Hydrochloric Acid → Estra-1,3,5(10),7-tetraen-3-ol

HRID 1781930Notes

Reaction equation

HRID 1781930 reaction equation
[CH3:1][C@@:2]12[C:18](=O)[CH2:17][CH2:16][C@H:15]1[C:14]1[C@@H:5]([C:6]3[CH:7]=[CH:8][C:9]([OH:20])=[CH:10][C:11]=3[CH2:12][CH:13]=1)[CH2:4][CH2:3]2.NN.[OH-].[K+].Cl>C(O)COCCO.O>[CH3:1][C@:2]12[CH2:3][CH2:4][C@H:5]3[C:14](=[CH:13][CH2:12][C:11]4[CH:10]=[C:9]([OH:20])[CH:8]=[CH:7][C:6]=43)[C@@H:15]1[CH2:16][CH2:17][CH2:18]2

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 9321HydrazineHCID 14797Potassium HydroxideHCID 223368Equilin

Product 1

HCID 15870996Estra-1,3,5(10),7-tetraen-3-olYield 14%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8117Diethylene GlycolSolvent

Procedure

To a suspension of equilin (100.2 mg, 0.3733 mmol) in 2 mL of diethylene glycol were added hydrazine (59 μL, 1.9 mmol) and potassium hydroxide (0.04 g, 0.7 mmol). The mixture was stirred in an oil bath at 200°-214° C. for 2 h, after which the cooled reaction was diluted with 10 mL of water, neutralized with 1N HCl, and extracted three times with 25 mL of ether. The combined organic extracts were washed with 10 mL of brine, dried over magnesium sulfate, filtered, concentrated, and purified by preparative TLC (silica gel, 15% ethyl acetate/hexane eluent) to give a yellow resin. Product was further purified by decolorizing with charcoal and recrystallization from aqueous ethanol to give tan crystals (13.2 mg, 51.9 μM, 14%), m.p. 130°-134° C.

Workup

  1. customafter which the cooled reaction
  2. extractionextracted three times with 25 mL of ether
  3. washThe combined organic extracts were washed with 10 mL of brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified by preparative TLC (silica gel, 15% ethyl acetate/hexane eluent)
  8. customto give a yellow resin
  9. customProduct was further purified
  10. customby decolorizing with charcoal and recrystallization from aqueous ethanol

Sources & evidence

ORD record
ord-cc1b14e0a7fe4a6e80978c8fa4432adb
Source dataset
uspto-grants-1997_05
Patent number
US05633392

Reaction notes

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