Formaldehyde → 17beta-Hydroxy-17alpha-methyl-6-methyleneandrosta-4,15-diene-3-one

HRID 274309Notes

Reaction equation

HRID 274309 reaction equation
[OH:1][C@@:2]1([CH3:22])[CH:7]=[CH:6][C@H:5]2[C@H:8]3[C@H:18]([CH2:19][CH2:20][C@:3]12[CH3:4])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:21])[CH2:14][CH2:15]1)[CH2:10][CH2:9]3.C=O.F[C:26](F)(F)C([O-])=O.C[NH2+]C1C=CC=CC=1>O1CCCC1.C(OCC)(=O)C>[OH:1][C@@:2]1([CH3:22])[CH:7]=[CH:6][C@H:5]2[C@H:8]3[C@H:18]([CH2:19][CH2:20][C@:3]12[CH3:4])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:21])[CH2:14][CH2:15]1)[C:10](=[CH2:26])[CH2:9]3

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 2724109N-Methylanilinium trifluoroacetateHCID 1567913617beta-Hydroxy-17alpha-methylandrosta-4,15-dien-3-one

Product 1

HCID 1567914917beta-Hydroxy-17alpha-methyl-6-methyleneandrosta-4,15-diene-3-oneYield 43.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

500 mg of 17β-hydroxy-17α-methylandrosta-4,15-dien-3-one in 8.3 ml of tetrahydrofuran is stirred at 60° C. under argon with 348 mg of paraformaldehyde and 2.2 g of N-methylanilinium trifluoroacetate. After 3.5 hours, the mixture is diluted with ethyl acetate, washed with water, dried over sodium sulfate, and concentrated under vacuum. After the crude product has been chromatographed on silica gel with a pentane-diethyl ether gradient, 226 mg of 17β-hydroxy-17α-methyl-6-methyleneandrosta-4,15-dien-3-one is obtained, mp 162° C. (from isopropyl ether).

Workup

  1. washwashed with water
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated under vacuum
  4. customAfter the crude product has been chromatographed on silica gel with a pentane-diethyl ether gradient

Sources & evidence

ORD record
ord-b8251a7cb1e8404081cc15d107ca2282
Source dataset
uspto-grants-1995_02
Patent number
US05389624

Reaction notes

Loading…