Sodium Bicarbonate → 15beta-Ethyl-3-methoxy-15beta-methylestra-1,3,5(10)-trien-17beta-ol

HRID 2256868Notes

Reaction equation

HRID 2256868 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][CH2:8][C@:9]1([CH3:30])[C@H:14]2[C@H:15]3[C@H:24]([CH2:25][CH2:26][C@:12]2([CH3:13])[C:11](=[O:29])[CH2:10]1)[C:23]1[CH:22]=[CH:21][C:20]([O:27][CH3:28])=[CH:19][C:18]=1[CH2:17][CH2:16]3.C(=O)([O-])O.[Na+]>O1CCCC1>[CH2:8]([C@:9]1([CH3:30])[C@H:14]2[C@H:15]3[C@H:24]([CH2:25][CH2:26][C@:12]2([CH3:13])[C@@H:11]([OH:29])[CH2:10]1)[C:23]1[CH:22]=[CH:21][C:20]([O:27][CH3:28])=[CH:19][C:18]=1[CH2:17][CH2:16]3)[CH3:7]

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 1056816215beta-Ethyl-3-methoxy-15beta-methylestra-1,3,5(10)-trien-17-oneHCID 21226445Aluminium lithium hydride

Product 1

HCID 1061628015beta-Ethyl-3-methoxy-15beta-methylestra-1,3,5(10)-trien-17beta-olYield 91.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Lithium aluminum hydride (48 mg; 1.26 mmol) was added to a solution of the 15α-ethyl-15β-methyl ketone (8) (80 mg; 0.25 mmol) in dry tetrahydrofuran at 0° C. Low temperature stirring was maintained for 5 min. Saturated aqueous sodium hydrogen carbonate was added and the mixture was filtered. Standard work-up of the filtrate (ethyl acetate) gave 15α-ethyl-3-methoxy-15β-methylestra-1,3,5(10) -trien-17β-ol (14) (75 mg; 89%), m.p. 133°-136° C. (from chloroform-methanol); [α]D +67° (c 0.9); υmax 3604 cm-1 (OH); δH 0.88 (3H, t, J 7.2 Hz, 15α-CH2CH3), 0.93 (3H, s, 15β-Me), 1.06 (3H, s, 13β-Me), 1.10 (1H, d, J 11.1 Hz, 14α-H), 1.32 obsc (2H, m, 15α-CH2CH3), 1.39 and 2.04 (each 1H, dd, J 13.2 and 10.0, and 13.2 and 7.9 Hz, 16α- and 16β-H), 2.84 (2H, m, 6-H2), 3.60 (1H, dd, J 10.0 and 7.9 Hz, 17α-H), 3.77 (3H, s, 3-OMe), 6.61 (1H, d, J 2.9 Hz, 4-H), 6.70 (1H, dd, J 8.6 and 2.9 Hz, 2-H), and 7.20 (1H, d, J 8.6 Hz, 1-H); δC 9.4 (C-152), 13.9 (C-18), 23.7 (C-151), 26.1 (C-11), 28.6 (C-7), 29.9 (C-6), 37.1 (C-12), 37.7 (C-8), 38.9 (15β-Me), 39.7 (C-15), 45.0 (C-9), 45.6 (C-14), 55.2 (3-OMe), 55.6 (C-13), 79.3 (C-16), 80.2 (C-17), 111.4 (C-2), 113.6 (C-4), 126.3 (C-1), 133.0 (C-10), 137.7 (C-5), and 157.5 (C-3) (Found: C, 80.0; H, 9.7%; M+, 328. C22H32O requires C, 80.4; H, 9.8%; M, 328) .

Workup

  1. temperaturewas maintained for 5 min
  2. filtrationthe mixture was filtered

Sources & evidence

ORD record
ord-8137d704fdc244da920dbe1a7605cf86
Source dataset
uspto-grants-1997_08
Patent number
US05656622

Reaction notes

Loading…