Hydrochloric Acid → HCID 11022977, compound

HRID 1357477Notes

Reaction equation

HRID 1357477 reaction equation
CCC(C)[BH-](C(C)CC)C(C)CC.[Li+].[CH3:15][O:16][C:17]1[C:18]([OH:36])=[CH:19][C:20]2[CH2:21][CH:22]=[C:23]3[C@@H:32]([C:33]=2[CH:34]=1)[CH2:31][CH2:30][C@@:28]1([CH3:29])[C@H:24]3[CH2:25][CH2:26][C:27]1=[O:35].Cl>C1COCC1.CO.[OH-].[K+].OO.O>[CH3:15][O:16][C:17]1[C:18]([OH:36])=[CH:19][C:20]2[CH2:21][CH:22]=[C:23]3[C@@H:32]([C:33]=2[CH:34]=1)[CH2:31][CH2:30][C@@:28]1([CH3:29])[C@H:24]3[CH2:25][CH2:26][C@@H:27]1[OH:35]

Participants

9

Reactant 3

HCID 313Hydrochloric AcidHCID 30827973-Hydroxy-2-methoxyestra-1(10),2,4,7-tetraen-17-oneHCID 3611392Lithium tri-s-butylborohydride

Product 1

HCID 11022977HCID 11022977, compoundYield 74%

Reagents, catalysts & solvents 5

HCID 784Hydrogen PeroxideCatalystHCID 887MethanolCatalystHCID 14797Potassium HydroxideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Under nitrogen, a solution of L-Selectride in THF (1 M, 0.081 mL, 0.081 mmol) was added dropwise to a solution of 2-methoxy-3-hydroxyestra-1,3,5(10),7-tetraen-17-one (19) (0.008 g, 0.027 mmol) in dry THF (1.0 mL) cooled to 0° C. in an ice bath. The reaction was allowed to warm to room temperature and stirred for 45 m. Methanol (3 drops) followed by methanolic KOH (3%, 3 drops) were added and the mixture was cooled to 0° C. in an ice bath. Hydrogen peroxide solution (30%, 5 drops) was added and the mixture was allowed to warm to room temperature. The reaction was diluted with water, acidified with HCl, and extracted with methylene chloride (3x). The organic fractions were washed with water (1x) and brine (1x), filtered through sodium sulfate, combined and concentrated in vacuo to give 0.006 g residue. This material was crystallized from ether/hexanes to give the purified product (20) (0.0037 g, 45.9%). NMR (300 MHz, CDCl3) δ 0.662 (s, 18-CH3), 3.376 (m, 17-H), 3.867 (s, 2-OMe), 5.402 (t, J=1.65 Hz, 7-H), 6.662 (s, 4-H), 6.692 (s, 1-H) ppm. Analysis Calc. for Cl9H24O3

Workup

  1. temperatureto warm to room temperature
  2. additionwere added
  3. temperaturethe mixture was cooled to 0° C. in an ice bath
  4. temperatureto warm to room temperature
  5. extractionextracted with methylene chloride (3x)
  6. washThe organic fractions were washed with water (1x) and brine (1x)
  7. filtrationfiltered through sodium sulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-72826e7346104ef5be65477519e121b8
Source dataset
uspto-grants-2003_07
Patent number
US06593321B2

Reaction notes

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