Potassium Acetate → (11beta)-21-(Acetyloxy)-11-hydroxypregna-1,4,16-triene-3,20-dione

HRID 34720Notes

Reaction equation

HRID 34720 reaction equation
C(O[C@:5]1([C@:29]2([CH3:30])[C@H:15]([C@H:16]3[C@H:26]([C@@H:27]([OH:31])[CH2:28]2)[C@:24]2([CH3:25])[C:19](=[CH:20][C:21](=[O:32])[CH:22]=[CH:23]2)[CH2:18][CH2:17]3)[CH2:14][CH2:13]1)[C:6](=[O:12])[CH2:7][O:8][C:9](=[O:11])[CH3:10])(=O)C.C([O-])(=O)C.[K+]>CN(C)C=O>[C:9]([O:8][CH2:7][C:6](=[O:12])[C:5]1[C@:29]2([CH3:30])[C@H:15]([C@H:16]3[C@H:26]([C@@H:27]([OH:31])[CH2:28]2)[C@:24]2([CH3:25])[C:19](=[CH:20][C:21](=[O:32])[CH:22]=[CH:23]2)[CH2:18][CH2:17]3)[CH2:14][CH:13]=1)(=[O:11])[CH3:10]

Participants

4

Reactant 2

HCID 517044Potassium AcetateHCID 14233395Prednisolone 17,21-diacetate

Product 1

HCID 102365(11beta)-21-(Acetyloxy)-11-hydroxypregna-1,4,16-triene-3,20-dioneYield 91.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
105 °C

Procedure

To a solution of the product of Example 13 (21.4 g) in 250 ml dimethylformamide, potassium acetate (25 g) was added. After stirring at 105° C. under nitrogen for 6 hours, the reaction mixture was cooled down to room temperature and poured into ice water (3 L). After filtration, crystallization from acetone afforded 21-acetoxy-11β-hydroxyl-1,4,16-pregnatriene-3,20-dione (17 g, 89.8%). Recrystallization gave yellowish long cubic, m.p.=203°-205° C. NMR (CDCl3) δ 1.25 (s, 3H, 13--CH3), 1.48 (s, 3H, 10--CH3), 2.18 (s, 3H, 21--Ac), 4.40 (m, 1H, 11--H), 4.94(m, 2H, 20--CH2O--). 6.02 (S, 1H, 4--H), 6.28 (dd, 1H, J=10 and 2 Hz, 2--H), 6.74 (m, 1H, 16--H), 7.30 (d, 1H, J=10 Hz, 1--H). Upon normal saponification there was obtained 11β,21-dihydroxy-1,4,16-pregnatriene-3,20-dione. Recrystallization from acetone gave needles (VI, 50.5%). m.p.=213°-215° C.; NMR (CDCl3) δ 1.25(s, 3H, 13--CH3), 1.49 (s, 3H, 10--CH3), 4.35-4.55 (m, 3H, 20--CH2 -- and 11--H), 6.02 (S, 1H, 4--H), 6.28 (dd, 1H, J=10 and 2 Hz, 2--H), 6.73(m, 1H, 16--H), 7.32 (d, 1H, J=10 Hz, 1--H).

Workup

  1. temperaturethe reaction mixture was cooled down to room temperature
  2. filtrationAfter filtration, crystallization from acetone

Sources & evidence

ORD record
ord-759aacbc27d54592a453b3eb42f58678
Source dataset
uspto-grants-1988_08
Patent number
US04762919

Reaction notes

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