Diisopropylamine → 1-(3-Butenyl)Cyclopentane Carboxylic Acid Methyl Ester

Temperatur

0 °C

To a solution of diisopropylamine (225 mmol, 31.6 mL) in THF (150 mL) was added dropwise a solution of n-butyl lithium (217.5 mmol, 87 mL, 2.5M) in hexanes at −10° C. while maintaining the temperature below 0° C. After addition, the solution was stirred for 30 min at 0° C. To this, a solution of methyl cyclopentane carboxylate (150 mmol, 19.23 g) in THF (30 mL) was added dropwise at −70° C. maintaining the internal temperature between −60 to −70° C. After addition, the reaction mixture was stirred for 1 h at −50 to −60° C. Then, a solution of 4-bromo-1-butene (142.2 mmol, 19.2 g) in THF (30 mL) was added dropwise and the light brown suspension was stirred for 1 h at −60 to −70° C. Then, it was allowed to warm to room temperature and stirred overnight. The reaction mixture was poured into a saturated solution of ammonium chloride (250 mL) and the mixture was extracted with ether (2×150 mL). The combined extracts were washed with a saturated solution of sodium chloride (150 mL) and dried over anhydrous magnesium sulfate. After filtration of the drying agent, the solution was concentrated under vacuum and the residue was distilled at 63-67° C./2.5 mm Hg to give 13.77 g (53%) of a colorless oil. HR MS (C11H16O2): Obs mass, 182.1311. Calcd mass, 182.1307 (M+).

1. temperaturewhile maintaining the temperature below 0° C
2. additionAfter addition
3. temperaturemaintaining the internal temperature between −60 to −70° C
4. additionAfter addition
5. stirringthe reaction mixture was stirred for 1 h at −50 to −60° C
6. stirringthe light brown suspension was stirred for 1 h at −60 to −70° C
7. temperatureto warm to room temperature
8. stirringstirred overnight
9. extractionthe mixture was extracted with ether (2×150 mL)
10. washThe combined extracts were washed with a saturated solution of sodium chloride (150 mL)
11. dry with materialdried over anhydrous magnesium sulfate
12. filtrationAfter filtration of the drying agent
13. concentrationthe solution was concentrated under vacuum
14. distillationthe residue was distilled at 63-67° C./2.5 mm Hg

ORD-Eintrag

ord-1feeabf392e34d62a56ed8caafa503f3

Quelldatensatz

uspto-grants-2004_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06806365B2