反应详情

温度

15 °C

A solution of bromine (0.114 ml.) in acetic acid (2 ml.) was added dropwise to a stirred solution of 11-(17β-acetoxy-3-oxo-oestra-4-en-7α-yl)undecanoic acid (Example 2; 0.5 g.) in a mixture of diethyl ether (5 ml.) and acetic acid (2 ml.) which was cooled to 15° C. and the mixture was stirred at that temperature for 30 minutes and then poured into water (50 ml.). The mixture was extracted three times with methylene chloride (30 ml. each time) and the combined extracts were washed with water, dried and rapidly evaporated to dryness under reduced pressure at a bath temperature below 20° C. A solution of the residue, which consisted of 11-(17β-acetoxy-2,6-dibromo-3-oxooestr-4-en-7α-yl)undecanoic acid in dimethylformamide (3 ml.) was immediately added to a stirred mixture of lithium bromide (1.0 g.), lithium carbonate (1.0 g.) and dimethylformamide (10 ml.) which was heated under reflux, and the mixture was stirred and heated under reflux for 30 minutes and then evaporated to dryness under reduced pressure. Water (20 ml.) was added to the residue and the mixture was acidified to pH 1 with aqueous N-hydrochloric acid and extracted three times with methylene chloride (20 ml. each time). The combined extracts were washed with water, dried and evaporated to dryness and the residue was purified by chromatography on a silica gel column using a 7:3 v/v mixture of toluene and ethyl acetate as eluant. There was thus obtained as an oil 11-(17β-acetoxy-3-hydroxyoestra-1,3,5(10),6-tetraen-7-yl)undecanoic acid.

1. extractionThe mixture was extracted three times with methylene chloride (30 ml
2. washeach time) and the combined extracts were washed with water
3. customdried
4. customrapidly evaporated to dryness under reduced pressure at a bath temperature below 20° C
5. additionwas immediately added to a stirred mixture of lithium bromide (1.0 g.), lithium carbonate (1.0 g.) and dimethylformamide (10 ml.) which
6. temperaturewas heated
7. temperatureunder reflux
8. stirringthe mixture was stirred
9. temperatureheated
10. temperatureunder reflux for 30 minutes
11. customevaporated to dryness under reduced pressure
12. additionWater (20 ml.) was added to the residue
13. extractionextracted three times with methylene chloride (20 ml
14. washThe combined extracts were washed with water
15. customdried
16. customevaporated to dryness
17. customthe residue was purified by chromatography on a silica gel column
18. additiona 7:3 v/v mixture of toluene and ethyl acetate as eluant