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

HRID 1107199Notes

Reaction equation

HRID 1107199 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

Conditions

Temperature
207 °C

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). See FIG. 157. 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-287feb41747940b0b753520ae198ae3e
Source dataset
uspto-grants-2000_05
Patent number
US06057439

Reaction notes

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