Hydrochloric Acid → 1-Cyclopropylpentane-1,3-dione

A stirred suspension of magnesium turnings (1.83 g, 75.0 mmol) in methanol (85 ml) was heated under reflux for 90 minutes. The suspension was cooled to room temperature and a solution of 3-ketopentanoic acid (17.4 g, 150.0 mmol) in methanol (15 ml) was added. The white suspension dissolved to give a pale yellow solution. The reaction was stirred at room temperature for 1 hour and then concentrated under reduced pressure to give a pale yellow solid which was dissolved in N,N-dimethylformamide (50 ml). In a separate flask carbonyldiimidazole (13.4 g, 83.0 mmol) was added portionwise to a stirred solution of cyclopropanecarboxylic acid (6.46 g, 75.0 mmol) in N,N-dimethylformamide (150 ml) at room temperature under nitrogen. The reaction was stirred for 90 minutes and then the magnesium salt previously prepared was added dropwise. The reaction was stirred for 3 days and then poured into 1.0M hydrochloric acid (150 ml). The aqueous phase was extracted with ether (3×200 ml) and the combined organic phases were dried over magnesium sulphate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel eluting with pentane:ethyl acetate (90:10, by volume) to provide the title compound (9.33 g) as a yellow oil.

1. temperaturewas heated
2. temperatureunder reflux for 90 minutes
3. dissolutionThe white suspension dissolved
4. customto give a pale yellow solution
5. concentrationconcentrated under reduced pressure
6. customto give a pale yellow solid which
7. stirringThe reaction was stirred for 90 minutes
8. additionwas added dropwise
9. stirringThe reaction was stirred for 3 days
10. extractionThe aqueous phase was extracted with ether (3×200 ml)
11. dry with materialthe combined organic phases were dried over magnesium sulphate
12. filtrationfiltered
13. concentrationconcentrated under reduced pressure
14. customThe crude product was purified by flash chromatography on silica gel eluting with pentane:ethyl acetate (90:10, by volume)

ORD-Eintrag

ord-1291d1b522d849b5bd105907c1ae4a87

Quelldatensatz

uspto-grants-2011_11

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08063044B2