Boron trifluoride etherate → HCID 11851463, compound

HRID 1750895Notes

Reaction equation

HRID 1750895 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].[C:22]12(O)[CH2:31][CH:26]3[CH2:27][CH:28]([CH2:30][CH:24]([CH2:25]3)[CH2:23]1)[CH2:29]2.B(F)(F)F.CCOCC>CCCCC>[C:22]12([C:19]3[C:2]([OH:1])=[C:3]([CH3:21])[C:4]4[CH2:5][CH2:6][C@@H:7]5[C@@H:16]([C:17]=4[CH:18]=3)[CH2:15][CH2:14][C@@:12]3([CH3:13])[C@H:8]5[CH2:9][CH2:10][C:11]3=[O:20])[CH2:31][CH:26]3[CH2:27][CH:28]([CH2:30][CH:24]([CH2:25]3)[CH2:23]1)[CH2:29]2

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 641521-AdamantanolHCID 14506961HCID 14506961, compound

Product 1

HCID 11851463HCID 11851463, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 8003PentaneSolvent

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) and 30 mg (0.197 mmol) of 1-adamantanol in 1 mL of anhydrous pentane was added 0.02 mL of boron trifluoride diethyl etherate while cooling with an ice bath and stirring. After stirring at 0° C. for 15 min. the reaction was stirred at room temperature for 45 min. Ice was added and the white solid that formed was filtered, washed with water and dried over P2O5. The crude product was purified by chromatography (silica gel eluted with 7% ethyl acetate in hexanes) to give 30 mg of pure product (68% yield). After recrystallization from methylene chloride-hexanes the product had: m.p. 262-263° C.; 1H NMR(CDCl3) δ0.90 (s, 3H, CH3), 2.13 (s, 3H, CH3), 2.7 (m, 2H, CH2), 7.11 (s, 1H, Ar—H); 13C NMR (CDCl3) δ11.02, 13.70, 21.44, 26.22, 26.67, 27.54, 28.95 (3∴C), 31.56, 35.84, 36.60, 36.98 (3×C), 37.63, 40.82 (3×C), 44.60, 47.91, 50.34, 121.41, 121.51, 131.45, 133.32, 150.79, 221.49. (Anal. calc'd. for C29H39O2: C, 83.21; H, 9.15. Found: C, 83.45; H, 8.94.)

Workup

  1. temperaturewhile cooling with an ice bath
  2. stirringAfter stirring at 0° C. for 15 min. the reaction
  3. stirringwas stirred at room temperature for 45 min
  4. additionIce was added
  5. customthe white solid that formed
  6. filtrationwas filtered
  7. washwashed with water
  8. dry with materialdried over P2O5
  9. customThe crude product was purified by chromatography (silica gel eluted with 7% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-3eca2960848c4f5fabe49cab9e90a645
Source dataset
uspto-grants-2015_10
Patent number
US09156876B2

Reaction notes

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