methyl 9-oxohexadecanoate

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Under a nitrogen atmosphere, methyl 9-oxo-hexadecanoate (No. 4984860; 2.39 g, 8.40 mmol) was dissolved in dichloromethane (47 mL), and the solution was cooled to 0° C. While maintaining the temperature at 0° C., 1,2-ethanedithiol (840 μL, 10.1 mmol), and borontrifluoride-ethylether complex (1.24 mL, 10.1 mmol) were sequentially added, and the mixture was stirred at 0° C. for 5 minutes and at room temperature for 2 hours. Water was added to the reaction solution to stop the reaction, and the solution was extracted with dichloromethane. The organic layer was sequentially washed with a saturated sodium bicarbonate aqueous solution and a saturated brine, and dried over anhydrous sodium sulfate. After the organic layer was filtered and the solvent was distilled off, the resulting residue was purified with SP1 (SiO2 cartridge, 5.0% ethyl acetate/n-hexane, Rf=0.5) to obtain methyl 8-(2-heptyl-[1,3]dithiolan-2-yl)-octanoate (No. 5553355; 2.57 g, 85% yield). While maintaining the temperature at 0° C. the reaction the solution was extracted with dichloromethane The organic layer was sequentially washed with a saturated sodium bicarbonate aqueous solution a saturated brine, and dried over anhydrous sodium sulfate After the organic layer was filtered the solvent was distilled off the resulting residue was purified with SP1 (SiO2 cartridge, 5.0% ethyl acetate/n-hexane, Rf=0.5)

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Under a nitrogen atmosphere, monomethyl azelate (6.70 g, 33.1 mmol), commercially available from Tokyo Chemical Industry Co., Ltd., was dissolved in toluene (60 mL), N,N-dimethylformamide (DMF, 25.6 μL, 0.331 mmol) was added thereto, and the solution was warmed to 60° C. While maintaining the temperature at 60° C., a solution of oxalyl chloride (2.94 mL, 34.8 mmol) in toluene (7.0 mL) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was stirred at 60° C. for 2.0 hours. Toluene and oxalyl chloride were distilled off under reduced pressure, and subsequently tetrahydrofuran (THF, 67 mL) was added to distill off the solvent. Under a nitrogen atmosphere, this crude product was dissolved in THF (50 mL), tris(2,4-pentadionato) iron (III) (Fe(acac)3, 0.585 g, 0.166 mmol) was added thereto, and the solution was cooled to −40° C. Subsequently, a dilution of n-heptyl magnesium bromide (1 M solution in THF, 36.4 mL, 36.4 mmol) with THF (30 mL) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at −40° C. for 1.5 hours. To the reaction solution was added 0.5 M aqueous hydrochloric acid solution (40 mL) to stop the reaction, and the solution was extracted with ethyl acetate. The aqueous layer was washed with ethyl acetate, and the organic layers were combined, washed sequentially with water, a saturated sodium bicarbonate aqueous solution, and a saturated brine and dried over anhydrous sodium sulfate. After the organic layer was filtered and the solvent was distilled off, the resulting residue was purified with SP1 (SiO2 cartridge, 10% ethyl acetate/n-hexane, Rf=0.2) to obtain methyl 9-oxo-hexadecanoate (No. 4984860; 7.33 g, 78% yield). While maintaining the temperature at 60° C. After completion of the dropwise addition Toluene and oxalyl chloride were distilled off under reduced pressure, and subsequently tetrahydrofuran (THF, 67 mL) was added to distill off the solvent Under a nitrogen atmosphere, this crude product was dissolved in THF (50 mL) the solution was cooled to −40° C After completion of the dropwise addition the mixture was stirred at −40° C. for 1.5 hours the reaction the solution was extracted with ethyl acetate The aqueous layer was washed with ethyl acetate washed sequentially with water a saturated sodium bicarbonate aqueous solution, and a saturated brine and dried over anhydrous sodium sulfate After the organic layer was filtered the solvent was distilled off the resulting residue was purified with SP1 (SiO2 cartridge, 10% ethyl acetate/n-hexane, Rf=0.2)