Acetic Acid → (E)-6-acetoxy-2-(3-cyclohexyl-3-oxoprop-1-enyl)bicyclo[3,3,0]octane

Temperatur

0 °C

Dimethyl(2-cyclohexyl-2-oxoethyl)phosphonate (3.3 g) was added to a stirred suspension of sodium hydride (0.34 g) and 1,4,7,10,13,16-hexaoxacyclooctadecane (10 mg) in dry tetrahydrofuran (90 ml) in an atmosphere of argon and the mixture was stirred for 12 hours. The mixture was then cooled to 0° C. and treated dropwise with 6-acetoxy-2-formylbicyclo[3,3,0]octane (1.05 g; prepared as described in Reference Example 21 and predominantly in the 2β-configuration). The reaction mixture was allowed to warm to room temperature and then it was stirred for a further period of 24 hours. A solution of glacial acetic acid (400 mg) in diethyl ether (1 ml) was then added and the mixture was concentrated in vacuo. The residue was dissolved in ethyl acetate (10 ml) and the resulting solution was washed with water (10 ml) and then with saturated aqueous sodium chloride solution (10 ml), dried over magnesium sulphate, and concentrated in vacuo. The resulting oil was treated with acetic anhydride (1 ml) and pyridine (4 ml) at 20° C. and left to stand for 12 hours. Concentration at 0.01 mmHg gave an oil, which was subjected to chromatography on a silica gel column, eluting with mixtures of ethyl acetate and hexane (1:6 v/v and then 1:1 v/v), to give (E)- 6-acetoxy-2-(3-cyclohexyl-3-oxoprop-1-enyl)bicyclo[3,3,0]octane (0.84 g), predominantly in the 2β-configuration.

1. customprepared
2. temperatureto warm to room temperature
3. stirringit was stirred for a further period of 24 hours
4. concentrationthe mixture was concentrated in vacuo
5. dissolutionThe residue was dissolved in ethyl acetate (10 ml)
6. washthe resulting solution was washed with water (10 ml)
7. dry with materialwith saturated aqueous sodium chloride solution (10 ml), dried over magnesium sulphate
8. concentrationconcentrated in vacuo
9. additionThe resulting oil was treated with acetic anhydride (1 ml) and pyridine (4 ml) at 20° C.
10. waitleft
11. waitto stand for 12 hours
12. concentrationConcentration at 0.01 mmHg
13. customgave an oil, which
14. washeluting with mixtures of ethyl acetate and hexane (1:6 v/v

ORD-Eintrag

ord-8420e38d297d4de68e98b6d63c19c103

Quelldatensatz

uspto-grants-1985_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US04517202