Boron trifluoride etherate → HCID 12134980, compound

HRID 1750894Notes

Reaction equation

HRID 1750894 reaction equation
[OH:1][C:2]1[CH:19]=[CH:18][C:17]2[C@@H:16]3[C@H:7]([C@H:8]4[C@@:12]([CH2:14][CH2:15]3)([CH3:13])[C:11](=[O:20])[CH2:10][CH2:9]4)[CH2:6][CH2:5][C:4]=2[C:3]=1[CH3:21].B(F)(F)F.[CH3:26]COCC.CC[CH2:33][CH2:34][CH3:35]>C(O)(C)(C)C>[CH3:26][C:34]([C:19]1[C:2]([OH:1])=[C:3]([CH3:21])[C:4]2[CH2:5][CH2:6][C@@H:7]3[C@@H:16]([C:17]=2[CH:18]=1)[CH2:15][CH2:14][C@@:12]1([CH3:13])[C@H:8]3[CH2:9][CH2:10][C:11]1=[O:20])([CH3:33])[CH3:35]

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 8003PentaneHCID 14506961HCID 14506961, compound

Product 1

HCID 12134980HCID 12134980, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

To a suspension of the known 3-hydroxy-4-methylestra-1,3,5(10)-trien-17-one (ref. Kaneko et al., 1964; Chemical Abstracts Registry Number [68969-90-4], 30 mg, 0.11 mmol) in 1 mL of anhydrous pentane and 0.5 mL of t-butanol, was added 0.03 mL of boron trifluoride diethyl etherate while cooling with an ice bath and stirring. After 20 min., the reaction was stirred at room temperature for 2.5 h. Ice was added and the solid that formed was filtered, washed with water and dried overnight in a vacuum desiccator. The crude product was purified by chromatography (silica gel eluted with 10% ethyl acetate in hexanes) and then recrystallized from methylene chloride-hexanes to give 20 mg of pure product (56% yield): m.p. 190-192° C.; 1H NMR(CDCl3) δ0.90 (s, 3H, CH3), 1.42 (s, 9H, C(CH3)3), 2.13 (s, 3H, CH3), 2.79-2.81 (m, 2H, CH2), 7.16 (s, 1H, Ar—H); 13C NMR (CDCl3) δ 11.06, 13.70, 21.44, 26.16, 26.60, 26.68, 27.54, 29.82 (3×C), 31.55, 34.43, 35.84, 37.63, 44.52, 47.89, 50.34, 121.42, 131.28, 133.00, 133.55, 150.56, 221.45. (Anal. calc'd. for C23H32O2: C, 81.13; H, 81.09. Found: C, 81.09; H, 9.59.)

Workup

  1. temperaturewhile cooling with an ice bath
  2. stirringthe reaction was stirred at room temperature for 2.5 h
  3. additionIce was added
  4. customthe solid that formed
  5. filtrationwas filtered
  6. washwashed with water
  7. customdried overnight in a vacuum desiccator
  8. customThe crude product was purified by chromatography (silica gel eluted with 10% ethyl acetate in hexanes)
  9. customrecrystallized from methylene chloride-hexanes

Sources & evidence

ORD record
ord-2f544e997c4747dfa079737536c02dce
Source dataset
uspto-grants-2015_10
Patent number
US09156876B2

Reaction notes

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