Ethanol → HCID 9801467, compound

HRID 1760846Notes

Reaction equation

HRID 1760846 reaction equation
[C:1]12([C:11]3[C:12]([OH:30])=[CH:13][C:14]4[CH2:15][CH2:16][C@@H:17]5[C@@H:26]([C:27]=4[CH:28]=3)[CH2:25][CH2:24][C@@:22]3([CH3:23])[C@H:18]5[CH2:19][CH2:20][C:21]3=[O:29])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.C(O)C.[BH4-].[Na+]>CO>[C:1]12([C:11]3[C:12]([OH:30])=[CH:13][C:14]4[CH2:15][CH2:16][C@@H:17]5[C@@H:26]([C:27]=4[CH:28]=3)[CH2:25][CH2:24][C@@:22]3([CH3:23])[C@H:18]5[CH2:19][CH2:20][C@@H:21]3[OH:29])[CH2:2][CH:3]3[CH2:4][CH:5]([CH2:6][CH:7]([CH2:9]3)[CH2:8]1)[CH2:10]2

Participants

5

Reactant 3

HCID 702EthanolHCID 4311764Sodium borohydrideHCID 12134978HCID 12134978, compound

Product 1

HCID 9801467HCID 9801467, compoundYield 59.5%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2-(1-Adamantyl)-3-hydroxyestra-1,3,5(10)-trien-17-one (250 mg, 0.62 mmol) was added to cold ethanol (25 mL) and methanol (10 mL) to give a turbid solution. Sodium borohydride (NaBH4, 140 mg) was added in one portion and the reaction was continued with stirring for 2 hours. Solvents were removed on a rotary evaporator and crushed ice was added. On standing overnight, the initially formed oil became a solid. The solid was filtered and washed with water until the filtrate was pH neutral. The solid was dried in a vacuum oven at 50° C. to give the crude product (0.25 g), which was purified by flash chromatography (silica gel eluted with 18% ethyl acetate in hexanes). The pure product (200 mg, 79.6%) was recrystallized from chloroform and hexanes to obtain crystals (150 mg), and was then characterized as follows: (i) melting point=174-175° C.; (ii) 1H NMR (CDCl3, 300 MHZ) δ0.81 (s, 3H, C18—CH3), 2.76 (m, 2H, C6—CH2), 3.73 (t, 1H, C17—H), 4.78 (s, 1H, C3—OH), 6.38 (s, 1H, C4—H), 7.16 (s, 1H, C1—H); (iii) 13C NMR (CDCl3, 300 MHZ) δ10.95, 23.02, 26.33, 27.12, 28.77, 28.98 (3×C), 30.49, 36.54, 36.71, 37.01 (3×C), 38.89, 40.68 (3×C), 43.20, 44.22, 49.96, 81.99, 116.84, 124.06, 132.06, 133.83, 135.20, 152.36.

Workup

  1. customto give a turbid solution
  2. customSolvents were removed on a rotary evaporator
  3. customcrushed ice
  4. additionwas added
  5. waitOn standing overnight
  6. filtrationThe solid was filtered
  7. washwashed with water until the filtrate
  8. customThe solid was dried in a vacuum oven at 50° C.
  9. customto give the crude product (0.25 g), which
  10. customwas purified by flash chromatography (silica gel eluted with 18% ethyl acetate in hexanes)
  11. customThe pure product (200 mg, 79.6%) was recrystallized from chloroform and hexanes

Sources & evidence

ORD record
ord-9ecc86191c354a929685dafa918a58d8
Source dataset
uspto-grants-2005_01
Patent number
US06844456B2

Reaction notes

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