Water → HCID 70447827, compound

HRID 543011Notes

Reaction equation

HRID 543011 reaction equation
BrBr.[C:3]([O:6][C@H:7]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:9])[C@@H:21]1[C:16](=[CH:17][C:18](=[O:25])[CH2:19][CH2:20]1)[CH2:15][C@H:14]3[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][C:36]([OH:38])=[O:37])(=[O:5])[CH3:4].O>C(O)(=O)C.C(OCC)C>[C:3]([O:6][C@H:7]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:9])[C:21]1[CH:20]=[CH:19][C:18]([OH:25])=[CH:17][C:16]=1[CH:15]=[C:14]3[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][C:36]([OH:38])=[O:37])(=[O:5])[CH3:4]

Participants

6

Reactant 3

HCID 962WaterHCID 24408BromineHCID 70448142HCID 70448142, compound

Product 1

HCID 70447827HCID 70447827, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
15 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-86ce25faf6af43aaae3b7fd0d5a1db21
Source dataset
uspto-grants-1987_04
Patent number
US04659516

Reaction notes

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