried over MgSO4 The residue was purified through flash chromatography on silica gel (MeOH/DCM 2/98)

反应条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred autoclave was charged, at room temperature, with 65.76 g(714 mmol) of glycerol, 2.15 g (17.6 mmol) of methyl valerate, 0.23 g (10 wt %) of camphosulfonic acid and 0.40 g (1.0 mol %) of Pd/C at 5%. The autoclave was then pressurized at 50 bar of dihydrogen gas H2, and then it was heated at 140° C. for 16 h, stirring vigorously. After 16 h of reaction, the reaction mixture was brought back to room temperature. The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) and was rinsed with absolute ethanol. The solvents were evaporated and the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml). The organic phase was washed with water (2×30 ml) and the CH2Cl2 was then evaporated at reduced pressure. The crude reaction product was purified on a flash silica column (eluent: cyclohexane/ethyl acetate=4:1˜1:1). 1-O-pentyl-glycerol ether was obtained at an isolated yield of 58%. After 16 h of reaction was brought back to room temperature The catalyst was filtered on a MILLIPORE® filter (a membrane filter) (0.45 μm) was rinsed with absolute ethanol The solvents were evaporated the organic products were extracted from the glycerol phase by extraction with CH2Cl2 (3×50 ml) The organic phase was washed with water (2×30 ml) the CH2Cl2 was then evaporated at reduced pressure The crude reaction product was purified on a flash silica column (eluent: cyclohexane/ethyl acetate=4:1˜1:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of lithium diisopropyl amide, which was prepared from diisopropylamine (6.6 g) in dry tetrahydrofuran (50 ml) and 15% butyl lithium in hexane solution (38 ml) at -65° to -60° C. in a nitrogen atmosphere, were added dropwise a solution of methyl pentanoate (7 g) in dry tetrahydrofuran (65 ml) followed by a solution of 5-bromo-1-pentene (9 g) in dry tetrahydrofuran (30 ml) at the same temperature. The mixture was stirred for 4 hours at -65° to 0° C. All the operations described above were carried out in a nitrogen atmosphere. Diluted hydrochloric acid (25 ml) and toluene (200 ml) were added at 0° C. to the mixture, which was further stirred. The organic layer was separated, washed with water, dried and concentrated. The resulting oily residue (9 g) was purified by silica gel column chromatography to give colorless oil of methyl 2-propyl-6-heptenoate (4.8 g). The organic layer was separated washed with water dried concentrated The resulting oily residue (9 g) was purified by silica gel column chromatography