Water → HCID 12851163, compound

HRID 1105848Notes

Reaction equation

HRID 1105848 reaction equation
O.O.O.[C:4]([O-:7])(=[O:6])[CH3:5].[C:8]([O-:11])(=[O:10])[CH3:9].[Pb+2].[CH3:13][C@@H:14]([C@@H:17]1[C@:34]2([CH3:35])[C@H:20]([C@H:21]3[C@H:31]([CH2:32][CH2:33]2)[C@:29]2([CH3:30])[C:24]([CH2:25][C@@H:26](O)[CH2:27][C@@H:28]2[OH:36])=[CH:23][CH2:22]3)[CH2:19][CH2:18]1)[CH2:15]O.O>CN(C)C=O.C(OC(=O)C)(=O)C>[C:4]([O:7][C@H:26]1[CH2:27][C@H:28]([OH:36])[C@@:29]2([CH3:30])[C:24](=[CH:23][CH2:22][C@@H:21]3[C@@H:31]2[CH2:32][CH2:33][C@@:34]2([CH3:35])[C@H:20]3[CH2:19][CH2:18][C@@H:17]2[C@H:14]([CH3:15])[CH2:13][O:10][C:8](=[O:11])[CH3:9])[CH2:25]1)(=[O:6])[CH3:5]

Participants

6

Reactant 3

HCID 962WaterHCID 22456Lead diacetate trihydrateHCID 56631149HCID 56631149, compound

Product 1

HCID 12851163HCID 12851163, compoundYield 41.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 7918Acetic AnhydrideSolvent

Procedure

To a solution of 2.4 g of lead diacetate-trihydrate in 180 ml of dimethylformamide and 24 ml of acetic anhydride was added 4.6 g of (20S)-20-methylpregn-5-ene-1α,3β,21-triol. After standing at room temperature for 24 hr., the mixture was poured onto 1 kg of a 3:1 water--ice mixture and then extracted with ether. The ether extract was washed with water, dried (Na2SO4) and evaporated by means of a water aspirator. The residue was chromatographed on 100 g of silica gel. Elution with 1:1 hexane--ether afforded 1.14 g (20%) of (20S)-3β,21-diacetyloxy-20-methylpregn-5-en-1α-ol, mp 148°-149°. Elution with ether gave first 0.24 g (4.6%) of (20S)-3β-acetyloxy-20-methylpregn-5-ene-1α,21-diol, mp 202°-203° and then 2.94 g (57%) of (20S)-21-acetyloxy-20-methylpregn-5-ene-1α,3β -diol, mp 121°-121°. Finally, elution with ethyl acetate afforded 0.79 g (17%) of starting triol.

Workup

  1. extractionice mixture and then extracted with ether
  2. extractionThe ether extract
  3. washwas washed with water
  4. dry with materialdried (Na2SO4)
  5. customevaporated by means of a water aspirator
  6. customThe residue was chromatographed on 100 g of silica gel
  7. washElution with 1:1 hexane

Sources & evidence

ORD record
ord-2320fd6f49144785814013a1cdb45102
Source dataset
uspto-grants-1982_01
Patent number
US04310467

Reaction notes

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